UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

The role of olefins in fouling of heat exchangers Asomaning, Samuel 1990

Your browser doesn't seem to have a PDF viewer, please download the PDF to view this item.

Item Metadata

Download

Media
831-UBC_1990_A7 A86.pdf [ 20.03MB ]
Metadata
JSON: 831-1.0058696.json
JSON-LD: 831-1.0058696-ld.json
RDF/XML (Pretty): 831-1.0058696-rdf.xml
RDF/JSON: 831-1.0058696-rdf.json
Turtle: 831-1.0058696-turtle.txt
N-Triples: 831-1.0058696-rdf-ntriples.txt
Original Record: 831-1.0058696-source.json
Full Text
831-1.0058696-fulltext.txt
Citation
831-1.0058696.ris

Full Text

THE ROLE OF OLEFINS IN FOULING OF HEAT EXCHANGERS By Samuel Asomaning M . Sc. (Eng.) Lvov Polytechnic Institute A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED SCIENCE in THE FACULTY OF GRADUATE STUDIES CHEMICAL ENGINEERING We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA May 1990 © Samuel Asomaning, 1990 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of OLt^M.C'Ji ^T^ft i» i l f lr ( The University of British Columbia Vancouver, Canada DE-6 (2/88) Abstract Chemical reaction fouling is one of several categories of fouling of heat exchangers. It is encountered mostly in petroleum, petrochemical, and food processing industries, where it results in severe economic penalties. Olefins have been associated with fouling during heating of organic mixtures, and gum formation during storage and use of hydrocarbon fuels. In this work, thermal fouling studies are reported for a number of olefins, present at 10 % wt. in kerosene, undergoing sensible heating in the liquid phase at relatively high heat fluxes. Experimental work was done on an available fouling rig consisting of an annular probe and a coiled wire probe mounted in parallel. The annular probe with its heated central core operated in turbulent flow whilst the coiled wire, with flow normal to it, was in the laminar flow regime. Runs were conducted both under oxygenated (air-saturated) and deoxygenated conditions. The range of bulk temperatures was from 70 - 85 °C, the initial wall temperatures were 180 - 205 °C, with a system pressure of 410 kPa (abs.). The range of heat fluxes was 150 - 350 kW/m2. Only minor differences were noted between the extent or rate of fouling on the two different probes. Runs at heat fluxes below 180 kW/m2 and bulk temperatures below 80 °C generally showed no measurable fouling with any of the olefins tested. Linear and falling rate fouling curves were observed at more severe conditions over 45 hours of typical runs. Under air saturated conditions, straight chain terminal olefins of Cg - Cg showed little or no measurable fouling. The longer chain length hexadecene—1, showed a significant increase in fouling. Moderate fouling was observed for 4-vinylcyclohexene. The cyclic olefins, dicyclopentadiene and indene, yielded the greatest Rf values, being ii about 30 - 50 times those of the straight chain terminal olefins. Under deoxygenated conditions, typical Rj values were a factor of about 30 below the corresponding values for air saturated conditions. Rj generally increased with increasing heat flux. Where the antioxidant initially present in the olefin was not removed before use, very little fouling occurred. The effects of deoxygenation, heat flux and species effects are discussed and a probable fouling mechanism involving formation of polymeric peroxides by autoxidation of the olefins suggested. The fouling rates over the linear portions of the fouling curves have been calculated and the deposit thermal conductivity based on the maximum fouling resistance and deposit thickness have been estimated. Analyses of selected deposits have been presented and compared with both theoretical calculations for the expected polymeric peroxides and values in the literature. ni Table of Contents Abstract ii List of Tables v List of Figures vi Acknowledgement vii 1 I N T R O D U C T I O N 1 2 L I T E R A T U R E R E V I E W 7 2.1 FOULING T Y P E S AND CATEGORIES 7 2.2 STAGES IN FOULING AND THEIR CORRESPONDING MODELS . . 10 2.3 C H E M I C A L R E A C T I O N FOULING 13 2.3.1 Oxidation of olefinic hydrocarbons 14 2.3.2 Autoxidation 16 2.3.3 Polymerization 21 2.3.4 Pyrolysis and pyrolytic reactions 23 2.4 E F F E C T OF PROCESS VARIABLES ON C H E M I C A L R E A C T I O N FOUL-ING 24 2.4.1 The role of sulphur compounds 24 2.4.2 Effect of nitrogen compounds 25 2.4.3 The role of oxygen in chemical reaction fouling 26 2.4.4 Effect of trace metals and wall material 28 iv 2.4.5 Effect of fluid velocity 30 2.4.6 Effect of particulates 31 2.4.7 Effect of hydrocarbon constituents 31 2.4.8 Effect of temperature 36 2.5 KINETICS AND M O D E L L I N G OF C H E M I C A L R E A C T I O N FOULING 37 2.6 MITIGATION AGAINST C H E M I C A L R E A C T I O N FOULING 41 2.6.1 Chemical mitigation 42 2.6.2 Cleaning 43 2.7 T H E FOULING RIG 44 2.7.1 The annular probe 46 2.7.2 The hot wire probe 47 3 B A C K G R O U N D T O T H E P R E S E N T W O R K 49 4 W O R K I N G F L U I D S 52 4.1 K E R O S E N E 52 4.1.1 Hygroscopicity of kerosene 53 4.2 U N S A T U R A T E D H Y D R O C A R B O N S 56 5 E X P E R I M E N T A L A P P A R A T U S 61 5.1 F L O W LOOP 61 5.2 Supply tank 62 5.3 TEST SECTIONS 65 5.3.1 Portable Fouling Research Unit 65 5.3.2 Hot Wire Probe 65 5.4 C O N T R O L CIRCUIT 69 v 6 EXPERIMENTAL PROCEDURE 73 6.1 M E A S U R E M E N T OF FLUID PROPERTIES 73 6.1.1 Measurement of density of test fluids 73 6.1.2 Determination of viscosity 73 6.2 C A L I B R A T I O N OF T H E E Q U I P M E N T 74 6.2.1 Orifice meter calibration 74 6.2.2 Calibration of Thermocouples 76 6.3 P R E P A R A T I O N OF C H E M I C A L S 76 6.4 G E N E R A L P R O C E D U R E FOR FOULING RUNS 77 6.5 C H E M I C A L ANALYSES 81 6.5.1 Analysis for peroxides 81 6.5.2 Determination of Bromine Number 84 7 RESULTS AND DISCUSSION 86 7.1 P R E L I M I N A R Y E X P E R I M E N T S 86 7.1.1 Heat Transfer Correlation Experiments 86 7.1.2 Preliminary Fouling Experiments 89 7.2 SOLUBILITY OF AIR IN K E R O S E N E - O L E F I N M I X T U R E S 92 ' 7.3 DISCUSSION OF FOULING RUNS 95 7.3.1 Terminal Olefins 98 7.3.2 Cyclo-olefins 99 7.3.3 Dicyclopentadiene 103 7.3.4 Indene 108 7.3.5 Effect of dissolved oxygen on the thermal fouling rates 116 7.3.6 Solvent effects 122 7.3.7 Species effects 123 vi 7.3.8 Deposit characterization 126 7.3.9 Fouling Mechanism 135 8 CONCLUSIONS A N D R E C O M M E N D A T I O N S 139 8.1 CONCLUSIONS 139 8.2 R E C O M M E N D A T I O N S 140 Nomenclature 142 Bibliography 146 Appendices 156 A D A T A C O L L E C T I O N A N D C A L C U L A T I O N S 156 A . l S A M P L E CALCULATIONS 158 A.2 C A L C U L A T I O N OF V O L U M E T R I C F L O W RATES 162 A.3 C A L C U L A T I O N OF T H E R M A L C O N D U C T I V I T Y OF DEPOSIT . . . 163 A.4 T A B L E S OF PERTINENT DATA 163 B M A X I M U M F O U L I N G RESISTANCES A N D INITIAL R A T E S 169 C P R O G R A M LISTINGS 174 C. l C O M P U T E R P R O G R A M S 174 D D A T A A N D RESULTS 180 D. l N O M E N C L A T U R E FOR DATA AND RESULTS 180 vii List of Tables 1.1 Hypothetical fouling related costs in a 100,000 bbl./day refinery [1] . . . 2 1.2 Estimates of Oil Refinery Fouling Related Costs in NATO Countries [2] . 3 2.3 The 5x5 Fouling Matrix [5] 8 2.4 Effects of Oxygenated Species Addition To Jet Fuel on Mass Deposition [21] 29 2.5 Deposit Formation Tendencies of Olefin-n-Decane Blends [33] 34 2.6 Economic Effects of Antifoulant Use on Crude Unit for for Hypothetical 100,000 Bbl/Day Refinery [1] 42 2.7 Chemicals commonly used in cleaning [51] 45 4.8 Physical Properties of a Typical Kerosene [63] 54 4.9 Physical Properties of Kerosene Used in the Present Work 55 4.10 Effect of Chemical Structure on Hygroscopicity [67] 56 4.11 Hygroscopicity of Kerosenes [67] 57 4.12 Structural Formulas of Olefins Used 59 4.13 Physical Properties of Olefins Used 60 7.14 Experimental Heat Transfer Correlations for Annular Probe 90 7.15 Experimental Heat Transfer Correlations for Coiled Wire 91 7.16 Parameters of Heat Transfer Correlation Run 91 7.17 Calculated Solubilities of Air and Oxygen in Kerosene 94 7.18 Initial Operating Conditions 96 7.19 Average Operating Conditions 97 viii 7.20 Comparison of the Maximum P F R U Fouling Resistances at High Heat Fluxl25 7.21 Comparison of the Maximum HWP Fouling Resistances at High Heat Flux 127 7.22 Deposit Formation Tendancies of Olefi.n-1-Decane Blends [14] 128 7.23 Analysis of Fluids and Deposits 132 7.24 Deposit Analysis of Fluids and Residue from Atmospheric Oxidation of Gasoline [62] 134 A.25 Calculated Thermal Conductivities of Deposits 164 A.26 Viscosity of Kerosene , 164 A.27 Densities of Test Fluids at Room Temperature 165 A.28 Discharge coefficients determined from calibration of P F R U orifice meter 166 A. 29 Discharge coefficients determined from calibration of HWP 166 B. 30 Maximum Thermal Fouling Resistances after 40 Hours for P F R U Probe . 170 B.31 Maximum Thermal Fouling Resistances after 40 Hours for H W P Probe . 171 B.32 P F R U Initial Fouling Rates 172 B.33 HWP Initial Fouling Rates 173 i x List of Figures 2.1 Autoxidation of Indene [61] 20 2.2 Initial Fouling Rate vs. Reciprocal of Clean Tube wall temperature [12] . 38 5.3 Flow Loop of Experimental Apparatus [80] 63 5.4 P F R U Probe [80] 66 5.5 Hot Wire Probe Flow Channel [80] 68 5.6 Control Circuit [80] 70 5.7 A C / D C Conversion Circuit [80] 71 5.8 Voltage Scaling Circuit 72 7.9 Fouling resistance versus time for Run 5, decene-1 100 7.10 Fouling resistance versus time for Run 15, hexadecene-1 101 7.11 Fouling resistance versus time for Run 6, 4-vinyl-l-cyclohexene 104 7.12 Fouling resistance versus time for Run 7, dicyclopentadiene with inhibitor 106 7.13 Fouling resistance versus time for Run 12, dicyclopentadiene 107 7.14 Fouling resistance versus time for Run 13 dicyclopentadiene 109 7.15 Fouling resistance versus time for dicyclopentadiene at different heat fluxes with P F R U probe 110 7.16 Fouling resistance versus time for Run 8, Indene 112 7.17 Fouling resistance versus time for Run 9, indene 114 7.18 Fouling resistance versus time for Run 10, indene 115 7.19 Indene oxygenated runs at different heat fluxes for P F R U 117 7.20 Fouling resistance versus time for Run 11, indene deoxygenated 118 x 7.21 Fouling Resistance versus time for Run 14, Dicyclopentadiene deoxygenatedl20 7.22 Comparison of P F R U oxygenated and deoxygenated runs for indene . . . 121 7.23 Photograph of fouled P F R U probe 129 7.24 Photograph of fouled coiled wires 130 7.25 Polymeric Indene Peroxide 131 7.26 Polymeric Cyclopentadiene Peroxide 133 A.27 Repeat of Run 8, indene at high heat flux 167 A.28 Repeat of Run 11, indene deoxygenated 168 x i Acknowledgement My sincere thanks to Dr. A. P. Watkinson, my supervisor, for his guidance throughout the execution of this project, and for his financial support both to me and towards the acquisition of equipment and materials for this project. I also wish to express my gratitude to the University of British Columbia for awarding me a University Graduate Fellowship. I wish to thank Dr. K . C. Teo of the Department of Chemical Engineering for deter-mining the boiling curve of the kerosene used in this work. Finally, my thanks to the faculty ,staff and fellow graduate students of the Department of Chemical Engineering who in one way or the other, contributed towards the realization of this project. xn Chapter 1 INTRODUCTION Fouling, which is the accumulation of undesirable deposits on a surface, impedes many processes, both domestic and industrial. Fouling usually reduces the coefficient of heat transfer and leads to a loss of heat input. Fouling has an adverse effect on flow of fluids in conduits, and on blood flow in arteries. It affects membrane permeation, and fouling leads to deactivation of catalysts in catalytic processing. The commonest example of fouling in the domestic situation is the scaling of hot water heaters and cooking utensils by hardwater. In industry, fouling must be avoided principally due to economic considerations, as it results in additional costs viz: 1. Additional capital costs — Heat exchanger designs make provision for fouling by including a fouling factor which results in an increase in surface area. This increase in surface area gives rise to increased capital costs which could have been avoided in the absence of fouling. 2. Energy losses — Fouling results in a reduction of the heat transfer coefficient which means that a larger driving force is needed to bring about a given heat flow. More-over, fouling results in additional pressure drop, as a result of the rough foulant surface, and a reduction in the flow area (inner diameter). This means more power is required in pumping the fluid. Efficiency is therefore reduced. 3. Antifouling maintenance — Chemicals and materials used to prevent fouling, and labour needed for cleaning of fouled equipment are costly. 1 Chapter 1. INTRODUCTION 2 Table 1.1: Hypothetical fouling related costs in a 100,000 bbl./day refinery [1] Annual fouling related expenses (thousands $) Capacity (bbl/day) Energy Throughput Maintenace and cleaning Total crude unit 100,000 1020 3730 35 4785 hydrotreaters 45,000 535 510 25 1070 visbreakers 10,000 1695 420 120 2235 reformer 25,000 1070 700 15 1785 Total 180,000 4320 5360 195 9875 4. Loss of production — Shutdown of plants for cleaning can be a major penalty. According to estimates by Van Nostrand et al. [1], the annual cost due to process side fouling of a hypothetical refinery with a capacity of 100,000 barrels a day, is about $10 million. The breakdown is shown in Table 1.1. Table 1.2 [2] shows estimates of fouling-related costs in oil refineries of NATO coun-tries. A British survey [3] estimates the costs associated with heat exchanger fouling alone to be about 0.3 % of the G.D.P. of the United Kingdom. These figures show the enormity of the problem of fouling. Thus, it can be appreciated that, even a partial solution of the problem of fouling in the oil processing industry alone, could mean enormous savings to the industry and perhaps to consumers. Chapter 1. INTRODUCTION 3 Table 1.2: Estimates of Oil Refinery Fouling Related Costs in NATO Countries [2] Country 1985 refining capacity Estimated fouling related (tonne/day) expenses (millions $/year ) Denmark 23,000 17 Norway 33,000 24 Portugal 40,000 30 Greece 53,000 39 Turkey 63,000 47 Belgium 89,000 66 Netherlands 200,000 148 United Kingdom 253,000 130 Canada 253,000 187 West Germany 264,000 195 France 266,000 197 Italy 374,000 277 USA 2,082,000 1,540 Luxemborg N / A N / A Iceland N / A N / A Spain N / A N / A Total 3,993,000 2,905 Chapter 1. INTRODUCTION 4 Amongst traditional methods of coping with the effects of fouling is, firstly the design approach. This is the effective design of heat exchangers to minimize the effects of fouling. A second approach is to take measures to reduce or eliminate fouling once the heat exchanger is in service. The first method takes into consideration the basic equations used in heat exchanger design and can be discussed as follows: In the design of heat exchangers, the heat flow between two streams is given by: Q = UAATm (1.1) where Q — heat flow, (W) U — overall heat transfer coefficient, (W/m2K) A — area of heat transfer, (m 2) ATm — mean temperature difference, (K) The overall heat transfer coefficient based on the the outside area of the tubes of a heat exchanger with cylindrical walls is expressed as a function of the thermal resistances of the tube wall, and the resistances inside and outside the tube. This overall heat transfer coefficient is given by: _1 = 1 | r0ln(r0/rj) ^ 1 r0 U h0 kw hi Ti In the design approach, a fouling resistance Rj given by: Rj — Rj0 -T RjiA0/Ai (1.3) Chapter 1. INTRODUCTION 5 is selected from the Tubular Exchangers Manufacturers Association (TEMA) [4] recom-mended values, and added to the sum of the other resistances. Thus 1 + Rf (1.4) Utotal Udirty U This approach may lead to oversizing of the heat exchanger. To minimize the effect of fouling, design conditions must be selected so as to minimize Rf. The design approach has come under criticism from heat transfer engineers and scientists on the grounds of the following: • The T E M A values of Rf are primarily restricted to water and hydrocarbon fluids, and shell and tube heat exchangers. Thus there are few values for other fluids and heat exchanger configurations. • The T E M A values do not take sufficiently into account the variation of Rf with process variables—fluid velocity, fluid composition, bulk and surface temperatures. • The values of Rf are not clearly defined as to whether they represent an asymptotic fouling resistance or resistance after a certain period of time. • The T E M A approach treats fouling as a steady state instead of a transient process. The second approach involves the use of chemical additives. For example an antioxi-dant may be used as a component of an antifoulant in organic streams. These additives are costly and may be ineffective at high temperatures, as some of the antioxidants degrade to form free radicals which accelerate the fouling process. Moreover, the effec-tiveness of antioxidants tends to be specific to a fouling stream. This necessitates a trial and error search for an additive which is suitable for a given application. This is less than desirable. Chapter 1. INTRODUCTION 6 Thus there has been a need to continue fouling studies with a view to finding a permanent and effective solution to the problem. Chapter 2 LITERATURE REVIEW 2.1 FOULING TYPES AND CATEGORIES In his work 'Thinking about Heat Transfer Fouling: A 5x5 matrix', Epstein [5] classifies the types and stages of fouling by the matrix shown in Table 2.3. Fouling is classified into the following broad categories: 1. Cystalhzation Fouling — This category of fouling is normally subdivided into pre-cipitation and solidification fouling in the fouling literature. Precipitation fouling is the crystallizing from solution of dissolved substances and is also known as scaling. In this type of fouling, salts with normal solubility precipitate on cold surfaces upon cooling, whilst salts with inverse solubility like Mg(OH)2, CaCOz, MgSi03, CaSiOz, CaS04 etc., precipitate on hot surfaces upon heating. This is the type of fouling encountered domestically in cooking utensils and hot water heaters where hard water is used. Solidification fouling involves the freezing of a pure liquid or the higher melting component of a multicomponent mixture onto a subcooled surface. For example, ice formation during cooling of water, or precipitation of paraffin wax from hydro-carbon solutions. 2. Particulate Fouling — This is the deposition of fine particles suspended in fluids on heat transfer surfaces. This type of fouling can be gravity or non-gravity controlled. 7 Chapter 2. LITERATURE REVIEW 8 Table 2.3: The 5x5 Fouling Matrix [5] Crystallization Fouling Particulate Fouling Chemical Reaction Fouling Corrosion Fouling Biological Fouling Initiation 1.1 1.2 1.3 1.4 1.5 Transport 2.1 2.2 2.3 2.4 2.5 Attachment 3.1 3.2 3.3 3.4 3.5 Removal 4.1 4.2 4.3 4.4 4.5 Aging 5.1 5.2 5.3 5.4 5.5 Chapter 2. LITERATURE REVIEW 9 Gravity controlled fouling which can more readily be eliminated by filtration is known as sedimentation fouling. Non-gravity controlled fouling involves mainly deposition of the finest particles in suspension. 3. Chemical Reaction Fouling — In this type of fouling, a reaction results in the for-mation of solid products or sludges which accumulate on the heat transfer surface. This reaction usually occurs in the vicinity of, or on, the surface, which is the hottest part of the system. This is the type of fouling frequently encountered in the petroleum, petrochemical and food processing industries. The walls of the heat transfer equipment may serve as a catalyst but do not take part in the reaction. There is also the possibility of the reaction occurring in the bulk with the produc-tion of insoluble fouling precursors, which then deposit by the particulate fouling mechanism. 4. Corrosion Fouling — This is the accumulation of corrosion products on the heat transfer surface. Corrosion fouling might be in-situ, where the surface itself takes part in the reaction or ex-situ where the corrosion takes place outside the heat ex-changer and the corrosion products enter with the process stream and are deposited by the particulate fouling mechanism. 5. Biological Fouling — This is the attachment to and growth of organic films con-sisting of microorganisms (bacteria, diatoms, yeast), or macroorganisms (mussels, algae, seaweed etc) on a heat transfer surface, resulting in the formation of slime — containing deposits. For industrial situations, fouling is often the result of interaction between different types. For example chemical reaction products may precipitate in bulk solution and deposit on a heat transfer surface by a particulate fouling mechanism, or a combination Chapter 2. LITERATURE REVIEW 10 of two or more types of fouling may occur, such as corrosion and chemical reaction fouling, where the corrosion products which promote reaction and the organic species both become incorporated into a film. 2.2 STAGES IN FOULING AND THEIR CORRESPONDING MODELS The stages in fouling which have been outlined by Epstein [5] and others are: 1. Initiation — This is associated with the delay or induction period before any ap-preciable fouling occurs. The initiation period is not always observed and depends on a host of factors, including the degree of supersaturation, surface temperature, surface roughness, and the type of fouling being observed. 2. Transport — This refers to the mass transfer of the fouling species, precursor, key reactant (such as oxygen in corrosion or chemical reaction fouling) or particle, with a bulk concentration Cb to the heat transfer surface where it has a concentration in the adjacent fluid of C„. Thus the mass deposition flux rrid is given by: md = kt(Cb-Ca) (2.5) where kt is the transport coefficient. In cases where the transport is dominated by diffusion, k, b ecomes km the mass transfer coefficient. 3. Attachment — After the transport of the fouling precursor, key component or particle to the wall region, attachment may follow. If the attachment process is rapid, then CB —> 0. For particles, the mass deposition flux is given by: — ktSpCb (2.6) Chapter 2. LITERATURE REVIEW 11 where Sp is the sticking probability or the probability that any particle reaching the surface sticks to the wall. In crystallization fouling, attachment is by surface integration. For crystallizing ions assuming stoichiometric equality between anions and cations, the surface integration flux is given by: md = K{Ct-CsatT (2.7) where kT is the attachment rate constant and Ctat is the saturation concentration at the surface temperature. Generally, n ^ 1. For simple sparingly soluble salts, n % 2. Combination of the mass transfer equation (2.5) and the crystal growth equation (2.7) gives: _ Cfe — C,at . . m d - (i/km) + i/kr(c,-c.atr-\ When mass transfer controls, (l/km) 3> l/kr(Cs — C5at)n_1, therefore md = km(Cb-C.at) (2.9) When surface attachment controls, l/km <C l/kr(C3 — Ctat)n~l and Cb ~ Ct, thus md = kT(Cb-C,at)n (2.10) In the case of chemical reaction fouling, the same approach can be taken with Csat — 0 in Equation 2.8 giving: Chapter 2. LITERATURE REVIEW 12 Q 4. Removal — Removal of part of the deposit may take place after attachment. The removal flux is often assumed to be directly proportional to the mass of deposit m and the shear stress on the heat transfer surface r 5 and inversely proportional to the deposit strength ip. Thus Taking into account the removal term, the rate of the fouling process is represented by the classical Kern and Seaton [45] model featuring simultaneous deposition and removal. dm m — = md-mT=md-— (2.13) where m m' ip mT rhd f3ra If rhd is assumed to be constant, that is the deposition goes on unabated, then integration of Equation 2.13 with the initial conditions 6 = 0, m — 0 yields: m = m"(l - e-e/e<) (2.14) And since dm dRf = - T -pskj Chapter 2. LITERATURE RE\TEW 13 where pj and kf are respectively the deposit's density and thermal conductivity, then by substitution, the thermal fouling resistance is given by: Here 8C is the average residence time of an element of fouling deposit on the heat transfer surface, or the time it will take to accumulate the asymptotic fouling de-posit given a linear fouling process and an initial deposition rate rhd- No removal occurs until 8C becomes less than some critical value, i.e. 5. Aging — Deposits which build up on the surface may undergo transformation with time resulting in a change in form. For an organic deposit, the transformation might lead to changes in the chemical structure as a result of further polymerization, condensation or dehydration reactions. This type of change, at a constant heat flux, may lead to an increase in ip, the deposit strength, and the deposit's temperature. The transformation can also lead to changes in the structure of the deposit such as degradation of hydrocarbon deposits, or gradual poisoning of microorganisms. This type of change may lead to a decrease in rp. Rf = R}(1 - e-6/e<) (2.15) Oc < {Qc)crit. Or 2.3 CHEMICAL REACTION FOULING Chemical reaction fouling results from chemical reaction of dissolved species which either become insoluble on the hot surfaces, or in the bulk of solution. Thus reactions Chapter 2. LITERATURE REVIEW 14 which lead to insoluble species are of interest. In chemical reaction fouling, the walls of the heat transfer surface are usually at a higher temperature than the bulk fluid and hence tend to produce more chemical reaction near or at their surface. The surface may catalyse the reaction, but unlike corrosion fouling, does not take part in the reaction. Chemical reaction fouling of organic streams is the result of complex chemical re-actions and mechanisms such as autoxidation, polymerization, condensation, pyrolysis, cracking, and coking. Chemical reaction fouling may be related to and may occur with precipitation, particulate and corrosion fouling. Where the reactions occur in bulk so-lution, the insoluble products precipitate on the heat exchanger wall with particulate fouling as the deposition mechanism. Products of corrosion might either serve as cat-alysts or deposit on the surface by particulate fouling. For organic fluids, oxidation processes are important contributors to fouling. 2.3.1 Oxidation of olefinic hydrocarbons For organics, the oxidation reaction involves among other things the elimination of a hydrogen atom to form a double bond, the electron abstraction from a nucleophilic centre, and the addition of oxygen or an oxygen-containing compound to a multiple bond or to a heteroatom (N,P,S). Oxidation of hydrocarbons is the source of most of the industrially important oxygen containing organic compounds. Oxidation of unsaturated compounds can be induced catalytically by transition met-als and their compounds, for example, platinum, palladium, vanadium, manganese, man-ganese dioxide, manganese acetate and compounds of cobalt, or by such strong oxidizing agents such as potassium permanganate, chromic acid, and osmium tetraoxide. Oxi-dation of unsaturated hydrocarbons especially alkenes, is easier than the oxidation of saturated or parafhnic hydrocarbons, and results mainly in the formation of oxygen con-taining compounds — epoxides, aldehydes, ketones, acids, esters, and alcohols. Chapter 2. LITERATURE REVIEW 15 The most important method for the conversion of olefins to epoxides involves oxidation with an organic peroxy acid R(CO)OOH or alkylhydroperoxide in the presence of a transition metal catalyst. The reaction of olefins with peroxy acids to produce epoxides has been known for a long time [86] as the epoxidation reaction. Olefins are nucleophiles in the epoxidation reaction [87], whilst the peroxy acids are electrophiles [88, 89]. The cheapest way of oxidizing olefins perhaps is by means of molecular oxygen. Molec-ular oxygen though, gives a variety of oxygen-containing compounds with little or no specificity. The various methods of oxidation can be broadly classified as controlled oxidation and uncontrolled or destructive oxidation. In controlled oxidation, the oxida-tion reaction is not performed to completion and results in the production of carbonyl compounds which are the primary products of the oxidation reaction. This is the type of oxidation used in most industrial processes for the production of oxygen containing compounds. As the temperature gets higher, and reaction conditions become more un-favourable, destructive oxidation sets in with the conversion of the carbonyl and other oxygen containing compounds to carbon (soot) and carbon dioxide. From the point of view of fouling, either form of oxidation is detrimental. Controlled oxidation produces carbonyl compounds which can undergo condensation to form low molecular weight polymeric units, which with time undergo degradation or destructive oxidation to form coke. Destructive oxidation on the other hand has the tendency to form coke directly and perhaps contributes to coking, which has been widely observed in gas side fouling and other high temperature processes. For chemical reaction fouling, the most important form of oxidation is autoxidation, which is the self induced oxidation by molecular oxygen. Chapter 2. LITERATURE REVIEW 16 2.3.2 Autoxida t ion Autoxidation has long been thought to be a major mechanism in chemical reaction fouling of heat exchangers. It is considered to be the cause of gum and sludge formation! in petroleum and petrochemical feedstocks. Autoxidation is thought to induce free radical polymerization processes which result in the formation of polymeric materials. The steps involved in autoxidation are well documented, and the basic autoxidation scheme can be summarized as follows: Initiation RH + Z- —• R + HZ R-2.1 Chain Propagation R- + 0 2 —• R00- R-2.2 ROO + RH —> ROOH + R R-2.3 Termination R-+R- —*R-R R-2.4 ROO- + R- —> RO -OR R-2.5 ROO- + ROO- —• RO - OR + 02 R-2.6 The initiation step involves a free radical of high reactivity, Z', attacking the hydro-carbon molecule with the removal of a hydrogen atom. This process can be catalysed by a transition metal ion, a Lewis acid, or by trace amounts of nitrogen and sulphur present in the hydrocarbon stream. Chapter 2. LITERATURE REVIEW 17 Mn+2 + 02 — • Mn+3 + (02) R-2.7 RH + (02) R+ (02H)~ R-2.8 (02H)- + Mn+3 —> Mn+2 +• 02H R-2.9 RH + (H02) —> R+ H202 R-2.10 The action of transition metal catalysts lies in the production of a free radical R, as in R-2.1, in R-2.10. Besides the formation of the free radical R-, the H202 formed is capable of forming peracids and hydroperoxides which further break down to form free radicals. At sufficiently high temperatures, there can be thermal reactions between oxygen and an olefin molecule to produce free radicals. RH + 02 —> R + R02H —> R-, RO- or R00- R-2.11 Activation energies are generally very high for the the initiation stage. The propagation step is the stage where oxygen reacts with a free radical resulting in the formation of a peroxide radical which attacks the olefin. At this stage, hydroperoxides accumulate in the system and gums are formed by the interaction between the free radicals and unsaturated hydrocarbons as in classical polymerization. It has been shown that the addition of olefins increases the rate of gum formation and deposition [7], which tends to confirm this stage of the mechanism. At the propagation stage, there is the formation of oxidation products — aldehydes, ketones, and acids, due to the breakdown of hydroperoxides. Also, the formation of polymeric peroxides are known to take place at this stage. Polymeric peroxides have the I I general formula (—C — C — 0 — 0—)n. They result from reaction between olefins that polymerize or copolymerize readily in the presence of oxygen, such as styrene, a-methyl styrene, indene, dienes and other conjugated olefins. Dienes and other conjugated olefins normally form 1:1 copolymers with oxygen with 1,2-, and 1,4- unsaturated linkages randomly distributed. The presence of unsaturation means such polymers are capable Chapter 2. LITERATURE REVIEW 18 of growing with time. Polymeric peroxides derived from olefinic monomers are usually viscous liquids or amorphous white powders. Polymeric peroxides are claimed by several authors [61, 62] to be the species responsible for deposit formation in light distillate fuels. This is a simplified mechanism. In a real fouling situation, the processes occuring in the bulk fluid or at the heat transfer surface are more complex than presented here. At low temperatures, these processes occur in parallel with oxidative polymerization, and at high temperatures, they occur in parallel with oxidative dehydrogenation. Oxidative dehydrogenation, R-2.12, produces more olefins which help sustain the propagation step. R - CH2 - CH3 + 1/202 —> R-CH = CH2 + H20 R-2.12 These stages in the autoxidation reaction have been experimentally confirmed by several authors [44, 64, 103, 104]. Brill [64] showed that autoxidation of low molecular weight olefins produces mainly epoxides and hydroperoxides as primary products. More-over, the rate of reaction decreases with decreasing olefin carbon number. Brill [103] further showed that in the case of acyclic olefins, the hydroperoxides formed are inter-mediate products and decompose or undergo rearrangement easily with the formation of primary oxidation products. Tabolsky et al. [104] reported that in the oxidation of olefinic hydrocarbons at low temperatures, the oxidation is always accompanied by scission or cleavage of hydrocarbon chains, and linkage of neighbouring chains together with absorption of oxygen. They suggested that these scission/linkage reactions play an important role in natural and artificial ageing of polymeric products. Van Sickle et al. [105, 106] reported that in the low temperature liquid phase ox-idation of olefins, non-volatile high boiling residues which are mainly dimers, trimers and low molecular weight polymeric peroxides, are always produced in parallel with and in addition to primary oxidation products. In the case of ethylene and propylene, the residues upon analyses were found to contain copolymers of fomaldehyde and acrolein Chapter 2. LITERATURE REVIEW 19 units with other primary oxidation products. They stressed the fact that these residues were produced in parallel to the oxidation reaction since they were observed even at low conversions and at low levels of primary oxidation products. That is, the residues were primary products. Several propositions have been made as to the mechanism responsible for deposit formation by olefinic species in heat exchangers. Evidence from the literature points to autoxidation by double bond addition as the major mechanism responsible for the formation of deposits. At the chain propagation stage of the autoxidation mechanism, the olefins undergo two major reactions viz. olefin-olefin polymerization R-2.14, R1 + RCH = CH2 —> R1 - CH2 - (R) C H R-2.13 R1 - CH2 - (R) C H R1 - CH2CH(R)CH2 — (R) C H etc. R-2.14 and olefin-oxygen copolymerization R-2.15. R1CH2 — (R) C H u ^ n R1 - CH2RCHOO-—> R1 - CH2RCHOOCH2 — (R) C H etc. R-2.15 The copolymerization reaction eventually results in the formation of polymeric per-oxides [61, 73, 74]. These polymeric peroxides are 2 - 5 units on the average in size. Their formation is enhanced by the presence of conjugated double bonds. This explains why indenes and dienes form gum and foul more readily than terminal olefins. With increasing oxygen pressures — and hence concentration, the olefin-oxygen copolymeriza-tion reaction predominates over the olefin-olefin polymerization reaction. At moderately high temperatures, some of these polymeric peroxides undergo decomposition to form both volatile and insoluble residues. Chapter 2. LITERATURE REVIEW 20 Figure 2.1: Autoxidation of Indene [61] Copolymerization of indene and oxygen leads to the formation of a polymeric peroxide and the reaction is believed to take place according to the mechanism shown in Figure 2.1 [61]. Here, polymers with larger numbers of units (up to 9) are formed. Cyclopentadiene also undergoes autoxidation with subsequent copolymerization with oxygen to form a polymeric peroxide according to a scheme similar to the indene mechanism shown in Figure 2.1. In sum, the experimental evidence available points to the fact that non-volatile low molecular weight polymeric products are always formed in olefinic autoxidation reactions Chapter 2. LITERATURE REVIEW 21 not only as secondary products but as primary products due to addition reactions and the cleavage and linkage of olefin chains. The oxidation of olefins always results in the formation of hydroperoxides with varying degrees of stability. These hydroperoxides act not only as initiators of polymerization reactions, but also decompose and rearrange to form unsaturated aldehydes. These unsaturated aldehydes polymerize or condense with other primary oxidation products thus enhancing the formation of deposits. The fact that this mechanism plays an important role in deposit formation in hydrocarbon feedstocks is confirmed by information on the analyses of deposits in the literature. 2.3.3 Polymerizat ion Polymerization is the formation of macromolecules through the joining together of small molecules (monomers) by covalent bonds. At some value of the molecular weight, the polymer tends to become insoluble in the low molecular weight solvent. The resulting precipitation will have implications for the fouling process. From the kinetic point of view, polymerization reactions are classified as (1) chain polymerization or free radical polymerization, and (2) condensation or stepwise polymerization. Cha in Polymerizat ion Chain polymerization takes place at relatively low temperatures as a result of the interaction between free radicals and unsaturated compounds. The mechanism of chain polymerization is similar to the autoxidation mechanism and consists of three steps: viz. initiation, propagation, and termination. 1. Initiation XH —• X- + H- R-2.16 Chapter 2. LITERATURE REVIEW 22 This is the breakdown of the initiator or catalyst. According to Odian, [8] this process is normally a thermal homolytic dissociation. The free radical formed reacts with an unsaturated compound. R-CH = CH2 + X- —> R- C H - CH2X R-2.17 2. Chain propagation. R- C H(CH2X) + R-CH = CH2 —• —>R- CH{CH2X) - {-CH2 - CH{R)-)nCH2~ R-2.18 3. Chain termination R - CH(CH2X) - (CH2 - CH)nR - CH2 - (R) C H + H- —• —> RCH(CH2X) - R{CH2 - CHR-)n - CH2 - {R)CH2 R-2.19 The chain termination occurs in several ways. It can result from a reaction be-tween two free radicals, or a disproportionation reaction when a hydrogen atom is transferred from one radical to another. It can also result from reaction between a free radical and the solvent or the adsorption of a free radical onto the surface of the heat exchanger, or reaction vessel. The rate of each step or the length of a chain formed depends on the concentration and reactivity of reaction partners. The polymer formed from chain polymerization is said to be "dead" in that it is inactive and cannot react. Chapter 2. LITERATURE REVIEW 23 Condensation In condensation or stepwise polymerization, a low molecular weight compound — wa-ter, ammonia etc, is always liberated. The polymer formed is reactive and is capable of undergoing further condensation. It proceeds by a slow mechanism of reaction between the functional groups of the monomers. monomer + monomer —> dimer - f - LW dimer + monomer —> trimer + LW dimer - f dimer —> tetramer + LW trimer + monomer —• tetramer -j- LW trimer + dimer —> pentamer + LW etc. Where LW is a low molecular weight compound. This process may go on until a molecule consisting of a large number of monomers is formed. 2.3.4 Pyrolysis and pyrolytic reactions Pyrolytic reactions are normally encountered in gas side fouling or reactions taking place at high temperatures. They are reactions that result in the thermal decomposition (degradation) of hydrocarbons. The conversion of hydrocarbons to carbonaceous species is represented thus: cracking, cyclization dealkylation, polycondensation Aliphatic hydrocarbons —> aromatics —> —• polycyclic aromatics and heavy residues > coke Gas side fouling as a result of thermal degradation and cracking, generally called coking, has been reviewed by Froment [9]. Thermal pyrolysis proceeds via a free radical mechanism. The products of the primary reactions undergo cyclization to form aromatics, Chapter 2. LITERATURE REVIEW 24 which then undergo condensation to form high molecular weight polycyclic aromatic systems [1.0]. Pyrolysis can also occur in liquids, and is an important mechanism of chemical reaction fouling in the absence of oxygen. 2.4 E F F E C T OF PROCESS V A R I A B L E S O N C H E M I C A L R E A C T I O N F O U L I N G 2.4.1 The role of sulphur compounds In treated process feedstocks, sulphur and its compounds occur mainly in the form of impurities at trace levels. A good number of studies have been done on the effect of sulphur on the rate of deposit formation. These have been reviewed in [18]. Experimental observations by several authors [11, 12, 13, 15, 77, 90] have shown that sulphur and its compounds play a detrimental role in heat exchanger fouling. Deposit analyses have shown sulphur contents from 5 to 25 %, depending on the source of test fluid. The effects of adding trace quantities of sulphur in the form of sulphides, disul-phides and thiophenes to a sulphur free jet fuel under both oxygenated and deoxygenated conditions have been shown experimentally by Taylor et al. [13, 14]. Under oxygenated conditions, the addition of disulphides showed a marked increase in deposit formation in the temperature range of 90 —230°C. The addition of thiophenes and sulphides under the same conditions on the other hand, resulted in little or no increase in deposit formation rates. It is generally held that the effect of sulphur compounds on the rate of deposit for-mation depends much on the relative stability of the sulphur compound concerned, to oxidation and decomposition. The role of sulphur compounds, it is believed, lies in their decomposition to form free radicals which then serve as initiators. Hausler [16] found that unsaturated hydrocarbons in the presence of sulphur and its Chapter 2. LITERATURE REVIEW 25 compounds fouled faster. He proposed that this resulted from a free radical mechanism initiated by an oxide of sulphur which was formed as a result of interaction between oxygen and sulphur in the system. Thus an increase in the concentration of oxygen resulted in more deposits being formed as a result of more free radicals being formed in the system. Daniel and Heneman [17] studied the effects of organo-sulphur compounds on jet fuel stability that showed both deleterious effects (thiols and dibenzothiophenes), and a reduction in deposit formation (aliphatic sulphides and disulphides). Indene, styrene and other very reactive olefins are known to participate in cooxidation reactions with sulphur compounds via the formation of hydroperoxides [80, 82, 107, 109]. Oswald [108] found that aromatic thiols add to indene even in the absence of peroxide catalysts, with the formation of indanyl derivatives — crystalline compounds soluble in hydrocarbons. These indanyl derivatives oxidize in the presence of peroxides to form insoluble sulfones and sulfoxides. Oswald's work [108, 109] on the cooxidation of indene and sulphur compounds throws some light on the role of olefin and sulphur compounds, in gum formation in liquid fuels. It especially explains why cracked fuels, which contain indenes and traces of sulphur compounds have been found by several researchers to be so suceptible to gum formation. Most of the studies done on the effects of sulphur on the chemical reaction fouling of heat exchangers are mass deposition studies. There have been no systematic thermal fouling studies reported on the sulphur species effect on fouling. 2.4.2 Effect of nitrogen compounds The effects of nitrogen compounds on deposit formation have been investigated by several authors [19, 20, 21, 22, 93, 96], and summarized in [18]. These effects are in many ways similar to the effects of sulphur compounds. Taylor [19] investigated the effect of trace amounts of nitrogen compounds on the deposit formation rates of jet fuels, Chapter 2. LITERATURE REVIEW 26 by adding 1000 ppm of different nitrogen compounds to oxygenated jet fuels and found a marked increase in deposit formation rates. The nitrogen compounds, he suggested, play a role similar to sulphur by producing free radicals which initiate autoxidation and polymerization reactions. Oswald and Noel [20] have shown that pyrroles form gums in fuel oils, shale oils, and naphthas as a result of polymerization reactions due to the interactions between the nitrogen and sulphur species with the hydrocarbons. Frankenfeld et al. [21] have found that the formation of deposits due to nitrogen species at high temperature conditions appears to proceed by different pathways than in the case of low temperature conditions during storage, where oxidative condensations dominate. Among nitrogen species, non basic heterocycles are known to cause deposits and non-condensed pyrroles are known to be more active than condensed aromatics such as indoles. The importance of pyrroles in deposit formation was first pointed out by Thompson et al. [22]. The most active of the pyrroles towards deposit formation is 2,5 dimethylpyrrole (DMP) as shown by Oswald and Noel [20]. Taylor [7] also showed that the adverse effect of DMP towards deposit formation increased with the amount of water in the system. Despite the adverse effects of nitrogen compounds on deposit formation, some nitrogen radicals, notably heterocyclic nitroxy radicals, have been established as inhibitors of radical chain reactions [110, 111]. They are especially effective in reactions involving the free radical R, due to their formation of stable compounds thus: R-+ = NO- —>= NOR R-2.20 Chapter 2. LITERATURE REVIEW 27 2.4.3 The role of oxygen in chemical reaction fouling The deleterious role played by oxygen in both free and combined forms in deposit formation is well documented [6, 11, 15, 26, 76, 91]. Oxygen is a key partner in the au-toxidation reaction. The drastic reduction of deposition rates with the rigorous exclusion of oxygen has been observed by many researchers. 6 Taylor et al. [26, 91] reported in their study of jet fuels that a rigorous exclusion of oxygen eliminated deposit formation up to a temperature of about 315°C, beyond which deposit formation was observed. They also observed that, at temperatures of up to 600°C, deoxygenated jet fuels exhibited relatively low rates of deposit formation. Thus they concluded that the adverse effect of oxygen on deposit formation is more pronounced at low temperatures. This is probably due to the fact that at high temperatures, pyrolytic reactions assume more importance than autoxidation reactions. Braun and Hausler [6] reported that a hydrocarbon stream that fouled very little at an oxygen concentration of 0.1 % fouled tremendously when aerated. Hausler et al. [15] also documented the adverse effects a gaseous atmosphere with a high ppm of oxygen had on a hydrocarbon feedstock. Canapary [11] reported that in his laboratory test rig, fouhng was considerably reduced by removing completely oxygen from the naphtha charged to hydrodesulfurizers, and that the heat transfer coefficients improved by as much as 80-90 % by purging the naphtha feedstock of oxygen using nitrogen. Butler et al. [76] reported a successful reduction of the fouhng rate by reducing the oxygen content of their gas oil, by stripping the gas oil with natural gas. Schwartz et al. [77] compared total gum formation in gasoline during storage at 110°C in the presence of air in sealed containers with continuosly aerated containers. They reported that in the sealed containers, the oxygen above the gasoline was consumed during the first half of the test with the formation of a minute amount of gum, whilst in the continuosly aerated Chapter 2. LITERATURE REVIEW 28 containers, much more gum was formed. The absorption of oxygen by hydrocarbon feedstock is facilitated by dissolved metals which act as catalysts. Dissolved oxygen has been shown to play a part in phenolic coupling reactions. In feedstocks containing phenols, such as in synthetic fuels produced from coals, phenolic coupling with the aid of oxygen has been found to lead to the formation of dimers, trimers and other insoluble polymeric materials [78]. The effects of oxygen on chemical reaction fouling are not limited to dissolved oxygen but also depend on oxygen-containing compounds. Taylor and Frankenfeld [21] showed that addition of 100 ppm 02 in the form of oxygen containing compounds to jet fuels resulted in deposit formation increasing significantly. The results are shown in Table 2.4. It is seen that peroxides are the major culprits. This might be due to the ease with which they break down to form free radicals, which initiate polymerization, and autoxidation induced polymerization reactions which result in the formation of insoluble polymeric species. Other oxygenated species show little effect. 2.4.4 Effect of trace metals and wall material Metals, both heterogeneous (heat transfer surface) and homogeneous (dissolved in the process stream), may contribute to chemical reaction fouling by catalysing the reactions involved. Trace metals also deposit by particulate fouling and thus add up to the bulk of fouling deposits. The effects of trace metals have been convincingly demonstrated by Crawford and Miller [23], and by Taylor [26]. Several authors [6, 11, 15, 16, 24] either directly or indirectly have indicated the adverse effects of trace metals on the rate of fouling. Crawford and Miller [23] doped their test fluid with 1 ppm metal in the form of their oxides or oil soluble salts, in the presence of sulphur, nitrogen, and olefins. This led to a 47 % increase in deposition rate. They found that in all cases, the deposition rate increased with increasing temperature. Chapter 2. LITERATURE R E V I E W 29 Table 2.4: Effects of Oxygenated Species Addition To Jet Fuel on Mass Deposition [21] Class of compound added Dissolved 02 content (ppm) Relative carbon deposition rate None 0.4 1.0 Peroxides 0.1 - 0.2 2 - 6 Carboxylic acids 0.2 0.9 - 2 Phenols 0.1 - 0.2 1 - 1.4 Furans — 0.95 - 1.0 Alcohols 3.0 - 0.9 0.9 - 1.4 Ketones 0.3 - 0.9 0.84 - 1.6 Esters 0.5 - 0.8 0.89 - 1.7 Compounds added at 100 ppm 02 level, Temperature in kinetic unit: zone 1 = 371°C, zone 2 = 427°C zone 3 = 482°C, zone 4 = 538°C,P = 6989 kPa Chapter 2. LITERATURE REVIEW 30 Metal ions have also been shown [15] to increase the rate of oxygen uptake by hydro-carbons. It has also been shown [15] that, by blending cracked stock which is olefin rich with a straight run cut which is paraffin rich, the rate of oxygen uptake is reduced. This attests strongly to the possibility of metal-initiated autoxidation and oxidative polymer-ization reactions where oxygen is a partner. Since paraffins take part in these reactions to a lesser extent, their addition reduces these reactions and hence the amount of oxygen uptake. Taylor [26] investigated the effects of trace metals by adding various dissolved metal complexes to his test fluid and observed that a 50 ppm metal added resulted in an increase of a factor of about 40-120 in the deposition rate. Eaton and Lux [27] studied the effect of metal chlorides and acids on petroleum oil fouhng. They found that HC1 as well as the salts FeCl^, MgCl2,CaCl2 all promoted fouling. Their relative effect depended on the amount of acid produced by hydrolysis. 2.4.5 Effect of fluid velocity Reports on the effect of fluid velocity on the fouhng rate in the literature are quite con-tradictory. This shows, probably, that these effects are not well understood. Watkinson and Epstein [12] observed a fall in the fouhng rate with an increase in the mass flow rate. Hausler et al. [15] also observed a similar dependency albeit at a different temperature. Scarborough et al. [28] also observed a decrease in the fouhng rate with an increase in mass velocity in their study of crude oil coking. However, Smith [25] in his study of aviation turbine fuels, reported an increase in fouhng rate with an increase in mass flow rate. Dickakian and Seay [29] also reported an increase in fouling rate with an increase in mass flow rate. Crittenden et al. [30] in their study of styrene polymerization fouhng observed that the initial fouhng rate was independent of the mass velocity, whereas at high surface temperatures, the fouhng Chapter 2. LITERATURE REVIEW 31-rate increased with increasing mass velocity. They explained this complex relationship between the mass velocity and the fouling rate as being due to transfer steps becoming more predominant at higher temperatures. Chantry and Church [31] recommended using high velocities in forced circulation reboilers, as high velocities lower the percentage vaporization per pass hence reducing polymerization of heavy components concentrated near the surface. Moreover they re-duce tube wall temperature, which leads to a reduction in fouling. High velocities have generally been thought to reduce fouling in the process industry, but adequate studies have not been done to substantiate this view. 2.4.6 Effect of particulates Particulate matter can enter a process stream through several ways, including in-situ and ex-situ corrosion, and polymerization in the bulk. Analyses of fouling deposits have always shown the presence of particulates. In the gas oil experiments of Watkinson and Epstein [12], analysis showed the gas oil particulates to contain about 4.6% ash and 5.4% sulphur. The analysis of the deposits formed showed a similar content of 9.9 % ash and 5.5 % sulphur. Moreover, when the gas oil was filtered of particulates from 39 mg/l to 0.1 mg/l, they observed that heating the gas oil increased the concentration of the particulates to 19 mg/l. Particulates were presumably generated by heating. Lambourn and Durrieu [32] analysed the deposits of the hottest crude/residue exchangers in a crude preheater train and found the particulates in the deposits to contain 50-70 % iron oxides and sulphides, and 50-30 % asphaltenes. Particulates, whether brought about by corrosion or reaction in the bulk, have adverse effects on fouling. They form colloidal systems or get entangled in the polymer sludges and later deposit on the heat transfer surface. Chapter 2. LITERATURE REVIEW 32 2.4.7 Effect of hydrocarbon constituents That the chemical composition of process feedstocks has a very significant effect on chemical reaction fouhng is beyond doubt. The effects of different organic compounds, in process feedstocks, are interrelated with the other variables in a complex manner that is not well understood. Paraffins are normally stable at relatively low temperatures but are very deleterious at high temperatures as producers of fouhng precursors. This is due to the fact that, the paraffins undergo thermal degradation — cracking etc., producing olefinic intermedi-ates which undergo condensation and cyclization ultimately forming coke as represented below. The addition of hydrogen to paraffinic feedstocks reduces the production of aromatics and hence cyclization, perhaps by hydrogenating the olefinic intermediates. At higher temperatures, the lower molecular weight paraffins are more stable than higher molecular has been confirmed by Taylor [26]. For a given temperature, branching decreases stability and increases deposit formation [33]. Addition of aromatics and naphthenes to paraffins reduces the rate of deposit formation, possibly due to the inhibition effect of aromatics and alkylaromatics at lower temperatures [34, 35]. Olefins and other unsaturated compounds undergo self addition, or addition to other unsaturated compounds. Terminal olefins are known to undergo addition even on stor-age. Some olefins like cyclohexenes form mixtures of unsaturated dimers, trimers and polymers even on standing. Irradiation of olefins results in bridging, isomerization and coupling. Bridging and especially coupling result in the formation of dimers. Olefins paraffins organic acids coke weight ones. Thus deposition rates increase with increasing carbon number. This fact Chapter 2. LITERATURE REVIEW 33 are widely known to be responsible for gum formation during storage of fuels [15] and in hydrocarbon streams. Hausler et al. [15] reported an increase in tendency toward gum formation by a feedstock with high levels of unsaturates, nitrogen and sulphur com-pounds. Canapary [11] indicated that olefins tend to accelerate organic fouling. Several studies on fuel stability have held olefins responsible for the formation of sludges, and gum during storage. Taylor [33], by doping jet fuels with up to 10 % by weight of olefins, showed a linear increase in the relative rate of deposit formation with the content of olefins. The rate also varied with the olefin type. The role of olefins is generally thought to be in their participation in the autoxidation reactions, with the production of hydroperoxides which decompose to form free radi-cals. These free radicals then initiate polymerization reactions which produce polymeric species. These polymeric materials either deposit or combine with particulates brought in by the process stream or produced in the bulk solution to form sludges and other deposits. These deposits settle on the heat transfer surface and with time age, and form hard coke. From the foregoing, it is evident that the addition of peroxides to feedstocks containing even traces of olefin is highly detrimental. A summary of deposit formation tendencies of some paraffin-olefin blends is shown in Table 2.5 [33]. Aromatics are generally stable especially at high temperatures. This stability de-creases with increasing length of the side chain and increases with increasing condensa-tion (number of rings). This stability was explained by Taylor as possibly due to the resonance stabilization effect of the 7r electrons in the benzyhc ring. Aromatics and alky-laromatics have been shown [33] to inhibit deposit formation rate of some paraffins up to some temperature. Petroleum constituents may be classified into oil, asphaltenes, resins, carbenes and carboids. The oils are made up of the volatile or fighter fractions — paraffins, isoparaf-fins, naphthenes, aromatics, olefins and other unsaturates. The asphaltenes and resins a- 2. LITERATURE REVIEW Table 2.5: Deposit Formation Tendencies of Olefin-n-Decane Blends Olefin Added to Binary blend Rate of Deposit Formation at 275°F (g/cm 2)/4hr.x 106 Deposition Rate Relative to n-Decane 10 % wt. olefin in n-decane in all blends, P = 20 kPa. Vinylcyclohexane 29.4 3.3 4-Vinylcyclohexene 198.0 22.0 Allylbenzene 91.2 10.0 4- P henyl- 1-butene 86.9 9.7 l-phenyl-2-butene 26.5 3.0 1,6-Octadiene 190.0 20.0 1-Decene 35.6 4.0 Indene 354.0 40.0 n-Decane 9.0 1.0 Chapter 2. LITERATURE REVIEW 35 constitute what is known as the heavy fractions. Carboids and carbenes are found in very minute quantities in virgin petroleum though their quantities increase after exposure to heat (in cracked petroleum, residuum or bottoms). The heavier fractions — mainly asphaltenes and resins — are solids at room tem-perature and are characterized by high carbon to hydrogen ratios, and the presence of heteroatoms. Their exact structure as well as their molecular weights are not well known and depend on the oil source, but available evidence [113, 114, 115, 116] points to a high degree of condensation and high molecular weights. The key criteria for differentiating be-tween asphaltenes and other components of the heavier fraction is their solubility. Hence asphaltenes are normally defined as the pentane-insoluble, benzene-soluble component of the heavier fraction, to distinguish them from resins which are soluble in pentane and other low molecular weight hydrocarbons. Asphaltenes consist primarily of polar aromatics with an appreciable content of naph-thenic aromatics and traces of saturates, heteroatoms (N,0,S) and trace metals. They exist in petroleum as colloids in the form of micelles, unlike resins which exist as true solutions. The fouling of crude oil has been shown to be highly dependent on the presence of asphaltenes [27, 36]. Eaton and Lux [27] found that a 5 % pitch - containing 16 % asphaltenes — in paraffin oil increased the fouling rate by a factor of about 90 whereas the same oil containing 10 % resins showed no fouling. This observation is explained in part by the colloidal structure of asphaltenes which makes them precipitate easily, and the fact that resins are normally soluble in solutions in which asphaltenes precipitate. According to Sachanen [37], asphaltenes are lyophobic with respect to low molecular weight paraffinic hydrocarbons. Thus in petroleum or petroleum fractions both aromatic hydrocarbons and resins are adsorbed by asphaltenes. After the adsorption of these molecules, the asphaltenes become finely divided and dispersed in the medium. Thus Chapter 2. LITERATURE REVIEW 36 the resins and aromatic hydrocarbons act as peptizing agents which help dissolve the asphaltenes. In the presence of species compatible to the resins, the adsorbed resins are dissolved, leading to depeptization of the asphaltenes and eventually their precipitation. Thus as long as the asphaltenes are kept dispersed, no precipitation and hence no fouhng will be observed. Resins will cause fouhng only after conversion to asphaltenes by high temperature condensation. Thus in crude oils where the content of unsaturated hydrocarbons is negligible, the major producers of foulants are asphaltenes. Pyrolysis of asphaltenes has been shown to produce little or no coke at medium temperatures [112] but at high temperatures, coking is rapid and severe. Naidu et al. [38] observed that low molecular weight (LMW) primary products of oxidation — aldehydes, ketones and acids — if further exposed to heat, undergo conden-sation with the formation of high molecular weight (HMW) viscous liquids and varnish. They found that these high molecular weight products formed are reactive and continue to grow with time. This gave them ample evidence to believe that the H M W products re-sulted not from polymerization but condensation. Spectroscopic analysis of their deposits showed the presence of unsaturation (diene linkages), and of ketones and aldehydes in all fractions of different molecular sizes. The polymer formed with time finally turned into an insoluble sludge which could not further be identified in the spectroscopic analysis. Naidu et al. suggested that the H M W substances were formed by an aldol condensation. They also found that metals had the same effect on the increase in deposit formation as in autoxidation, with mild steel having the most adverse effect and copper the least. Ob-viously, much has to be done to investigate the role of condensation reactions in chemical reaction fouhng. Chapter 2. LITERATURE REVIEW 37 2.4.8 Effect of temperature Temperature, both surface and bulk fluid, is perhaps the most important variable in chemical reaction fouling for a given chemical system. Most chemical reaction fouling studies in the literature point to a strong dependence of the fouling rate on temperature. Many authors have predicted an Arrhenius type dependence of the fouling rate on temperature. For the gas oil fouling, Watkinson and Epstein [12] proposed the following equation for the initial fouling rate. (iRl/de)e,0 = H^ e (- i20,ooo/* 9 r . ) ( 2 1 6 ) ub This shows an Arrhenius type dependence of the initial fouling rate on temperature. They found that in the temperature range 146 — 204°C, the fouling rate increased sharply with temperature. Assuming that the fouling rate is proportional to the rate constant, Equation 2.16, suggests that the activation energy is about 120 kJ/mole. Eaton and Lux [27] reported rapid fouling in paraffin oils when the temperature difference between the probe surface and the bulk temperature was very wide. On the other hand, when the bulk fluid and the probe surface were at the same temperature, fouling was minimal. Figure 2.2 [12] shows a sample plot of fouling rate dependence on temperature. 2.5 K I N E T I C S A N D M O D E L L I N G O F C H E M I C A L R E A C T I O N F O U L -I N G The knowledge of the precise kinetics of chemical reaction fouhng, though important, is very limited due to the complex nature of the processes involved. The complexity is due in part to the presence of many species, many of which are undefined, in the fouhng systems, and the absence of knowledge of the exact reactions taking place in the system. Chapter 2. LITERATURE REVIEW 38 5 0 0 00 a cr _z o I00h 50 10 o c \ o \ \ \ \ o X7 \ \ \ \ x ^ \ x \ \ \ W lbm/sec \ Oil B \ O 0-242 A 0-1 78 V 0-362 \ V A Oil B ^ N Oil A (100% Q recirculated) \ 118 126 IOOO /T W c •R-'XIO 3 1-34 Figure 2.2: Initial Fouling Rate vs. Reciprocal of Clean Tube wall temperature [12] Chapter 2. LITERATURE REVIEW 39 Most models in the literature often do not represent or approach what happens in real life fouhng situations. This deviation from actual fouhng behaviour is due in part to the multitude of assumptions needed to simplify the complex fouhng behaviour. Most models assume an isothermal process and hence results are given for a particular temperature, but in heat exchangers, there exist steep temperature gradients which lead to a fouhng distribution. Other models assume the fouhng process is controlled by one foulant, thus neglecting all other fouhng precursors in the system. The result is that the models tend to depict a first or nth order reaction of one species on the heat exchanger surface, thus leading to an over simplification. Most models adopt some or all of the following premises in deriving a kinetic model for the system concerned. • Diffusion (convection) of reactants from bulk fluid to the reaction interface. • Chemical reaction — an undefined nth order reaction. • Diffusion(convection) of reaction products back to the bulk fluid. • Attachment of reaction products to the surface. • Removal from surface by shearing action of flowing fluid. Several models are based on the film theory of heat and mass transfer [43]. Moreover most fouhng studies are done under accelerated conditions. These factors make it difficult and unreliable to use these models to predict industrial process side fouhng. Watkinson and Epstein [12] proposed a model which involves transfer, adhesion and removal. The initial rate is given by: dRf — aiJS-p (2.17) Chapter 2. LITERATURE REVIEW 40 where J is the flux of the foulant given by: J — km(Cb - Cw) and Sp is the sticking probability factor. a,e(-E/R.T.) S, - ^ (2-18) Thus for km assumed proportional to Ub, and for rough surfaces (f=constant) the intial fouhng rate is given by: {-dT)e=° - ° 3 ub ( 2 - 1 9 ) This equation agrees, to a large extent, with the results obtained from the gas oil exper-iments. For a chemical reaction controlled first order reaction, independent of velocity and with a low Sp, the initial fouhng rate becomes: (^),=„ = *<ChA-EIW.) (2.20) This equation suggests no effect of velocity on the initial fouhng rate. Fernandez-Baujin and Solomon [102] improved upon the film theory model suggested by Nelson [43] by introducing a reaction kinetics term, thus making it a two stage mass transfer and reaction model. This model was used to describe a vapour state pyrolysis study involving coking in cracking furnaces. They proposed a fouhng rate given by: *0± = J _ r 9l i (221) de Pfkf[i/kt + i/kTl K ' ' Crittenden et al. [42] extended the two stage mass transfer and reaction kinetics above to include the possibility of the foulant removal by convective mass transfer. Thus Chapter 2. LITERATURE REVIEW 41 introducing a back diffusion term into the Fernandez-Baujin and Solomon equation, they obtained the expression: = pjk-f[l/ktC+l/K-kDCDi] ( 2 - 2 2 ) where kT the reaction rate constant follows an Arrhenius type relationship. Paterson and Fryer [125] proposed an initial fouhng rate by assuming that the hotter laminar sublayer in a fouhng system acts as a chemical reactor. Thus by using arguments based on reac-tion kinetics, they derived for the initial fouhng rate, the equation, = jf-bexp{-EIRgT8) (2.23) where, (3S is a constant for a given system. This equation has the same form as the Watkinson and Epstein equation. A l l the models with removal terms follow the classical Kern and Seaton [45] model with deposition and removal terms. The Watkinson and Epstein model correlates very well the initial fouhng rate but predicts less well the asymptotic fouhng resistance dependence on velocity. For chemical reaction fouhng, it may be a good model since asymptotic fouhng resistances are seldom encountered. The major drawback of the Crittenden et al. model is the difficulty of obtaining an accurate value for the concentration of the foulant Cm at the fluid deposit interface, since it is not an observable quantity. Therefore, there is the need for more work to give an exact quantitative view of the chemical reaction fouhng process. Chapter 2. LITERATURE R E V I E W 42 2.6 MITIGATION AGAINST CHEMICAL REACTION FOULING Due to the seriousness of heat exchanger fouhng, and the pressure to utilize energy more efficiently, reduce cost of production and hence make processes more economical, a host of methods have been devised to minimize or eliminate fouhng once heat exchangers are in operation. These methods can be broadly classified as chemical mitigation, involving the use of additives to prevent fouhng, and cleaning i.e. removing the deposits once fouhng has occurred. 2.6.1 Chemical mitigation Control of chemical reaction fouhng is carried out primarily by using inhibitors, sur-face coating with polymeric substances and paints, and by the use of antifoulants. The economic effects of the use of antifoulants is summed up in Table 2.6. Antifoulants work by stabilising incipient polymer forming materials and/or by preventing the agglomera-tion of polymers already formed. Corrosion inhibitors also reduce fouhng by minimizing the synergistic effects of corrosion on fouhng. However, the use of inhibitors to minimize chemical reaction fouhng has not been en-tirely successful. According to Hausler and Thalamayer [15], the use of inhibitors in their runs were successful only up to 300°C after which they became ineffective. This suggests the effectiveness of inhibitors is temperature dependent. Taylor [47] also reported that, the effectiveness of inhibitors occured only over a certain range of temperature. These observations might be due to the fact that inhibitors break down at higher temperatures forming free radicals which are active and so initiate polymerization reactions. Accord-ing to Emanuel [48], if the autoxidation reaction results in a branched chain polymer formation, then the action of inhibitors is not effective. In the patent literature numerous patents on the use of inhibitors [49, 50, 51] to Chapter 2. LITERATURE R E V I E W 43 Table 2.6: Economic Effects of Antifoulant Use on Crude Unit for for Hypothetical 100,000 Bbl/Day Refinery [1] Fouhng Related Expenses (Thousands of US Dollars/year) Energy Throughput Cleaning Antifoulant Total Without Antifoulant 1020 3730 35 — 4785 With Antifoulant 265 2050 15 155 2485 Savings 755 1680 20 -155 +2300 Cost of antifoulant $ 5.20 a gallon. Chapter 2. LITERATURE REVIEW 44 prevent or reduce fouling, and on the use of coatings such as pofymeric paints [52, 53] to render the surface inert and hence reduce fouhng, are reported. From the patent literature and experimental evidence, it is apparent that the use of antifoulants and additives requires a case by case approach. To develop a general approach to the use of antifoulants, the precise kinetics and mechanism of the chemical reaction involved should be known. 2.6.2 Cleaning Cleaning of fouled heat exchangers is important to restore their efficient performance. It is also important that cleaning be done very well as deposits left behind promote rapid fouhng. Methods employed are both mechanical and chemical. Cleaning can be on-line where the heat exchangers are cleaned whilst in operation or off-line where cleaning is done during shutdowns. Amongst methods initiated to effect on-line mechanical cleaning of heat exchangers is the use of spongy rubber balls which constantly circulate in the heat exchanger [46]. The spongy balls are slightly larger than the inside diameter of the heat exchanger tubes and are slightly compressed as they move through the tubes. The rubbing action of the balls cleans the tubes. Another method involves the use of brushes that are periodically backflushed through the heat exchanger tubes. Brushes are sent through the tubes by fluid flow. A four-way valve then returns the brush for another round through the tube by temporarily reversing the flow of the hquid in the heat exchanger tubes. These methods are known to achieve substantial savings [55, 56, 57], but are generally useful in moderate temperature aqueous systems. Off-line mechanical cleaning methods include using high pressure water jets with water under pressures up to 20,000 psi., to blast deposits in heat exchanger tubes. Steam cleaners are also used and are similar to the water jets. They inject steam into the tubes Chapter 2. LITERATURE REVIEW 45 or the shell of a heat exchanger, and are good at removing deposits that require thermal loosening and that cannot be removed by pressure alone. Another common method of cleaning makes use of a device known as a lance. Various cutting heads mounted on the end of the lance rotate and help remove deposits. They tend to remove deposits that water and steam jets cannot remove. Chemical cleaning of heat exchangers has several advantages over mechanical cleaning [58]. Chemical cleaning can be performed in-situ without taking apart the heat exchanger. It is relatively rapid and effective and the solutions reach normally inaccessible areas. Heat transfer surfaces are not damaged mechanically and complete surface treatment is achieved. Moreover it requires less labour than mechanical cleaning. Table 2.7 [51] gives commonly used chemicals. 2.7 T H E F O U L I N G R I G The fouhng rig used in this work consisted of two test sections — an annular probe and a hot wire, mounted in parallel. The rig, built by P. E. Fetissoff [80] and modified by H. Muller-Steinhagen for subsequent work [71, 124], was used previously in studies of styrene polymerization fouhng and particulate fouhng from heptane. Details of the test loop are given in Chapter 5. 2.7.1 The annular probe The annular probe or the Portable Fouhng Research Unit (PFRU) was designed, con-structed and supplied by the Heat Transfer Research Incoporated (HTRI). It is described in detail in [60, 80]. It consists of a heated rod with thermocouples imbedded in the walls of the heated surface. The measured temperature is that of the stainless steel some dis-tance below the surface. Heating is done indirectly by means of a 32 fi nichrome wire Chapter 2. LITERATURE REVIEW 46 Table 2.7: Chemicals commonly used in cleaning [51] Acids Alkalis Complexing Agents Oxidants Solvents Others Hydro-chloric, Caustic soda, E D T A , Potassium permanganate, Aromatics, Inhibitors, Nitric, Ammonia, Gluconates, Sodium Bromate, Aliphatic, Surfactants, Sulph-uric, Trisodium, Sodium Nitrate, Chlorinated, Antifoams, Hydro-fluoric, Sodium Metasilicate, Sodium Hypochlorite, Solvent Emulsifiers, Biocides, Citric Soda ash Ammonium Persulphate Dewatering Formulations Dispersants Chapter 2. LITERATURE REVIEW 47 inside the rod. The tube surrounding the heated section includes a glass portion to allow for visual observation of the heated section. Two mixing chambers each containing a chromel-constantan thermocouple are located at the entry and exit of the test sections for measuring the bulk fluid temperature. The test fluid is recirculated around the loop by means of a pump. At time zero, the overall heat transfer coefficient for the clean surface is calculated from the measured wall temperatures Tw as: — = — — - (2.24) Uc Q/A { V where Q is the electrical power input to the probe. After fouhng, the overall heat transfer coefficient becomes: w, - n § 7 ^ ( 2'2 6 ) hence, the fouhng resistance is given by: R> - wrk=hlwr <226> 2.7.2 The hot wire probe The Hot Wire Probe (HWP) is based on the UOP Monirex Fouhng Probe [5, 6]. It uses a Type 302 stainless steel wire of diameter 0.125mm. The wire is held between two busbars and screwed into a rectangular duct. Flow is normal to the coiled wire. The wire uses DC electrical heating. The power input to the hot wire is determined by current and voltage measurements, from whence the heat flux is calculated. The surface temperature is calculated from resistance measurements and given by: Chapter 2. LITERATURE REVIEW 48 r . = ( | - ^ - - i ) / a + r 0 where Rext — is the resistance of the external circuit RD — is the resistance of the wire at time zero T0 — is the temperature at which RD is determined R — is the resistance of the wire at time t a — is the temperature coefficient of the resistance Two thermocouples located immediately above and below the hot wire, measure the bulk temperature of the fluid. Knowing Tt and Tb. The heat transfer coefficient is calculated from rp f h = W ( 2 ' 2 7 ) Knowing the heat transfer coefficient under clean h0 and fouled hf conditions, the fouhng resistance is calculated from: (2.28) Chapter 3 BACKGROUND TO THE PRESENT WORK Most papers which have appeared in the literature on organic fouhng have been con-cerned with mass deposition studies, as compared with pure thermal fouhng. Very little work has been concerned with linking the chemistry of the fluid media to thermal fouhng characteristics. Taylor's studies on deposit formation in jet fuels [7, 13, 14, 33] were the first to examine the effect of species type on the rate of deposition. Taylor's initial studies were conducted under reduced pressure and at such temperature conditions that evaporation occured. This is comprehensible since Taylor's work was primarily concerned with the degradation of jet fuels in supersonic aircraft, at temperatures far above the boiling points of these fluids. Subsequent work by Taylor was done at elevated pressures of 69 atmospheres. Moreover, Taylor's work involved determining the deposit formation rate, that is the amount of deposit formed per area per time and not the thermal fouhng resistance. This leaves open the questions as to whether the olefins tested foul under the liquid phase conditions commonly encountered in the chemical industry and whether the re-ported values of the deposit formation rates are related to thermal fouhng rates. Hence the necessity arose to evaluate the conditions of temperature under which olefinic species foul and those under which fouhng does not occur, and to compare the thermal fouhng characteristics obtained with Taylor's deposit formation rates. Secondly, research on organic fouhng suggests a classical autoxidation mechanism 49 Chapter 3. BACKGROUND TO THE PRESENT WORK 50 as a result of which free radicals are formed which act as initiators of the subsequent polymerization reactions which produce the polymeric sludges and gum-like materials encountered in fouhng deposits. This inference of an autoxidation mechanism is usually made on the basis of data from pure kinetic studies available from the literature. These kinetic studies take place under conditions that differ greatly from conditions under which fouhng studies are carried out. No attempt has been made to prove that organic fouhng proceeds via such a mechanism. This is due in part to the complexity of reactions and conditions encountered in fouling experiments. Thirdly, most research in organic fouhng in the literature has been mass deposition studies which are relatively easily done. There is little work on pure thermal fouhng attempting to link the results of a thermal fouhng study to mass deposition studies available in the hterature. If a hnk between the two can be established, results of mass deposition studies could be used to predict thermal fouling without having to repeat the thermal fouhng equivalents of all the deposition studies done to date. Thus this work attempts to link the results of thermal fouhng to some of the mass deposition studies in the hterature. The temperatures chosen for this study were such that thermal degradation and crack-ing would not be important, therefore it offers the opportunity to determine whether the results are consistent with autoxidation theory. If autoxidation is the mechanism of foul-ing, then there exists the possibility of detecting the presence of some intermediates such as hydroperoxides which decompose to form the free radicals. As well, no fouling should be observed if oxygen is rigorously excluded from the reaction mixture. Deoxygenated runs will therefore throw some further light on whether olefins foul primarily through autoxidation induced polymerization reactions or through pure thermal polymerization or both. Chapter 3. BACKGROUND TO THE PRESENT WORK 51 Moreover, since thermal fouhng as a result of polymerization reactions has been thor-oughly examined only for styrene — which undergoes pure thermal polymerization, it is of interest to find out whether other unsaturated compounds follow the styrene trend. This work thus builds on earlier work done on styrene polymerization fouling [80] which was done on the same fouhng rig as the present work. The aims of this work are: o To measure the thermal fouhng characteristics of different olefinic species under the same conditions of bulk temperature, pressure, and heat flux, and to compare the results obtained with deposition studies in the literature. « To investigate whether olefins foul under relatively low temperature non-evaporative conditions, and if fouhng does take place, to establish the range of temperatures necessary. e To attempt to establish whether unsaturated compounds foul by thermal polymer-ization, or autoxidation induced polymerization or both. Therefore, this work will concern itself with examining the effects of the fluid chem-istry on the fouhng rates as opposed to the fluid mechanics of the system. Thus runs will be performed under conditions of constant flow rate, heat flux, and pressure. Chapter 4 WORKING FLUIDS 4.1 KEROSENE The solvents used as carrier fluids in the present work were kerosene supplied by Imperial Oil Canada Limited, and n-heptane supplied by B D H Chemicals of Canada. Kerosene was chosen as the solvent due to the following reasons: • It has a high thermal stability (especially at the temperature the present work was carried out). • It has a high flash point about 58°C as compared to pure paraffins for instance —4°C for n-heptane. Thus the possibility of fire harzards is reduced. • It is less volatile than pure paraffins. • It is much less expensive than a pure component of the same average molecular weight. The major disadvantage associated with kerosene is the lack of the major physical constants in the hterature. This makes it difficult to estimate the values of fluid mechnical parameters using correlations from the hterature. n-Heptane on the other hand, combines almost all the advantages of kerosene with the fact that it is very pure and that all its physical properties are known. Its major disadvantages are a low flash point, a high volatility and its substantial cost. 52 Chapter 4. WORKING FLUIDS 53 Kerosene is a petroleum fraction produced by overhead distillation of crude petroleum in the boiling range of 150 - 290°C. It is normally composed of paraffinic, naphthenic and aromatic hydrocarbons. The composition of each of these components varies depending on the petroleum oil from which it was distilled. Olefins are normally practically absent as indicated by the low iodine and bromine numbers of kerosene. Paraffinic and naphthenic hydrocarbons have high chemical and thermal stability. They degrade only at high temperatures. Table 4.8 [63] shows a summary of the properties of a typical kerosene. Commercially sold kerosene contains additives including gum inhibitors, metal deactivators, corrosion inhibitors, anti-static inhibitors, and thermal stabilizers. The presence of a particular additive depends on the end use of the kerosene. The kerosene used contained a thermal stabilizer though it was not possible to find its identity. Table 4.9 shows the physical properties of the kerosene as received. 4.1.1 Hygroscopici ty of kerosene A knowledge of the hygroscopicity of kerosene is important because under high tem-perature conditions, the water dissolved in the kerosene can become free water, forming water slugs — free water appearing as a separate layer — or suspended in the kerosene in the form of tiny droplets giving the kerosene a cloudy or emulsion like appearance. At high temperatures, this entrained water affects the chemical behaviour and stability of the kerosene and may be important in fouhng or corrosion of the reaction vessel. The hygroscopicity of hydrocarbons is determined by their chemical structure and molecular weight. The hygroscopicity is generally inversely related to the molecular weight, independent of the structure. Among different structures, paraffins have the least hygroscopicity followed by naphthenes, olefins and the aromatic hydrocarbons, which are the most hygroscopic. Thus the low molecular weight petroleum fractions (gasolines) Chapter 4. WORKING FLUIDS 54 Table 4.8: Physical Properties of a Typical Kerosene [63] Color, Saybolt (ASTM D156-64) +30 Odor Mild APIGravi ty at 15.6°C 43.0 Specific Gravity at 15.6°C 0.811 Flash Point (T.C.C.), (°C) 60 Aniline Point, (°C) 70 Viscosity (centistokes at 0°C): 2.75 Freezing Point (°C) -32 Sulphur, (%) 0.024 Distillation Range:(ASTM D1078-49) I.B.P., (°C) 190 10 % 220 50 % 230 90 % 250 Chapter 4. WORKING FLUIDS 55 Table 4.9: Physical Properties of Kerosene Used in the Present Work Specific Gravity at 20°C 0.803 Flash Point 45°C Viscosity (centistokes at 45°C) 1.35 Bromine Number 1.13 Peroxide Number 0.1 Distillation Range I. B. P., (°C) 50 3.5% 99 8 % 139 26 % 180 43 % 200 71 % 220 Chapter 4. WORKING FLUIDS 56 Table 4.10: Effect of Chemical Structure on Hygroscopicity [67] Hydrocarbon Compound Formula Solubility of water (% weight) 25°C 55°C Paraffin Naphthene Aromatic Iso-octane Cyclohexane Benzene C's His CeH 12 C6H6 0.0037 0.0049 0.0400 0.0055 0.0087 0.0570 are more hygroscopic than high molecular weight fractions (kerosenes). The relationship between hydrocarbons and their hygroscopicity is best illustrated by Table 4.10. Thus it is evident that the hygroscopicity of kerosene depends on its composition and temperature, the higher the aromatic content, the more hygroscopic the kerosene. Gen-erally though, kerosene is considered not very hygroscopic in relation to other petroleum fractions. Table 4.11 shows the data on the hygroscopicity of three types of kerosene. 4.2 UNSATURATED HYDROCARBONS The unsaturated hydrocarbons used as fouling hquids which were added to the carrier fluids, were limited to those containing the olefinic carbon-carbon double bond. The selection was such as to permit the overlapping with some of the olefins used by Taylor [33], and to cover a range of types of olefin. The olefins used were decene-1, octene-1, hexadecene-1, indene (indonaphthene), Chapter 4. WORKING FLUIDS 57 Table 4.11: Hygroscopicity of Kerosenes [67] Solubility of Water (% wt.) in Kerosene with- Aviation Aviation Temperature out aromatics kerosene kerosene (°c) JP-5 JP-1 - 5 — 0.001 0.002 0 0.002 0.002 0.004 10 0.003 0.005 0.006 20 0.005 0.007 0.008 30 0.010 0.001 0.012 40 0.015 0.0016 0.018 Chapter 4. WORKING FLUIDS 58 1,5-cylooctadiene, 4-vinyl-l-cyclohexene (4-ethenyl-l-cyclohexene), and dicyclopentadi-ene (3a,4,7,7a,-tetrahydro-4-,7-methano-lH-indene) — a dimer of cyclopentadiene. The 1,5 cyclooctadiene, 4-vinyl-l-cyclohexene, and the dicyclopentadiene contained the in-hibitor p-tertiary butyl catechol. This inhibitor was removed by distillation before use. Tables 4.12 and 4.13 respectively show the physical properties and the structural formu-las of the olefins used. It should be noted that the selection included terminal olefins (decene-1, octene-1, and hexadecene-1), cychc dienes (1,5-cyclooctadiene, and dicy-clopentadiene), a cyclo-olefin (4-vinylcyclohexene), and a condensed or bicyclic olefin (indene). The olefins were supplied by the Aldrich Chemical Company. They were used as supplied except for the removal of the inhibitor. Chapter 4. WORKING FLUIDS 59 Table 4.12: Structural Formulas of Olefins Used Compound Structural Formula Decene—1 CH3 - {CH2)7 -CH = CH2 Octene-1 CH% — (CH2)s — CH — CH2 Hexadecene—1 CHZ - [CH2)1Z -CH = CH2 4-Vinyl-l-cyclohexene 9 C H = C H 2 1,5-Cyclo-octadiene CO Indene Co Dicyclo-pentadiene Chapter 4. WORKING FLUIDS 60 Table 4.13: Physical Properties of Olefins Used Compound Molecular Formula Molecular Mass Boihng point °C Density kg/m3 Freezing point °C Refractive index 4-Viny l - I -cy clohexene 108.18 127 834 -73.4 1.4640 1,5-Cyclo-octadiene C&H12 108.18 150.8 882 -56.4 1.4905 Octene-1 112.22 121.6 714 -101.7 1.4087 Indene CgHs 116.60 182.6 996 -1.8 1.5768 Dicyclo-pentadiene Cl0-ffl2 132.21 170.0 980 -58.0 1.5100 Decene-1 C10-H20 140.27 170.9 741 -66.3 1.4212 Hexadecene-1 C\§H32 224.43 284.4 781 4.1 1.4411 Chapter 5 EXPERIMENTAL APPARATUS 5.1 FLOW LOOP The flow loop which was originally assembled by Fetissoff [80], had to be re-assembled for this work. The test fluid is pumped around the flow loop from a pressurized supply tank by a Sihi model C A O 3102KKE stainless steel pump. The pump was driven by a 3 horsepower 3 phase Westinghouse motor. This pump generated leak problems during the course of the project and was replaced by a Paramount Model 11-819 centrifugal pump, supplied by Pumps and Power Limited of Vancouver B.C. , Canada. This pump was driven by a Leland-Newman 3 horsepower 3 phase motor manufactured by Newman Industries, England. The process fluid exits the pump via a 1/2 in. Type 316 stainless steel tube. This stream is subdivided into two, one part is returned to the supply tank via a stainless steel 1 in. pipe. The other part is further subdivided into two, and flows across two orifice meters to the test sections. The orifice meters are connected to two Merriam Model 10AA 25WM manometers each with a range of 30 inches. These manometers indicate the pressure drop across the orifice meters, which are used in the calculation of the flow rates through the test sections. The flow rate through the P F R U test section is regulated by means of a Whitey 8RF8 regulating valve. After the regulating valve, the stream passes through a mixing chamber located at the entry to the P F R U test section. A thermocouple located in the mixing chamber measures the P F R U entering 61 Chapter 5. EXPERIMENTAL APPARATUS 62 fluid temperature. The test fluid then flows through the P F R U test section, to the second mixing chamber where a thermocouple measures the P F R U exiting bulk fluid temperature. The flow across the HWP is regulated by means of a Whitey 31RF4 regulating valve. The flow through the regulating valve is so small that it ensures laminar flow across the hot wire. Immediately below and above the hot wire are two thermocouples for measuring the hot wire entering and exiting bulk fluid temperatures. The streams from the two test sections are joined and returned to the supply tank via a Jamesbury clincher valve and a 1/2 in. Type 316 stainless steel tube. This stream is mixed with the fluid in the supply tank and enters the pump via a 1 in. stainless steel pipe for recirculation. A Nupro RL3 pressure relief valve is connected between the 1/2 in. stainless steel tube from the pump and the 1 in. stainless steel pipe to the pump. This enables the fluid from the pump to circulate via the 1 in. pipe when the pressure in the system exceeds 100 psig. The relief valve can be adjusted to withstand pressures of up to 250 psig. The flow loop is shown in Figure 5.3. 5.2 Supply tank The supply tank was made from an 8 in. Type 316 stainless steel pipe. The tank has an internal diameter of 20.3 cm. and a depth of 29.2 cm. The supply tank has an active volume of 9.4 litres. The bottom of the tank was sealed with a 0.64 cm thick Type 316 stainless steel plate. A 1.2 cm thick Type 316 stainless steel ring with 12 equally spaced bolt holes was welded to the top to form the bottom flange. The cover was made of a 1.2 cm thick stainless steel plate with 12 equally spaced bolt holes to match the bottom flange. Between the two flanges is a neoprene gasket which helps effectively seal the tank. Two holes are drilled and tapped with 1/2 in. N P T through which the cooling coil is Chapter 5. EXPERIMENTAL APPARATUS 63 PUMP a cn. OPM DIFFERENTIAL PRESSURE MANOMETER Sm STIRRER MOTOR TC4 PFRU SURFACE THERMOCOUPLES ' MC MIXING CHAMBER TC THERMOCOUPLE HT HEATING TAPE PR PRESSURE RELIEF VALVE ® PRESSURE GAGE IH IMMERSION HEATER Figure 5.3: Flow Loop of Experimental Apparatus [80] Chapter 5. EXPERIMENTAL APPARATUS 64 fitted into the tank. The coohng coil is connected to the building water suppl}' by means of a 1/2 in. copper pipe. The exit from the coohng coil is connected to a tygon tube with the aid of hose clamps and leads to the sewer. The coohng coil was made from a 3/8 in. by 0.35 in. Type 316 stainless steel 316 tube. A flat six blade turbine impeller is connected to a 10 mm stainless steel shaft. This shaft is attached to a disc shaped magnet, housed in a thin walled gland plate, and screwed into the top flange. The outside drive magnet encompassing the shaft magnet is connected to a G.K. Heller Electronic Controlled Model GT 21 laboratory stirrer and motor controller. A J-shaped 1/4 in. Type 316 stainless steel tube is fitted to the top flange. One end of this tube lies directly below the impeller and the other end is connected to a Whitey 42S4 ball valve, which is connected to a Gilmont flowmeter. The Gilmont flowmeter is connected to the nitrogen cylinder or the air source. This tube is used for gas sparging of the fluid in the supply tank. Another hole in the top flange, is used for fining the supply tank. A Marsh Mastergauge Type 100-355 pressure gauge is attached to the top flange and used to indicate the pressure in the tank. A 500 Watt Vulcan L6 immersion heater is fitted into the top flange by means of male connectors. Copper wires are screwed into the ends of this immersion heater and connected to a Thermoelectric 100 Model 32106-02 temperature controller. A 1/2 in. hole drilled into the bottom of the supply tank serves as a means of draining the supply tank. Another 1 in. hole connects the supply tank to the pump via a 1 in. stainless steel pipe. Two 1/2 in. N P T nipples are connected to the side of the supply tank one below the other. The top one is connected to the return hne and the bottom one to the recycle line. On the opposite side of the tank is a third hole through which the supply tank chromel-alumel thermocouple is connected. The chromel-alumel thermocouple is then connected to a thermoelectric temperature controller and to a Ballantine Panel Chapter 5. EXPERIMENTAL APPARATUS 65 Miliivoltmeter. The Power to the supply tank's immersion heater is controlled by a Superior Electric Company powerstat model 3PN 1168. Four baffles 2.54 cm. in width and spaced at 90 degrees intervals are welded to the inside of the tank. The supply tank is wrapped by a 600 watt Electrothermal heating tape. 5.3 T E S T SECTIONS 5.3.1 Portable Fouling Research Unit The Portable Fouling Research Unit (PFRU) test section consists of the P F R U probe shown in Figure 5.4 mounted in an annulus. The P F R U was supplied by Heat Trans-fer Research Incorporated (H.T.R.I). The probe consists of a Type 316 stainless steel sheathed resistance heater with four thermocouples located close to the heating surface. It has an entrance length of 10.2 cm. The diameter of the probe is 10.74 mm. The outer diameter of the annulus is 25.4 mm. The heated length is enclosed in a pyrex glass tube to allow for its easy observation. A Marsh Mastergauge Type 100-355 pressure gauge (0-200 psig) is connected to the outer assembly to indicate the pressure of the P F R U test section. Power to the P F R U probe is supplied by the 230 volt outlet from the building's electrical supply. The resistance heater coil of the probe is a 32 $7 nichrome wire and its power is controlled by a Powerstat 236 and measured by a Sensitive Research Volt-Amp wattmeter. Figure 5.5 shows the P F R U probe. 5.3.2 Hot Wire Probe The Hot Wire Probe (HWP) design is based on the UOP Monirex fouhng probe [16]. The flow chamber consists essentially of three flat stainless steel plates sealed with teflon gaskets and screwed together to form a rectangular duct of cross section 4 cm by 1.3 cm. Chapter 5. EXPERIMENTAL APPARATUS DIMENSIONS IN mm. MATERIAL: SS 30A Figure 5.4: P F R U Probe [80] Chapter 5. EXPERIMENTAL APPARATUS 67 A threaded hole at a distance of 45.4 cm from the top end of the plate is drilled into the top plate. This hole allows for visual observation of the hot wire probe. Two holes are drilled into the sides of the middle plate and tapped with 1/8 in. NPT and connected with 1/8 in to 1/4 in male connectors which hold the busbars holding the coiled wire. The busbars are made from Type 316 stainless steel rods with diameters of 1/8 in. A hole is drilled into the side of each busbar and fitted with a hexagonal wrench. Thus when the coiled wire is connected to the busbars, they are held in place by the wrenches. The busbars are fitted into 1/8 in teflon tubes to electrically isolate the busbar from the metallic parts of the rectangular duct and hence the whole fouhng rig. A threaded hole 1cm in depth is drilled into the end of each busbar. These holes hold copper wires — by means of screw connections. The copper wires are connected to a Sorensen Power Supplier, two Data Precision Model 2480 Multimeters, and to the Doric Datalogger for the measurement of the voltage drop across the hot wire, and current through it. Flow of fluid is normal to the coiled wire. Two thermocouples located 19 mm downstream and upstream from the coiled wire are used in measuring the bulk fluid temperature. A Marsh Mastergauge Type 100-3SS pressure gauge (0 - 200 psig.) is fitted via a tee joint and a 1/8 in. stainless steel tube into a third hole in between the two thermocouples to indicate the HWP pressure. After the wire is set into position, the opening for visual observation is closed by a screw cap fitted with an O-ring. The two test sections are mounted in parallel. A Type 302 stainless steel wire of diameter .125 mm was used. The wire was supplied by Goodfellow Advanced Materials, Cambridge England. Figure 5.5 shows a schematic drawing of the hot wire probe assembly. ter o. EXPERIMENTAL APPARATUS 68 BACK PLATE MIDOLE PLATE SILVER SOLOEREO FRONT PLATE SIOE VIEW OF ASSEMBLY Yl TUBE FIATTENEO TO 15.5x7.8 mm ELLIPSE o 0 o 0 0 0 3 o 0 o 3 P *• 0 0 f ¥ ? 0 o o 0 o 0 4 o 0 af 0 0 o 0 o o 0 0 0 0 0 0 0 0 -—80.0— mm SEALED WITH 0.5 mm TEFLON GASKET Bolt holes not shown in side view. i n Malarial: SS304 Figure 5.5: Hot Wire Probe Flow Channel [80] Chapter 5. EXPERIMENTAL APPARATUS 69 5.4 CONTROL CIRCUIT The control panel contains the selector switches, powerstats, and manometers that control the experimental apparatus. Figure 5.6 is a circuit diagram of the control panel. The chromel constantan thermocouples that record the probe and bulk fluid temperatures are connected to an Omega chromel constantan jack panel whose output on the one hand is connected to a Messumschalter Type U P M F Selector Switch and on the other hand is connected through a Doric 235 modem to a Doric 235 Datalogger. The switch is connected to an Omega Model 670E digital thermometer. The voltage and current output from the P F R U are converted to DC signals by an A C / D C conversion circuit shown in fig 5.7. Since a Doric datalogger was used in place of the Fluke datalogger used by Fetissoff, the voltage and current signals from the. A C / D C conversion circuit were stepped down by means of a voltage scaling circuit shown in Figure 5.8. The output of this circuit was then passed on to the Doric 235 datalogger for recording. The 115 and 230 volts power supply to the panel are connected to a magnetic relay switch. A thermoelectric 100 Model 32106-02 temperature controller which receives one of the P F R U thermocouples' signal, is connected in series with this magnetic relay switch. Thus when the temperature controller receives a signal greater than the value it is set at, power to the system is cut off. This ensures that the P F R U probe is not heated beyond 650°F, at which it will burn out. Chapter 5. EXPERIMENTAL APPARATUS 70 TEMP. EQUALIZER HEATING TAPE PERU A PFRU B PFRU C PFRU ENTER PFRU EXIT HWP ENTER HWP EXIT POWERSTAT OATALOGGER RELAY SWITCH MULTIMETER TO DATALOGGER OMV DIGITAL MIILIVOLTMETER OT DIGITAL THERMOMETER TC TEMPERATURE CONTROLLER SS SAFETY SWITCH ITEMP. CONTROLLER) Figure 5.6: Control Circuit [80] Chapter 5. EXPERIMENTAL APPARATUS 71 50 VPIV DIODE BRIOGE Rj 75 _yv R 2 2 k.-n- MAX. R 3 12.4 R 4 4.99 k_a_ R g 2 k^x. MAX. R 6 8.66 k_n_ R ? 16.2 k^_ T t 6.3 VCT. 8 A to 115 V TL 20 VCT. 0.3 A to 115 V T3 20 VCT 0.3 A to 115 V C, 33 (I? C, 22 p.? DL DATALOGGER Figure 5.7: A C / D C Conversion Circuit [80] Chapter 5. EXPERIMENTAL APPARATUS 72 + 14 + DC ANALOG K> — VOLTAGE TO BE MEASURED Vm ~ REDUCED VOLTAGE (TO DATALOGGER) R1 = 70 kOhms. R2 = 6 kOhms. Figure 5.8: Voltage Scaling Circuit Chapter 6 E X P E R I M E N T A L P R O C E D U R E 6.1 M E A S U R E M E N T OF FLUID PROPERTIES 6.1.1 Measurement of density of test fluids The densities of the kerosene and kerosene-olefin mixtures were measured using a density bottle which is first weighed empty at a temperature of 20°C. The bottle is then charged with the test fluid and immersed in a water bath at a temperature of 20°C The bottle is then wiped clean, dried and weighed again. The density of the sample is then calculated as a ratio of the mass of the test fluid to the volume. The density was measured three times and the average of the three taken. The error given by this method is about 0.01 %. The densities of the olefins were taken as those supplied by the manufacturer. 6.1.2 Determination of viscosity The viscosity of the working fluid was determined using a Haake Rotovisko — a rotary viscosimeter. The viscosity by the Haake Rotovisko is generally given by: Ii = U.S.K (6.29) where U — a speed factor inversely related to the rpm. 73 Chapter 6. EXPERIMENTAL PROCEDURE 74 S — a scale reading on the unit. K — constant and varies with the rotating bob and stationary cup used. To begin with, the constant K is determined using specially supplied fluids of known viscosity at given temperatures. The sample is then introduced into the gap between 2 coaxial concentric cylinders, the outer one being stationary, whilst the inner one rotates. The resistance of the fluid to the rotation of the inner bob is a measure of the viscosity. Thus a U (speed) is selected and the corresponding S determined from the instrument. Knowing (7,5, and K, the viscosity of the sample is calculated. 6.2 C A L I B R A T I O N OF T H E E Q U I P M E N T 6.2.1 Orifice meter calibration The aim of calibrating the orifice meter is to determine the discharge coefficient. Knowledge of the discharge coefficient allows the flow rate to be calculated from pressure drop measurements. The orifice meters were calibrated by passing a liquid of known viscosity and density such as water through the orifice meters, measuring the amount of liquid passing in a known time and the pressure drop across the differential pressure manometers. A clean and dry 500 ml measuring cylinder was weighed. Then the connections between the orifice meters and the test sections were undone to allow the liquid flowing across the orifice meters to be collected. The valves to the manometers were closed and the pump was started. The valves were then opened and the flow rate through the orifice meter was allowed to reach a steady state. The measuring cylinder was weighed and used in collecting the flowing liquid for about 40 seconds, and then reweighed. The manometer readings were also recorded. Chapter 6. EXPERIMENTAL PROCEDURE 75 The orifice meters were reconnected to the test sections and the joint at the point where the two streams from the test sections were rejoined was disconnected. The above procedure was repeated for each of the test sections, closing the valve of one test section whilst the other is being calibrated. The procedure was repeated for about 8 different flow rates. The mass flow rate was calculated from: ra2 — mi mass now rate = (6.30) where ? T i 2 — mass of cylinder and liquid. mi — mass of cylinder, t — collection time. Knowing the mass and hence the volume flow rate, the discharge coefficient of the orifice meter is calculated from: *=H^ (6-3i) where Vi — volumetric flow rate Crf — discharge coefficient Ap,. — cross sectional area of orifice meter gc — conversion factor, gravitational to absolute units Chapter 6. EXPERIMENTAL PROCEDURE 76 Ap pressure drop across the orifice meter, gravitational units P the density of the fluid di orifice diameter d2 pipe diameter velocity of approach factor Knowing the coefficient of discharge, the volume or mass flow rate can be calculated from pressure drop measurements using the formula above. 6.2.2 Cal ibra t ion of Thermocouples The thermocouples were calibrated using a Hewlett Packard Model 2801 quartz ther-mometer. The thermocouple concerned and the probe of the quartz thermometer were put in ice. The ice was then heated through the melting point to the boiling point of water and the temperature readings taken. The temperature of the thermocouple was measured using an Omega model 670E digital thermometer. The values obtained were compared with those from the quartz thermometer. For temperature readings beyond 100°C, glycerine was used in place of water. The thermocouples were then connected to the Doric 235 datalogger and the above procedure repeated. The temperatures obtained from the datalogger were then compared to those obtained from the quartz and digital thermometers. 6.3 P R E P A R A T I O N O F C H E M I C A L S Three of the olefins used — 1,5-cyclooctadiene, 4-vinyl-l-cyclohexene, and dicy-clopentadiene, contained from 50 - 200 ppm of an inhibitor (p-tertiary butyl catechol) to prevent undesirable polymerization during storage. For the solution containing any of Chapter 6. EXPERIMENTAL PROCEDURE 77 these olefins to foul, it was necessary that it be inhibitor-free. Thus these olefins were distilled to remove the inhibitor. A Penn State Column was used to distill the olefins under vaccum. The Penn State Column consists of a packed section 37 cm by 1.05 cm diameter, equivalent to 52 theoretical plates at total reflux. The packing is made up of stainless steel hehxes each with an internal diameter of 3/64 in. The column is initially flooded by heating the liquid at a power of about 100 Watts. After flooding, the power is reduced to about 60 - 70 Watts, and allowed to remain at total reflux for about 2 hours for the system to come to equilibrium, after which the collection of distillate begins. The Penn State Column is very efficient but very slow. Therefore, it requires a lot of time before the distillation of a liter of solution is completed. The kerosene contained a stabilizer whose nature was unknown. This stabilizer was not removed prior to it being used. 6.4 GENERAL PROCEDURE FOR FOULING RUNS 1. The supply tank and pipes are cleaned using methyl isobutyl ketone (MIBK) sol-vent. Then pure kerosene is pumped around the test rig for several hours at tem-peratures of 80-100° C. 2. The supply tank, pipes and pump are drained and the whole system dried by blowing air through the system for several hours. 3. The P F R U probe is wiped clean using MIBK and acetone, and inserted into the P F R U test section. The P F R U thermocouples are plugged into the P F R U thermo-couple jack. 4. A Type 302 stainless steel wire of length 125 mm is cut and made into a coil of diameter 1.2 mm. On the average, about 25 turns are made. The coiled wire Chapter 6. EXPERIMENTAL PROCEDURE 78 is heated in an oven for about three days at a temperature of about 280 °C to ensure that it gives reproducible values of the wire temperature. It is positioned in between the two busbars with the help of the hexagonal wrenches. The busbars male connectors. The screw cap is then screwed into place. 5. The supply tank is then gravity fed with kerosene to about 50-60 % of its volume at room temperature. Then the olefin is poured into the tank using a funnel and tygon tubing. The gravity feeding with kerosene then continues until the whole system is full. The volume of fluid used is about 10-11 litres. 6. In the case of the oxygenated runs, the air valve is turned on and the stirrer is activated. The air is allowed to bubble through the system with the feed valve on the top flange of the supply tank about 20 % opened. This goes on for about 8-10 hours to ensure saturation of the test fluid with air (oxygen). 7. In the case of the deoxygenated runs, the supply tank is fed to about 80 % of its volume. The nitrogen valve is opened and the feed valve about 50 % opened. This allows any oxygen entrapped in the test fluid to be displaced by the nitrogen. The oxygen purging continues overnight. The olefin is added the next day. This ensures that the olefin does not undergo any reactions during the period the oxygen is being purged. 8. The concentration of the olefin is calculated from: are pushed into the HWP test section and secured in place by means of swagelok % Weight of Olefin = .100 (6.32) Wolef + (Vayet - V 0 l e f ) . p k l where Chapter 6. EXPERIMENTAL PROCEDURE 79 Wotej — Weight of olefin. V0ief — Volume of olefin. Veytt — Volume of system. pker — density of kerosene. 9. The pump is started and the liquid in the supply tank is allowed to mix very well with the liquid in the rest of the system. 10. The control panel is activated and the digital thermometer and multimeters are turned on. 11. After complete mixing is assured, a sample of the hquid is taken through the drain valve at the bottom of the supply tank. 12. The supply tank is pressurized to about 410 kPa (abs.). The pressurization is done with air in the case of of oxygenated runs, and nitrogen in the case of deoxygenated runs. 13. The flow control valves are set to the desired flow rates. 14. The heating tapes and the immersion heater are turned on 15. Power to the datalogger (and the power supplier) are turned on to enable them to warm up. 16. The value of RQ is determined. The bulk temperature is measured and the wire is energized with minimum power and then with maximum power. Starting from the minimum power, values of voltage and current are measured for increasing values of power. The resistances are determined and plotted against the values of power. The intercept on the resistance axis gives RD at the given bulk temperature. Chapter 6. EXPERIMENTAL PROCEDURE 80 17. The power to the P F R U probe is turned on and the powerstat set to the value that gives the desired heat flux. 18. The wire is energized until the ratio of P F R U surface area to H W P surface area equals the ratio of their electrical power dissipation values. This ensures that the two probes are operating at the same heat flux. 19. The coohng water flow rate is adjusted to bring the bulk temperature to the desired value, and the system is allowed to come to equilibrium. 20. At the steady state, the datalogger is started with a scanning sequence of 20 min-utes. 21. The manometer pressure drop readings, the readings on the pressure gauges, and the room temperature are recorded. 22. During the run, the H W P power is adjusted to make up for power loss due to fouhng. 23. Fluid samples are taken at intervals of about 10 hours each. 24. After 50 hours, the run is stopped by turning off power to the probe, the heating tapes, and the immersion heaters. 25. The coohng water flow rate is increased and the temperature of the whole system is brought to that of the room. 26. The system is drained using the drain valve. 27. The screw cap is opened and the coiled wire is removed. Chapter 6. EXPERIMENTAL PROCEDURE 81 28. The P F R U probe is removed and the deposit if any is measured and photographed. The deposit is removed and stored in a clean container for analysis. The probe is cleaned with MIBK and acetone. 29. The whole system is cleaned, dried and prepared for the next run. 30. As necessary precautions, the P F R U probe is always turned off before the pump is shut down. This is to prevent the P F R U heater from burning out when no liquid is flowing around the probe. Moreover, the centrifugal pump is run when and only when there is liquid in the system, since running the pump dry will result in damage to the rotary seals and bearings. 6.5 C H E M I C A L A N A L Y S E S 6.5.1 Analys is for peroxides Titration was used to determine the presence if any of peroxides and hydroperoxides during the course of the runs. The method used was a modified form of A S T M D1022-76 [68, 69]. The quantity determined was the peroxide number which is the number of milhequivalents of active oxygen present in a liter of sample under test. The method used was based on the chemical reaction of the peroxide bond with the ferrous ion producing a ferric ion as follows: I I I I (-C -C -O - 0 - ) + 2FeS04 + H2SOA —• -COH - COR + Fe2(S04)3 I | I i The ferrous ion is colourless in the presence of potassium thiocyanate indicator, whilst the ferric ion is red. A potassium thiocyanate indicator is added to the sample; if a red colour appears, the sample is titrated with a standard solution of titanous chloride to the disappearance of the red colour. The volume of the titanous chloride used and that Chapter 6. EXPERIMENTAL PROCEDURE 82 of the sample are used in calculating the peroxide number. The reagents are prepared as follows: 1. Glacial acetic acid — Bought from B D H Chemicals and used as is. 2. Potassium thiocyanate — This is the indicator for the reaction. It is prepared by dissolving lOOg of potassium thiocyante in distilled water and diluting it to 1 litre. This provides a potassium thiocyanate solution of 100 g/L. 3. Ferrous sulphate solution — 5 litres of methanol, and 3.5 litres of distilled water are put into a 10 litre dark stock bottle. This solution is purged of any air by bubbling CO2 from a carbon dioxide cylinder through a tube reaching the bottom of the stock bottle. In a separate stock bottle, 50 ml. of concentrated sulphuric acid (specific gravity 1.84) is added to 2 litres of distilled water. This solution is purged of air using carbon dioxide. Then 92 grams of ferrous ammonium sulphate is added while stirring. This solution is then added to the solution in the 10 litre stock bottle. The resulting solution is warmed whilst stirring and purging it of air till a complete solution is made. The 10 litre stock bottle is then attached to the carbon dioxide cyhnder and blanketed with carbon dioxide to keep it from coming into contact with air. 4. Potassium Dichromate — This solution is prepared by dissolving 0.4903 grams of pure potassium dichromate in distilled water and diluting it to 1 litre. 5. Titanous Chloride solution — An 0.007 mol/L titanous chloride solution is prepared by adding 27 ml. of 20 per cent stock solution of T iC/3 to 2 litres of distilled water, and storing the solution under oxygen-free nitrogen. This solution is standardized using the 0.005 mol/L potassium dichromate solution. To standardize, 50 ml. of the stock solution of ferrous sulphate solution is put into a 250 ml. Erlenmeyer Chapter 6. EXPERIMENTAL PROCEDURE 83 flask and 1 ml of the potassium thiocyanate indicator is added. Then exactly 25 ml. of the 0.005 mol/L potassium dichromate solution is pipetted into the flask and the resulting solution titrated with titanous chloride to the disappearance of the red colour. The volume of titanous chloride used is recorded and the normality calculated from: ZVDMD M t = ~Wr~ ( 6 ' 3 3 ) where Vp — volume of dichromate solution MD — molarity of dichromate soluiion VT — volume of titanous chloride solution Mx — molarity of Titanous chloride solution The test for peroxide is carried out by titration. 1 ml. of the ferrous sulphate solution and 1 ml. of the indicator are pipetted into a 250 ml. Erlenmeyer flask. Ten to fifteen ml. of the sample is measured into this flask and immediately titrated with a standard solution of titanous chloride to the disappearance of the red colour. The volume Vx of the titanous chloride solution used and sample volume S are recorded. The peroxide number is calculated from: where (6.34) Chapter 6. EXPERIMENTAL PROCEDURE 84 P is the peroxide number(milhequivalent active 02 / l i ter) VT is the volume of titanous chloride in milhlitres M is the molarity of the titanous chloride solution S is the volume of the sample The stock ferrous sulphate solution and the standard solution of titanous chloride should always be freshly prepared, and blanketed with either carbon dioxide or oxygen free nitrogen. Moreover, the titanous chloride solution should always be standardized before use. This method is the most sensitive and hence the most suitable in cases where minute amounts of peroxide are present. In cases where large amounts of peroxide are present this method gives low values of the peroxide number. Therefore in cases where large amounts of peroxide were detected using the above method, the thiosulfate method A S T M D1832-65 was used to confirm the value of the peroxide number. 6.5.2 Determinat ion of Bromine Number The bromine number of the kerosene was determined using the Lewis and Bradstreet method [69, 126]. The bromine number, expressed in centigrams of bromine per gram of sample, is a measure of the amount of unsaturation in the sample. The bromine reacts with the multiple bonds converting them into saturated species. Thus the amount of bromine (% by weight) reacting with 100 grams of sample under specified conditions is used as an indication of the amount of multiple bonds in the sample. A sample of the kerosene was pipetted into a flask containing 20 ml. of K B r and 15 ml. of n-heptane. The contents of the flask were titrated using an excess of 0.5 mol/L potassium bromide—potassium bromate solution to a faint yellow colour. Then 5 ml. of saturated potassium iodide solution was added and the liberated iodine was titrated with Chapter 6. EXPERIMENTAL PROCEDURE 85 Na2S203 using starch as an indicator. The bromine number was calculated from: {AC - DE)7.99 B = w where B — bromine number (centigrams bromine per gram sample) A — molarity of bromate-bromide solution C — volume of bromate-bromide solution D — molarity of thiosulfate solution E — volume of thiosulfate solution W — weight of sample (6.35) Chapter 7 RESULTS A N D DISCUSSION 7.1 P R E L I M I N A R Y E X P E R I M E N T S 7.1.1 Heat Transfer Correlation Experiments Experiments were conducted on the fouhng rig to compare the values of the convec-tive heat transfer coefficient obtained experimentaUy with those obtained from accepted correlations. The aim of these runs was to find out how accurate, consistent and re-producible the values of the convective heat transfer coefficients obtained from the rig were. The hquid used was water because all the physical constants are known and readily available. The supply tank was filled with water pressurized to 410 kPa (abs). The water was heated and its temperature brought to equilibrium before readings were taken. These experiments were conducted both for the annular probe and the coiled wire. Following Muller-Steinhagen et al. [71], the correlations tested for the annular probe were: 1. The Dittus and Boelter equation [117] for turbulent flow in pipes. Nuc = 0.023 Re0SPr0A (7.36) 2. The Wiegand equation [118] for turbulent flow in annuli. 86 Chapter 7. RESULTS AND DISCUSSION 87 Nuc = 0.023Re0-8PrOA(d0/di)OA5 (7.37) 3. The Morand and Pelton equation [119] for turbulent flow in annuli. Nuc = 0.02Re0S5Pr0-5(do/di)0-53 ( 7.38) 4. The Taborek equation [120] for turbulent flow in pipes. Nuc = 0.0143 Re085 Pr05 (7.39) 5. The Gnielinski equation [121] for turbulent flow in pipes. f/8(i2e - 1000.)Pr , , where £ = {1.82logRe - 1.64)~2 The equations tested for the coiled wire were: 1. The Leveque equation [122] for laminar flow over flat plates. Nuc = 0 . 664#e° - 5 Pr a 3 3 (7.41) Chapter 7. RESULTS AND DISCUSSION 88 2. The Ulsamer equation [123] for laminar flow over tubes and wires. Nuc = CRenPr 0.31 (7.42) where C = 0.91, n=0.385, 0.1 < Re < 50 C = 0.6, n=0.5, 50 < Re < 10,000 For the coiled wire an equivalent diameter of irdw/2 was used [71]. The experimental convective heat transfer coefficients were calculated from: (7.43) where for the annular probe, the surface temperature is calculated from the measured probe wall temperatures as follows: where ATO is the thermal conductivity of the metal. The resistance s/\m is evaluated using the method of Wilson [72]. Values of s for two of the thermocouples were available from the manufacturer. The third was determined as part of this work. The values of s/X are presented in Appendix A. l . For the coiled wire, z = Tw - ^-Q/A Q = I2(V/I-Rext) and z = ( R — Rt Ro ~ Ri 'ext •ext. - l ) / a Chapter 7. RESULTS AND DISCUSSION 89 The calculated convective heat transfer coefficient was evaluated from: Nuc = (7.44) where Lch is the characteristic length of the heated sections of the probes, and Ay is the thermal conductivity of the fluid, and Nuc = f{Re,Pr, d/L) The results of the convective heat transfer correlation experiments are shown in Tables 7.14 and 7.15. and the conditions of these experiments are shown in Table 7.16. The best predictions for the annular probe were given by the Taborek and Gnielinski equations. The Wiegand equation gave large errors of the order of 30 %. The Dit-tus/Boelter and Monrad/Pelton equations were somewhere in between the two. For the coiled wire, the best prediction was given by the Leveque equation. The predictions, especially those of the PFRU, were consistent with the results of Muller-Steinhagen et al. [124], who found that the Dittus/Boelter equation always gave values lower than the measured heat transfer coefficient, whilst the Monrad/Pelton and Wiegand equations gave higher values, with the other two correlations giving values around the measured one. In the case of the HWP, they found that the Ulsamer equation always gave higher values than the measured heat transfer coefficient. The above results suggested that the experimental apparatus, techniques and calculation methods were adequate to proceed with the fouhng study. 7.1.2 Preliminary Fouling Experiments The aim of the preliminary fouhng experiments was to ascertain whether heating the sol-vent — kerosene, resulted in deposit formation under the conditions of this work. Three Chapter 7. RESULTS AND DISCUSSION 90 Table 7.14: Experimental Heat Transfer Correlations for Annular Probe Correlation Author h Calculated W/m2K h Measured W/m2K % Deviation from measured value 1.Turbulent flow in pipes Nu = .023Re°-8PrOA Dittus/ Boelter 5114 5835 12 2. Turbulent flow in annuli Nu = 0.023Re°-8PrOA(d0/di)OA5 Wiegand 7492 5835 28 3. Turbulent flow in annuli Nu = .02i?e°- 8 Pr°- 3 3 ( t i o /d l ) 0 - 5 3 Monrad/ Pelton 6607 5835 13 4.Turbulent flow in pipes Nu = .0143.Pe°- 8 5 Pr 0 ' 5 Taborek 5715 5835 2 5.Turbulent flow in pipes £ = (l.MLogRe - 1.64) N u _ ?/8(fie-iooo)pr f l ( d / L ) ] Gnielinski 6131 5835 5 er 7. RESULTS AND DISCUSSION Table 7.15: Experimental Heat Transfer Correlations for Coiled Wire. Correlation Author h Calculated W/m2K h Measured W/m2K % Deviation from measured value Nu = 0.664fle°- 5Pr°- 3 3 Leveque 5021 4863 3 Nu = 0.9lRe°-5Pr0-385 Ulsamer 6654 4863 36 Table 7.16: Parameters of Heat Transfer Correlation Run V U Re Pr Tt T b Heat Flux m3/hr m /5 °C °C kW/m2 P F R U 0.94 0.654 26650 2.16 142 82 349.98 HWP 0.0125 0.0066 3.7 2.16 136 83 259.49 Chapter 7. RESULTS AND DISCUSSION 92 runs were carried out using only kerosene under 375 kPa pressure and air saturated con-ditions. The first run was carried out at a heat flux of 200 kW/m2, a surface temperature of 180°C, and a bulk temperature of 75°C The second run was at a heat flux of 250 kW/m2, a surface temperature of 184°C and a bulk temperature of 82° C The bulk fluid velocity for the first and second runs was 0.56 m/s for the P F R U and 0.02 m/s for the HWP. The corresponding Reynolds numbers were 9830 for the P F R U and 4.9 for the H W P respectively. The last run was at a heat flux of 300 kW/m2, a surface temperaure of 198, and and a bulk temperature of 87°C. The bulk fluid velocities and Reynolds numbers were the same as for the first two runs. Al l the runs lasted 50 hours. Over the period of 50 hours, no fouling was observed on any of the probes in any of the runs. The results of these runs gave the assurance that the solvent is thermally and perhaps chemically stable under the conditions of this work. Besides the absence of thermal degradation, the stabihty of the kerosene under air saturated conditions indicated that the solvent did not take part in any measurable autox-idation or autoxidation-induced polymerization reactions. The kerosene was composed mainly of paraffins, with little unsaturates as confirmed by the low bromine number of 1.13. Therefore, the most probable reaction it would undergo under heating would be cracking which could subsequently lead to polymerization and coking. But cracking re-actions were not expected because of the low temperatures involved. At the highest heat flux, the surface temperature was 198°C. It was concluded that the kerosene was stable and presumably had no direct contribution to deposit formation in this work. 7.2 SOLUBILITY OF AIR IN KEROSENE-OLEFIN MIXTURES Prior to starting each run, with the exception of the deoxygenated runs, the kerosene— olefin mixture was saturated with air by bubbling air through it at temperatures of 25 Chapter 7. RESULTS AND DISCUSSION 93 - 40°C, for several hours. The test, fluid was also pressurized under an air atmosphere throughout the duration of the run. To estimate the concentration of dissolved air and hence oxygen in the test fluid, the A S T M standard D3827-79 — "The estimation of the solubility of gases in petroleum and other organic liquids", was used. The method is based on Hildebrand's regular solution theory and uses solubility parameters of both gas and liquid. The method works well for distillate fuels such as kerosene where there is little or no polarity and hydrogen bonding. The method was used to calculate the Ostwald coefficient, the Bunsen coefficient and the concentration in parts per million by weight (ppmw) of gas in solution. The method has a standard error of about 12 % for air and 17 % for oxygen. The solubility is estimated as follows: The solubility parameter of the liquid 5 a is calculated as: St = 5.88/3 + 3.60 The solubility parameter S 2 °f the gas is obtained from a table of solubility parameters of gaseous solutes in A S T M D 3827-79. The solubility parameters for oxygen, air, and nitrogen are 3.79, 3.27 and 2.95 respectively. The Ostwald coefficient L, which is the ratio of the volume of gas absorbed to the volume of absorbing liquid is calculated from: I = e((0.165(5 a - 5 2 ) 2 - 2.66)(1 - 273/T) - 0.625a - 0.101(8.6 - 5 2 ) 2 + 5.73) The Ostwald coefficient is corrected hy multiplying the Ostwald coefficient calculated by a fuel factor obtained from a table in A S T M D3827-79. The fuel factors for oxygen, air and nitrogen are 1.28, 1.44, and 1.70 respectively. The Bunsen coefficient B which is the volume of gas at standard temperature and pressure which is absorbed by a unit volume of solvent at the temperature of measurement under a partial pressure of 1 atmosphere is calculated from: Chapter 7. RESULTS AND DISCUSSION Table 7.17: Calculated Solubilities of Air and Oxygen in Kerosene 94 Component Ostwald Coefficient L cm3/cm3 Bunsen Coefficient B cm3/cm3 atm. Concentration ppmw at 293 K, 410 kPa Air 0.162 0.615 997 o2 0.233 0.880 1575 N2 0.140 0.528 827 = 273PL T where T is the temperature at which the solubility is being determined and p is the partial pressure of gas in the test fluid. To obtain the concentration of the dissolved gas, the density of the liquid at the specified temperature is calculated from: pT = p[l - 0.000595(r - 288.2)/p 1 2 1] and the concentration in ppmw from: G = U.6BM2/PT where M2 is the molecular mass of the gas. The calculation yielded the solubilities for air, oxygen and nitrogen shown in Table 7.17. Chapter 7. RESULTS AND DISCUSSION 95 7.3 DISCUSSION OF FOULING RUNS For the purposes of the discussion of the fouhng runs, the olefins have been grouped into 4 categories viz. terminal olefins, cyclo-olefins, indene, and dicyclopentadiene. A l l but two runs — Runs 11 and 14 — were held under oxygenated conditions. The flow rates were constant at 0.8 m3/hr. for the P F R U and 0.04 m3/hr. for the hot wire probe. These correspond to Reynolds numbers of about 9800 for the P F R U and 5 for the HWP. The volume of test fluid used was about 9-11 litres. The mass of olefin used was always 1 kg and the concentration of the olefin in kerosene was 10 % wt. Tables 7.18 and 7.19 show respectively the initial and average operating conditions for the experimental runs. Detailed output as a function of time for all runs is given in Appendix D. Runs 8 and 11 for indene were repeated to check whether the results of the experiments were reproducible. The fouhng curves for these runs are shown in Figures A.27 and A.28 Appendix A. A comparison of Figures 7.16 and 7.20 with A.27 and A.28 shows that, the relative thermal fouhng resistances and fouhng rates are almost identical. Therefore, the results of the experimental runs were considered reproducible Chapter 7. RESULTS AND DISCUSSION 96 Table 7.18: Initial Operating Conditions P F R U H W P Run T, Tb U0 k W / q T. Tb U0 k W / q # Foulant °C °C {m2K) kW/m2 °C °C {m2K) kW/m2 1 Decene-1 180 70 1.803 198.32 140 70 2.010 140.71 2 Decene-1 185 70 2.232 256.66 160 70 2.038 183.47 3 Octene-1 190 70 2.236 268.32 175 70 1.959 205.75 4 1,5-Cyclo-octadiene 190 70 2.236 268.32 170 70 1.956 195.66 5 Decene-1 204 90 3.070 349.99 206 85 2.932 354.78 6 4-Vinyl-cyclohexene 198 82 2.565 297.49 198 78 2.456 294.77 7 Dicyclo-pentadiene 198 80 2.521 297.49 198 79 2.497 298.43 8 Indene 198 81 2.543 297.48 198 83 2.578 297.87 9 Indene 183 85 2.504 247.91 183 85 2.519 248.13 10 Indene 180 85 2.087 198.33 180 85 2.090 198.57 11 Indene de-oxygenated 198 84 2.622 298.94 198 82 2.611 302.86 12 Dicyclo-pentadiene 187 85 2.763 281.84 185 82 2.5757 265.30 13 Dicyclo-pentadiene 183 82 2.063 208.37 180 82 2.0504 200.94 14 Dicyclo-pentadiene 198 84 2.602 297.48 197 81 2.549 296.91 deoxygenated 15 Hexadecene-1 198 82 2.5689 297.99 198 82 2.6393 306.16 Chapter 7. RESULTS • AND DISCUSSION Table 7.19: Average Operating C onditions 97 Initial Heat Initial Average Transfer Surface Bulk Fluid Average Run Coefficient Temperature Temperature Heat Flux # Foulant kW/m2K °c °C kW/m2 P F R U HWP P F R U HWP P F R U HWP P F R U H W P 1 Decene-1 1.803 2.010 180 140 72 72 196.34 150.82 2 Decene-1 2.232 2.038 185 160 73 72 252.68 182.84 3 Octene-1 2.236 1.959 190 175 74 73 266.92 199.88 4 1,5-Cyclo-octadiaene 2.236 1.956 190 170 74 73 270.42 193.29 5 Decene-1 3.070 2.932 204 206 88 85 357.41 360.45 6 4-Vinyl-cyclohexene 2.565 2.456 198 198 84 82 298.86 293.81 7 Dicyclo-pentadiene 2.521 2.497 198 198 80 81 293.61 296.21 8 Indene 2.543 2.578 198 198 81 80 299.24 295.32 9 Indene 2.504 2.519 183 183 83 82 246.26 248.94 10 Indene 2.087 2.090 180 180 82 83 196.57 198.90 11 Indene de-oxygenated 2.622 2.611 198 198 87 82 299.02 299.33 12 Dicyclo-pentadiene 2.763 2.575 187 185 81 80 258.03 254.41 13 Dicyclo-pentadiene 2.063 2.050 183 180 83 81 215.51 201.19 14 Dicyclopen-tadiene de- 2.602 2.549 198 197 84 81 301.80 297.58 oxygenated 15 Hexadecene-1 2.59 2.639 198 198 84 82 297.73 307.28 Chapter 7. RESULTS AND DISCUSSION 98 7.3.1 Terminal Olefins The terminal olefins used were decene-1, octene-1, and hexadecene-1. Runs 1, 2, 3, 5, and 15 involved terminal olefins. A l l the five terminal olefin runs were conducted under air-saturated conditions. The decene—l run was at an average P F R U heat flux of 196 kW/m2, and an average H W P heat flux of 150.8 kW/m2. The average bulk fluid temperatures were 72°C for both probes. No fouhng was observed for this run over a period of 50 hours. The probes remained clean and there was little change in the test fluids' physical appearance. This run was repeated at a higher average heat flux of 252.7 kW/m2 for the annular probe and 183.5 kW/m2 for the coiled wire. The average bulk fluid temperatures remained about the same at 73°C for the annular probe and 72°C for the coiled wire. This run too produced no measurable fouhng over a period of 50 hours. After the two runs involving decene—l produced no measurable fouhng, octene—l, the next terminal olefin was tried. The average P F R U heat flux for this run was 266.9 kW/m2 and the average bulk temperature was 74°C. The average HWP heat flux and bulk temperature were 199.9 kW/m2 and 73°C respectively. The octene run also showed no measurable fouhng. The low heat fluxes and bulk temperatures were in keeping with the initial aim of this project, namely to find out whether olefins fouled under low temperature, non-evaporative conditions. The lack of success with the first three runs prompted the use of higher heat fluxes and bulk temperatures. Thus Run 5 was conducted using decene—l at an average heat flux of 357.4 kW/m2 for the P F R U , and 360 kW/m2 for the coiled wire. The average bulk fluid temperatures were 88°C and 85°C for the annular probe and coiled wire respectively. Run 5, produced some fouhng both on the annular probe and the coiled wire. The thermal fouhng resistance versus time curve is shown in Fig 7.9 There was an induction period of about 4 hours. The thermal fouhng resistance for the P F R U probe peaked at a value of about 0.025 (rn2K)/kW after 15 Chapter 7. RESULTS AND DISCUSSION 99 hours and remained almost constant at that value to the end of the run. The deposit on the annular probe was thin and hard, and could only be removed by soaking the probe in methyl-isobutyl ketone and scrubbing the deposit off the probe. The HWP showed a similar fouhng rate. The thermal fouhng resistance was higher on the HWP than on the P F R U , and exhibited a sawtooth nature. It is apparent from the plot that fouhng was minimal and proceeded at a moderate rate of about 0.003 (m2K)/kWh. The hot wire probe showed relatively more vigorous fouhng activity than the annular probe. The results of the decene-1 and octene-1 runs prompted the use of a high molecular weight straight chain olefin. According to Brill et al. [103], the products of the autoxi-dation of high molecular weight olefins include insoluble residues which are the result of chain cleavage and linkage reactions. These residues, if they are formed, are a potential source of fouling precursors. Moreover, work done by Norton et al. [70] on the oxidation of high molecular weight olefins indicates the formation of sohd polymeric peroxides. The high molecular weight olefin used was hexadecene-1, which consisted of about 98 % hexadecene-1 with the remaining being its isomers. The run was done at a P F R U heat flux of about 298 kW/m2 and a bulk temperature of about 84°C. The average HWP heat flux was 307 kW/m2 and the average bulk fluid temperature was 82°C. Fouhng was observed in this run and the results are shown in Figure 7.10. The fouhng curve was almost linear and the fouhng rate was greater for the P F R U than for the HWP. Over a period of 49 hours, fouhng resistances of 0.27 and 0.19 (m2K)/kW respectively were reached on the two probes. 7.3.2 Cyclo-olefins The cyclo-olefins used in this work were 1,5-cyclooctadiene, 4-vinylcyclohexene, and dicyclopentadiene. For the purposes of this discussion, dicyclopentadiene is treated in a separate section. Conditions for the runs involving the former two cyclo-olefins, Runs 4 Chapter 7. RESULTS AND DISCUSSION 0.090 0.075 H o.oeoH 0.045 0.030H 0.015H RUN 5 DECENE-1 • = PFRU Tb=8a?C A - HWP Tb=85UC PFRU: q=357kW/m? HWP: q=360kW/m A A A A A A A A ^ A D l A AAf i A A A A " A A 5 A A A A A A A A A A A » A A A 100 A A C P C • B • AD A D 0.000 $000 ! 0.0 7.0 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure 7.9: Fouling resistance versus time for Run 5, decene-1 Chapter 7. RESULTS AND DISCUSSION 101 0.34-1 0.3CH 0.26H CO £, w o 00 00 w S 0.10H E> O 0.08 0.22 H 0.18 0.14H 0.02 RUN 15 HEXADECENE • = PFRU Tb=84TC A = HWP Tb=82°C PFRU: q=298 kW/m£ HWP: q=307 kW/m"1 riBI 3 • • • CP A' B S 0 0 ELo "4 • 0 . 0 2 - f— r— r — 0.0 7.0 I ' 1 ' I 1 1 ' 1 1 I 14.0 21.0 28.0 35.0 42.0 49.0 TIME (HOURS) Figure 7.10: Fouling resistance versus time for Run 15, hexadecene-1 Chapter 7. RESULTS AND DISCUSSION 102 and 6, are given in Table 7.19. The cyclo-olefins used are very reactive species especially in the presence of air. Hence, they all contained the inhibitor p-tertbutyl catechol when received. The presence of this inhibitor warranted the redistillation of these olefins. Run 4 involved 1,5-cyclooctadiene (re-distilled) at an average heat flux and bulk fluid temperature of 267 kW/m2, and 74° C respectively for the P F R U , and 200 kW/m2 and 73°C respectively for the hot wire probe. The fluid was pressurized to about 410 kPa and air-saturated. No measurable fouhng was detected for Run 4 over a period of 50 hours on either of the probes. Since 1,5-cyclooctadiene is a very reactive compound, it is difficult to explain why no fouhng occurred, apart from the low heat flux and possibly the low bulk fluid temperature. Run 6 involved 4-vinyl-l-cyclohexene. This run was performed at a heat flux of about 299 kW/m2, for the P F R U probe, and 294 kW/m2 for the HWP. The average bulk fluid temperatures were 84°C and 82°C for the P F R U and HWP respectively. The test fluid developed the appearance of a murky emulsion over the run. This probably was the result of polymerization in the bulk fluid of the 4-vinylcyclohexene, resulting in a dispersion of tiny particles of polymer in the bulk fluid. The fouhng resistance versus time curve for the 4-vinyl-l-cyclohexene run is shown in Figure 7.11. There was no induction period, however some negative fouhng resistances were observed during the first hour of the run, due perhaps to surface roughness effects. Fouhng was vigorous and the thermal fouhng resistance increased linearly with time for the first 15 hours of the run, reaching a value of 0.12 (m2K)/kW for the P F R U probe. After the initial 15 hours, the fouling rate decreased and probably would have reached an asymptotic value of about 0.2 (m2K)/kW had the run been extended for long enough. At the end of 45 hours, the thermal fouhng resistance had reached a value of about 0.155 (m2K)/kW, a change of about 0.03 (m2K)/kW in the final 30 hours. During this period, the thermal fouhng resistance showed some evidence of a sawtooth shape. Chapter 7. RESULTS AND DISCUSSION 103 The thermal fouhng resistance versus time curve for the HWP was similar to that of the P F R U except that at any given time, it had a lower value than that of the P F R U . The initial HWP fouhng rate was also lower than that of the P F R U . The HWP also showed a hnear thermal fouhng resistance with time for the first 21 hours, and reached a value of about 0.11 (m2K)/kW during that time. The fouhng rate then fell, exhibiting a sawtooth nature. The maximum HWP thermal fouhng resistance over the period of the run was about 0.13 (m2K/kW). The rapid fouhng of 4-vinyl-l-cyclohexene is consistent with thermal polymerization fouhng as shown by studies on styrene polymerization fouhng [80]. Taking into account the state of the test fluid after the run, it seems reasonable to assume that thermal polymerization on the probe surface and in the bulk were major contributors to fouhng in this run. 7.3.3 Dicyclopentadiene There were a total of 4 runs involving dicyclopentadiene. Dicyclopentadiene poly-merizes readily when in contact with air. Thus the dicyclopentadiene acquired contained about 200 ppm of the inhibitor p-tertiary butylcatechol. Run 7 was carried out with di-cyclopentadiene containing the inhibitor. The average P F R U heat flux was 294 kW/m2 and the average bulk fluid temperature was 80°C. The average H W P heat flux was 296 kW/m2 and the average bulk fluid temperature was 81°C. A long induction period of about 30 hours was observed at a thermal fouhng resistance of about 0.015 (m2K)/kW for the P F R U and about 0.02 (m2K)/kW for the HWP. The finite fouhng resistance during the long induction period was probably due to the fact that the dicyclopentadiene was slightly polymerized — a condition which is very difficult to avoid even in the presence of an inhibitor, or in the case of freshly distilled dicyclopentadiene. Thus deposition — possibly by a particulate fouling mechanism — of the tiny polymer particles suspended in the bulk fluid, apparently began as soon as power Chapter 7. RESULTS AND DISCUSSION 104 0.18 0.16 0.14 ^ 0.12 o O.IOH ?s CO CO 0.08 W « S 0.06 H o 0.04 H 0.02 ^ 0.00^ RUN 6 4-VINYL-1-CYCL0HEXENE • o • • • L B JgsBBi B ° c f t j • • A A A A & A A N A * ^ A A A • A * • = PFRU. Tb=84?C A - HWP, Tb=82uC PFRU: q=299kW/m| HWP: q=294 kW/m* A A 7.0 28.0 I • 35.0 I 1 42.0 14.0 21.0 A TIME (HOURS) Figure 7.11: Fouling resistance versus time for Run 6, 4-vinyl-l-cyclohexene 49.0 Chapter 7. RESULTS AND DISCUSSION 105 to the probe was turned on. The thermal fouhng resistance observed in the first 30 hours of the run is therefore thought to be due to particulate deposition of polymer particles that existed in the bulk fluid prior to the start of the run. After the 30 hour induction period, there was a sharp rise in the thermal fouhng resistance both for the P F R U and HWP. The reason for the sharp rise in the thermal fouhng resistance is possibly due to the inhibitor being rendered inactive or somehow being degraded after a long exposure to heat. The thermal fouhng resistance versus time curve is shown in Figure 7.12. The inhibitor was distilled out of the dicyclopentadiene and two runs with inhibitor free dicyclopentadiene were performed under oxj'genated (air-saturated) conditions. To avoid the slight polymerization of the dicyclopentadiene as much as possible, it was distilled some few hours prior to the beginning of the run, and transferred directly from the collection flask of the distillation set up to the supply tank. Run 12, the first of these two runs was at heat fluxes of 258 and 254 kW/m2 for the P F R U and H W P respectively. The corresponding average bulk fluid temperatures were 83°C and 81°C. The fouhng resistance versus time plot for this run is shown in Figure 7.13. There was a short induction period of about 5 hours for both the P F R U and HWP, after which both curves were of the falling rate type. The P F R U thermal fouhng resistance rose rapidly to about 0.45 (m2K)/kW within 20 hours of the start of the run. Thereafter, it increased very slowly. The sawtooth nature observed in some other runs was almost absent for the P F R U . The HWP showed relatively less fouhng. Its thermal fouhng resistance peaked at about 0.3 (m2K)/kW in about 35 hours after the start of the run. The fouhng rate for the first 5 hours after the induction period was rapid and almost identical to that of the P F R U , but dropped drastically with time. In the second run involving inhibitor-free dicyclopentadiene (Run 13), the P F R U heat flux was at a lower value of 216 kW/m2 and that of the HWP at 201 kW/m2. The average bulk fluid temperature was 83°C for the P F R U and 81°C for the HWP. The Chapter 7. RESULTS AND DISCUSSION 106 s CO J , H O OQ »—i 00 w « f—( O 0.14 0.12 0.10-0.08-0.06 0.04-0.02 RUN 7 DICYCLOPENTADIENE WITH INHIBITOR • = PFRU Tb=8l"C A = HWP Tb=80°C PFRU: q=293 kW/m| HWP: q=296 kW/m • • • g • • A ^ IQ A 0.00 I 0.0 AA 8 ° • B~ A • • • ft • B A A A S 7.0 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure 7.12: Fouhng resistance versus time for Run 7, dicyclopentadiene with inhibitor Chapter 7. RESULTS AND DISCUSSION 107 1.05 0.90-0.75-0.60-0.45-0.30-0.15-R U N 12 D I C Y C L O P E N T A D I E N E • = P F R U . Tb=81°C A = H W P , T b = 8 0 ° C P F R U : q=258 kW/m^ H W P : q = 2 5 5 k W / n r • AA A ^ A B A A S * A A A A 0.00-f! 0 7.0 14.0 21.0 28.0 35.0 42.0 T I M E ( H O U R S ) 49.0 Figure 7.13: Fouling resistance versus time for Run 12, dicyclopentadiene Chapter 7. RESULTS AND DISCUSSION 108 thermal fouhng resistance versus time curves are shown in Figure 7.14. There was an induction period of less than 2 hours. The P F R U thermal fouhng resistance showed a lot of scatter. The thermal fouhng resistance increased for the first 10 hours and then remained nearly constant for the next 10 hours. It then began increasing again peaking at a thermal fouhng resistance of 0.2 (m2K)/kW. In this run the H W P thermal fouhng resistance showed much less scatter than that of the P F R U . Nevertheless, it exhibited a sawtooth nature showing a series of declines and rises similar to the plot for the P F R U . The initial fouhng rate was lower than that of the P F R U . The H W P thermal fouhng resistance after 40 hours of the run was about 0.13 (m2K)/kW Figure 7.15 shows a plot of the two runs at different heat fluxes for the P F R U . The plot shows clearly the effect of heat flux on the initial fouhng rate and the maximum thermal fouhng resistance. The tendency is for both the initial rate and the maximum thermal fouhng resistance to increase with increasing heat flux. Moreover, the higher the heat flux the less scatter and sawtooth shape the curve exhibited. 7.3.4 Indene Indene was run at five different heat fluxes in kerosene namely, Runs 8, 9, 10, 11 and 16, and an additional run, Run 17, in n-heptane. Runs 8, 9, 10 and 16 were under oxygenated conditions whilst Run 11 was deoxygenated. Run 11 is discussed in a separate section under the heading 'Effect of dissolved oxygen on fouhng runs'. Run 17 is discussed under 'Solvent effects'. Run 8 was at the highest heat flux. The average P F R U heat flux was 299.2 kW/m2, and that of the H W P was 295.3 kW/m2. The average bulk fluid temperatures were 81°C and 80°C for the P F R U and HWP respectively. The indene run at the highest heat flux fouled heavily. The plot for the thermal fouhng resistance is shown in Figure 7.16. There was a brief induction period when some negative thermal fouhng resistances were Chapter 7. RESULTS AND DISCUSSION 109 0.28 0.24-0.20-0.16-0.12-0.08-0.04-0.00 ^  R U N 13 D I C Y C L O P E N T A D I E N E • = P F R U . Tb=83~C A = H W P , T b = 8 r C P F R U : q=216 kW/rru H W P : q=201 kW/m^ goo • A. A Az A A A A  A A A A " A A A If • CP A DO • A A Z S • A A A A A A A A A . A A A A A A : A A A A A A A A A Q A A ^ 0.0 7.0 14.0 21.0 28.0 35.0 T I M E ( H O U R S ) 42.0 49.0 Figure 7.14: Fouhng resistance versus time for Run 13 dicyclopentadiene Chapter 7. RESULTS AND DISCUSSION 110 0.7-T DICYCLOPENTADIENE HEAT FLUX EFFECTS £, w o CO t—I CO w o •-3 O 0.6 H 0.5 H 0.4 H 0.3 A 0.2-OH 0.0 • = q=258 kW/m£ A = q=216 kW/rrT off • - « H • • p • • an A A 14.0 21.0 i 1 — 28.0 1 35.0 TIME (HOURS) 42.0 49.0 Figure 7.15: Fouling resistance versus time for dicyclopentadiene at different heat fluxes with P F R U probe Chapter 7. RESULTS AND DISCUSSION 111 observed. The P F R U thermal fouling resistance had an almost linear shape for the first 20 hours of the run by which time it had reached a value of about 0.6 {rn2K)jkW. After 20 hours of the run, the temperature of the annular probe went beyond the sustainable value and hence power to the probe was cut off by the control circuit. For the remainder of the run, a heat flux of 240 kW/m2 was used. For about 4 hours after the reduction in heat flux, the thermal fouhng resistance fell to about 0.5 (m2K)/kW and then started in-creasing again until it reached a maximum thermal fouhng resistance of 0.75 (m2K)/kW after 40 hours of the run. A similar drop in Rf occured in a repeat run (Figure A.27 Appendix A), the drop is thought to be due to a sloughing off of part of the deposit caused by contraction during coohng as the heat flux was reduced. The coiled wire was able to sustain the high temperature and hence fouhng was more consistent. The HWP fouhng curve was also almost hnear in shape for about 20 hours of the run, following a 13 hour induction period. The nature of the fouhng curves suggests a vigorous reaction at the probe surface resulting in the accumulation of an appreciable amount of deposit. Except for the dis-ruption in the P F R U fouhng resistance, the fouhng curves were generally smooth and almost hnear after the induction period. The indene run was repeated at a medium heat flux. The P F R U heat flux was 246 kW/m2 and the H W P heat flux was 249 kW/m2. The average bulk fluid temperatures were 83°C for the P F R U and 82°C for the HWP. The results of this run are shown in Figure 7.17. There was no induction period for either the coiled wire or the annular probe. The thermal fouhng resistance exhibited a sawtooth nature for both probes, but was more pronounced for the P F R U probe. The P F R U thermal fouhng resistance increased at a rapid rate and in a near hnear fashion for the first 10 hours to a value of about 0.15 (m2K)/kW after which the first decline occured. The dechne went on until! the 17th hour, when it began rising again. The thermal fouling resistance reached Chapter 7. RESULTS AND DISCUSSION 112 1.20 RUN 8 INDENE 1.05-0.90 0.75-0.60 0.45 0.30-0.15-0.00 O, • = PFRU Tb=8rC A = HWP Tb=80°C PFRU: q=299 kW/m| HWP: q=295 kW/m^ q reduced A\ to 240 kW/mz * 1 * 0.0 7.0 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure 7.16: Fouling resistance versus time for Run 8, Indene Chapter 7. RESULTS AND DISCUSSION 113 a maximum value of about 0.225 (m2K)/kW after 40 hours. The H W P thermal fouhng resistance increased rapidly at values almost equivalent to the PFRU's for the first 5 hours until the first decline set in. This dechne did not last long however, and the fouling resistance began increasing again in an almost hnear manner until it reached a fouhng resistance of 0.18 (m2K)/kW. It then declined for a while and began rising again till it reached a maximum fouhng resistance of 0.2 (m2K)/kW after 40 hours of the run. The next indene run under air saturated conditions was Run 10. The average heat fluxes were 196.6 kW/m2 and 198.9 kW/m2 for the P F R U and HWP respectively. The average bulk fluid temperature for the P F R U was 82°C and for the H W P 83°C. This run like the preceding run showed little or no induction period. The fouhng curves exhibited a sawtooth nature. Fouhng was more intense for the H W P than the P F R U though the difference was not very great. The fouling curves seem to approach an asymptotic value after 35 hours of run. The fouhng curve for this run is shown in Figure 7.18. The last indene run in the oxygenated series was Run 16 at a heat flux of 150 kW/m2 and an average bulk fluid temperature of 75°C. This run was performed with the view to achieving two basic aims. Firstly, given that the indene has shown the propensity to foul under all conditions of temperatures and heat fluxes tested, it became necessary to find out whether the indene will still foul under conditions of rather very low bulk fluid temperatures and heat fluxes. Secondly, the experiment was set up to tie in with a series of fouhng experiments being done at the Argonne National Laboratories in the U.S.A., where the nature of the equipment being used limits the heat flux to a maximum of about 150 kW/m2. With the exception of the heat flux and bulk fluid temperature, the conditions of this run were the same as the other oxygenated runs. After 50 hours of the run, no measurable fouhng was detected on either of the probes. Figure 7.19 shows a plot of the 3 oxygenated indene runs on the P F R U at various heat fluxes. It is apparent from the plot that the immediate effect of increasing the heat flux Chapter 7. RESULTS AND DISCUSSION 114 I C\2 o 55 CO I—I CO o i O 0.35 0.30H 0.25 H 0.20 0.15H 0.10-J 0.05 A R U N 9 I N D E N E • = P F R U , T b = 8 3 C A = H W P , T b = 8 3 ° C P F R U : q = 2 4 6 k W / m f HWP: q = 2 4 9 k W / r r T • So A A A • a 4 H" 4 0.00 .0 -1 r 7.0 14.0 21.0 28.0 T I M E ( H O U R S ) — i 1 1 1 35.0 42.0 49.0 Figure 7.17: Fouling resistance versus time for Run 9, indene Chapter 7. RESULTS AND DISCUSSION 115 I CV o CO CO O g o 0.28 0.24-0.20-0.16-0.12 0.08-0.04 0.00 R U N 10 I N D E N E • = P F R U , Tb=82°C A = H W P , Tb=83°C P F R U : q=196 k W / r r u H W P : q=198 k W / i r T * A A A A A A A A o A A A A Bo B • § A A A A A ^ A A A A A A A A A 0 | A A - A <=»' A A A • • og °§_soo«B .0 7.0 14.0 21.0 28.0 35.0 T I M E ( H O U R S ) 42.0 49.0 Figure 7.18: Fouling resistance versus time for Run 10, indene Chapter 7. RESULTS AND DISCUSSION 116 is to increase the initial fouhng rate and the maximum thermal fouhng resistance. That is the initial fouhng rate is directly dependent on the heat flux and hence the probe's surface temperaure. In addition to this as the heat flux rises the curves exhibit less of the sawtooth nature and increasingly, more smoothness is observed, except where the heat flux was changed. A similar tendency was observed for the dicyclopentadiene runs. This heat flux and hence surface temperature effects seem to uphold the generally held view that the rate of fouhng is dependent on the wall temperature and that the higher the wall temperature, the more intense is the deposition of fouhng precursors. 7.3.5 Effect of dissolved oxygen on the thermal fouling rates It is a widely held view that, in situations where autoxidation and autoxidation in-duced reactions are the principal source of fouhng precursors, deoxygenation eliminates or minimizes heat exchanger fouhng. Therefore, two runs of species which are known to foul under oxygenated conditions were conducted under deoxygenated conditions to determine the effects if any, of oxygen on the thermal fouhng rate. The two runs were Run 11 involving indene, and Run 14 involving dicyclopentadiene. The average heat flux for Run 11 was 299 kWjm2 for both the P F R U and HWP probes. The average bulk fluid temperature was 87°C and 82°C for the P F R U and H W P respectively. The P F R U heat flux for Run 14 was 301.8 kW/m2, and that of the hot wire was 297.6 kW/m2. The average bulk fluid temperatures for this run were 84°C and 81°C for the P F R U and HWP respectively. Fouling was observed in these runs though at a much reduced rate. Figure 7.20 shows the thermal fouhng resistance versus time curves for the indene deoxygenated run. During the first 2 hours of the run, some negative fouhng resistances were observed. The thermal fouhng resistance then increased to about 0.025 (m2K)/kW for the P F R U probe and 0.02 (m2K)/kW for the HWP during the first 10 hours and then levelled off. It then Chapter 7. RESULTS AND DISCUSSION 117 1.0 0.9H 0.8H 0.7 H 0.6H 0.5 H o CO CO w « 0.4 O i—t • - 3 JZ> 0.3 O fe INDENE HEAT FLUX EFFECTS • A O q = 2 9 9 k W / m p q = 2 4 6 k W / m p q=196 kW/r r i q reduced to 240 k W / m 2 ^ • • ff • • • 14.0 21.0 28.0 35.0 42.0 49.0 TIME (HOURS) Figure 7.19: Indene oxygenated runs at different heat fluxes for P F R U Chapter 7. RESULTS AND DISCUSSION 118 0.08 0.07 H 0.06 H 0.05 0.04 H 0.03 H 0.02 H O.OH o.oo H R U N 11 I N D E N E D E O X Y G E N A T E D • = P F R U , Tb=85°C A = H W P , Tb=83°C P F R U : q = 2 9 9 k W / m | H W P : q = 2 9 9 k W / m ^ B d 8 D D D 3A ° ° a 1 0 — r, a ° g D § •• A H A W ° AAA A A t A A A ^ AAAA A A A A. A - " A H ^ A _ „ A A A A A A A Q A A A A J ° A * A 6? A ^ V A A A A • A A A A A * • • • A g • £ A ° A 0 >A D 7.0 14.0 21.0 28.0 35.0 T I M E ( H O U R S ) 42.0 49.0 Figure 7-20: Fouling resistance versus time for Run 11, indene deoxygenated Chapter 7. RESULTS AND DISCUSSION 119 stayed almost constant until the end of the experiment. The dicyclopentadiene run also showed some negative fouhng resistances, during the first 2 hours of the run. Fouhng was near hnear for the first 35 hours and exhibited a sawtooth nature. The maximum thermal fouhng resistance after 40 hours was 0.08 (m2K)/kW for the P F R U and 0.1 (m2K )/kW for the HWP. The P F R U showed a higher initial fouhng rate but the fouhng resistance fell off considerably to a value lower than that of the HWP after 30 hours of the run. The HWP showed some sawtooth behaviour and up to about 30 hours was shghtly below that of the P F R U . Figure 7.21 shows the fouhng resistance versus time curve for the dicyclopentadiene deoxygenated run. Figure 7.22 shows the indene deoxygenated run plotted side by side the equivalent oxygenated run. From the plot it is apparent that the deoxygenated runs appear to offer further evi-dence of the fact that the deposits were produced as a result of an olefin-oxygen reaction. The reaction could be coplymerization, autoxidation, or autoxidation induced polymer-ization. For the indene oxygenated run, the maximum thermal fouhng resistance was 25 times that of the deoxygenated run for the P F R U and 45 times in the case of the HWP at equivalent heat fluxes. For the dicyclopentadiene, the maximum fouhng resistance for the deoxygenated run at about 260 kW/m2 was 5.5 times that of the deoxygenated run at a much higher heat flux of 298 kW/m2. In the case of the HWP, the equivalent ratio was about 3.5. Irrespective of the exact type of reaction, a comparison of the oxygenated and deoxygenated runs appear to suggest oxygen as a major and an important part in the chemical reactions producing the foulants. Since for the deoxygenated experiments, the system may not have been purged of dissolved oxygen completely, some residual oxygen may have reacted with the olefin. After this oxygen was consumed, no further reaction took place and hence the fouhng resistance remained constant. Thus the small amount of foulants produced in this case may have been limited by the amount of oxygen in the system. It is surmised that in these experiments the thermal fouhng resistance increased Chapter 7. RESULTS AND DISCUSSION 120 0.22-0.18-0.14-~ 0.10-0.06-0.02--0.02-RUN 14 DICYCLOPENTADIENE DEOXYGENATED • = PFRU Tb=84°C * = HWP Tb=81°C PFRU: q=301 kW/m? HWP: q=293 kW/m':: 0.0 7.0 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure 7.21: Fouling Resistance versus time for Run 14, Dicyclopentadiene deoxygenated Chapter 7. RESULTS AND DISCUSSION 121 1.0-0.9-EFFECTS OF DISSOLVED OXYGEN CO 0.8-0.7-0.8-g 0.5 CO 1—1 CO w K 0.4-J O t-J ID 0.3-O 0.2 0.1 0.0 • = OXYGENATED A = DEOXYGENATED ff q reduced to, 240 kW/m2 • • • • C? • • 7.0 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure 7.22: Comparison of F F R U oxygenated and deoxygenated runs for indene Chapter 7. RESULTS AND DISCUSSION 122 as long as there was dissolved oxygen in the bulk fluid. Clearly, it would have been desirable to have a measure of dissolved oxygen in these runs. 7.3.6 Solvent effects Since chemical species behaviour can change in different solvents, an experiment with a different solvent was included in an attempt to investigate the importance of such an effect. A run with dicyclopentadiene in heptane at a heat flux of 250 kW/m2 showed no fouhng. Run 17, using indene in heptane was carried out under air saturated conditions, at a P F R U heat flux of 250 kW/m2 and a bulk temperature of about 80°C. The HWP heat flux was 248.4 kW/m2 and the bulk temperature was 81°C. Over a period of 30 hours, no fouhng was detected. The heat flux was subsequently increased to 300kW/m2. As no deposition was detected 10 hours after this increment in heat flux, the heat flux was increased for a second time to 350 kW/m2. Boiling occured at this heat flux and a slight deposition of a yellowish chalk-hke material was detected on the probe. On the other hand, a considerable mass 50g) of a yellow gum-like sludge precipitated in the bulk fluid. A sample of the gum was titrated using both titanous chloride and sodium thiosulfate. The titration yielded a peroxide number of 26 or 215.68 ppmw active oxygen. After the sample was left to stand for some days, it turned into a sticky yellowish brown mass. This further change in colour might possibly be due to ageing of the gum-like mass as a result of further oxidation in air. An elemental analysis yielded a carbon to hydrogen to oxygen ratio of 77 : 6.09 : 17.26. A l l indications point to the possibility that the precipitate was a polymeric peroxide. The fact that bulk precipitation rather than fouhng was observed when heptane was used as a solvent under heat fluxes which produced extensive fouhng with kerosene as a solvent indicates the importance of solubility and precipitation phenomena. Solvent effects need further investigation. Chapter 7. RESULTS AND DISCUSSION 123 7.3.7 Species effects The results of this work suggest that various olefinic species differ in their contribution to heat exchanger fouhng depending on the test conditions. The results show that olefins are very sensitive to heat flux or surface temperature under the conditions of this work. Terminal olefins exhibited the least tendency towards deposit formation. Amongst the terminal olefins, those of low molecular weight showed little or no tendency to foul under moderate conditions of temperature pressure, and heat flux. The fact that high molecular weight olefins such as hexadecene-1 produced more foulants than octene-1 or decene—1 might possibly be the result of bridging, coupling, chain cleavage and linkage reactions rather than polymerization reactions. This fact is consistent with studies of atmospheric oxidation of olefins in the hterature [70, 103, 105], which show that high molecular weight species are more suceptible to the production of polymeric peroxides and other insoluble species via such reactions. The cyclo-olefins, on the other hand, produced fouhng in all the experiments involving them with the exception of 1,5-cyclooctadiene. This observation reinforces the view that dienes and other conjugated olefins can be major sources of foulants in heat exchanger fouhng in the petroleum and the petrochemical industry. The fact that the cyclooctadiene produced no fouhng might possibly have been due to the low bulk fluid temperature and heat flux of the experiment rather than a lack of reactivity of the compound. Indene fouled under almost all the conditions tested. The behaviour of indene was not surprising since studies on gum formation in petroleum fractions have directly or indirectly implicated indene as a key participant in the process of gum formation [82, 108, 109], At the high heat flux of 295-350 kW/m2, shown in Figure 7.19, all the olefins tested showed some fouhng. Moreover, the ease at which foulants were produced as measured Chapter 7. RESULTS AND DISCUSSION 124 by the fouhng rates and maximum thermal fouhng resistance increased in the order decene—l, 4-vinylcyclohexene, hexadecene-1, and indene. The maximum thermal fouhng resistances for the P F R U is shown in Table 7.20. The fouhng resistance for indene was a factor of 50 times that of decene-1, 4.5 times that of vinylcyclohexene, 3 times that of hexadecene-1, and 1.6 times that of dicyclopentadiene at a much lower heat flux of 260 kW/m2. The fouhng resistance for 4-vinylcyclohexene, was ten times that of decene—l, and that of hexadecene-1 was 16 times that of decene—l. With oxygenated indene, the final fouhng resistance was 37 times that of indene under deoxygenated conditions. For dicyclopentadiene the corresponding ratio was 9. Moreover, the dicyclopentadiene under deoxygenated conditions yielded a fouhng resistance 3 times greater than that for indene under deoxygenated conditions. A comparison of the inhibited dicyclopentadiene run with the other runs makes the effects of the inhibitor more clear. At the high heat flux, the air-saturated and inhibited dicyclopentadiene fouled a factor of 2 times less than the deoxygenated dicyclopenta-diene, which suggests that chemical inhibition by an antioxidant is more effective than rigorous purging. Given that the inhibited dicyclopentadiene could have fouled less but for the slight polymerization, it seems possible that the inhibitor could reduce the fouhng capability of the dicyclopentadiene to almost zero. Dicyclopentadiene was not tested at the high heat flux because from evidence obtained from other runs concerning its fouhng rate, there was the behef that the P F R U probe would not be able to sustain the surface temperature at the maximum fouhng resistance. The maximum fouhng resistances for the HWP at the high heat flux are shown in Table 7.21. The maximum fouhng resistance for indene was 30 times that of decene-1, 7 times that of the 4-vinylcyclohexene, and 4.7 times that of hexadecene—1. Moreover, the fouhng resistance for dicyclopentadiene under deoxygenated conditions was 5 times that of indene under deoxygenated conditions. And the fouhng resistance for inhibited Chapter 7. RESULTS AND DISCUSSION 125 Table 7.20: Comparison of the Maximum P F R U Fouhng Resistances at High Heat Flux Run # Compound Heat Flux kW/m2 Rf at 40 hr. {m2K)/kW Rf ratio relative to decene-1 Rf ratio relative to indene 5 Decene-1 357 0.015 1 0.02 6 4-Vinyl-1-cyclohexene 298 0.16 10 0.21 7 Dicyclo-pentadiene (inhibited) 294 0.04 2.5 0.05 8 Indene 299 0.75 50 1 11 Indene deoxygenated 299 0.02 1.3 0.03 14 Dicylo-pentadiene deoxygenated 298 0.085 5.5 0.11 15 Hexadecene-1 298 0.25 16 0.33 12 Dicyclo-pentadiene * 260 0.45 30 0.6 * Run 12 was at the medium heat flux Chapter 7. RESULTS AND DISCUSSION 126 dicyclopentadiene was 2.5 times less than that of dicyclopentadiene under deoxygenated conditions. The comparison of the species effect shows clearly that dicyclopentadiene has a greater tendency to foul than indene. This might possibly be due to the fact that dicyclopen-tadiene fouls not only as a result of autoxidation reactions but also as a result of some form of thermal polymerization. However, the difference is not very significant and thus both compounds can be considered to be typical of species that contribute greatly to fouling of heat exchangers. The difference between indene and dicyclopentadiene on the one hand and the terminal olefins on the other is very large. This suggests that at very low concentrations of olefins, indene and other conjugated dienes might be much more important as sources of foulants than terminal olefins. Hence they might be the target species as far as measures at minimizing fouhng are concerned. Table 7.22 shows Taylor's ratios of the mass deposition rates of the olefins used in his work to n-decane and decene-1. It is apparent from the table that decene-1 resulted in more deposit formation compared to the present work. This is consistent with the fact that Taylor's work took place under conditions where the test fluid was under vaporization so the decene-1 was capable of undergoing thermal degradation, cyclisation and perhaps coking. These same conditions are favourable to the thermal or autoxidation induced polymerization of 4-vinylcyclohexene, with the result that 4-vinylcyclohexene also shows slightly more deposition. While the relative ratios of the thermal fouhng resistances of this work are not numerically equal to Taylor's, the relative tendencies to foul are the same. This suggests that if both mass deposition and thermal fouhng studies are done under exactly the same conditions, the results might be identical. Chapter 7. RESULTS AND DISCUSSION 127 Table 7.21: Comparison of the Maximum HWP Fouhng Resistances at High Heat Flux Run # Compound Heat Flux kW/m2 Rf at 40 hr. (m2K)/kW Rf ratio relative to decene—l Rf ratio relative to indene 5 Decene—l 360 0.03 1 0.03 6 4-Vinyl-1-cyclohexene 294 0.13 4 0.14 7 Dicyclopentadiene (inhibited) 296 0.04 1.3 0.04 8 Indene 295 0.9 30 1 11 Indene deoxygenated 299 0.02 0.6 0.02 14 Dicyclopentadiene deoxygenated 297 0.1 3.3 0.11 15 Hexadecene—1 307 0.19 6 0.21 12 Dicyclo-pentadiene * 254 0.032 2.8 0.35 Run 12 was at the medium heat flux Chapter 7. RESULTS AND DISCUSSION 128 Table 7.22: Deposit Formation Tendancies of Olefi.n-1-Decane Blends [14] Unsaturated Species Ratio of Deposition Rate Relative to n-decane Ratio of Deposition Rate Relative to decene-1 Decene—l 4 1 4- Vinyl-I-cy clohexene 22 5.5 Indene 40 10 7.3.8 Deposit characterization Figures 7.23 and 7.24 show typical photographs of fouhng deposits for runs at low heat flux for both the annular and coiled wire probes. For the runs at low heat flux, the deposits were fairly smooth, though not uniform, due possibly to sloughing of parts of the deposit. The deposits for the runs at high heat flux were thick and uniformly distributed on the probe's surface. The top layers of the indene deposits at high heat flux were loose and could be removed easily. There were spots where periodic sloughing of parts of the deposit due probably to the shearing action of the flowing fluid was evident. The dicyclopentadiene deposits on the other hand were firmly attached and in most cases could only be removed by scraping with a knife. The outside diameter of the fouled P F R U probe was measured by vernier calipers, in runs where fouhng was severe. Average deposit thickness was calculated and using the the maximum fouhng resistances, the thermal conductivity of the deposit was estimated. The results are presented in Table A.25, Appendix A. Deposit thickness varied from 0.07 Chapter 7. RESULTS AND DISCUSSION 129 to 0.99 mm, and thermal conductivities from 0.44 for the 4-vinylcyclohexene deposit to 1.4 W/mK for the indene deposit. These values must be considered as approximations only. The polymeric peroxides of indene and cyclopentadiene are known to be stable [70, 73, 74]. The structure for polymeric indene peroxide is shown in Figure 7.25. According to Heinz and Kern [73] the polymeric peroxide of cyclopentadiene has either a 1,2 or 1,4 structure with the presence of unsaturated bonds. The structure proposed by Heinz and Kern is shown in Figure 7.26. Thus if the deposits were polymeric peroxides of indene and cyclopentadiene, then based on these structures the theoretical carbon to hydrogen to oxygen ratio should be 72.48 : 5.03 : 21.48 for the indene and 60 : 8 : 32 for the dicyclopentadiene. Some of the deposits collected from the P F R U probe were sent to the Canadian Microanalytical Laboratory for elemental analysis. The results are shown in Table 7.23, along with analyses of the kerosene, and an indene/kerosene mixture. The reported values of C : H : 0 are quite close to those expected from the polymeric peroxide structures but not exactly in agreement. The discrepancy between the calculated ratios of carbon, hydrogen and oxygen and the results of the analyses might be due to several reasons. Amongst these reasons are the possibility that the deposits are not homogeneously polymeric peroxide and might contain components of insoluble residue from side reactions including condensation, cleavage and scission of hydrocarbon chains. Secondly, at the high temperature of the probe surface the polymeric peroxides adjacent to the probe surface may have undergone decomposition leading to a variety of insoluble products. These products may not necessarily be polymeric peroxides. Morrel et al. [62] studied the atmospheric oxidation of two gasohnes (light distillates). The first one was cracked gasoline from a Pennsylvanian crude. The second was reformed gasohne from a West Texas crude. The light distillates as well as the deposits obtained as residue from the oxidation reaction were analysed for carbon, hydrogen, oxygen, peroxide, Chapter 7. RESULTS AND DISCUSSION 130 Figure 7.23: Photograph of fouled P F R U probe Chapter 7. RESULTS AND DISCUSSION 131 Figure 7.24: Photograph of fouled coiled wires Chapter 7. RESULTS AND DISCUSSION 132 H H O - O OO Figure 7.25: Polymeric Indene Peroxide H -1 I r-CH Cf4-0-O-\ / C H 2 -H - C H - CH-0 -O-X CH-1 , 4 - S T R U C T U R E 1 , 2 - S T R U C T U R E Figure 7.26: Polymeric Cyclopentadiene Peroxide Chapter 7. RESULTS AND DISCUSSION 133 Table 7.23: Analysis of Fluids and Deposits Source c % H % 0 % N % Kerosene (solvent) 85.90 12.92 — < 0.1 Indene/kerosene (test fluid ) 84.35 12.94 — < 0.1 Indene (deposit from Run 10) 72.47 4.48 22.63 0.47 Indene (deposit from Run 17 run) 77.05 6.09 17.26 0.15 Dicyclopentadiene (deposit from Run 13) 63.82 4.87 31.05 0.26 Amount of oxygen obtained by a difference Chapter 7. RESULTS AND DISCUSSION 134 aldehyde and acid units. A unit represents the amount of oxidation product in 10 cm 3 of oil. The units are calculated from the peroxide, aldehyde and acid numbers. Thus a 1000 cm 3 of oil with a peroxide number of 0.4 will have 40 peroxide units. The results of the deposit analysis are shown in Table 7.24. The presence of large numbers of peroxide, aldehyde and acid units is consistent with the autoxidation mechanism. Though Morrel et al. indicated that the residues were mainly polymeric peroxides they were not specific as to the compounds. But the sources of the gasoline — cracked and reformed — suggests that the presence of dienes, indenes sulphur and perhaps even asphaltenes cannot be ruled out. The results of the deposit analysis compare favourably with the results of the present work given in Table 7.23. 7.3.9 Fouling Mechanism From the observations made during the execution of this work, it seems reasonable to believe that for the conditions of heat flux, surface and bulk temperatures of this work, the olefins fouled primarily via an autoxidation or autoxidation-induced polymerization mechanism. As a result of bubbhng air through the test fluid prior to the run, a fixed amount of oxygen is dissolved in the test fluid. This dissolved oxygen undergoes reaction with the olefin producing a form of insoluble copolymer or polymeric peroxide on the surface of the probe, or in the bulk fluid. Linear Rf versus time behaviour would be expected for a chemical reaction fouhng where the fluid/deposit interface temperature remains constant with time, as would be the case for constant heat flux operation where a uniform smooth deposit occurred on the heat transfer surface. The rate of fouhng would be expected to increase markedly with surface temperature or the heat flux. From Figures 7.15 and 7.19 and Table 7.19, it is clear that fouhng is essentially hnear and fouhng rates have increased by a factor of about 5 over a 20°C wall temperature increase for indene, and about a factor of 3 for a Chapter 7. RESULTS AND DISCUSSION 135 Table 7.24: Deposit Analysis of Fluids and Residue from Atmospheric Oxidation of Gasoline [62] G asoline/Resi due % C % H % 0 Peroxide Units Aldehyde Units Acid Units Light distillate (Pennsylvanian crude) 86.1 13.9 — — — — Residue (Penn.) 69.8 8.7 21.1 3196 680 51 Light distillate (W. Texas crude) 85.5 14.3 — — — — Residue (W. Texas) 73.6 9.6 16.4 1402 72 24 Amount of oxygen obtained by a difference Chapter 7. RESULTS AND DISCUSSION 136 5°C wall temperature increase for dicyclopentadiene. Fouling rates were calculated for the hnear portions of the curves, and are listed in Tables B.32 and B.33 Appendix B. The sawtooth behaviour may be due to periodic sloughing of parts of the deposit. This behaviour is more pronounced at the medium and lower heat fluxes tested and is illustrated in Figures 7.13, 7.16 and 7.17. The tendency towards a falling or asymptotic behaviour noted towards the end of numerous runs may be due to depletion of oxygen or some aging phenomena. The fact that the extent of fouhng decreased by a factor of 30 when the dissolved oxygen was reduced from about 230 ppmw to near zero argues strongly for the autoxidation mechanism. The effect of the presence of the antioxidant seen by comparison of Figures 7.12 and 7.13 whereby the stripping of the antioxidant from the solution results in an increase in fouhng resistance of a factor of 5 to 20 in spite of a decrease in heat flux leads further cre-dence to the mechanism. Finally, consistency of the deposit analyses with that expected from the formation of polymeric peroxide further supports the proposed mechanism. From the studies of Russell [85] on the oxidation of indene, it can be inferred that indene reacts with oxygen in equimolar amounts. Thus if autoxidation is the mechanism and oxygen is the limiting reactant, then knowing the concentration of dissolved oxygen in the test fluid, the approximate amount of foulants which can be produced can be estimated. This calculation is based on the assumption that all the dissolved oxygen is consumed in the reaction producing the deposit. The reaction between indene and oxygen can be simplified to: 202 + 2CgHs — • (C9H80'2)2 where (CQHS02)2 is the polymeric indene peroxide. From the calculation of the solubility, the amount of dissolved air in the test fluid is 997 ppm by weight, at room temperature Chapter 7. RESULTS AND DISCUSSION 137 and a pressure of 410 kPa. Since oxygen makes up about 23 % by weight of air, the amount of dissolved oxygen in the test fluid can be estimated as: Amount of dissolved 02 = (0.23)(997) = 229.31 ppmw. Thus the weight of dissolved oxygen in 10 litres of solution is: (8000 g hquid)(229.31 g 0 2 ) 10* g liquid = 1-834 g O a Thus the number of moles of oxygen is given by: No. of moles 02 = = 0.0573 From the stoichiometric equation, assuming that no oxygen is transfered in from the air above the fluid in the storage tank, 2 moles of oxygen reacts with 2 moles of indene, producing 1 mole of polymeric indene peroxide. Thus 0.0573 moles oxygen react with 0.0573 moles indene to form 0.0287 moles polymeric peroxide of molecular weight 296 grams. Thus Amount of polymeric indene peroxide which could be produced = (0.0287)(296) = 8.5 g. This value is about twice the approximately 4 grams of deposit obtained for the indene high heat flux run. This discrepancy can be due to the fact that only half the oxygen reacted, or that some of the foulants remained in the bulk fluid and did not deposit on the probe's surface. An amount of about 50 grams of wet precipitate was obtained from the indene in heptane run. This figure suggests that the oxygen may have been more soluble in heptane, and some of the oxygen above the liquid in the tank may have reacted. Though an autoxidation mechanism is presumed, no stable peroxides or hydroper-oxides were detected in the fluid during the kerosene runs. What was detected can at Chapter 7. RESULTS AND DISCUSSION 138 best be described as trace amounts. On the other hand, titration of a sample of the sludge from the indene in heptane run resulted in a peroxide number of about 26 which translates into about 215.68 ppmw active oxygen. The absence of stable peroxides or hydroperoxides in the kerosene runs can be partly explained if it is assumed that the reaction took place on the probe surface instead of in the bulk fluid, and what was found in the test fluid was remnants of polymeric peroxides which had been degraded at the probe's surface due to the high temperature and hence showed none of the properties of peroxides. This is a reasonable assumption since the test fluids after the kerosene runs were clear with the exception of the 4-vinylcyclohexene run, and showed no signs of precipitation having occured. Moreover, there was only a slight change in density at the end of the run. Further support for the reaction occuring on the probe's surface rather than in the bulk or fluid film comes from the essentially equal rates and extents of fouhng shown by the two probes. If insoluble fouhng precursors were formed in the bulk or in the fluid film, transfer or sticking processes would be important. It would be unlikely that these processes would have the same rates in the turbulent flow of the annular probe and in the laminar flow past the coiled wire. Chapter 8 CONCLUSIONS AND RECOMMENDATIONS 8.1 CONCLUSIONS The thermal fouhng resistances of some olefinic hydrocarbons present at 10 % wt. in kerosene have been measured as a function of time and the heat flux effects have been partially investigated. It has been found that at low heat fluxes and hence low wall temperatures, and low bulk fluid temperatures, the olefins studied showed no measurable fouhng. For instance, none of the runs done at bulk temperatures of 70-75°C showed any measurable fouhng. Similarly none of the runs at heat fluxes below 198 kW/m2 and hence surface tempera-tures of below 180°C showed any measurable fouhng, over 50 hour periods. The chemical reaction fouhng thus appears to have a threshold wall temperature of around 180°C for the olefins tested. At more severe conditions (heat flux 300 kW/m2, wall temperature 198 °C) fouhng resistances of up to 0.9 m2K/kW were produced in 40 hours under air saturated conditions. From the results of the present work, it can be concluded that, the susceptibihty to fouhng increases in the order, straight chain low molecular weight terminal olefins, cyclo-olefins, indene and conjugated dienes. It has been established that, under the temperature conditions of this work, deoxy-genation reduces the thermal fouhng resistance to a minimum. This suggests that the 139 Chapter 8. CONCLUSIONS AND RECOMMENDATIONS 140 production of foulants is primarily the result of oxidation — autoxidation and autox-idation induced reactions. Moreover, the predominance of autoxidation reactions is a probable indication that there is little contribution from thermal polymerization. De-posit analyses were consistent with the expected composition of polymeric peroxides. The presence of an anti-oxidant limited fouhng to a very low level. Thus for wall tem-peratures below 200 °C a rigorous and effective exclusion of oxygen and addition of inhibitors might be very important steps for minimizing fouhng in olefinic species. This work confirmed observations previously made in styrene polymerization fouhng, that for chemical reaction fouhng the rates of fouling are essentially the same in turbulent flow in the annular probe, and in laminar flow over the coiled wire probe at comparable heat flux and bulk temperature. 8.2 RECOMMENDATIONS As a logical continuation to these series of chemical reaction fouhng studies, it is recom-mended that some or all of the following be included in future work: • Since oxygen is clearly a key species, the effects of oxygen pressure should be established, and an oxygen probe utilized to monitor dissolved oxygen content during all experiments. • Some of the runs in this work be repeated at high heat fluxes of about 400-450 kW/m2 with bulk temperatures in the range of 100-120°C at pressures of 550-690 kPa (abs.), under deoxygenated conditions. Such runs will help explain the role of thermal polymerization. • In the case of the dicyclopentadiene, it is recommended that runs with inhibitors be repeated, but prior to these runs, the tiny polymer particles be filtered out. This Chapter 8. CONCLUSIONS AND RECOMMENDATIONS 141 will permit a more exact determination of the effects of the inhibitor. • It is recommended that the indene and dicyclopentadiene runs at a heat flux of 300 kWjm2 be repeated firstly, by varying the concentration of olefin possibly from 2-10 %, and secondly by varying the bulk fluid velocity. These runs can facilitate the establishment of the concentration and velocity effects. • It is recommended that a run involving a mixture of more than one olefin be investigated. Moreover the effects of solvents should be further developed. • For comparison purposes, it is recommended that some of the runs in this experi-ment be repeated using a heat exchanger with a different configuration. Nomenclature La t in Symbols ttl - a 4 dimensionless constants A area of heat transfer surface, (m 2) B Bunsen coefficient, (cm 3/cm 3atm.) C concentration, (kg/rn3) C3 dimensionless constants concentration of foulant at the liquid deposit interface, (kg/m3) d diameter of pipe, (m) E activation energy, (J/mol.K) f friction factor G concentration in ppmw h convective heat transfer coefficient, (W/m2K) I current, (Amperes) k thermal conductivity, (W/mK) kD mass transfer coefficient (m/s) K attachment rate constant (m/s) transport coefficient, (m/s) kf foulant thermal conductivity, (W/mK) L Ostwald coefficient (cm3/cm3) L length of P F R U heated section, (m) md mass deposition flux, (kg/m2s) 142 Nomenclature removal flux, (kg/'m2s) m" asymptotic mass per unit surface area, (kg/m2) P partial pressure of gas, (Njm2) P peroxide number Pd dimensionless probability function Q heat flow, (Watts) q heat flux, (Watts/m2) R electrical resistance, (Ohms) Rext electrical resistance of the external circuit, (Ohms) Rj thermal fouhng resistance, (m2KjkW) R} asymptotic thermal Fouhng Resistance, (m2K/kW) Rg universal gas constant, (J/mol.K) R0 electrical resistance of coiled wire at zero power, (Ohms) Rw thermal resistance of tube wall, (m2K/kW) s distance between thermocouple location and heating surface, ( St solubihty parameter of liquid, ( (J /m 3 ) 1 / 2 ) S2 solubility parameter of gas, ( ( J /m3 ) 1 / 2 ) Sp sticking probability T temperature, (K, °C) t time, (s) U overall heat transfer coefficient, (W/m2K) ub bulk fluid velocity, (m/s) V voltage, (volts) V volume, (m 3) X deposit thickness (m) Nomenclature UA Greek Symbols j3 dimensionless contact angle r shear stress, (N/m2) xj) deposit strength 6 time, (s) 9C time constant, (s) pf foulant density, (kg/m2) pt density of liquid at temperature T, (kg/m3) a temperature coefficient of resistance, (K~1) A thermal conductivity, (W/mK) /A viscosity, (kg/m.s) Subscripts b bulk c clean c convective d deposit f fouled i inside heat exchanger tube m mean o outside heat exchanger tube o initial p probabihty s surface sat. saturation w wall Nomenclature Superscripts n order of reaction * asymptotic Dimensionless Groups Nu Nusselt number, (hD/k) Pr Prandtl number, (Cpfi/k) Re Reynolds number, (U^D/v) Bibliography Van Nostrand, W. L. , S. H. Leach, and J . L. Haluska, "Economic Penalties As-sociated with the Fouhng of Refinery Heat Transfer Equipment." in Fouhng of Heat Transfer Equipment, eds Somerscales E.F.C. and J. G. Knusden, Hemisphere Publising, Washington, 619-643, (1981). Institute of Petroleum. 1987, in B. D. Crittenden "Chem. Reaction Fouhng of Heat Exchangers.", in Fouhng Science and Technology. NATO ASI Series eds. L. F. Melo, T. R. Bott, and C. Bernardo, Kluwer Academic Pubhshers. (1988). Thackery P. A. , "The cost of fouhng in Heat Exchange Plant", in Fouhng — Science or Art? 1-9. Institution of Chemical Engineers Conference, University of Surrey, Guildford, U.K. , (1979). Standards of the Tubular Exchangers Manufacturing Association (TEMA) 6 t h edi-tion, 140-142, T E M A , New York, (1978). Epstein, N . , "Thinking about Heat Exchanger Fouhng a 5x5 matrix". Heat Transfer Engineering vol. 4 No. 1, 43-56 Jan.- Mar. (1983). Braun, R., and R. H. Hausler, "Contribution to the Understanding of Fouhng Phe-nomenon! in the Petroleum Industry. Paper 76-CSME/CSCHE-23, 16th National Heat Transfer Conference, St. Louis, MO., Aug. (1976). Taylor, W. F., "Kineticts of Deposit Formation in Hydrocarbons: Heterogenous and Homogeneous Metal Effects", J . Applied Chem. vol. 18, 251-254 (1968). Odian, G., Principles of Polymerization, 2 n d ed. John Wiley and sons. N.Y. (1981). Froment, G. F. "Fouhng of Heat Transfer Surfaces by Coke Formation in Petro-chemical Reactors", in Fouhng of Heat Transfer Equipment 441-435, eds Somer-scales, E. F. G., and J . G. Knudsen, Hemisphere, Washington 1981. Fitzer, E. , K. Mueller, and W. Scheefer, In Chemistry and Physics of Carbon vol. 7, 237-383, ed. Walker, P. C. Jr, Marcel and Dekker, New York, (1971). Canapary, R. C. "How to Control Refinery Fouhng", Oil and Gas Journal, 114-118 Oct. (1961). 146 Bibliography 147 Watkinson, A. P. and N. Epstein, "Gas Oil Fouling in a Sensible Heat Exchanger". Chemical Engineering Progress Symposium Series vol. 65, No 92, 84-90, (1969). Taylor, W. F., T. J. Wallace, "Kinetics of Deposit Formation of Hydrocarbons — Effect of Trace Sulphur Compounds". Ind. Eng. Chem. Prod. Res. and Dev. vol. 7, No.3, 198-202, (1968). Taylor, W. F. "Deposit Formation from Deoxygenated Hydrocarbons — Effect of Trace Sulphur Compounds". Ind. and Eng. Chem. Prod. Res. and Dev. 15, 64-68, (1976). Hausler, R. H. , and C. E. Thalmeyer, "Fouhng and Corrosion in Feed Effluent Exchangers. Discussion of a New Test Method." API Division of Refining 40th mid year meeting Chicago. Preprint No. 06-75, May (1975). Hausler, R. H. , "New Test will Show Fouhng". The Oil and Gas Journal, 56-63, June 4, (1973). Daniel S. R. and F. C. Heneman, "Deposit Formation in Liquid Fuels — Effect of Selected Organo-Sulphur Compounds on Stability of a Jet Fuel". Fuel 62, 1265-1268, (1983). Watkinson, A . P. "Critical Review of Organic Fluid Fouhng". Argonne National Laboratory. Report A N L / C N S V - T M - 2 0 8 , December (1988). Taylor, W. F., and J . W. Frankenfeld, "Deposit Formation from Deoxygenated Hydrocarbons — Effects of Trace Nitrogen and Oxygen Compounds ". Ind. and Eng. Chem. Prod. Res. and Dev. vol. 17, 86-90, (1978). Oswald, A. A. , and F. Noel, "Role of Pyrroles in Fuel Instability." J . Chem. Eng. Data 6, 294-301, (1961). Frankenfeld, J . W., W. F. Taylor and D. W. Brinkeman, "Storage Stability of Synthetic Fuels from Oil Shale. Parts 1, 2, and 3". Ind. and Eng. Chem. Prod. Res. and Dev., vol. 22, 608-627, (1983). Thompson, R. B., J . A. Chenicek, L. W.Druge and T. Symon, "Stability of Fuel Oils in Storage — Effects of Some Nitrogen Compounds." Ind. Eng. Chem. 43, 935, (1951). Crawford, J . E. and J . M . Miller, "Refinery Process Fouhng — Effects of Trace Metals and Remedial Techniques". Proc. API section III (Refining) vol. 43, 106-114, (1963). Bibliography 148 Perera, .W. G. and K. Rafigue ," Coking in a Fired Heater." The Chemical Engineer, 107-111, Feb. (1976). Smith, J . D. "Fuel for Supersonic Transport: Effects of Deposits on Heat Transfer to Aviation Kerosene." Ind. Eng. Chem. Prod Res. and Dev. vol. 8, No.3, 299-308, July (1969). Taylor, W. F. "Mechanism of Deposit Formation in Wing Tanks." paper 680733, SAE Aeronautics and Space Eng. Meeting, Los Angeles, October (1968). Eaton, P. and R. Lux, "Laboratory Fouhng Test Apparatus for Hydrocarbon Feed-stocks." A S M E HTD 35, 33-42, (1984). Scarborough, C. E., A. C. Charington, R. Diener, and L. P. Golan, "Coking of Crude Oil at High Heat Flux Levels". Chem. Eng. Prog. vol. 75 No. 7, 41-46, July (1979). Dickakian, G. and S. Seay "Asphaltene Precipitation — Primary Crude Oil Fouhng Mechanism." Oil and Gas Journal 86 No. 10, 57-50, March 7 (1988). Crittenden, B. D., S. A.Hout, and N. J. Alderman, "Model Experiments of Chem-ical Reaction Fouhng." Chem. Eng. Res. and Des. 65, 165-170 (1987). Chantry, W. A. , and D. M . Church, "Design of High Velocity Forced Circulation Reboilers for Fouling Service". Chem. Eng. Prog. 54, No 10, 64-67, (1988). Lambourn, G. A. and M . Durrieu, "Fouhng in Crude Oil Preheat Trains", in Heat Exchangers — Theory and Practice eds. Taborek, Hewitt and Afgan. Hemisphere Publishing Co., New York p.841, (1983). Taylor, W. F. and J . J . Wallace, "Kinetics of Deposit Formation from Hydrocarbons — Fuel Composition Studies". Ind. and Eng. Chem. Prod. Res. and Dev., vol. 8, 375-380, (1969). Giammaria, J . J . and H. D. Noris, "High Temperature Initiation of Paraffin Ox-idation by Alkyl Aromatics." Ind. and Eng. Chem. Prod. Res. and Dev. 1, 16-18 (1962). Cranton, G., F. Noel, "Aromatics and Lubricant Basestock Oxidation." Institute of Petroleum, London (1974). Latos, E. J . and F. H. Franke, "Relative Thermal Fouhng Rates of Petroleum and Shale Oils." Corrosion 82 paper 103 N A C E March (1982). Bibliography 149 [37] Sachanen, A . N . , Petr. Z. 21 144 (1925), in A. N . Sachanen Chemical Constituents of Petroleum. Reinhold Publ. Corp. New York, (1945). [38] Naidu, S. K . , E. E. Klaus, and L. J . Duda, "Evaluation of Liquid Phase Oxidation Produts of Ester and Mineral Oil Lubricants", Ind. and Eng. Chem. prod. Res. and Dev. 23 613-619 (1984). [39] Taborek, J . , T. Aoki, R. B. Ritter, J. W. Palen, J . G. Knudsen "Predictive Methods for Fouhng Behaviour", Chem. Eng. Prog. 68, 59 Feb. (1972). [40] Fetissoff, P. E., A. P Watkinson and N . Epstein "Comparison of Two Fouhng Probes.", Proc. 7th Int. Heat Transfer Conf, vol. 6, 391-396, (1982). [41] Palen, J . W., and J . W. Westwater, "Heat Transfer and Fouhng During Pool Boiling of Calcium Sulphate solutions". AIChE Chem. Eng. Prog. Symposium series, vol. 62, No.64 77-86, (1966). [42] Crittenden, B. D., S. T. Kolacskowski and S. A. Hout, "Modelling of Hydrocarbon Fouling". Chem. Eng. Res. and Dev. 65, 171-179, (1987). [43] Nelson, W. L. , Refiner and Nat. Gas Man. vol. 13 No 7, 271-276, and vol. 13 No 8, 292-298, (1934). [44] Bateman, L. , "Olefin Oxidation", Quarterly Reviews vol. 8, 147-167, (1954). [45] Kern, D. Q. and R. E. Seaton,"A Theoretical Analysis of Thermal Surface Fouhng." Brit. Chem. Eng. vol. 4 No. 5, 258-262. (1959). [46] Garret-Price et al. Fouhng of Heat Exchangers — Characteristics Costs, Prevention, Control and Removal. Noyes Pubhcation, Park Ridge N. J. , (1985). [47] Taylor, W. F., "Kinetics of Deposit Formation from Hydrocarbons IV: Additives and Surface Coating Effects". J . of Applied Chem., vol. 19, 222-226, (1969). [48] Emanuel, N . M . , E. T. Denisov, and Z. K . Maizus, Liquid Phase Oxidation of Hydrocarbons, Plenum Press, New York, (1967). [49] Miller, R. F., and M . P. Nicholson, U.S. Patent No. 4556476, Dec. (1985). [50] Chiang, J . T., M . Langsam, US Patent No. 4451625 March (1984). [51] Atlantic Richfield Co. Japan Patent No. 61130242 June (1986). [52] Wemp, L. K . , B. D. Bauman, US Patent No. 4420591 Dec. (1983). [53] Mitsui Petrochemical Company. Japan Patent No. 58138718 Aug. 1983. Bibliography 150 [54] Reich, L. and S. S. Stivala, Autoxidation of Hydrocarbons, and Polyolefins. Marcel and Dekker Inc., New York, (1969). [55] O'Neil, G. W., Jr. et al. "Online Tube Cleaner Saves $2 milhon/yr". Electrical World, p. 44 (1979). [56] Stegelman, A. F. and R. Renfflen, "Online Mechanical Cleaning of Heat Exchang-ers", in Garret-Price et. al., Fouhng of Heat Exchangers — Characteristics Costs, Prevention and Control p. 64 Noyes Publications, Park Ridge N . J . (1985). [57] Amertap Corporation Information Bulletin 8304- 8304-02-410-09. "Amertap Tube Cleaning Systems Sponge Balls". Amertap Corporation Woodbury, New York. [58] French, M . A. , "Chemical Cleaning in Practice.", in Progress in the Prevention of Fouhng in Industrial Plant". p68-81. Proceedings of a conference. Nottingham University, U .K. 1-3 April (1981). [59] Roebuck, A. H. , and C. A. Bennet, "Heat transfer Payback is a Key to Chemical Cleaning Choice". Oil and Gas Journal 93-96 Sept. 5 (1977). [60] Fischer, P., J . W. Suitor, R. B. Ritter, "Fouhng Measurement Techniques." Chem. Eng. Prog. vol. 71 No7, 66-72 July (1975). [61] Scott, Gerald, Atmospheric Oxidation and Antioxidants. Elsevier Publishers Co. Amsterdam, 1965 [62] Morrel, J . C , C. G. Dryer, C D . Lowry Jr. and G. Egloff, "Gum in Cracked Gasoline: Formation and Composition", Ind. and Eng. Chem., vol. 28, p465-470 (1936). [63] Mellan, I., Handbook of Solvents., vol. 1, Rheinhold Publishers Corp. New York, (1957). [64] Brill , A . F., "The Origin of Epoxides in the Liquid Phase Oxidation of Olefins with Molecular Oxygen.", J . Am. Chem. Soc. vol.85, 141-145, (1963). [65] Bott, T. R. and M . M . V . P. S. Pinheiro, "Biological Fouhng — Velocity and Temperature Effects." Canadian J. of Chemical Eng. 55, 473 (1977). [66] Banchero, J . T., and K . F. Gordon, Advances in chemistry series. No 27, 105 A.C.S. Washington D.C. 1960. [67] Papov, K. K. , N . A. Ragozin, Technical Dictionary of Fuel and Oils, State Publish-ing House (1955) in N . A. Ragozin Jet Propulsion Fuels, Pergamon Press (1961). Bibliography 151 [68] A S T M D1022-76, Annual Book of A S T M Standards, vol. 23. A S T M Philadelphia, Pa. (1979). [69] Littmann, E. R. Methods of Analysis for Petrochemicals, p.331. Chemical Publish-ing Co. Inc. New York, N . Y . (1958). [70] Norton, C. J . and D. E. Drayer "Liquid Phase Oxidation of High Molecular Weight 1-Alkenes", in R. F. Gould (ed.) Oxidation of Organic Compounds. Advs. in Chem. Ser. vol 75, A. C. S. Washington D. C. (1968). [71] Muller-Steinhagen, H. , A. P. Watkinson, N . Epstein, 'Subcooled Boiling and Con-vective Heat Transfer to Heptane Flowing inside an Annulus and Across a Coiled Wire'. Parts 1 and 2, J . of Heat Transfer vol. 108, 922-933 (1986). [72] Wilson, E. E., " A Basis for Rational Design of Heat Transfer Apparatus." Trans. A. S. M . E. vol. 37, P 42, (1915). [73] Gutman, V . , "Beitrage Kinetik der Indenpolymerisation V : Polyindenperoxyde." J . Polymer Sci. vol. 3, No. 4 518-524 (1948). [74] Kern, W., A. R. Heinz, "Autoxidation of Cyclopentadiene and Subsequent De-composition and Analysis of Polymeric Peroxide." Makromol. Chemie vol. 16, 81 (1955). [75] Fetkovich, J . G., G. N . Granneman, L. M . Mahahnaham and D. L. Meier, Proc. of the 4th Conf. on Ocean Thermal Energy. New Orleans, VII-15 to VII-24 March (1977). [76] Butler, R. C , W. N . McCurdy, "Fouhng Rates and Cleaning in Refinery Heat Exchangers." Trans, of A S M E 843-847, October (1949). [77] Schwartz, F. G., M . L. Whisman, C. S. Allbright and C. C. Ward, "Storage Stabil-ity of Gasoline — Fundamentals of Gum Formation." Bull. 626 Bureau of Mines, Washington (1964). [78] Jones, L. and N . C. L i , "Aging of SRC-11 Middle Distillates from Ihnois No 6 Coal Part I." Fuel 62 1150-1160 (1963). [79] Crittenden, B. D. and E. M . H. Khater, "Fouhng in a Hydrocarbon Vapourizer." Proc. 1** U.K. National Conference on Heat Transfer, Inst, of Chemical Eng. sym-posium series, vol. 1, No.86 (1984). [80] Fetissoff, P. E., "Comparison of Two Fouhng Probes.", M.A.Sc. Thesis, The Uni-versity of British Columbia, (1982). Bibliography 152 [81] Ford, J . F., R. C. Pitcketty and V.O. Young, Tetrahedron 4, 325 (1958). [82] Oswald, A. A . , "Organic Sulphur Compounds I: Hydroperoxide Intermediates in the Co-oxidation of Mercaptans and Olefins". J . of Organic Chem. vol. 24, 443 (1959). [83] Brooks, B. I., "The Chemistry of Gasohnes with Respect to Gum Formation and Discolouration", Ind. and Eng. Chem. 18, 1198-1203 (1926). [84] Denison, G. H.,and P. C. Condit, "Oxidation of Lubricating Oils: Mechanism for Sulphur Inhibition", Ind. and Eng. Chem. 37, 1102-1108 (1945). [85] Russel, G. A. 'Oxidation of Unsaturated Compounds 3: Products of the Reaction of Indene and Oxygen'. J . Am. Chem. Soc. 78, 1035-1041, (1956). [86] Prilezhaev, N . Ber. Dtsh. Chem. Ges. 42, 4811, (1909). [87] Medvedev, S. and 0. Blokh, "Velocity of Reaction Between Peracids and Cyclo-hexene", J . Phys Chem.(Moscow) 4, 721-730 (1933); Chemical Abstracts vol. 29, 6492 (1935). [88] Vilkas, M . " L ' acide p - nitroperbenzoique", Bull. Soc. Chim. Fr. pl401, (1959). [89] Ogata, Y . , and I. Tabushi, "Kinetics of Epoxidation of Substituted a-Methylstilbenes", J . Am. Chem. Soc, 83, 3440-3444, (1961). [90] Thompson, R. B., J . A. Chenicek, L . W. Druge, and T. Symon, "Stability of Fuel Oils in Storage — Effect of Sulphur compounds." Ind. and Eng. Chem. 41, 935 (1951). [91] Taylor, W. F., "Deposit Formation from Deoxygenated Hydrocarbons I: General Features." Ind. and Eng. Chem. Prod. Res. and Dev. 13, No2, 133-138, (1974). [92] Pritchard, A. M . , K. A . Peakall, and E. Smart, Procd. of Inter. Conf. on Water Chem. of Nuclear Reactor Systems. 139-146, Oct. (1977). [93] Dahhn, K. E. , S. R. Daniel and J . H. Worstell, "Deposit Formation in Liquid Fuels — 1. Effect of Coal Derived Lewis Bases on Storage Stabihty of Jet A Turbine Fuel." Fuel 60, 477-480, (1981). [94] Worstell, J . H. , and S. R. Daniel, "Deposit Formation in Liquid Fuels — 2. Effect of Selected Compounds on Storage Stabihty of Jet A Fuel." Fuel 60, 481-484, (1981). [95] Jones, L., R. N . Hazlett, N . C. L i , and J . Ge, "Storage Stabihty Studies of Fuels Derived from Shale and Petroleum." Fuel 63, 1152-1156, (1984). Bibliography 153 [96] Cooney, J . V . , E . J . Beal, and R. Hazlett, "Mechanism of Syncrude Degradation II: Examination of Shale-Derived Polar Fractions and their Effects on Storage of Diesel Fuel.", Ind. and Eng. Chem. Prod. Res. and Dev. vol. 24, 294-300 (1985). [97] Vranos, A. P., P. J . Marteny, B. A. Knight, "Determination of Coking Rates in Jet Fuels.", in Fouhng of Heat Transfer Equipment, eds. EFC Somerscales and J G Knudsen, Hemisphere Publ. Co., New York, 489-499 (1981). [98] Steele, G. L. , D. W. Brinkman and M . L. Whisman, "Predictive Test Method for Coking and Fouhng Tendancy of Used Lubricating Oil." in Fouhng in Heat Transfer Equipment eds. E. F. C. Somerscales and J . G. Knudsen, Hemisphere Publ. Co., 483- 488 (1981). [99] Knudsen, J . G., "Fouhng in Heat Exchangers." Heat Exchanger Design Handbook, Hemisphere Publ. Corp. Washington (1983). [100] Ruckenstein, E. and D. C. Prieve, "The Rate of Deposition of Brownian Particles under the action of London and Double Layer Forces." J . Chem. Soc. Faraday II vol. 69, 1522-1536 (1973). [101] Wachel, L. J., "Exchanger Simulator: Guide to Less Fouhng." Hydrocarbon Pro-cesing vol. 65, No. 11 107-110 (1986). [102] Fernandez-Baujin, J . M . , and S. M . Solomon, Industrial and Laboratory Pyrolyses. eds. L. F. Albright and B. L. Crynes, ACS Symposium Series No 32, 345-372, (1976). [103] Bril l , W. F., "The Isomerization and Rearrangement of Pure Acychc Hydroperox-ides." J . A m Chem. Soc. vol. 72, 1942-1952 (1950). [104] Tobolsky, A . V. , D. J . Metz and B. B. Mesorobian, "Low Temperature Autoxidation of Hydrocarbons: The Phenomenom of Maximum Rates." J . Am. Chem. Soc. vol. 72, 1942-1952 (1950). [105] Van Sickle, D. E. , F. R. Mayo, and R. M . Arluck, "Liquid Phase Oxidation of Cyclic Alkenes." J . Am. Chem. Soc. vol.87, 4824-4832 (1965). [106] Van Sickle, D. E. , F. R. Mayo, R. M . Arluck, and M . G. Syz, "Oxidation of Acychc Alkenes." J . Am. Chem. Soc. vol. 89, 967-977 (1967). [107] Kharasch, M . S., W. Nudenberg and C. N . Mantell, "Reactions of Atoms and Free Radicals in Solution III: The Reaction of Olefins with Mercaptans". J . Org. Chem. Soc. vol. 16, 524 (1951). Bibliography 154 Oswald, A . A. , "Organic Sulphur Compounds II: Synthesis of Indanyl Aryl Sul-phides, Sulfoxides, Sulfones." J . Org. Chem. vol. 25, 467 (1960). Oswald, A. A. , "Organic Sulphur Compounds III: Cooxidation of Mercaptans with Styrene and Indene." J. Org. Chem. vol. 26, 842-846 (1961). Shapiro, A . B., L. P. Lebedeva, V . I. Suskina, Vysokomol. Soed. (Polymer Science) vol. 15A 5673 (1973). Azori, M . , F. Fudes, A. Rockenbauer and P. Simon, Kinet. Catal. Letters vol. 8, 137 (1978). Savage, P. E. , M . T. Klein, S. G. Kukes "Asphaltene Reaction Pathways 1: Ther-molysis." Ind. Eng. Chem. Proc. Des. Dev. vol. 24, 1169-1174 (1985). Speight, J . G., R. J . Pancirov, Prep — Am. Chem. Soc. Div. of Pet. Chem. vol. 28, 1319 (1983), cited in Speight J . G., The Chemistry and Technology of Petroleum, Marcel and Dekker, New York, (1980). Schucker, R. C , C. F. Kereshan, Prep. — Am. Chem. Soc. Div. of Fuel Chem. vol.25 155 (1980), cited in Speight J . G., The Chemistry and Technology of Petroleum, Marcel and Dekker, New York, (1980). Posedov, I. A. , Y . V. Pokonova, 0. G. Popov, V. A. Proskunykov, J Appl. Chem. USSR vol. 48, 2120 (1975). Posedov, I. A. , Y . V. Pokonova, 0. G. Popov, V. A. Proskunykov, J . Appl. Chem. USSR vol. 50, 1516 (1977). Dittus, F. W., and L. M . K . Boelter, "Heat Transfer in Automobile Radiators of the Tubular type." Universiy of California Press, vol. 2 No 13 (1930). Wiegand, J . H. , "Discussion of Annular Heat Transfer Coefficient for Turbulent Flow." Transactions AIChE vol., 41, No 5, 147-152 (1945). Monrad, C. C. and J . F. Pelton, "Heat Transfer by Convection in Annular Spaces", Transactions of AIChE, vol.38, 593-608 (1942). Taborek, J . Heat Transfer Inc. in H. Muller-Steinhagen et al. "Subcooled Boiling and Convective Heat Transfer for Heptane Flowing Inside an Annulus and Past a Coiled Wire. II: Correlation of Data." J . of Heat Transfer vol. 108, 928-933 (1986). Gnielinski, V . in H. Muller-Steinhagen J . of Heat Transfer vol. 108, 928-933, (1986). Drew, T. B. , "Mathematical Attacks on Forced Convection Problems." Trans, of AIChE vol. 26, 26-80 (1931). Bibliography 155 [123] Ulsamer, J., In H. Muller-Steinhagen et al. J. of Heat Transfer vol. 108, 928-933 (1986). [124] Muller-Steinhagen, H. , F. Reif, N . Epstein, and A. P. Watkinson, "Particulate Fouhng During Boihng and Non-Boihng Heat Transfer", Proc. 7th Intern. Heat Transfer Conf. vol. 5 2555-2560, Hemisphere Publishing (1986). [125] Paterson, W. R., and P. J. Fryer, 'A Reaction Analysis of Fouhng.' Chem. Eng. Sci. vol. 43, 1714-1717 (1988) [126] Lewis, J . B. and R. B. Bradsheet, Ind. and Eng. Chem. vol. 12, 387 (1940). Appendix A DATA COLLECTION AND CALCULATIONS Data collected from the fouhng rig were, for the annular probe, the three wall tem-peratures, the entry and exit bulk fluid temperatures, the power supphed to the probe and the manometer Az reading. The wall temperatures were converted to the surface temperature using the formula: T. = Tw-jQ/A where s/A was first determined from the Wilson method [72]. The surface area A is determined from A —irDl. where D is the diameter of the heater, and I the length of the heated section. The heat flux of the PFRU probe was calculated from the power Q as: q = Q/A The bulk and surface temperatures were each averaged and the heat transfer coefficient under clean surface conditions was calculated as: _ Tso — Tbo K ~ (Q/A)a and that of the fouled surface from: J _ = Ta-Tb hf Q/A Knowing the heat transfer coefficients under clean and fouled conditions, the thermal fouhng resistance was calculated from: hj hc 156 Appendix A. DATA COLLECTION AND CALCULATIONS 157 For the hot wire probe, the data collected were the voltage drop across and current through the hot wire, the entry and exit bulk fluid temperatures, and the manometer Az reading. The power supphed to the hot wire was computed from: 2 V Q = I (y — Rext) and the heat flux from: q = Q/A The surface area A is calculated from A = TDI, where D is the diameter of the coiled wire and I is the length. The resistance of the coiled wire was calculated from: * - 7 The surface temperature of the coiled wire was computed from: T. = ( * ^ - l ) / a + r . JX0 — /text where Ra is the resistance of the wire at zero power and at a temperature Ta. This resistance is determined before each run. Rext. is the resistance of the external circuit. Knowing the heat flux q, the surface and the bulk temperature T, and Tb, the heat transfer coefficients and fouhng resistances are calculated as for the P F R U . Appendix A. DATA COLLECTION AND CALCULATIONS 158 A . l SAMPLE CALCULATIONS P F R U U N D E R INITIAL CONDITIONS A sample of the three wall temperatures of the clean surface are Tw\ — 199.3 °C, TW2 — 200.5 °C, and Tw$ = 204.0 °C. The local surface temperature is calculated from the wall temperatures as: where ( f ) r c i = 7.Q92A0~3(m2K)/kW, (f )TC2 = S.3Z3.10-3{rn2K)/kW, and ) T C 3 = 1.667.lO-2{m2K)/kW. Thus, TSl = 197.01, TS2 = 198.021, T S 3 = 199.04 and the average value is given by Tto = (197.01 + 198.02 + 199.04)/3 = 198.02°C The heat flow and area are given by: Q = 1020 W A = 0.0034287m2 From whence the heat flux is calculated as: q0 = ^ = 297.48 kW/m2 The bulk fluid temperature under clean surface conditions is evaluated as the average of the entry and exit bulk fluid temperatures. Tbl = 78°C Tb2 = 84°C7 Tbo = {Tbl+Tb2)/2 = SrC Appendix A. DATA COLLECTION AND CALCULATIONS 159 The inverse of the initial heat transfer coefficient is calcualated from: 1 T — T so bo = 0.3934 (m2K)/kW h0 g0 P F R U U N D E R FOULED CONDITIONS: A sample of three of the wall temperatures, under fouled conditions, read by the thermocouples are TWl = 215°C, TW2 = 216.3°<7, and TW3 = 220°C. The surface temperatures are calculated from the wall temperatures as: T. = Tw-jQ/A Thus, Tsl = 213.0°C Ts2 = 214.9°C T,3 - 220.0°C and the mean surface and bulk fluid temperatures are given by: T, = (T a l + T.2 + r j 3)/3 = 214°C Tb = {Tbi+Tb2)/2 = 84°C Where Tbi and Tb2 are the entry and exit bulk fluid temperatures respectively of the P F R U probe. The power input to the probe at that time was: Q = 1025 W and hence the heat flux is given by: Appendix A. DATA COLLECTION AND CALCULATIONS 160 q= 298.947 kW/m2 The heat transfer coefficient under fouled conditions is evaluated from: _L = T> ~ T b = 0.4349 (m2K)/kW hf q The thermal fouhng resistance is calculated as the difference between the reciprocals of the overall heat transfer coefficients under clean and fouled conditions. Rf = - = 0.042 (m2K)/kW hf ha HWP U N D E R INITIAL CONDITIONS For the Hot Wire Probe, sample initial conditions are given by: I = 1.1778 Amp., V = 12.4838 Volts, Ra = 9.10 Ohms., Rext = 0.038 Ohms, Tbl = 81°C, Tb2 = 85°C, Ta = 22°C and A = 0.00004918 m 2 . Hence the power to the probe, and heat flux are evaluated respectively as: Q = I2{V/I - Rext) = 14.6507 W q= Q/A = 297.87 kW/m2 And the resistance, surface and bulk temperatures are evaluated respectively as: R = V/I = 10.5992 Ohms. Tao = {*~_R:xt - l) I a + Ta = 198°C where a the temperature coefficient of the electrical resistance is 0.00094 K~l. Tbo = (Tbl + Tb2)/2 = 83°C The film heat transfer coefficient under clean conditions is calculated as: 0.3879 (m^K)fkW 1 _ Tso Tbo Appendix A. DATA COLLECTION AND CALCULATIONS 161 HWP U N D E R F O U L E D CONDITIONS The voltage, current and bulk fluid temperatures are given as; V = 12.4280 Volts, I = 1.1690 Amps., T0i — 77°C, and Tb2 = 81°C. The relevant parameters are evaluated from these values as for the initial conditions. R = 10.6313 Ohms Q = 14.4764 W q = 294 .32W/m 2 Ts = 201.76°C7 Tb = 79°C and the heat transfer coefficient under fouled conditions is calculated as: = 0.4171 m2K/kW The thermal fouhng resistance is calculated from: Rs = = 0.0292 m2K/kW hf hc Appendix A. DATA COLLECTION AND CALCULATIONS 162 A.2 CALCULATION OF VOLUMETRIC FLOW RATES The volume flow rates are calculated as follows. Using the P F R U as a sample, the ori-fice discharge coefficient Cd = 0.6102, the orifice diameter d2 = 0.0158 m, the manometer differential pressure AZ = 6.5 in., fi = di/d2, hence d\ = fid2. Therefore, the ori-fice cross-sectional area A„ = f32ird2/4 = 4.9488.10-5m2. The density of the flowing test fluid is p = 792.4 kg/rn3 and the density of the mecury in the manometer pm = 13643 kg/m3. The difference between the densities of the mercury and flowing fluid 8p = Pm — P — 12850 kg/m3, and the pressure drop Ap = AzAp = 2121.63 kg/m2. Thus the volumetric flow rate is calculated as: The bulk fluid velocity and Reynolds number are calculated as follows: The equiva-lent diameter of the annulus deg is given by: where da is the annulus outer diameter and d{ is the annulus inner daimeter. The cross-sectional area of the annulus is given by 2gc(Ap) d, •eg (d0 - d{) = 0.025 - 0.0107 = 0.0143 m Thus the bulk fluid velocity is given as U = V 0.56 m/s (3600)(0.000401) The Reynolds number is calculated from: Re = Udeqp _ (0.5611)(0.0143)(792.4) a ~ 0.00065 = 9781 Appendix A. DATA COLLECTION AND CALCULATIONS 163 A.3 CALCULATION OF THERMAL CONDUCTIVITY OF DEPOSIT The deposit thickness x of the indene Run 8 at high heat flux was 0.99 mm, that of Run 9 at medium heat flux was 0.31 mm, and that of Run 10 at low heat flux was 0.19 mm. The deposit thickness of the dicyclopentadiene Run 12 at the high heat flux was 0.31 mm, that of Run 13 at low heat flux was 0.14 mm, and that of Run 6, 4-Vinyl-l-cyclohexene was 0.07 mm. Since, dRf 1 . dx. If = k~^d6~' then integrating with boundary conditions x = 0, Rf — 0 gives: from whence u x = R, where Rf is Rfmax- Using this equation the thermal conductivities calculated are pre-sented in the Table A.25. A.4 TABLES OF PERTINENT DATA Table A.30 shows the measured densities of kerosene and kerosene-olefin mixtures at room temperature. Tables A.31 and A.32 show the discharge coefficients, for the P F R U and H W P orifice meters respectively. The average discharge coefficient for the P F R U orifice meter is 0.6102 and for the HWP orifice meter 0.6928. The measured viscosities of the kerosene are tabulated in Table A.29. Figures A.27 and A.28 show plots of Runs 8 and 11 performed to check the reproducibility of the experiments. Appendix A. DATA COLLECTION AND CALCULATIONS 164 Table A.25: Calculated Thermal Conductivities of Deposits Run # Compound Deposit thickness x in mm. Thermal conductivity W / m K 8 Indene 0.99 1.32 9 Indene 0.31 1.41 10 Indene 0.19 1.36 12 Dicyclo-pentadiene 0.31 0.69 13 Dicyclo-pentadiene 0.14 0.67 6 4-Vinyl-1-cyclohexene 0.07 0.44 Table A.26: Viscosity of Kerosene Temperature 44 54 64 74 84 94 °C Measured Viscosity 1.067 0.936 0.830 0.726 0.652 0.588 x 106 cP Appendix A. DATA COLLECTION AND CALCULATIONS 165 Table A.27: Densities of Test Fluids at Room Temperature Density at Density at Test Fluid beginning of run end of run kg/m3 kg/m3 Kerosene 803.4 — Indene/Kerosene 807.2 809.9 Dicyclopenta-diene/Kerosene 810.7 811.4 4-Vinylcyclo-hexene / Kerosene 795.6 795.9 Hexadecene/ Kerosene 790.6 791.2 Cycloocta-diene/Kerosene 810.2 810.5 Decene -1/Kerosene 795.4 795.9 Octene -1/Kerosene 780.7 780.8 Appendix A. DATA COLLECTION AND CALCULATIONS 166 Table A.28: Discharge coefficients determined from calibration of P F R U orifice meter Manometer Ah reading (in.) 4.0 6.0 7.0 8.0 9.0 13 Volume flow rate m 3 /hr . 0.604 0.751 0.8 0.854 0.905 1.087 Orifice Meter Discharge 0.613 0.613 0.609 0.608 0.610 0.608 Coefficient Table A.29: Discharge coefficients determined from cahbration of HWP Manometer Ah reading (in Volume flow rate m3/hr. Orifice discharge coefficient 4.0 6.0 0.015 0.018 0.689 0.689 8.0 10.0 0.021 0.024 0.701 0.698 12.0 15.0 0.025 0.029 0.700 0.689 Appendix A. DATA COLLECTION AND CALCULATIONS 167 1.20 C\2 o 55 CO t—I CO « o 55 »—i 5D o fe 1.05 0.90-0.75 0.60-0.45 0.30-0.15 0.00 RUN 8B INDENE • = PFRU Tb=79°C A - H W P Tb=?2°C PFRU: q=292 kW/mjr HWP: q=237 kW/m q reduced to 230 kW/m 1 q reduced to 175 kW/m7 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure A.27.: Repeat of Run 8, indene at high heat flux Appendix A. DATA COLLECTION AND CALCULATIONS 168 0.08 RUN 11B INDENE DEOXYGENATED II 0.07 0.06 o , • = PFRU, Tb=83wC A = H W P , Tb=83°C PFRU: q=301 kW/m^ HWP: q=292kW/m^ 0.05-0.04-0.03-0.02 0.01 • ED' A • "AA AAA4§> p UP \ < rtP A AJH Cf^ Q A\ • P • • A A A £ A A A A A = I _ ^ * • A AA • AAV A • • 4 £ > 0.00-0* A A A A A A A' • 7.0 14.0 21.0 28.0 35.0 TIME (HOURS) 42.0 49.0 Figure A.28: Repeat of Run 11, indene deoxygenated Appendix B MAXIMUM FOULING RESISTANCES AND INITIAL RATES Tables B.30 and B.31 show the maximum fouhng resistances for the P F R U and HWP respectively, and their ranking relative to decene-1. Tables B.32 and B.33 show the initial fouhng rates calculated from the P F R U and HWP fouhng curves respectively. These were obtained by doing a least squares fit over the range of fouhng resistances where the curves were linear. The time range over which the fit was done is given in the tables. 169 Appendix B. MAXIMUM FOULING RESISTANCES AND INITIAL RATES 170 Table B.30: Maximum Thermal Fouhng Resistances after 40 Hours for P F R U Probe Run # Compound Atmosphere Heat Flux kW/m2 at 40 hours (m2K)/kW 1 Decene-1 oxygenated 196 No measurable fouhng 2 Decene-1 252 No measurable fouhng 3 Octene—1 267 No measurable fouhng 4 1,5-Cy clooctadiene 270 No measurable fouhng 5 Decene-1 357 0.015 6 Vinylcyclohexene 298 0.16 7 Dicyclopentadiene inhibited 294 0.04 8 Indene oxygenated 299 0.75 9 Indene 260 0.22 10 Indene 198 0.14 11 Indene deoxygenated 299 0.03 12 Dicyclopentadiene oxygenated 260 0.45 13 Dicyclopentadiene 215 0.21 14 Dicyclopentadiene deoxygenated 298 0.085 15 Hexadecene-1 oxygenated 298 0.25 Appendix B. MAXIMUM FOULING RESISTANCES AND INITIAL RATES 171 Table B.31: Maximum Thermal Fouling Resistances after 40 Hours for HWP Probe Run # Compound Atmosphere Heat Flux k W / m 2 at 40hours m2 K / k W 1 Decene-1 oxygenated 150 No measurable fouhng 2 Decene-1 182 No measurable fouhng 3 Octene-1 199 No measurable fouhng 4 1,5-Cyclooctadiene 193 No measurable fouhng 5 Decene-1 » 360 0.03 6 Vinylcyclohexene 294 0.13 7 Dicyclopentadiene inhibited 296 0.04 8 Indene oxygenated 295 0.9 9 Indene i) 246 0.20 10 Indene 199 0.16 11 Indene deoxygenated 299 0.02 12 Dicyclopentadiene oxygenated 254 0.32 13 Dicyclopentadiene 201 0.15 14 Dicyclopentadiene deoxygenated 298 0.1 15 Hexadecene-1 oxygenated 298 0.19 Appendix B. MAXIMUM FOULING RESISTANCES AND INITIAL RATES 172 Table B.32: P F R U Initial Fouling Rates Initial Fouling Rate Range of time Run # (m2K)/kWhr. data fitted in hours 5 0.0027 3 - 1 0 6 0.0139 1 - 11 8 0.0406 4 - 2 0 9 0.0154 0 - 11 10 0.0051 1 - 11 11 0.0032 2 - 1 4 12 0.0399 3 - 1 8 13 0.0110 2 - 1 0 14 0.0030 2 - 2 4 15 0.0073 3 - 2 4 Appendix B. MAXIMUM FOULING RESISTANCES AND INITIAL RATES 173 Table B.33: H W P Initial Fouling Rates Initial Fouling Rate Range of time Run # (m2K)/kWhr. data fitted in hours 5 0.00382 3 - 1 0 6 0.00574 1 - 21 • 8 0.05177 14 — 28 9 0.00779 2 - 1 7 10 0.00776 1 - 11 11 0.00219 2 - 1 4 12 0.0206 3 - 1 4 13 0.0031 3 - 2 6 14 0.00220 3 - 2 1 15 0.00610 3 - 1 7 Appendix C PROGRAM LISTINGS C. l COMPUTER PROGRAMS C INDENE-1 IMPLICIT REAL*4(A-H,0-Z) DIMENSION TSK126),TS2(126),TB1(126),TB2(126),QF1(126) DIMENSION R(126),U1(126),U2(126),RF1(126),RF2(126),QF2(126) DIMENSION IT(126),TT(126),X(9,126),IPAK(5000) C C This i s a program to calculate and plot the thermal fouling C resistances. C C NOMENCLATURE C C TS1 the average surface temperature of the PFRU probe. C TS2 the average surface temperature of the HWP. C TBI i s the bulk f l u i d temperature of the PFRU probe. C TB2 i s the bulk f l u i d temperature of the hot wire probe. C TT i s time in minutes. C RO i s the resistance of the hot wire at zero power. C REXT i s the resistance of the external c i r c u i t . C ALPH i s the temperature coefficient of the stainless steel C 302 wire. C Al is the surface area of the PFRU probe. C A2 i s the surface area of the hot wire probe. C U01 i s the overall heat transfer coefficient of the clean C PFRU surface C U02 i s the overall heat transfer coefficient of the clean C hot wire surface. C Ul i s the overall heat transfer coefficient of the PFRU C probe C U2 i s the overall heat tansfer coefficient of the hot C wire probe. C R i s the resistance of the hot wire. C V is the voltage across the hot wire. C RI i s the current through the hot wire. C QF1 i s the PFRU heat flux. C QF2 i s the hot wire probe heat flux. C RFI is the thermal fouling resistance of the PFRU probe. C RF2 i s the thermal fouling resistance of the hot wire C probe. C C READ(5,*)M,N READ(5,*)R01T0,REXT,ALPH,A1,A2,U01,U02 READ(5,*)TS11,TS22,TB11, TB22.QF11,QF22 C C Read i n the surface temperatures. C C READ(5,*)((X(I,J),I=i,M),J=l,N) 174 Appendix C. PROGRAM LISTINGS C Average PFRU surface temperatures. C DO 20 1=1,N TSl(I)=(X(l,I)+X(2,I)+X(3,I))/3. TBl(I)=(X(4,I)+X(5,I))/2. 20 CONTINUE C C Calculate HWP surface and bulk f l u i d temperatures. C DO 30 1=1,N R(I)=X(7,I)/X(8,I) TS2(I)=(((R(I)-REXT)/(R0-REXT))-1)/ALPH TS2(I)=TS2(I)+T0 TB2(I)=X(9,I) 30 CONTINUE C C C Calculate the PFRU heat fluxes, heat transfer coefficients and C thermal fouling resistances by c a l l i n g the subroutine PFRU. C CALL PFRU(TS1,TB1,A1,N.M.X.UOl,QF1,RF1) C C Calculate the PFRU heat fluxes, heat transfer coefficients, and C thermal fouling resistances by c a l l i n g the subroutine HWP. C CALL HWP(TS2,TB2,A2,N,M,X,U02,QF2,RF2) C TT(1)=0.0 IT(1)=0 DO 40 1=2,N TT(I)=TT(I-l)+20. IT(I)=TT(I) 40 CONTINUE C C Calculate the averages over the run of the heat fluxes, C and bulk temperatures C SUM1=0. SUM2=0. SUM3=0. SUM4=0. DO 50 1=1, N SUM1=SUM1+TB1(I) SUM2=SUM2+TB2(I) SUM3=SUM3+qFl(I) SUM4=SUM4+QF2(I) 50 CONTINUE TB1AV=SUM1/N TB2AV=SUM2/N QF1AV=SUM3/N QF2AV=SUM4/N C C Print out the i n i t i a l and average conditions, data and results. C WRITE(6,380) 380 FORMAT(//26X, 'ROT 8, INDENE AT HIGH HEAT FLUX'///) WRITE(6 390) 390 FORMAT(26X,'INITIAL CONDITIONS:'///) WRITE(6,410) 410 FORMAT(4X,'UPFRU',5X,'UHWP',5X,'TPFRU',4X,'THWP',4X,'TBPFRU',4X #,' TBHWP', 4X,; QPFRU', 5X,' QHWP' / ) WRITE(6,420)U01,U02,TS11,TS22,TBI1,TB22,QF11,QF22 420 F0RMAT(2X,F8.3,2X,F8.3,2X,F6.2,3X,F6.2,2X,F6.1,3X,F6.1,3X, #F8.2,2X,F8.2) WRITE(6,430) 430 FORMAT(///26X,'AVERAGE CONDITIONS:'///) Appendix C. PROGRAM LISTINGS 176 WRITE (6,440) 440 FORMAT(4X,'TBPFRU',4X,'TBHWP',6X,'QPFRU',8X,'QHWP'/) WRITE(6,450)TB1AV,TB2AV,QF1AV,QF2AV 450 F0RMAT(3X,F6.2,4X,F6.2,3X,F10.2,3X,F10.2/) WRITE(6,460) 460 F0RMATC///3X,'TIME',3X,'PTEMP',4X,'HTEMP',3X,'PTB', $4X,'HTB',6X,'PHF',7X,'HHF',7X,'PFR',6X,'HFR'//) WRITE(6,470)(IT(I),TS1(I),TS2(I),TB1(I),TB2(I),QF1(I),QF2(I) $,RF1(I),RF2(I),I=1,I) 470 F0RMAT(2X,I4,2X,F7.2,2X,F7.2,2F7.1,2X,F8.3,2X,F8.3,2X,F7.4 $,F9.4) C C Plot fouling resistance versus time curves. C Scale values of time for the x-coordinate. C DO 10 11=1,N TT(II)=TT(II)/60. 10 CONTINUE C CALL DSPDEV('PLOT') CALL NOBRDR CALL COMPLX C C Define size of page and area of plot C CALL PAGE(8.5,11.0) CALL AREA2D(5.2,6.8) C C Label axis C CALL MIXALF('INSTR') CALL YNAME('FOULING RESISTANCE (Qm(E0.7)2 (EX)K())/kW$»,100) CALL XNAME('TIME (()H0URS())$',100) CALL YAXANG(O.O) CALL XTICKS(2) CALL YTICKS(2) CALL GRAF(0.0,7.0,50.0,0.00,0.150,1.2) CALL THKFRM(0.04) C C Plot fouling resistances against time C CALL FRAME CALL MARKER(O) CALL CURVE(TT,RFI,126,-1) CALL MARKER(2) CALL CURVE(TT,RF2,126,-1) C C Draw Legend C MAXLIN=LINEST(IPAK,500,50) CALL MIXALF('INSTR') CALL LINESCPFRU T(L0.3)b(EX)=81(E0.8)o(EX)C$'.IPAK.l) CALL LINESCHWP T(L0.3)b(EX)=80(E0.8)o(EX)C$',IPAK,2) CALL MYLEGN(' ',1) CALL LEGEND(IPAK,2,0.6,5.5) CALL MIXALF('INSTR') CALL LINES('PFRU: q=299 kW/m(E0.8)2$',IPAK,1) CALL LINES('HWP: q=295 kW/m(E0.8)2$',IPAK,2) CALL LST0RY(IPAK,2,0.6,5.0) CALL BLREC(.35,4.6,2.6,1.5,.02) CALL MESSAG('RUN 8 INDENE$',100,1.80,6.4) CALL ENDPL(O) CALL DONEPL STOP END C Appendix C. PROGRAM LISTINGS c SUBROUTINE PFRU(TSl,TBl,Al,N,M,X,U01,qFl,RFl) IMPLICIT REAL*4(A-H,0-Z) DIMENSION QF1(126),TS1(126),TB1(126),U1(126),RF1(126),X(9,126) C C Calculate heat fluxes C DO 10 1=1,N C QF1(I)=X(6,I)/A1/1000. C C C Calculate heat transfer coefficient. C U1(I)=QF1(I)/(TS1(I)-TB1(I)) C C Calculate thermal fouling resistance. C RF1(I)= 1/UKD-1/U01 10 CONTINUE RETURN END C C SUBROUTINE HWP(TS2,TB2,A2,N,M,X,U02,qF2,RF2) IMPLICIT REAL*4(A-H,0-Z) DIMENSION QF2(126) ,U2(126),TS2(126),TB2(126),RF2(126),X(9,126) C DO 10 1=1,N C C Calculate heat fluxes C QF2(I)=X(7,I)*X(8,I)/A2/1000. C C Calculate heat transfer coefficient C U2(I)=QF2(I)/(TS2(I)-TB2(D) C C Calculate thermal fouling resistance C RF2(I)=1/U2(I)-1/U02 10 CONTINUE RETURN END Appendix C. PROGRAM LISTINGS IMPLICIT REAL*4(A-H,L,0-Z) C C NOTATION C C This program was used i n calculating the s o l u b i l i t y of a i r C oxygen and nitrogen i n kerosene, the flow rates of the Hot C Wire and PFRU probes and the corresponding Reynolds numbers. C C P — P a r t i a l pressure of gas in atmospheres. C SI S o l u b i l i t y parameter of of l i q u i d C S2 Equivalent s o l u b i l i t y parameter of gas. C F Fuel factor C M2 Molecular weight of gas. C L Ostwald coefficient. C B Bunsen coefficient. C D Density of l i q u i d at 15 degrees Celsius. C DT Density of l i q u i d at specified temperature. C T Temperature at which s o l u b i l i t y i s calculated. C G S o l u b i l i t y i n parts per mill i o n by weight. C C C Calculation of S o l u b i l i t i e s . C P=4.06 T=293. D=0.8 Sl=5.88*D+3.6 S2=3.79 F=1.28 M2=32. L=EXP( (0.1655* (S1-S2)**2-2.66)* (1. -273. /T)-0.62*Si-0.101* # (8.6-S2)**2+5.731)*F B=273.*P*L/T DT=D*(1-0.000595*(T-288.2)/(D**1.21)) G=44.6*B*M2/DT WRITE(6,100)L,B,G 100 FORMAT(//6X,'OSTWALD COEFFICIENT L =',F8.4//,6X, # 'BUNSEN COEFFICIENT B =',F8.4//6X,'SOLUBILITY IN PPM =',F8.4//) C C C Calculation of PFRU Flow rates. C C ZP Pressure drop across PFRU o r i f i c e meter i n inches. C CDP PFRU o r i f i c e discharge coe f f i c i e n t . C BETAP Dimensionless contact angle of PFRU o r i f i c e meter. C D Diameter of o r i f i c e C GC Acceleration due to gravity. C DM Density of mercury. C DL Density of test f l u i d . C A0P Crossectional area of PFRU o r i f i c e meter. C VFP Volume flow rate of PFRU probe C REP PFRU Reynolds number. C PR Prandtl number C DO Outer diameter of annulus C Dl Inner diameter of annulus. C UP Bulk velocity of test f l u i d . C DEQP Equivalent diameter of annular probe C VIS Dynamic viscosity of test f l u i d . C VISK Kinematic viscosity of test f l u i d . C RH0 Density of test f l u i d . C ADUCT HWP duct crosectional area. C c ZP=6.5 CDP=0.6102 BETAP=0.5024 Appendix C. PROGRAM LISTINGS D=0.0158 GC=9.81 DM=13643. DL=792.4 PI=3.14159265 A0P=BETAP*BETAP*PI*D*D/4. DRHO=DM-DL DELP=DRH0*ZP*2.54/100. C C Calculate flow rate. C VFP=3600.*CDP*A0P*SqRT(2*GC*DELP/DL/(l.-BETAP**4)) C C Calculate PFRU Reynolds number. C D0=0.025 DI=0.0107 DEQP=D0-DI VIS=0.00065 RH0=792.4 VISK=VIS/RH0 AC=PI*(D0*D0-DI*DI)/4. UP=VFP/3600./AC REP=UP*DEqP/VISK C C Calculation of HWP flow rate and Reynolds number. C Nomenclature i s the same as f o r the PFRU with the C 'P' denoting PFRU replaced by 'H' for HWP. ZH=24. CDH=0.6928 BETAH=0.0748 DZ=ZH*2.54/100. DELH=DRH0*DZ C C Calculate flow rate. C A0B=BETAH*BETAH*PI*D*D/4 VFH=3600*CDH*AOH*SORT(2*GC*DELH/DL/(1-BETA**4)) C C Calculate HWP Reynolds number. C DW=0.000125 DEQH=PI/2*DW ADUCT=0.04*0.013 UH=VFH/ADUCT/3600. REH=UH*DEqH/VISK WRITE(6,200)VFP,REP 200 FORMAT(///9X,'PRFU FLOW RATE=',F8.4,4X,'PFRU REYNOLDS NUMBER # F12.2//) WRITE(6,300)VFH,REH 300 FORMAT(//9X,'HWP FLOW RATE=',F8.4.5X,'HWP REYNOLDS NUMBER=', # F12.2//) STOP END Appendix D DATA AND RESULTS D.l NOMENCLATURE FOR DATA AND RESULTS H T E M P — H W P average surface temperature (°C) P T E M P — P F R U average surface temperature (°C) HHF — Hot wire heat flux (kW/m2) PHF P F R U heat flux (kW/m2) I ('IF, — Hot wire probe's bulk fluid temperature (°C) P T B — PFRU's bulk fluid temperature (°C) HFR — HWP thermal fouhng resistance ((m2K)/kW) P F R — P F R U thermal fouhng resistance ((m2K~)/kW) T H W P — HWP surface temperature (°C) T P F R U — P F R U surface temperature (°C) TBHWP— HWP bulk fluid temprtaure (°C) QHWP — HWP heat flux (kW/m2) Q P F R U — P F R U heat flux (kW/m2) U H W P — HWP initial heat transfer coefficient (kW/(m2K)) U P F R U — P F R U initial heat transfer coefficient (kW/(m2K)) V F P — P F R U volume flow rate (m3/hr) V F H — HWP volume flow rate (m3/hr) R E P — P F R U Reynolds number R E H — H W P Reynolds number 180 Appendix D. DATA AND RESULTS 181 RUN 5, DECENE-1 INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU 3.070 2.932 204.00 206.00 90.0 AVERAGE CONDITIONS: TBHWP 85.0 qPFRU 349.99 QHWP 354.78 TBPFRU 88.00 TBHWP 85.00 TIME PTEMP QPFRU 357.41 HTEMP PTB QHWP 360.45 HTB VFP 0.81 PHF REP VFH 9760 0.04 HHF REH 4.9 PFR HFR 0 205 .00 205, .50 89 .0 86, .5 352, .903 371, .213 0, .0000 -0. .0072 20 205, .00 205, .32 91 .5 90, .0 347, .070 371, .216 0, .0000 -0. ,0171 40 208, .33 205.42 92 .0 93. .5 352, .903 371, .132 0, .0000 -0. ,0262 60 206, .00 203, .40 92 .5 89. .0 347, .070 371, .760 0, .0000 -0. ,0200 80 206, .33 195, .95 96 .0 87, .0 347, .070 373, .878 0, .0000 -0. ,0363 100 204, .33 205, .62 91 .0 87, ,0 341, .237 370, ,910 0, .0000 -0. ,0079 120 198 .67 206, .64 84 .0 84, .5 344 .154 370, .541 0 .0000 0, .0019 140 201 .00 206, .83 90 .0 82, .0 344, .154 370, .484 0 .0000 0. .0092 160 201, .00 208, .60 87 .5 80, .0 349, .987 369, .832 0, .0000 0, .0200 180 200, .33 207, .76 87 .0 78, .5 347, .070 370, .144 0 .0000 0, .0215 200 202, .67 208, .68 87 .0 77, .5 352, .903 369, .914 0, .0023 0, .0269 220 202, .67 205. .16 87 .0 77. .0 352, .903 371, .052 0, .0020 0. .0177 240 203, .00 205. .35 85 .5 77, .0 347, .070 370, .995 0, .0120 0. .0182 260 204, .33 213. .85 85 .0 85, ,5 349, .987 369, .275 0, .0149 0, ,0198 280 205, .00 219, ,22 85 .0 92, ,0 349. .987 367. ,374 0, .0171 0, ,0186 300 207 .00 224, .90 86 .5 96, .0 352, .903 365, .662 0, .0151 0, .0248 320 208, .33 226, .43 88 .0 97, .0 354, .362 365, .150 0, .0134 0, .0267 340 209, .33 213, .99 89 .0 91, .5 354, .362 368, .863 0, .0134 0. .0044 360 211, .33 213, .25 90 .0 84, .5 358, .736 369. .037 0, .0120 0, ,0212 380 208, .33 210, .84 89 .5 79, ,0 352, .903 369, .723 0, .0109 0. ,0289 400 206, .00 208, .62 88 .5 76, ,0 347, .070 370. .354 0, .0129 0. .0304 420 207, .33 207, .97 88 .5 73, ,5 349, .987 370. ,608 0, .0143 0. ,0351 440 210. .33 207, ,14 88 .5 72, .0 358. .736 370. .865 0, .0137 0. ,0367 460 211. .33 207, .87 89 .0 72, .0 358, .736 370, .637 0, .0151 0, ,0389 480 210, .33 208, .33 89 .5 72, .5 352, .903 370, .549 0, .0163 0, .0388 500 211, .33 210, .56 90 .0 78, .5 355, .820 369, .809 0, .0151 0, ,0294 520 210, .67 212, .32 90 .0 81, ,5 352, .903 369, .322 0, .0163 0. .0265 540 209, .33 211, .39 90 .0 84, ,0 352, .903 369, .607 0, .0129 0. .0169 560 208, .33 212, ,79 89 .0 85, ,5 354, .362 369. .179 0. .0106 0. .0171 580 210, .33 217, ,09 90 .5 86, ,5 354, .362 367. ,812 0, ,0120 0. ,0273 600 212. .67 216, ,83 91 .0 87, .5 355. .820 367. .788 0. ,0163 0. ,0239 620 215. .67 217. .29 90 .5 87. ,5 355. .820 367. ,645 0. .0257 0. ,0253 640 209, .00 218. .62 87 .0 87, .5 349, .987 367, ,191 0, .0229 0, .0294 660 208, .00 219, .54 84 .0 87, .5 355, .820 367, ,015 0. .0223 0. .0321 680 207, .67 220.49 84 .0 85, ,5 354. .362 366, .675 0. .0229 0. .0404 700 208, .00 219, .48 82 .5 85. ,5 358, .736 366, ,824 0, ,0243 0. ,0375 720 207, .33 220, ,70 83 .0 84. .5 352, .903 366, ,508 0, ,0266 0. ,0439 740 207, .00 221, ,00 82 .5 88. ,0 354, ,362 366, ,313 0. ,0257 0. ,0354 760 207, .00 221. .66 83 .0 83. ,5 349, ,987 366, .114 0. .0289 0. ,0496 780 210. .33 222. ,04 83 .0 83. ,5 358, ,736 366. ,000 0. .0294 0. 0508 800 206. ,67 217. ,23 80 .5 83. ,5 357, ,278 367. ,454 0. ,0272 0. 0362 820 206, .33 218, ,64 80 .0 83. ,0 354, .362 367, ,027 0, ,0309 0.0418 840 206, .33 215.45 79 .5 82. ,0 358, ,736 367, .996 0, ,0277 0. ,0349 Appendix D. DATA AND RESULTS 860 204, .67 215, .44 80 .5 82 .0 • 349. ,987 368, .051 0, .0294 0.0348 880 207, .33 215, .45 81 .0 81 .5 355, ,820 367, .996 0, ,0294 0.0363 900 207, .67 214, .52 81 .0 81 .5 357, ,278 368, .281 0, ,0294 0.0335 920 207 .33 215 .36 81 .0 81 .5 357. .278 368 .025 0, .0274 0.0360 940 207 .00 215.44 81 .0 81 .5 357. .278 368, .051 0, .0271 0.0362 960 206 .00 214 .60 81 .0 82 .0 352, .903 368, .308 0, .0280 0.0323 980 205 .67 215, .07 80 .5 82 .0 354, .362 368, .165 0, .0274 0.0337 1000 204, .67 214, .52 80 .5 81 .5 349, ,987 368, .281 0. .0292 0.0335 1020 205, .67 214, .52 80 .5 81 .5 352, ,903 368, .227 0, .0286 0.0335 1040 204, .67 215, .36 81 .5 81 .5 349. ,987 367, .970 0. .0257 0.0361 1060 207, .67 215, .18 82 .0 82 .0 354. ,362 367, .972 0. .0294 0.0342 1080 207, .67 215, .54 82 .0 81. .5 357. .278 367, .968 0. .0257 0.0366 1100 207 .67 215 .26 83 .0 82 .5 355, .820 368, .053 0, .0249 0.0330 1120 206 .67 214 .25 83 .0 82 .5 355, .820 368, .257 0, .0223 0.0300 1140 207, .67 214 .34 83 .0 83 .0 352, ,903 368, .284 0, .0280 0.0289 1160 205, .33 214, .16 83 .5 83 .5 349, .987 368, .286 0, .0223 0.0270 1180 206, .67 214, .06 82 .5 82 .5 354, ,362 368, .314 0, .0249 0.0295 1200 205, .33 215, .08 83 .5 83 .5 347. ,070 368, .055 0. .0252 0.0298 1220 205, .33 215, .36 83 .0 83 .0 349, ,987 367, .970 0, ,0237 0.0320 1240 204, .00 215, .28 83 .5 84, .5 344. ,154 367, .944 0, .0243 0.0277 1260 205 .33 219 .24 84 .0 84 .5 347, .070 369, .153 0, .0234 0.0373 1280 204, .67 217 .37 84 .5 86 .5 347, .070 369, .725 0, .0209 0.0262 1300 205 .67 217 .36 84 .5 85 .0 349. .987 369 .780 0, .0206 0.0302 1320 207 .33 217, .54 86 .0 84 .0 352, .903 369, .778 0, .0180 0.0334 1340 206, .00 216, .61 86 .5 83 .5 347. .070 370, .064 0, .0186 0.0320 1360 208, .33 216, .51 86 .0 85 .0 352, ,903 370, .092 0, .0203 0.0276 1380 206, .00 215, .39 86 .5 85 .5 349. ,987 370, .436 0, .0157 0.0229 1400 205, .33 215, .76 86 .5 86 .0 347, ,070 370, .376 0. .0163 0.0226 1420 205, .33 216, .05 86 .5 87 .0 347, ,070 370, .235 0. ,0166 0.0208 1440 206 .33 214, .09 87 .0 87 .5 347, .070 370 .837 0, .0177 0.0136 1460 207, .33 217, .92 87 .5 87 .5 349, .987 369 .663 0, .0166 0.0251 1480 210, .67 218, .47 88 .5 88 .5 354. .362 369, .546 0, .0186 0.0240 1500 211. .33 218, .00 88 .5 88 .5 354. .362 369, .689 0, .0206 0.0226 1520 209, .33 218, .10 88 .5 89 .0 352. .903 369, .661 0, .0169 0.0215 1540 209, .33 219, .42 88 .5 88 .5 352, ,903 369, .205 0, .0169 0.0269 1560 208, .67 218, .38 87 .5 88 .5 354. ,362 369, .575 0, .0160 0.0237 1580 209.67 217, .82 88 .5 88, .5 352, ,903 369, .746 0, .0177 0.0220 1600 210. .33 218, .30 88 .5 89, .0 354. ,362 369, .494 0. .0177 0.0222 1620 208, .67 218, .20 88 .5 89 .0 349. .987 369, .577 0, .0177 0.0219 1640 210, .67 218, .39 89.0 89 .0 352, ,903 369, .520 0, .0186 0.0224 1660 211, .33 218, .12 90 .0 89 .5 354, .362 369, .496 0, .0161 0.0204 1680 211. .67 218, .31 90 .0 89 .0 354. ,362 369, .439 0. .0180 0.0223 1700 212, .33 218, .39 89 .5 89 .5 354, .362 369, .465 0, .0209 0.0211 1720 212, .00 218, .57 89 .5 88, .5 354, ,362 369, .518 0. .0199 0.0243 1740 213, .00 216, .93 89 .5 89, .5 358, ,736 369, .018 0, .0187 0.0176 1760 216, .00 216, .15 91 .5 89, .0 358. ,736 368, .781 0, .0215 0.0171 1780 213. ,33 217. .75 91 .5 88, .0 349, .987 369, .556 0. .0219 0.0234 1800 215, .67 217, .70 93 .0 87 .0 352. ,903 369, .254 0, .0223 0.0262 1820 215, .67 217.43 93 .0 86 .0 354, ,362 369, .971 0, .0209 0.0275 1840 214, .67 216, .76 93 .5 85 .0 354, ,362 370, .281 0, .0163 0.0281 1860 216.67 215, .94 93 .5 84, .5 354. ,362 370, .374 0, .0214 0.0272 1880 215, .67 215. .38 93 .0 84, .5 358, ,736 370.491 0, ,0166 0.0256 1900 216. .67 216, ,69 93 .5 84, .0 358, ,736 370. .145 0, ,0171 0.0307 1920 216. .67 214, ,82 93 .5 84, .5 358. .736 370. .718 0. .0169 0.0238 1940 216. .33 217, ,71 94 .0 84, .0 354. ,362 369. .885 0, ,0194 0.0338 1960 215, .67 216.69 94 .0 84 .0 354, ,362 370, .090 0, .0172 0.0308 1980 215, .67 215, .67 94 .0. 84 .0 354, ,362 370, .405 0, ,0177 0.0277 2000 217. .00 216, .32 93 .5 84, .5 355. .820 370, .205 0, ,0214 0.0284 2020 217. .67 216. .60 94 .5 84, .5 355, .820 370, .119 0, ,0209 0.0292 2040 217. .67 217, ,07 95, .0 84, .5 352, ,903 369, .976 0. ,0214 0.0306 2060 216. .33 215, ,95 93, .5 84, .0 358. ,736 370, .264 0, ,0166 0.0287 2080 217. .33 211, ,38 93, .5 84, .0 358. ,736 371, ,776 0, ,0192 0.0149 2100 215. .00 215, .75 93, .0 84, .5 358. ,736 370. .431 0. .0149 0.0266 2120 215. ,33 216. .97 93, .5 83, .5 354. ,362 370, ,004 0. ,0177 0.0330 2140 215. ,67 218, .28 93 .5 84, .5 354. .362 369, .658 0, .0194 0.0342 Appendix D. DATA AND RESULTS 2160 218, .33 216, .32 93 .5 84. ,5 358.736 370, .205 0, .0214 0, .0284 2180 217 .33 215 .48 93 .5 84, .0 358, .736 370 .462 0 .0192 0, .0272 2200 215 .67 216 .89 93 .5 84, .0 354, .362 369, .978 0, .0194 0, .0315 2220 216 .00 217 .74 93 .5 84, .5 358, .736 369, .665 0 .0157 0, .0327 2240 216 .67 218 .12 93 .5 84, .0 358.736 369, .496 0, .0177 0, .0353 2260 217, .33 217, .84 93 .5 84, ,0 358, .736 369, .582 0, .0194 0, .0344 2280 217, .00 217, .55 93 .5 84. .5 357, .278 369, .722 0, .0200 0, .0321 2300 217, .33 218, .58 94 .0 84, ,5 354, ,362 369.408 0, .0223 0, .0352 2320 217, .33 218, .21 93 .5 84. ,5 358, ,736 369. .522 0, .0206 0. ,0341 2340 218 .67 219, .23 93 .5 85, .0 358, .736 369, .262 0 .0214 0.0358 2360 217 .00 218 .00 93 .5 85, .0 358, .736 369, .689 0 .0186 0, .0320 2380 217.67 217 .53 93 .5 84, .5 358, .736 369, .833 0, .0206 0, .0320 2400 215 .67 218, .19 93 .5 84, .5 354, .362 369, .632 0, .0196 0, .0340 2420 216, .67 217, .54 93 .5 84, ,5 355, .820 369, .778 0, .0200 0, ,0321 2440 216, .00 217, .92 93 .5 83. .0 355, .820 369, .663 0, .0186 0, .0373 2460 217, .00 217, .55 93 .5 83. ,0 355. .820 369, .722 0, .0214 0, ,0362 2480 214, .67 211, .77 93 .5 83. .5 355, .820 371, .552 0, .0149 0, .0175 2500 215.00 211 .86 94 .5 82, .5 352.903 371, .523 0, .0157 0, .0205 2520 216 .00 211 .02 94 .5 82, .5 355, .820 371, .781 0 .0157 0, .0180 2540 216, .33 212, .41 94 .5 82, .5 355, .820 371, .351 0 .0166 0, .0221 2560 216, .00 211, .39 94 .5 83, .0 352, .903 371, .667 0, .0180 0, .0177 2580 217, .00 213, .07 95 .0 83, .5 354, .362 371, .151 0, .0186 0, .0214 2600 216.00 212, .69 94 .5 83. .0 354, ,362 371. .266 0, .0173 0. ,0216 2620 218, .33 212, .14 95 .0 83. ,5 358. ,736 371. .438 0, .0180 0, ,0186 2640 216, .67 214. .08 94, .5 85, ,0 355, ,820 370. .892 0, .0179 0, .0203 2660 216, .33 214, .73 94 .5 85, ,0 355.820 370, .691 0 .0165 0, .0223 2680 214, .67 213, .83 95 .0 86, .5 349, .987 370, .757 0, .0158 0, .0157 2700 212, .33 213, .82 95 .0 85, ,5 344, .154 370, .813 0, .0149 0, .0183 2720 213, .33 214, .38 95 .5 85, .5 347, .070 370, .696 0, .0136 0, .0199 2740 215, .00 215, .12 96 .0 86. ,5 349, ,987 370, .466 0, .0142 0. .0195 2760 212, .33 215, .87 96 .5 88. ,0 341, ,237 370, .183 0, .0139 0. ,0177 2780 220. .33 217, .46 97 .0 88. ,5 354, .362 369. .751 0, .0223 0, ,0210 2800 216. ,00 217. .26 92, .5 87. ,5 354, .362 369, .864 0. .0229 0, .0231 2820 207, .67 215, .31 86 .5 86, .0 352, .903 370, .409 0, .0171 0, .0214 2840 209, .67 216, .05 89 .0 84, .0 352, .903 370, .235 0, .0163 0, .0289 2860 211, .33 218.47 91 .0 83, .0 352, .903 369, .546 0, .0157 0. .0389 2880 211, ,00 217, .45 92 .0 83, .0 349, .987 369, .806 0, .0139 0, .0358 2900 212, ,67 219, ,34 93 .5 83. ,5 352, .903 369. .124 0, .0123 0, ,0403 2920 212, .67 224, .23 94, .0 84, .0 349, .987 367, ,746 0. .0129 0, .0536 2940 214. ,67 222. .51 95, .0 84. ,5 349, .987 368. .370 0, ,0157 0, ,0469 2960 217, ,67 222. .33 95, .5 85. ,0 349. .987 368. ,373 0. ,0229 0. .0451 2980 214. .33 222, .79 91, .5 85, .0 347, .070 368, .285 0, .0280 0. .0464 Appendix D. DATA AND RESULTS 184 RUN 6, 4-VINYL-l-CYCLOHEXENE INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU qHWP 2.565 2.454 198.00 198.00 82.0 78.0 297.49 294.77 AVERAGE CONDITIONS: TBPFRU TBHWP QPFRU QHWP VFP REP VFH REH 84.00 82.00 298.86 293.81 0.81 9760 0.04 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 205, .0 195 .5 81, .5 78 .0 320.821 293, .158 -0, .0050 -0, .0090 20 204, .3 196 .3 80, .0 79 .0 320.821 295, .268 -0, ,0024 -0, .0096 40 206, .3 197 .8 81, .0 79 .0 326.654 295, .154 -0, .0062 -0, .0044 60 215. .0 199 .0 87, .0 78 .0 320.821 294, .474 0, .0091 0, .0030 80 221. ,0 201 .4 89, .0 78 .5 326.654 294, .070 0. .0142 0, .0092 100 220. ,3 202 .9 90. .5 78 .5 320.821 293, .466 0. .0148 0, .0143 120 220. ,7 203 .4 93, ,0 79 .0 323.738 293, .591 0. .0044 0, .0144 140 208. ,3 201 .9 80, .0 79 .5 326.654 294, .195 0. .0029 0, .0077 160 216. ,0 202 .2 78, .0 80 .5 326.654 294, .270 0, ,0325 0 .0053 180 219, .7 212 .1 79, .0 86 .5 326.654 292, .263 0, .0407 0, .0184 200 222, .0 209 .7 80, .0 85 .5 326.654 293, .156 0, ,0448 0.0138 220 219. .3 207 .1 80, .5 84 .0 320.821 293, .976 0. .0428 0, .0100 240 219. .3 207 .1 81, .5 84 .5 320.821 293, .976 0, .0397 0, .0083 260 215. .7 209 .1 78. .0 85 .5 320.821 293.496 0. .0392 0, .0118 280 220. ,0 208 .9 81, .5 86 .5 320.821 293, .935 0, ,0418 0, .0078 300 221. ,0 208 .5 82, .0 83 .5 323.738 293. .835 0. ,0394 0, .0166 320 222. ,0 209 .4 82, ,0 86 .0 323.738 293. ,570 0, ,0425 0, .0112 340 223, .7 209 .5 83, .0 86 .0 326.654 293, .595 0, ,0407 0.0116 360 227. .0 210 .3 85, .5 83 .5 326.654 293, .281 0, ,0433 0, .0224 380 229, .7 213 .5 86, .0 82 .0 326.654 292 .585 0, ,0499 0, .0384 400 231, .0 212 .3 86, .0 80 .5 320.821 292, .801 0, .0620 0, .0396 420 235, .3 212 .3 87, .0 79 .0 320.821 292, .801 0. ,0724 0, .0447 440 240. .7 210 .5 82, .5 79 .5 329.571 293, .330 0. ,0900 0, .0367 460 239, .3 213 .2 83, .0 80 .0 320.821 293, .000 0. ,0974 0, .0442 480 239, ,0 215 .9 82, ,5 81 .5 323.738 292. .205 0. ,0935 0, .0485 500 239, .3 214.0 82, .0 80 .0 320.821 292, .710 0, .1005 0, .0470 520 241, .7 214 .1 82, .0 82 .0 326.654 292 .734 0, .0989 0, .0405 540 241, .3 215 .0 82, .5 83 .0 320.821 292, .470 0, .1052 0, .0403 560 243, .3 216 .9 81, .0 83 .5 326.654 291, .940 0, .1070 0, .0449 580 243, .0 213 .0 80, .0 83 .0 323.738 292, .950 0, ,1136 0, .0333 600 243, .3 214 .3 80. .0 84 .0 326.654 292. .296 0. ,1101 0, .0344 620 242. .7 216 .3 80. .0 83 .0 323.738 291, .816 0, ,1125 0. .0448 640 246, ,0 217 .0 80. ,5 83 .5 326.654 291, ,964 0. ,1167 0, .0453 660 247, ,3 217 .2 81. ,0 84 .0 326.654 292, .014 0. .1193 0. .0443 680 247. .7 221 .5 81, .0 84 .5 326.654 291, .078 0, ,1203 0, .0571 700 247, .0 220 .3 81, .0 84 .0 326.654 291, .294 0, ,1183 0, .0549 720 245. .7 216 .2 81, .5 83 .5 323.738 292. .254 0, ,1172 0, .0425 740 248, .3 216 .3 82, ,0 83 .0 326.654 292. .279 0, ,1193 0, .0445 760 246. ,0 222 .5 81, ,0 83 .0 323.738 290. ,838 0. ,1197 0, .0657 780 245. ,7 224 .7 82, ,0 83 .5 320.821 290, ,382 0, ,1202 0, ,0715 800 247, .0 226 .9 82, ,0 84 .0 323.738 289, ,927 0. ,1197 0, ,0773 820 249. ,7 227 .0 82. .5 84 .5 328.113 289, ,951 0, ,1196 0. ,0760 Appendix D. DATA AND RESULTS 840 247 .0 229 .3 83 .0 85, .0 320, .821 289, .495 0, ,1213 0, .0818 860 248, .3 228 .1 83, .5 84, .0 323, .738 289, .711 0, .1192 0, .0813 880 247, .3 228 .1 84, .0 83, .0 320, .821 289, .711 0, ,1192 0. .0847 900 248, .7 229 .4 85, .5 83, .5 320.821 289, .520 0, ,1187 0, .0873 920 250, .7 226 .1 87, .0 83, .0 320, .821 290, .216 0, .1202 0. .0779 940 251, .7 227 .1 88, .0 82, ,5 320. ,821 289. .976 0, .1202 0, ,0831 960 252, .7 229 .1 89, .0 82, ,0 320. ,821 289. .471 0. .1202 0, ,0916 980 253. .0 232 .4 89, .5 81, ,5 320, ,821 288. ,774 0. .1197 0. .1045 1000 254, .3 225 .0 90, .5 81, .0 320, .821 290, .456 0, .1207 0, .0811 1020 255, .0 231 .5 92, .0 79, .5 317, .905 289, .039 0, ,1228 0, .1080 1040 258, .3 227 .3 93, .0 80, .5 320. .821 290, .000 0, ,1254 0, .0903 1060 255, .7 231 .3 91, .0 82, .5 317, .905 289, .962 0, .1281 0. .0973 1080 253, .7 235 .7 88, .0 82, ,5 317. ,905 289, .024 0, ,1312 0. .1120 1100 243, .7 230 .6 76, .5 81, .0 320. .821 290. .276 0, .1311 0, .0999 1120 243, .7 235 .6 77, .0 78, ,5 320. ,821 288. .999 c. .1296 0. ,1252 1140 242, .3 229 .3 78, .0 78, .0 320, .821 290, .468 0. .1223 0, .1057 1160 246, .0 230 .1 79, .0 77, .0 320, .821 290, .178 0, .1306 0, .1120 1180 245, .3 228 .9 79, .5 78, .0 320, .821 291, .343 0. .1270 0, .1044 1200 244, .3 236 .2 79, .5 79, .5 320. .821 289, .631 0, .1239 0, .1241 1220 242, .3 234 .0 80, .0 80, .0 316.446 290. .089 0, .1231 0, .1148 1240 243, .7 232 .8 80, .0 80. .0 317. .905 290. .305 0, .1249 0. ,1109 1260 251. .7 232 .2 80, .0 80. .5 320. ,821 290. .645 0. .1452 0. ,1070 1280 247, .0 232 .5 80, .5 81, .0 317.905 290, .718 0, .1338 0, .1064 1300 247, .3 230 .5 81, .0 80, .0 320, .821 291, .225 0, .1285 0, .1030 1320 247, .0 230 .1 82, .0 81, .0 317, .905 291, .126 0, ,1291 0, .0982 1340 249, .0 234 .3 83, .0 81, .0 320, .821 290, .163 0. .1275 0, .1125 1360 250, .7 235 .8 83, .0 81, .0 320. .821 290, .020 0, ,1327 0, ,1176 1380 249, .0 235 .9 83, .0 81. .5 320. .821 290. .044 0, ,1275 0, .1163 1400 252. .0 234 .6 84, .0 82, ,0 320. .821 290. ,236 0. .1337 0. ,1103 1420 247, .0 235 .6 83, .0 82. ,0 317. ,905 289. ,970 0. .1260 0. .1135 1440 251, .3 235 .8 85, .0 82, .5 320, .821 290, .020 0. .1285 0, .1125 1460 252, .7 236 .9 86, .5 83, .0 320, .821 289, .778 0, ,1280 0, .1145 1480 254, .7 237 .0 87, .0 83, .0 320. .821 289, .803 0. ,1327 0, .1148 1500 253, .0 237 .1 88, .0 83. .0 320, ,821 289, .827 0. .1244 0, .1152 1520 255. .3 236 .9 88, .0 82. .0 323. .738 289, .778 0, ,1270 0. .1178 1540 261, .3 236 .4 89, .0 82, ,5 326. ,654 290. ,142 0, .1376 0, .1144 1560 260. .7 234 .4 90, .0 82, ,0 320. ,821 290. ,187 0, .1420 0. .1095 1580 259, .3 235 .0 86, .0 82, .5 323.738 290, .310 0, .1455 0, .1097 1600 251, .3 234 .5 80, .0 83, .0 320, .821 289, .240 0, ,1441 0, .1064 1620 249, .0 234 .6 79, .0 83, .5 320, .821 289, .264 0, ,1400 0, ,1050 1640 250. .7 235 .8 79, .0 83, .0 323. ,738 289, ,048 0, .1403 0. .1107 1660 250. .0 235 .6 79, .0 83. ,0 323, ,738 288. .999 0, .1383 0. .1100 1680 248. .7 234 .9 79. .5 83, ,0 323. ,738 289. .338 0. .1326 0, .1078 1700 247, .3 235 .0 80. .0 83, .5 320, ,821 289. ,362 0. ,1317 0. .1065 1720 246, ,7 236 .8 80. ,0 84, ,0 320. ,821 288. .807 0. .1296 0, .1109 1740 244, .3 236 .8 80, .0 84, .0 317, .905 288, .807 0. ,1270 0, .1109 1760 246, .7 237 .5 80, .5 84. .5 320, .821 288, .954 0, .1280 0, .1115 1780 244. .7 236 .5 80, .0 84, ,0 323. .738 289, .219 0, .1187 0, .1099 1800 247. .7 237 .7 81, .0 83, .5 323, ,738 289, .003 0. .1249 0, .1156 1820 250, .7 237 .7 81, .5 83, ,5 326, ,654 289. .003 0. .1280 0. ,1156 1840 252, ,7 237 .8 82, .0 84, .0 328, ,113 289, ,027 0. ,1302 0. .1143 1860 248, ,7 237 .9 81, ,5 84. .0 323, ,738 289, ,052 0. ,1264 0. ,1146 1880 247, .3 238 .1 81, .5 84. .5 326, .654 289, .101 0, ,1177 0, .1137 1900 249, .7 237 .3 80, .5 85, .0 326, .654 289, ,391 0, .1280 0, .1091 1920 253. .7 237 .8 80, .0 85, .5 328, .113 289, .027 0. ,1394 0. .1092 1940 252, ,7 238 .0 80, .0 86, .0 328, .113 289, .076 0. ,1363 0, .1082 1960 249. .7 238 .5 80. ,0 86, .5 326, .654 289. .174 0. ,1295 0, .1080 1980 252, ,3 237 .4 81, .5 86. .0 328. .113 289. .415 0. ,1307 0. ,1061 2000 251, .7 237 .5 82, ,5 86. ,0 326. ,654 289.439 0. ,1280 0, .1064 2020 256, .7 239 .4 85.0 86, .5 328, .113 288.909 0. .1333 0, .1112 2040 257, .0 239 .6 85, .0 86, ,0 328, .113 288, .958 0. ,1343 0, ,1137 2060 251, .3 239 .8 85, .0 86. .0 320. .821 289, .467 0. ,1285 0, .1141 2080 251, ,0 240 .2 84, ,0 86. ,5 320. .821 289. .565 0. ,1306 0. .1139 2100 251, .7 239, .2 83, ,0 87. ,0 323. ,738 289. .831 0. ,1311 0. .1089 2120 255. ,0 240, .1 86, ,0 87. ,5 323. ,738 289. ,541 0. ,1321 0. ,1101 2140 250. ,0 243, .1 83. .0 87. ,0 320. ,821 288. ,768 0. ,1306 0. ,1220 2160 251. ,7 240, .1 83. ,0 86. ,5 320. ,821 289. ,541 0. 1358 0. ,1135 Appendix D. DATA AND RESULTS 2180 251 .0 242 .5 83 .0 86 .5 320 .821 289 .107 0, ,1337 0, .1215 2200 251 .0 240 .3 82.0 86 .0 320 .821 289, .590 0. .1368 0, .1159 2220 251 .0 242, .6 81.0 86 .0 320 .821 289, .131 0, ,1400 0, .1236 2240 257 .7 239 .2 81 .0 85 .5 328 .113 289, .831 0, .1485 0, .1140 2260 256 .7 243 .4 81 .0 85 .0 328 .113 288, .841 0, .1455 0, .1299 2280 259, .3 242 .2 82, .0 85 .0 326 .654 289, .058 0, ,1530 0, .1259 2300 261, .7 241, .5 82, .0 85, .5 328 .113 289, .373 0, ,1577 0, .1216 2320 252, .7 240, .4 78 .0 85, .0 323 .738 289, .614 0, ,1496 0. .1197 2340 252 .0 242, .6 78, .0 84, .5 323, .738 289, .131 0, ,1475 0, .1287 2360 252, .3 242, .6 81, .0 84, .0 320 .821 289, .131 0, ,1441 0, .1304 2380 253, .0 242, .7 81, .0 84, .0 320, .821 289, .156 0, .1462 0. .1307 2400 252, .7 241, .7 81, .5 84, .0 323, .738 289, .422 0, .1388 0. ,1275 2420 255, .7 241, .6 83, .0 84, .5 323, .738 289, .397 0. ,1434 0, .1254 2440 254, .3 238, .4 83, .0 84, .5 320, .821 290, .121 0. .1441 0. .1145 2460 254, .7 240, .6 83, .5 85, .0 320, .821 289, .663 0. ,1436 0, ,1204 2480 254, .0 240, .6 84, .0 85, .5 320, .821 289, .663 0. .1400 0, .1187 2500 257, .7 241, .6 84, .0 86, .0 320, .821 289. .397 0. .1514 0. .1203 2520 252. .0 240, .6 84, .0 86, .0 317, .905 289, .663 0. ,1385 0, .1170 2540 259, .3 242, .5 85, .0 85, .5 320, .821 289, ,107 0. ,1535 0, .1249 2560 256. .0 241, .0 85, .0 85, .0 317, .905 289. ,736 0. ,1480 0, .1215 2580 264, .0 241. .1 87, .0 84.0 323, .738 289, .761 0. .1568 0, ,1253 2600 255. .3 241, .6 83, .5 84. .0 317. .905 289, ,883 0. ,1506 0. ,1271 2620 257, .3 241, .5 82, .0 84. .0 323, .738 289, .858 0. ,1517 0. ,1268 2640 255, .3 241, .3 82, .0 83, .5 323, .738 289, ,810 0. ,1455 0. ,1277 2660 255, .3 241, .5 83, .5 83, ,0 320, .821 289, ,858 0. ,1457 0, .1302 2680 253. .0 240, .3 84, .0 83, .0 317. .905 290. .076 0. ,1417 0. ,1262 2700 257. .3 240, .3 85, ,0 83, .5 320, .821 290. .076 0. ,1472 0. ,1245 2720 254. .7 241, .4 85, ,0 82, ,0 317. .905 289, .834 0. ,1438 0. ,1332 2740 257. ,0 241, ,3 85, .0 82, .0 320, .821 289. .810 0. ,1462 0. ,1328 2760 258, .3 241, .4 86, .0 82, ,5 320, .821 289. .834 0. ,1472 0. ,1315 2780 257, ,3 240. ,3 86, .0 83, .0 317. ,905 290. ,076 0. 1490 0. ,1262 2800 259. .3 243. .2 86, .5 83. ,0 317, .905 289. .278 0. ,1537 0. ,1360 2820 262. .0 244. .3 86. .5 83. .5 320, .821 289. ,036 0. 1571 0. ,1379 2840 260. .3 244. .4 86. ,5 84. .0 320. .821 289. ,061 0. 1519 0. 1366 Appendix D. DATA AND RESULTS 187 RUN 7, DICYCLOPENTADIENE WITH INHIBITOR INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU QHWP 2.521 2.497 198.00 198.54 80.0 79.0 297.49 298.43 AVERAGE CONDITIONS: TBPFRU TBHWP 80.00 81.00 TIME PTEMP 0 198, ,3 20 199, .0 40 200. ,0 60 201, .0 80 201, .3 100 201, .3 120 201, .7 140 202, .3 160 202. .3 180 202. .0 200 202, .0 220 202, .3 240 202, .7 260 202, .7 280 201, .3 300 201. .0 320 201, .0 340 201. .0 360 201, .0 380 201, .0 400 201, .0 420 200, .7 440 200, .7 460 200, .7 480 201, ,0 500 199, .0 520 201, .7 540 200, .7 560 202. .7 580 202. .3 600 202. .7 620 202, ,0 640 202, .3 660 202, .3 680 202. .3 700 203, .0 720 203, ,3 740 204, ,0 760 198. .3 780 198. ,0 QPFRU QHW 293.61 296 HTEMP PTB HTB 198.5 81.5 79.0 200.1 81.5 79.0 202.5 81.5 79.5 203.2 81.5 80.0 204.2 79.0 80.0 204.6 78.5 81.0 205.4 78.5 80.0 205.6 81.0 80.0 205.9 81.0 80.0 206.5 80.0 79.0 206.2 81.0 79.0 206.5 81.0 79.5 206.1 81.5 79.0 206.6 81.0 78.0 206.6 80.0 78.0 206.8 80.0 78.0 206.7 79.5 78.0 207.0 80.0 78.0 206.9 79.0 79.5 207.1 80.5 79.0 207.1 80.0 79.0 207.1 78.0 80.0 207.3 78.0 81.0 206.9 78.0 80.0 207.5 76.5 81.0 207.8 77.0 81.0 207.4 77.5 81.5 207.9 78.5 82.0 207.8 79.5 82.0 207.7 80.5 81.0 207.7 81.5 81.0 207.9 82.0 81.0 207.8 82.5 80.5 207.9 82.5 80.0 207.8 83.5 80.5 207.5 84.5 80.5 207.9 82.0 80.0 208.1 82.0 80.0 208.0 78.0 80.0 208.1 78.0 79.0 P VFP REP .21 0.81 9760 PHF HHF 286. .989 299, .385 288. .156 298, .972 290. ,197 298, .348 297, .780 298 .167 297, .489 297 .784 297. .489 297 .714 297, .489 297.482 282, ,031 297, .452 282. ,323 297, .291 284. ,656 297, .190 283.489 297, .301 284, .656 297, .260 284. .948 297, .351 284. .656 297, .934 286. .989 297, .713 286. ,698 297, .682 289. .031 297, .662 286. .114 297, .552 288, .447 297, .531 287, .864 297, .451 289, .031 297, .401 293. .697 297.451 292, .531 297, .391 293, .697 297, .481 297. ,489 297, .380 295, .156 297, .270 297, .780 297, .411 294. .864 297, .290 297. .489 297, .320 294. ,572 297, .300 292. ,531 297, .229 290. ,197 297, .169 289, .322 297, .149 289, .322 297, .219 286, ,698 297, .199 284, ,948 297, .139 293, ,114 297, .099 294. ,572 296, .968 290. .489 296. .998 286. .698 296. .968 VFH REH 0.04 4.9 PFR HFR 0. ,0075 0, ,0001 0. ,0082 0, .0052 0. ,0088 0, ,0117 0, .0017 0, ,0125 0. .0117 0, .0156 0. .0133 0, .0138 0. ,0145 0. .0199 0. ,0306 0, .0203 0. ,0302 0, ,0214 0. .0290 0. .0268 0. .0273 0, .0258 0. .0267 0, ,0252 0. ,0257 0, ,0256 0. ,0278 0, ,0304 0. ,0232 0, ,0307 0. .0225 0, ,0311 0. ,0208 0, ,0308 0. .0233 0, .0318 0. .0234 0, .0265 0, .0190 0, .0287 0, .0191 0, .0289 0, ,0181 0, .0254 0, ,0198 0, ,0229 0, ,0181 0, ,0249 0. .0189 0, ,0236 0, ,0138 0, .0246 0, ,0174 0, ,0215 0, ,0147 0. .0215 0, ,0145 0, ,0211 0, .0140 0. ,0241 0. ,0146 0. .0240 0. ,0139 0, ,0249 0. .0146 0, .0262 0, ,0146 0, .0281 0. ,0149 0, ,0261 0. ,0163 0, .0253 0, ,0144 0, ,0281 0, .0146 0, .0288 0. ,0147 0. ,0284 0, ,0190 0. ,0321 Appendix D. DATA AND RESULTS 800 202, .0 207 .8 78 .0 79 .0 293, ,114 297. .029 0, ,0235 0, .0313 820 199, .7 207 .8 78 .0 78 .0 286. .698 297, ,029 0, ,0248 0. .0346 840 200, .7 207 .7 74 .5 78 .0 297. ,489 297. .059 0. .0245 0. ,0342 860 201, .0 208 .0 77 .0 78 .0 298. ,655 297. ,018 0, ,0156 0. ,0353 880 201, .3 208 .3 77 .5 79 .0 296, .614 296, .908 0. .0179 0, .0330 900 201, .3 208 .3 78 .5 79 .0 295, .156 296, .908 0, ,0166 0, ,0330 920 201, .7 208 . 5 78 .5 79 .0 296, .322 296, .877 0. ,0161 0, .0334 940 201, .7 208 .4 79 .0 79 .0 294, .864 296. .928 0, ,0164 0, .0333 960 203, .0 208 .3 80 .5 78 .5 295, .156 296, .958 0, ,0155 0, .0345 980 203, .0 208 .4 82 .0 78 .5 291. .364 296. .928 0, ,0157 0, .0349 1000 204, .0 208 .6 83 .0 78 .5 291. .364 296. .847 0, ,0157 0, .0355 1020 201, .7 208 .6 82 .5 78 .5 287, .864 296. ,797 0, ,0144 0, .0356 1040 202, .3 208 .6 82 .5 78 .0 287. .864 296. ,797 0. .0167 0, .0373 1060 202, .7 208 .7 83 .0 78 .0 285. .531 296. ,747 0. ,0195 0. .0375 1080 203 .0 208 .6 83 .0 78 .0 285, .531 296, .847 0, .0207 0, .0372 1100 202, .7 208 .6 84 .0 78 .0 273, .573 296, .847 0, .0342 0, .0372 1120 204, .3 208 .4 83 .5 78 .5 285, .531 296, .807 0. .0236 0, .0349 1140 205, .3 208 .5 86 .0 79 .0 285, .531 296, .827 0. .0184 0, .0335 1160 206, .0 208 .8 82 .0 79 .0 296, .905 296, .717 0. .0181 0, .0345 1180 203, .7 208 .9 79 .5 79 .5 293, .989 296.687 0. .0228 0, .0333 1200 203, .0 208 .8 79 .5 79 .0 286, .698 296, .767 0, .0312 0, .0344 1220 202, .3 208 .9 79 .5 79 .0 289. .614 296, .737 0, ,0246 0, .0348 1240 203, .0 208 .9 79 .5 80 .0 297. .489 296. .687 0. ,0156 0, .0316 1260 204, .0 209 .0 80 .5 80 .0 297, .489 298. .516 0, .0156 0, .0318 1280 204 .0 208 .9 80 .5 80 .0 297, .489 298, .546 0. .0156 0 .0314 1300 204 .0 209 .1 80 .5 80 .0 295, .739 298, .536 0, .0180 0, .0321 1320 204, .7 208 .9 80 .5 80 .0 296, .614 298, .616 0. .0190 0, .0315 1340 205, .0 209 .0 80 .5 80 .0 296, .905 298, .586 0. .0198 0, .0320 1360 204, .7 208 .8 80 .0 80 .5 297, .197 298, .647 0. .0199 0, .0294 1380 205, .3 208 .9 80 .5 80 .0 298, .364 298, .616 0. .0188 0, .0315 1400 205, .0 208 .9 80 .5 80 .0 294, .572 298, .667 0. .0231 0, .0314 1420 204, .7 208 .9 79 .0 80 .0 293, .989 298, .616 0. ,0279 0, .0315 1440 204, .7 208 .7 77 .5 79 .5 296. .905 298. ,677 0. .0287 0, .0324 1460 203, .3 209 .2 76 .5 79 .5 296, .614 298.556 0, .0280 0 .0341 1480 204, .7 209 .2 77 .5 79 .5 299, .822 298, .576 0, .0246 0, .0343 1500 205, .7 209 .0 79 .5 79 .0 298, .947 298, .637 0. .0225 0, .0352 1520 206, .0 209 .1 80 .5 79 .0 298, .072 298, .606 0. .0215 0, .0356 1540 205, .7 209 .2 80 .5 79 .0 295, .447 298, .556 0, .0241 0, .0357 1560 207, .0 209 .2 81 .0 79 .0 298, .072 298, .576 0. ,0231 0, .0360 1580 207, .3 201 .6 81 .5 79 .0 296. .031 300. .425 0, .0255 0, .0103 1600 208, .0 209, .2 81 .5 79 .0 330. .154 298. .506 -0. ,0164 0. .0359 1620 209, .0 209, .5 83 .0 79 .5 299, .822 298. ,465 0, ,0207 0. .0353 1640 209. .0 209, .5 84 .0 79 .5 296. .905 298. ,465 0. ,0214 0. .0353 1660 209, .7 209 .5 84 .5 79 .5 297.780 298, .395 0, .0208 0, .0352 1680 210, .0 209 .6 85 .0 79 .5 299, .239 298, .364 0. .0182 0, .0356 1700 207, .7 209 .7 84 .5 80 .0 293, .697 298, .384 0, .0198 0, .0342 1720 208, .3 209 .6 83 .5 80 .0 297, .489 298, .485 0. .0201 0, .0339 1740 209, .3 209 .8 84 .0 80 .0 297. .780 297. .680 0, ,0213 0, .0345 1760 209, .7 209 .9 84 .5 81 .0 297, .780 297. .288 0. ,0208 0, .0316 1780 210. .0 209, .9 85 .0 81 .0 298. ,072 298. .253 0, ,0198 0. .0316 1800 210, .3 210, .7 85 .5 82 .0 296. ,614 297. ,830 0. ,0213 0. .0308 1820 210. .7 210, .3 85 .5 81 .0 297. .489 298.404 0. ,0212 0. ,0328 1840 210, .7 210, .3 85 .5 81 .5 296. ,614 298. .474 0. .0224 0. .0313 1860 211, .0 210 .3 85 .5 81 .0 296, .905 298, .354 0. .0231 0, .0330 1880 211, .3 210 .3 85 .5 81.0 296. .031 298, .333 0. .0255 0. .0327 1900 211, .7 210 .3 85 .5 81 .0 296. .031 298. .354 0, ,0266 0. .0330 1920 211, .7 210 .5 85 .5 81 .0 296. .031 298, ,323 0, ,0266 0. ,0334 1940 212. .3 210, .3 85 .5 80 .0 296. .031 298. .404 0. ,0289 0. .0362 1960 213. .0 210, .6 85 .5 80 .0 298. ,655 298, ,243 0. .0273 0. ,0373 1980 213. .3 210, .6 86 .0 80 .0 298. ,655 298, ,243 0. ,0268 0, ,0373 2000 213. .7 210, .9 86 .5 79 .0 298, ,947 298, .182 0. .0258 0, .0415 2020 214. .3 210, .9 87 .5 79 .5 298. .655 298, .182 0. ,0251 0, ,0399 2040 215. .0 212, .2 88 .0 79, .0 298, ,655 297. ,879 0. ,0257 0. ,0458 2060 215. .0 212, .2 88 .5 78 .0 296. .905 297, .829 0. .0265 0, ,0493 2080 215. .7 212, .6 89 .0 78 .0 296. .322 297, ,808 0. .0279 0, .0507 2100 216. .7 212, .6 89 .5 78 .0 296. ,614 297, .808 0. ,0292 0, ,0507 2120 217. ,0 212, .8 89 .5 78 .5 300. ,697 297. ,727 0. .0244 0, .0496 Appendix D. DATA AND RESULTS 2140 215. .7 212 .8 89 .5 78 .5 291, .656 297, .778 0, .0330 0. ,0495 2160 217. ,7 212 .9 89 .0 78 .5 294, .572 297, .697 0. ,0372 0. .0500 2180 218. .0 212 .8 88.0 79 .0 297 .489 297, .727 0, .0374 0, .0479 2200 218, .0 213 .0 88 .0 79 .0 292, .531 297, .647 0, .0448 0. .0485 2220 219, .7 213 .0 87 .5 79 .0 294, .864 297, .596 0, .0487 0, .0487 2240 221, .3 213 .7 88 .0 79 .0 296, .031 297, .395 0, .0508 0, .0509 2260 222, .0 213 .8 88 .0 78 .0 291, .656 297, .364 0, .0599 0. .0547 2280 223, .7 214 .2 88 .0 78 .5 298, .655 297, .324 0, ,0547 0. .0542 2300 224, .7 214 .7 88 .5 78 .5 295, .156 297, .202 0. ,0618 0, ,0559 2320 225. .7 214 .9 88 .5 78 .0 288, ,739 297, .142 0. .0755 0, .0584 2340 227. .3 215 .0 86 .0 78 .0 291. ,947 297. .162 0. ,0845 0, ,0587 2360 230, .0 215 .1 86 .0 78 .5 293, .989 297, .182 0, .0902 0, .0573 2380 231, .7 215 .5 86 .0 78 .5 301, .280 297, .091 0, .0839 0, .0586 2400 236, .3 216 .0 86 .5 79 .0 282, .614 296, .970 0, .1306 0, .0586 2420 246, .3 216 .4 87 .0 79 .0 318, .488 296, .828 0, .1007 0. .0601 2440 240, .0 216 .6 87 .5 79 .0 298, .072 296, .798 0, .1121 0. .0605 2460 238, ,3 216 .6 88 .0 79 .0 291, .072 296, .748 0, .1169 0. .0606 2480 240. .3 216 .8 88 .0 79 .0 292, .531 296, .738 0. .1212 0. .0614 2500 239. ,7 217 .2 88 .5 80 .0 293, .989 296, .647 0, .1146 0. .0593 2520 238. .7 218 .0 88 .5 80 .0 288. .156 296, .465 0. .1216 0. ,0619 2540 242, .3 218 .0 88 .5 80 .0 296 .031 296, .465 0, .1201 0, .0619 2560 242, .7 218 .5 88 .5 80 .5 295, .447 296, .344 0, .1222 0, .0619 2580 247, .3 218 .4 89 .0 80 .5 318, .780 296, .374 0, .0971 0, .0615 2600 244, .7 218 .6 89 .5 81 .0 312, .947 296, .313 0, .0963 0, .0607 2620 242, .7 218 .7 88 .0 81 .0 308, .280 296, .283 0, .1021 0, .0611 2640 241, .7 218 .8 88 .0 81 .0 311, .488 296, .303 0, .0938 0. .0614 2660 239. .7 220 .0 88 .0 81 .0 304, .780 296, .030 0, .0981 0. .0653 2680 240. ,0 220 .4 86 .5 81 .5 309, ,155 295.769 0, .0969 0, .0651 2700 238. .7 220 .5 86 .0 81 .5 309. ,738 295. .789 0. .0933 0. ,0653 2720 238, .7 220 .8 84 .0 81 .5 312, .655 295, .748 0, .0951 0, .0665 2740 236, .7 226 .2 84 .5 81 .5 303, .322 294, .505 0, .1021 0, .0843 2760 233, .3 227 .2 82 .5 82 .0 296, .614 294, .213 0, .1089 0, .0863 2780 233, .3 229 .6 82 .0 82 .0 293, .697 293, .717 0, .1157 0, .0940 2800 235. .7 229 .8 83 .0 82 .0 297, .197 293, .707 0, .1141 0. .0947 2820 236. .3 231 .1 83 .0 82 .0 298, .655 293. .354 0, .1138 0. .0993 2840 236, .7 231 .5 84 .0 82 .0 297. ,489 293. .313 0, ,1136 0, ,1004 2860 236. ,7 232 .3 84 .0 81 .5 297. ,197 293. .151 0. ,1141 0. ,1050 2880 237, ,3 233 .3 84 .5 81 .5 300, .989 292. .888 0. ,1082 0, ,1083 2900 234, .7 235 .6 84 .0 81 .5 295, .739 292, .273 0, .1099 0, ,1161 2920 235, .0 237 .0 83 .0 81 .5 294, .281 292, .040 0, .1169 0, .1207 2940 237, .7 237 .4 84 .0 82 .0 297, .489 292, .019 0, .1170 0, ,1205 2960 238, ,0 237 .6 84 .0 82 .0 300, .989 291, .938 0, .1121 0, .1211 Appendix D. DATA AND RESULTS 190 ROT 8, INDENE AT HIGH HEAT FLUX INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP 2.542 2.578 198.00 198.54 81.0 83.0 QPFRU QHWP 297.48 297.87 AVERAGE CONDITIONS: TBPFRU TBHWP QPFRU QHWP VFP REP VFH REH 81.08 79.45 299.24 295.32 0.81 9762 0.04 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 203, .33 193, .60 87 .5 79, .0 297.489 294, .306 -0. ,0034 0, .0015 20 203. .67 192, .67 88 .0 79, .0 302, .155 294, .536 -0, ,0100 -0, ,0020 40 202. .33 193. .30 84 .0 79, .5 303, .322 294, ,386 -0, ,0027 -0, .0013 60 205. .33 193. .31 87 .5 80, .0 302, .739 294, .388 -0, ,0036 -0. .0030 80 208, .33 193, .54 92 .0 80 .0 300 .989 294. .343 -0, .0063 -0, .0022 100 205, .33 194, .18 86 .0 81 .0 301, .572 294, .195 0, .0029 -0. ,0032 120 206, .67 194, .29 79 .0 80, .0 305 .655 294, .170 0, .0249 0, .0006 140 206, .67 194, .42 78 .5 80, .0 296 .322 294, .153 0, .0397 0, .0011 160 206, .67 194, .51 80 .0 80, .0 296, .322 294, .123 0, .0346 0, .0014 180 206, .67 194. .52 80 .5 79, .0 295, .739 294, .125 0, .0338 0, .0049 200 205. ,67 199. ,19 81 .0 79, .0 296, .031 293, .027 0, .0283 0. .0223 220 207. .00 199. .63 82 .0 79, .5 303, .322 292, .929 0, .0193 0, .0222 240 207, .33 201, .33 83 .0 79 .0 307 .988 292, .529 0 .0109 0, .0303 260 205, .00 200, .68 83 .0 78, .0 296 .322 292, .677 0, .0189 0, .0313 280 206, .00 200, .68 84 .0 78, .0 293 .989 292, .677 0, .0222 0, .0313 300 209. .00 200, .99 85 .5 78, .0 297, .489 292, .599 0, .0223 0, .0324 320 214. .00 201. .11 84 .0 78, .0 298, .947 292, .576 0, .0420 0, .0329 340 216, ,33 201. .33 83 .0 78, .0 299, .822 292, .529 0, .0519 0, .0337 360 220. ,00 201. .54 82 .0 79, .5 300, .989 292. .479 0, .0657 0. .0294 380 221, .00 201, .77 82 .0 79 .0 303 .322 292, .431 0, .0654 0, .0319 400 221, .00 201, .88 83 .0 79, .0 300 .989 292.408 0, .0657 0, .0324 420 223. .00 201, .89 81 .0 80, .0 302, .155 292, .411 0, .0771 0, .0290 440 224, .33 202. .93 83 .0 81, .0 300, .989 293, .104 0, .0767 0, .0281 460 231. ,00 203, .57 83 .5 80, .0 305, .655 292, .954 0, .0898 0, .0339 480 234, .33 208. ,32 84 .0 81, .0 306, .238 291. .859 0. .0981 0. ,0484 500 238, ,00 206, ,08 84 .0 81, ,0 310, .322 292. .387 0. .1034 0. .0399 520 241, .00 205, .74 85 .0 81, .5 296, .322 292, .460 0, .1336 0, .0369 540 245, .67 207. .15 85 .5 82, .0 296, .905 292, .137 0, .1466 0, .0405 560 248, .33 206, .92 86 .5 82, .0 298, .655 292, .184 0, .1491 0. .0397 580 252, ,33 206, .29 87 .0 81, .0 293, .989 292, .337 0, .1696 0. .0407 600 257, ,00 206, .30 87 .0 81, .0 298, .655 292. ,340 0, .1764 0, .0407 620 270, ,33 207. ,60 86, .0 81, .0 297, .489 292, .041 0, .2268 0, .0456 640 277, ,33 207, ,76 85, .0 80, .5 305, .655 292. ,479 0. .2364 0, ,0472 660 287. .33 207. .91 82 .0 80, .0 306, .238 292, .917 0, .2777 0, .0488 680 302, .33 208, .00 81 .5 80, .5 305, .655 292, .887 0, .3297 0, .0474 700 303. .67 208. ,05 80 .0 80, .5 299, .822 293, .350 0, .3532 0, .0469 720 307, .67 208. .27 80 .0 80, .0 299, .822 293, .302 0, .3665 0. .0494 740 307, ,33 207, .95 79, .0 80, .0 300, .989 293. .378 0. .3658 0, .0482 Appendix D. DATA AND RESULTS 760 308. .00 210.21 79, .0 80 .0 300, .989 292, .850 0, .3680 0, .0567 780 315. .33 217.52 80, .0 79 .0 296. .322 291, .631 0, .4014 0, .0871 800 322. ,00 219.08 80, .0 79 .0 297. .489 291, .286 0, .4207 0, .0930 820 331. .00 221.39 81, .0 78 .0 298. .072 291, .213 0, .4459 0, .1045 840 328. ,00 223.97 81, .0 78, .0 296. .322 290, ,648 0, .4407 0, .1143 860 337. ,00 228.73 81, .5 78, .0 300. .989 289, ,569 0.4561 0, .1326 880 337. ,00 232.05 82, .0 79 .0 300.405 290, ,172 0.4560 0, .1395 900 342, .33 233.26 82, .5 79 .0 299, .822 294, .549 0, .4738 0, .1358 920 346, .33 240.75 83, .0 79 .0 300, .989 294, .232 0, .4821 0, .1618 940 351, .00 241.96 84, .0 79 .0 299, .822 297, .219 0, .4977 0, .1604 960 353, .33 242.86 85, .0 78 .5 305, .655 297, .017 0, .4851 0, .1655 980 355, .33 243.74 86, .0 78 .5 302, .155 296, .809 0, .4986 0 .1688 1000 364, .33 244.19 85, .5 78 .5 300, .989 296, .707 0, .5336 0 .1705 1020 363, .33 244.87 85, .5 78 .5 296, .905 296, .555 0, .5429 0 .1731 1040 363, .33 246.44 84, .0 78 .0 296. .322 296, .199 0, .5498 0, .1808 1060 366, .00 247.78 83, .5 78 .0 296, .322 295, .892 0, .5605 0, .1859 1080 369, ,00 263.33 82, .0 78 .0 296. .322 292.384 0, .5757 0, .2460 1100 373, .33 270.96 81, .0 78 .0 298. .655 295, .274 0, .5860 0, .2656 1120 376, ,33 276.53 81, .0 78 .5 297. ,489 294, .037 0, .5999 0, .2856 1140 375, .33 282.81 80, .0 79 .0 296. .322 292, .638 0, .6038 0, .3086 1160 365.67 286.47 80.0 79 .0 296. .322 291, .840 0 .5712 0 .3230 1180 353, .00 302.39 80, .0 79 .5 298, .072 289, .294 0 .5231 0 .3826 1200 356, .67 310.97 79, .0 79 .0 298, .655 287, .917 0 .5369 0 .4178 1220 356, .67 316.90 78 .0 79 .0 298, .947 287, .616 0 .5393 0 .4392 1240 363. ,00 333.82 80, .0 80 .0 298, .655 284, .040 0 .5548 0 .5057 1260 369. .00 324.55 80, .5 80 .0 299, .239 288, .189 0 .5713 0.4607 1280 361, .67 340.43 81, .0 80 .0 299, .239 285, .243 0, .5451 0, .5251 1300 356, .67 344.84 81, .0 80 .0 299, .822 288, .401 0 .5266 0, .5304 1320 354, ,67 349.94 82, .0 80 .0 299, .239 291, .780 0, .5184 0, .5372 1340 352, ,33 356.01 83, .0 80 .0 300.405 294, .963 0, .5037 0, .5478 1360 352. ,33 358.68 84, .0 80 .5 299, .822 294, .406 0, .5022 0, .5570 1380 351, ,00 364.96 85, .0 80 .0 302. .739 293, .105 0.4858 0, .5843 1400 355, ,67 367.28 85, .5 80 .0 303. .322 292, .628 0, .4979 0, .5938 1420 352, ,00 372.02 86 .0 80 .0 305, .655 300, .920 0 .4774 0 .5825 1440 357, ,00 376.45 87 .0 79 .5 303, .322 299, .586 0 .4973 0 .6033 1460 341. .33 384.57 88, .0 79 .5 304, .489 297, .881 0, .4392 0, .6362 1480 346. ,67 386.66 89, .0 79 .5 305, .072 297, .450 0, .4518 0, .6448 1500 352, .33 387.33 87, .0 79 .0 299, .822 297, .317 0, .4922 0, .6491 1520 356. ,67 393.88 87, .5 79 .0 300, .405 295, .968 0, .5032 0, .6760 1540 358, ,67 395.20 87, .0 79 .0 300, .989 295, .697 0, .5098 0, .6814 1560 358, ,00 400.24 87, .0 79 .0 300, .989 294.672 0, .5075 0, .7022 1580 358. ,33 406.89 85, .0 79 .0 299, .822 293, .318 0, .5188 0, .7300 1600 360, ,67 406.90 85, .5 79 .0 296, .322 293.321 0, .5358 0, .7300 1620 361, .00 411.75 85, .0 79, .5 299. .239 292. .350 0, .5295 0, .7486 1640 362, .00 416.22 85, .0 79 .5 293. .989 291. .460 0, .5494 0. ,7674 1660 364, .67 417.46 83, .0 79 .5 299. .822 291, .218 0. .5466 0. .7726 1680 368. ,33 421.01 82. .0 79, .5 297. .489 290. .518 0. .5697 0. .7876 1700 371, .00 422.74 81, .0 80 .0 297.489 298, .873 0, .5820 0, .7589 1720 370, ,33 426.27 80, .0 80 .0 297.489 298, .162 0, .5831 0. .7734 1740 373, ,67 549.64 80, .0 80 .0 297. .489 275, .116 0, .5943 1, .3192 1760 373, ,33 428.09 78, .0 81 .0 297.489 306, .605 0, .5999 0, .7441 1780 372, ,67 437.90 77, .0 81 .0 297, .489 304.568 0, .6011 0, .7839 1800 369, ,67 440.89 77, .0 82, .0 297. .489 303, .956 0, .5910 0, .7928 1820 369. ,33 443.37 76, .0 81 .0 297. ,489 303, .459 0, .5932 0, .8062 1840 370, .67 444.32 76, .0 81, .5 297, ,489 303, .262 0. .5977 0. ,8085 1860 371. .67 445.17 77, .5 81, .0 297. ,489 303. .045 0. .5960 0. .8138 1880 370. .67 446.11 78, .0 81, .0 297.489 302, .903 0. .5910 0, ,8175 1900 371. ,67 447.20 78, .0 81, .0 297, .489 302. .677 0. .5943 0, ,8220 1920 371. ,33 449.12 79, ,0 81, .0 297, ,489 302, .288 0, .5899 0, .8299 1940 370. ,33 451.09 79, ,5 80, .0 297. .489 301, .851 0. ,5848 0, ,8415 1960 371, ,00 456.22 79, .5 80 .0 297, .489 300, .821 0, .5871 0, .8628 1980 371, ,33 459.58 80, .0 80, .0 297.489 300. ,155 0, .5865 0. .8767 2000 369. .67 462.52 80, .5 79, .0 297, .489 299. .572 0, .5792 0, ,8923 2020 369. .33 463.52 80, .0 79, .5 297.489 299, ,379 0, .5798 0, ,8948 2040 367. .33 453.07 79, ,0 79, .0 297.489 301.469 0, .5764 0, ,8529 2060 377. ,67 453.63 78, ,0 78, .0 297, .489 301, ,358 0, ,6145 0, ,8585 2080 368. ,33 441.41 77, ,0 78, .0 297.489 303, ,838 0, ,5865 0, ,8082 Appendix D. DATA AND RESULTS 2100 366 .67 442, .23 77 .0 78 .0 2120 364, .33 442, .38 76 .0 78 .5 2140 364, .33 442, .52 76 .0 78 .5 2160 365, .67 442, .64 77 .0 78 .5 2180 365, .33 442, .66 78 .0 79 .0 2200 362, .67 454, .39 77, .0 79 .0 2220 363, .00 454. .54 76, .0 79 .0 2240 362, .67 454. .83 75, .0 79 .0 2260 361, .33 454, .97 74, .0 78 .0 2280 360, .00 455. .11 74, .0 78 .5 2300 347, .67 454, ,86 74, .0 78 .5 2320 354. .67 456. .38 72, .0 78 .0 2340 355. .00 446, ,13 70, .0 78 .0 2360 355. .00 449, ,08 70, .0 78 .5 2380 370. .00 448, ,80 68, .0 78 .5 2400 370. .67 449. ,36 66, .5 79 .0 2420 389, ,67 449, ,51 72, .5 79 .0 2440 396. ,67 451. ,07 74, .5 79 .0 2460 412. .00 447. ,32 76, .5 79 .0 2480 417. ,33 452. .34 77, .5 79 .0 2500 420. .33 447. ,34 77, .5 80 .0 297.489 303, .673 0. .5809 0, .8115 297.489 303, .647 0, .5764 0, .8105 297.489 303, .620 0, .5764 0, .8110 297.489 303, .590 0, .5775 0, .8116 297.489 303, .592 0, .5730 0, .8099 297.489 301, .178 0, .5674 0, .8585 297.489 301, .153 0, .5719 0, .8591 297.489 301, .099 0, .5742 0, .8603 297.489 301, .071 0, .5730 0, .8642 297.489 301, .043 0, .5686 0. .8631 297.489 295. .231 0, .5271 0, ,8869 297.489 294, .979 0. .5574 0, ,8948 297.489 297. .088 0, .5652 0, ,8512 297.489 296. ,516 0. ,5652 0, .8619 297.489 296, .571 0, ,6223 0, .8607 297.489 296, .463 0. ,6296 0, .8614 297.489 296, .437 0, ,6733 0, ,8620 297.489 296, ,138 0. ,6901 0, ,8685 297.489 296, ,885 0, ,7350 0.8527 297.489 295, .892 0, .7495 0. .8738 297.489 296, ,887 0, .7596 0. .8494 Appendix D. DATA AND RESULTS RUN 9 INDENE MEDIUM HEAT FLUX INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU QHWP 2.504 2.519 183.00 183.00 84.0 84.5 247.91 248.13 AVERAGE CONDITIONS: TBPFRU TBHWP QPFRU QHWP VFP REP VFH REH 83.07 83.25 246.26 248.94 0.81 9760 0.04 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 183. .3 182, .5 87 .0 83 .0 244. ,407 246, .580 -0. ,0052 0, .0067 20 183, .7 182, .7 88 .5 83 .5 239. ,158 246, .559 -0. ,0014 0, .0052 40 186. .0 184, .7 84 .5 84 .5 244. ,991 246. .147 0. .0150 0, .0103 60 186, .3 182 .8 87 .5 82 .0 245, .574 246, .539 0. .0031 0.0119 80 186. .7 183 .6 88 .5 82 .0 247, .324 246. .379 -0. .0024 0, .0154 100 189, .3 184 .1 89 .0 83 .0 249, .657 246, .287 0, .0025 0, .0134 120 191. .7 184, .8 87 .5 83 .0 250. .241 246, .153 0. .0169 0, .0165 140 193, .0 182, .8 88 .0 81 .0 247. .907 246, .588 0, .0242 0, .0159 160 194. .3 183, .8 89 .0 82 .0 247. .907 246, .842 0. .0255 0, .0156 180 195, .7 186, .0 88 .5 83.0 246. .449 246, .820 0, ,0355 0, .0205 200 196, .3 186, .9 88 .5 82 .0 250. ,824 247.407 0. .0306 0, .0269 220 197, .7 191, .1 88 .0 79 .5 246. .157 248, .212 0. ,0462 0, .0527 240 198, .0 191, .7 88 .0 83 .0 244. ,991 248. .328 0. ,0497 0, .0407 260 198, .7 193, .2 87 .5 82 .0 247. .324 248, .819 0. ,0501 0, .0499 280 199. .3 195, .4 86 .0 82 .0 245. ,574 249, .311 0, ,0622 0. .0579 300 203, .0 197, .4 86 .0 82 .0 253. ,740 249. .717 0. ,0618 0, .0652 320 202 .3 201 .3 80 .0 81 .0 253, .740 250, .556 0, .0828 0. .0833 340 201, .7 198 .8 80 .5 82 .0 242, .658 251, .595 0, .1000 0, .0674 360 202, .7 198, .5 80 .5 82 .5 243. .241 251, .659 0. .1029 0, .0638 380 205, .7 198, .1 80 .5 84 .0 243. .824 251, .731 0, .1140 0, .0564 400 205, .0 197, .0 80 .5 86 .0 250. .241 251, .970 0, .0982 0, .0435 420 206, .0 196, .0 80 .5 84 .0 250. ,824 252, .185 0, ,1010 0, .0471 440 203, .7 195, .9 79 .0 83 .0 247. .324 252, .206 0, .1047 0. .0505 460 205, .0 195, .9 78 .5 82 .0 246. ,741 252, .177 0. .1133 0, .0549 480 205, .7 196, .4 79 .0 82 .0 247. ,324 252. .081 0. .1128 0. .0568 500 207, .0 195, .7 79, .5 83 .0 249. ,074 252, .223 0. .1126 0, ,0499 520 207, .3 198. .3 79, .5 82 .5 249. .657 251. .710 0. .1127 0. .0629 540 206. .3 198. .1 78, .5 82 .0 248. ,491 251. .731 0. .1151 0, ,0643 560 206, .3 198, .2 76 .0 82 .0 247. .907 251, .706 0. .1264 0, .0648 580 203, .3 198, .2 76 .0 81 .0 246. .157 251, .703 0, ,1179 0, .0687 600 204, .0 198, .5 69 .5 81 .0 245. .574 251, .657 0. .1484 0, .0697 620 205, .3 198, .7 71 .5 81 .0 246. ,157 251, .564 0, .1443 0, .0709 640 204, .7 199, .0 72 .0 82 .5 246. ,741 251, .496 0. .1383 0, .0664 660 205, .7 200, .4 72 .5 82 .0 244.407 251, .213 0. .1455 0, .0744 680 206, .0 200, .9 73, .0 83 .5 244, ,991 251, .121 0. ,1435 0, .0705 700 206, .7 200. .8 73, .5 82 .5 244. ,991 251. .147 0. ,1442 0, ,0740 720 207. .0 199, .8 73, .5 81 .0 245, ,574 251, .360 0. ,1443 0, .0755 Appendix D. DATA AND RESULTS 740 207 .7 200 .0 74 .5 81 .0 246 .157 251 .309 0 .1416 0, .0764 760 209 .0 200 .8 75 .0 82 .0 244 .991 251 .147 0 .1476 0, .0760 780 208 .7 201 .1 75 .5 79 .0 247 .907 251 .072 0 .1378 0, .0894 800 210 .3 201 .0 76 .5 79 .0 246 .157 251 .098 0 .1443 0, .0890 820 209 .7 201 .8 77 .5 78 .0 242 .658 250 .936 0 .1453 0. .0965 840 209 .3 201 .7 78 .5 79 .0 241.491 250 .962 0 .1424 0, .0921 860 210 .3 202 .0 79 .0 78 .0 246 .157 250 .913 0 .1342 0, .0970 880 210 .7 208 .8 79 .5 79 .0 243 .824 249 .528 0 .1386 0, .1233 900 210 .7 208 .9 79 .5 79 .0 244.407 249 .502 0 .1373 0, .1238 920 211 .3 209 .3 80 .5 82 .0 242 .658 249 .434 0 .1398 0, .1134 940 211 .0 209 .2 81 .0 83 .0 241 .491 249 .410 0 .1390 0, .1090 960 211 .0 207 .7 81 .5 83 .5 242 .074 249 .717 0 .1356 0, .1003 980 211 .7 210 .4 82 .5 84 .5 242 .658 249 .181 0 .1330 0, .1082 1000 211 .3 209 .9 82 .5 84 .5 242 .658 249 .276 0 .1316 0, .1062 1020 211 .3 210 .1 82 .5 85 .5 243 .824 249 .227 0 .1290 0. ,1032 1040 212 .3 209 .1 83 .5 84, .0 244 .407 249 .440 0 .1278 0, .1045 1060 211 .3 209 .3 83 .5 83, .0 244 .407 249 .396 0 .1237 0. ,1096 1080 212 .0 209 .2 84 .5 84, .0 243 .824 249 .415 0 .1236 0, ,1050 1100 213 .0 209 .1 84 .5 84, .0 244 .407 249 .440 0 .1264 0. ,1045 1120 210 .7 209 .0 85, .5 84, .5 239, .158 249, .466 0, .1240 0, ,1021 1140 210 .0 209 .2 85, .0 83, .0 244, .407 249, .419 0, .1121 0, ,1091 1160 210 .7 209 .4 80, .5 83, .0 244, .407 249, .398 0, .1332 0, ,1097 1180 211 .7 209 .9 79, .5 83, .5 244, .407 249 .281 0 .1414 0, ,1103 1200 212 .3 213 .1 82, .5 82, .0 241.491 248 .650 0, .1383 0, ,1304 1220 210 .7 213 .3 83, .5 81, .0 242, .658 248, .627 0, .1247 0. .1350 1240 212 .3 212 .9 84, .5 80, .0 243, .824 248, .699 0 .1249 0, .1374 1260 213, .3 212 .2 85, .5 80, .0 244, .991 248, .833 0, .1224 0. .1342 1280 214 .3 211 .9 85, .5 80, .0 244, .991 248, .882 0, .1265 0, .1332 1300 215 .3 214 .6 86, .5 80, .0 247, .324 248, .369 0, .1216 0. ,1448 1320 216, .7 213 .3 85, .5 80, .0 245, .574 248, .629 0, .1348 0, ,1390 1340 215, .7 212 .3 83, .0 80, .0 246, .157 248, .819 0, .1396 0. ,1349 1360 216 .7 214 .1 83, .5 80, .5 245, .574 248, .467 0, .1429 0, .1407 1380 216, .0 215 .5 84, .5 80. .0 247. .324 248, .186 0, .1323 0. ,1491 1400 226, .0 216 .7 87, .0 80, .0 245, .574 247, .954 0, .1667 0, ,1544 1420 225, .7 221 .5 86, .5 80. .0 244. .991 247, .021 0, .1687 0. ,1759 1440 224, .3 223 .2 87. .5 81, .5 247. .324 246, .742 0, .1539 0. ,1774 1460 226, .7 219 .3 90. .5 82, .5 247. .907 247. .532 0, .1499 0. ,1559 1480 230, .7 219 .6 92. .5 82. .5 247. .324 247. .916 0, .1593 0. ,1562 1500 231, .0 220 .3 94. .5 83, .0 243. .824 248. .191 0, .1605 0. ,1563 1520 228, .3 219 .4 91, .5 83. ,0 243. ,241 248, .383 0. .1632 0. ,1521 1540 229, .3 221 .7 90. .0 83, .0 240. .324 247. .939 0, .1804 0. 1623 1560 229, .3 222 .7 89, .0 84, ,0 244. ,407 247, .730 0. .1748 0. 1631 1580 221, .3 222 .6 82. .0 84, .0 244. .407 247. ,751 0, .1707 0. 1625 1600 229, .0 222 .9 80, .5 84, ,0 244. .407 247, ,707 0. .2082 0. ,1636 1620 229. .7 223 .4 80, .5 85, ,0 247. .324 247, .615 0, .2038 0. ,1618 1640 232, .7 224 .4 84. .5 85, .5 245. ,282 247. .404 0. ,2047 0. ,1646 1660 230. .0 225 .4 81, ,5 86, ,0 245. ,574 247, ,218 0, ,2054 0. 1669 1680 233, ,0 226 .9 83. ,0 86. .0 245. ,574 246. ,938 0, ,2115 0. 1735 1700 232, .3 226 .2 81. ,5 86. ,0 246. .157 247. ,092 0, ,2134 0. 1705 1720 229, ,0 227 .9 82, ,5 87. ,0 247. .324 247. ,236 0, ,1930 0. 1730 1740 232, ,0 221 .0 85. ,5 88. ,0 246. .741 248. ,704 0. ,1944 0. 1378 1760 236, ,3 222 .6 85, ,5 88. .0 245. .574 248. ,549 0. ,2149 0. 1446 1780 237, ,3 223 .8 84. .5 88. ,0 245. ,574 248. ,316 0. .2230 0. 1500 1800 235, .7 223 .7 84. .5 89. ,0 246. ,741 248. .344 0. .2133 0. 1455 1820 234, .7 222, .1 84. .5 89. ,5 247. ,324 248. ,677 0. ,2078 0. 1361 1840 235. .7 223, .4 84. ,0 89. ,0 247. ,907 248.425 0. ,2124 0. 1441 1860 234, .3 222, .2 83. ,5 88. ,0 251. ,990 248. ,665 0. ,1992 0. 1429 1880 234. .7 223, .9 84. ,0 88. ,0 251. ,990 248. ,337 0. ,1986 0. 1504 1900 235, .0 222, .2 84. ,5 78. ,5 252. ,574 248. ,695 0. ,1965 0. 1807 1920 236. ,0 223, .5 84. ,5 86. ,5 247. ,907 248. ,442 0. ,2118 0. 1545 1940 235. .7 224, .5 84. ,5 89. ,0 248. ,491 248. ,256 0. ,2090 0. 1487 1960 234. ,7 224, .9 84. ,5 87. 0 247. 324 248. 190 0. ,2078 0. 1585 1980 235. ,0 223. .8 84. ,5 87. 0 250. ,824 248. 402 0. ,2007 0. 1536 2000 233. ,7 222. .9 83. ,5 87. 0 250. 824 248. 569 0. 1993 0. 1500 2020 234. ,3 224. .0 82. ,5 86. 0 251. 407 248. 361 0. 2046 0. 1589 2040 232. ,3 224. .7 82. 5 86. 0 250. 241 248. 246 0. 1994 0. 1616 2060 234. ,3 225, .1 82. 5 86. 0 250. 824 248. 154 0. 2060 0. 1638 Appendix D. DATA AND RESULTS 2080 233 .7 225 .1 83, .5 86, .0 251, .990 248, .154 0, .1966 0. ,1638 2100 234 .0 226 .2 83, .5 85, .5 252, .282 247, .944 0, .1972 0, .1707 2120 234 .7 229 .0 83, .5 85, .5 247, .907 247, .405 0, .2104 0. ,1831 2140 234 .7 228 .0 84, .5 86, .0 250, .824 247, .621 0, .1993 0. ,1763 2160 233 .0 228 .6 83, .5 86, .0 250, .824 247, .508 0, .1967 0, ,1791 2180 232 .7 229 .0 83, .5 85, .0 246, .449 247.448 0, .2059 0. ,1850 2200 228 .3 229 .3 84, .5 85, .0 245, .866 247, .450 0, .1857 0, ,1860 2220 229 .0 230 .5 84, .5 85, .5 245, .574 247, .226 0. .1891 0. ,1896 2240 230 .0 230 .0 79, .0 84, .5 245, .574 247, .354 0, .2155 0, ,1911 2260 229 .7 227 .5 79, .5 84, .5 244, .699 247, .960 0. .2143 0. ,1798 2280 231 .0 229 .8 78, .0 85, .5 246, .449 248, .679 0. .2215 0, ,1831 2300 231 .3 230 .5 79. .5 83, .0 247, .324 248, .539 0, .2146' 0. ,1964 2320 231 .3 229 .8 81. .0 82, .0 247, .616 248. .685 0. .2078 0, ,1973 2340 231 .0 229 .8 82. .5 82, .0 245, .574 248. .687 0, .2054 0, .1973 2360 233 .0 228 .8 84. .5 82, .0 244, .407 248. ,876 0. .2082 0. .1930 2380 232 .3 230 .5 86. .5 82, ,0 245, .574 248, .548 0, .1945 0, .2006 2400 234.7 230 .8 87, .5 83, .5 247, .324 248. ,501 0, .1957 0, .1957 2420 235 .0 230 .7 88, ,5 83, .5 244. .407 248, .527 0, .2001 0, .1952 2440 235 .3 230 .9 90, ,0 84, ,5 246, .157 248. ,481 0, ,1911 0, ,1923 2460 235 .7 230 .9 91, ,5 82, ,5 242, ,074 248.484 0, ,1962 0, ,2004 2480 235 .3 231 .2 91, ,5 82, ,0 246, .157 248. ,439 0, .1850 0, .2035 2500 236 .0 231 .2 89, ,0 82, ,0 242. .658 248. ,443 0, ,2064 0, ,2036 Appendix D. DATA AND RESULTS RUN 10, INDENE LOW HEAT FLUX INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU QHWP 2.087 2.090 180.00 180.0 85.0 85.0 198.3 198.57 AVERAGE CONDITIONS: TBPFRU TBHWP QPFRU QHWP VFP REP VFH REH 82.00 83.00 196.57 198.91 0.81 9760 0.04 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 190. .67 187, .01 81. .0 86, ,0 195. ,993 198, ,099 0, .0032 -0. .0214 20 193. .33 190, .93 85, ,0 86, ,0 195. .409 197. ,151 -0. ,0020 0. .0009 40 194. .33 192, .66 86. .0 86, ,5 196. ,576 196. ,957 -0. ,0053 0. ,0077 60 196, .00 193, .29 85, .0 82, .0 198, .326 197, .016 0, .0033 0, .0336 80 196, .00 194, .19 85. .0 83, .0 197. .743 197, .073 0, .0050 0, .0329 100 196, .00 195, .36 86, .5 84, .0 191. .326 197, .088 0, .0160 0, .0337 120 195, .00 196, .67 85, .5 83. .0 190. ,743 197, .082 0, .0177 0, .0455 140 194, .00 197.41 82, .0 83, .0 197. .159 197, .284 0. .0117 0. .0486 160 196. .00 198, .95 82, .5 82, ,0 198, .326 197, .400 0. .0159 0. .0612 180 194. .33 199, .30 82, .0 82, .0 198. ,909 197, .584 0, .0084 0. .0624 200 190. .33 200, .34 79. .0 81. ,0 198, ,909 197. ,620 0. ,0034 0. ,0726 220 189. .33 200, .53 78. .0 79, ,5 199. ,492 197. ,950 0. .0017 0. ,0801 240 191, .33 200, .95 80, .0 80, .0 193, .659 198, .403 0, .0185 0, .0783 260 189, .33 201, .09 78, .0 82, .0 193, .076 198, .381 0, .0203 0, .0690 280 189, .67 201, .48 78, .5 82, .0 198, .326 198, .400 0, .0042 0, .0709 300 192, .67 201, .20 79, .5 83, .0 198, .326 198, .484 0, .0143 0, .0642 320 193, .00 201, .60 81, .0 83, .0 198. .909 198. ,420 0, .0067 0, .0664 340 194, .00 201, .86 80, .5 83, .0 193, .076 198, .419 0, .0315 0, .0678 360 192, .67 202, .13 80, .5 82, .5 193. ,659 198.417 0, .0228 0.0716 380 192, .67 202, .13 80, .0 82. .0 193. .076 198. .417 0. .0272 0. ,0741 400 192, .33 203, .49 79, .0 85. ,0 198. ,326 198. .161 0. .0151 0. ,0666 420 193, .67 202 .14 80, .0 80. .0 198, .326 198, .334 0. .0168 0, .0846 440 193, .67 202 .41 80, .5 81, .0 195, .993 198, .333 0, .0210 0, .0808 460 194, .67 202, .53 81, .0 80, .0 198, .326 198, .353 0, .0168 0, .0865 480 195, .00 202, .67 81, .0 81, .0 195, .409 198, .331 0, .0270 0, .0822 500 194, .33 202, .53 80, .0 81, .0 198. .909 198, .353 0, .0184 0, .0814 520 195, .33 202, .93 81. .5 81. .5 199. .492 198.330 0, .0143 0, .0810 540 200, .00 202, .93 83, .5 82. .0 200. .659 198, .330 0, .0242 0, .0784 560 199, .67 202, .94 82, .0 82. ,0 198. ,326 198. .289 0. .0369 0. .0786 580 197. .33 203, .33 81. .0 81. .0 199. .492 198. .266 0. .0268 0. .0857 600 197, .67 203 .47 81, .0 81. .0 195, .993 198, .244 0, .0389 0, .0865 620 199, .33 203, .47 81, .5 81, .0 193, .659 198, .244 0, .0521 0, .0865 640 199, .00 203, .60 81, .0 82, .5 193, .659 198, .223 0, .0530 0, ,0797 660 199, .67 203, .60 81, .0 82, .0 198, .326 198, .223 0. .0420 0, .0822 680 202, .67 203, .87 82, .5 80, .5 197, .159 198. .221 0, .0531 0, .0911 700 201, .00 204, .00 82, .0 80. .5 195. .993 198. .200 0. .0508 0, .0918 720 201, .67 204, .00 82. .0 80, .0 197, ,159 198. .200 0, ,0506 0. .0943 740 202, .33 203, .99 81. ,0 81, .0 196. ,576 198, ,241 0, ,0609 0. ,0891 760 202 .67 204.26 80.0 82, .0 195, .409 198, .198 0, .0714 0.0856 780 202 .33 204, .67 78, .0 83, .0 196, .868 198, .134 0, .0752 0, ,0828 800 202, .67 204, .67 78, .5 83, .0 196, .576 198, .134 0, .0753 0, ,0828 Appendix D. DATA AND RESULTS 820 202, .33 204, .93 79 .0 83, .0 195.409 198, ,133 0. .0748 0. ,0841 840 205, .33 205, ,74 80 .0 83, .0 198, .326 198. ,045 0, ,0756 0. .0885 860 204, .67 206, ,14 79 .5 83, .0 198, .034 198, ,022 0, .0757 0. ,0905 880 202, .00 206, ,81 77 .5 83, .0 195, .409 197, .957 0, ,0808 0. .0941 900 202, .00 208. ,03 78 .5 83, .0 194, .826 197, ,763 0, .0775 0. .1009 920 202, .67 210, .21 78 .5 83, .0 195, .409 197. .462 0. .0791 0. ,1129 940 204, .00 211, .29 80 .0 83, .0 195, .409 197.331 0. .0782 0. .1188 960 204, .00 211. .14 79 .0 82, .5 197, .159 197. .394 0. .0776 0. ,1204 980 205, .67 211, .55 79 .5 82, .5 198, .034 197, .371 0, .0807 0. .1225 1000 205, .67 211, .41 80 .0 81, .5 196, .576 197, .392 0. .0829 0. ,1268 1020 207, .67 211, .40 81 .0 78, .5 198, .326 197.434 0, .0823 0. .1418 1040 207, .67 211, .39 81 .0 78, .0 198, .326 197, .475 0, .0823 0. ,1442 1060 207, .67 212. ,05 80 .5 78, .0 198, .326 197, .451 0, .0848 0. .1476 1080 208, .00 212. .04 81 .0 78, .0 198, .326 197.492 0, .0840 0. ,1474 1100 208, .00 212. .27 81 .5 78, .0 197, .743 197, .656 0, .0834 0, ,1480 1120 208, .67 212, .53 82 .5 79, .5 197, .743 197, .654 0, .0817 0. ,1418 1140 210, .67 212. .93 82 .5 79, .0 197, ,743 197, .631 0, .0918 0, .1464 1160 . 201, .67 214, .98 71 .5 81, .0 192.493 197, .350 0, .1199 0, ,1476 1180 201, .00 213, .05 69.0 79, .5 194, .243 197, .692 0, .1232 0, .1442 1200 205, .33 213, ,04 72 .0 79, .0 194, .243 197, .734 0, .1301 0, ,1466 1220 205, .33 213, .99 72 .5 79, .0 194, .826 197.625 0, .1254 0, .1518 1240 206, .33 213, ,83 73 .5 80, .0 194, .534 197, .729 0, .1265 0, .1455 1260 207, .67 214, .10 75 .5 80, .0 194, .826 197, .727 0, .1220 0, .1469 1280 207, .33 214, ,77 75 .5 80, .0 194, .826 197, .661 0, .1203 0, ,1505 1300 207, .67 214. .20 76 .5 80, .0 194, .826 197, .830 0, .1169 0, .1471 1320 208, .67 214, ,74 77 .0 80, .0 195, .409 197, .785 0, .1174 0, ,1500 1340 209, .00 214.59 77 .5 80, .0 195.409 197, .848 0, .1166 0, .1490 1360 209, .67 214, .71 77 .5 80, .5 195, .993 197, .910 0, .1180 0, ,1468 1380 209, .67 216, .21 77 .5 80, .0 195, .993 197.714 0, .1180 0, .1576 1400 209, .67 216, .05 78 .5 80, .0 196, .284 197, .819 0, .1119 0, ,1565 1420 210, .67 217, .14 80 .0 80, .0 196, .576 197, .688 0, .1084 0. .1624 1440 210, .67 216, .86 80 .5 79, .5 196, .576 197, .772 0, .1058 0, .1632 1460 215, .00 216. .42 83 .5 79, .5 195, .409 197, .920 0, .1166 0, .1605 1480 214, .00 216, .54 83 .0 79, .5 192, .493 197, .981 0, .1242 0. .1609 1500 217, .00 216. ,66 86 .5 79, .0 199, .492 198, .042 0, .0978 0, .1638 1520 217, .67 216, .78 86 .5 79, .0 199, .492 198, .062 0, .1011 0, .1644 1540 218, .00 216. .77 87 .0 80, .0 200, .076 198, .104 0, .0984 0, ,1591 1560 217, .67 217, .18 86 .5 80, .0 199, .492 198, .080 0, .1011 0, .1612 1580 219, .00 217, .16 87 .5 81, .0 199, .492 198, .122 0, .1028 0, ,1560 1600 210, .67 216, .33 80 .5 83, .0 199, .492 198, .293 0, .0961 0. .1411 1620 214, .33 217, ,42 79 .5 83, .5 200, .076 198, .162 0, .1176 0, .1445 1640 215, .00 217. .96 81 .0 83, .5 193, .076 198, .117 0, .1377 0, .1474 1660 216, .33 219. ,33 82 .0 84, .5 195, .409 197, .943 0, .1311 0, .1498 1680 212, .33 218. .21 79 .5 84, .5 197, .159 198, .157 0, .1174 0, .1435 1700 211, .67 218. .20 78 .0 83, .0 195, .993 198, .198 0, .1256 0, .1509 1720 214, .67 218.46 80 .5 83, .0 195.409 198, .238 0, .1302 0. .1520 1740 214, .33 218. .45 81 .0 84, .0 195.409 198.279 0, .1260 0, .1468 1760 213, .67 218, .57 81 .0 84, .0 195.409 198, .299 0, .1226 0, .1473 1780 212, .67 218. .56 79 .5 85, .0 197, .159 198, .341 0, .1191 0, .1421 1800 212, .67 218, .83 79 .0 82, .0 197.451 198, .339 0. .1206 0. .1586 1820 213, .00 218, ,82 78 .5 81, .0 197, .451 198.380 0, .1248 0, .1634 1840 211, .67 218. ,43 77 .0 83, .5 197, .159 198, .321 0. .1267 0, .1491 1860 212, .33 218, ,98 76 .5 84, .0 197, .159 198. .276 0. .1326 0. .1495 1880 212, .00 219, ,38 76 .5 84, .0 197, .159 198. ,253 0, .1309 0. .1516 1900 212, .00 220, ,75 76 .0 85, .0 197, .159 198. ,078 0, .1334 0. ,1540 1920 211, .00 220, ,74 74 .5 85, .0 197. .451 198. .120 0. .1350 0. .1538 1940 211. .00 221, ,00 73 .5 86. ,0 195, .993 198. ,118 0, .1452 0. .1501 1960 211. .33 220. ,85 72 .5 86, .0 197, ,159 198, ,181 0. .1478 0. .1492 1980 211, .33 220, .99 72 .5 86. .0 196. .868 198, .159 0, .1489 0. ,1499 2000 211, .00 221, .12 73 .0 89. .0 195, .993 198, ,179 0, .1477 0. .1354 2020 211, .00 221, .52 73 .0 89, .5 193, ,076 198, ,156 0, ,1584 0. ,1350 2040 211. .00 221, .22 73 .0 89, ,0 199.492 198, ,282 0, ,1354 0. ,1356 2060 210. .00 221, .90 73 .0 88, ,0 193, ,076 198, .216 0, ,1532 0. .1443 2080 212, .67 219. .41 73 .5 88, ,0 197, .159 198, .646 0, ,1495 0. ,1302 2100 210. .00 222. .57 74 .0 88, ,0 199, ,492 198. .190 0, ,1254 0. ,1477 2120 211, .33 222 .,70 74 .5 87, ,5 197, .743 198, .210 0, ,1356 0. ,1508 Appendix D. DATA AND RESULTS 2140 213, .00 222 .70 75 .5 87 .5 197 .451 198 .210 0. ,1400 0, ,1508 2160 213, .33 222 .69 76 .0 87 .5 197 .743 198 .252 0. .1381 0, ,1506 2180 213, .00 222 .82 77 .0 86 .0 197 .743 198 .272 0, ,1314 0, ,1588 2200 214, .00 222 .67 77 .5 86 .0 197 .159 198 .335 0, ,1360 0, ,1578 2220 214, .00 222 .93 78 .5 86 .0 196 .576 198 .333 0, .1329 0, .1591 2240 214, .00 223.06 79 .5 86 .0 196 .284 198 .353 0, ,1289 0, ,1597 2260 215, .00 222, .77 81. .0 86 .0 197, .159 198.437 0, ,1233 0, ,1580 2280 215, .00 222, .77 81. .5 86, .5 197, .159 198, .437 0, .1208 0. ,1554 2300 208, .00 223, .04 73, .5 86, .5 197, .159 198.436 0, ,1258 0, .1568 2320 213, .67 224, .54 76. .5 86, .0 197, .159 198, .281 0, ,1394 0. .1674 2340 216, .00 225, .36 80, .0 86, .0 197, .159 198 .192 0, ,1334 0, ,1719 2360 215, .33 224, .52 82, .5 87, .5 197, .159 198, .364 0. ,1174 0. ,1594 2380 217, .33 224, .59 84, .5 88, .5 197, .743 202, .419 0, ,1154 0, .1410 2400 217, .00 224, .86 86, .0 89, .0 198, .326 202, .418 0. ,1042 0. .1399 2420 217, .67 225, .26 87, .0 89, .0 198, .326 202, .394 0. .1025 0, .1419 2440 218, .33 224, .84 86, .0 89, .0 198, .909 202, .501 0. ,1089 0. .1395 2460 219, .00 225, .10 86, .5 89. .0 198, .326 202, .500 0. .1117 0, , 1408 2480 220, .67 225, .78 87, .5 89, .0 197, .743 202, .432 0. ,1171 0. ,1444 2500 219, .67 225, .76 87, .0 87, .0 197, .159 202, .474 0. ,1165 0. ,1540 2520 220. .33 226, .04 87, .5 87, .0 197, .159 202, .430 0. ,1174 0, .1556 2540 220. .67 226, .44 87, .0 86, .0 197, .743 202, .407 0. ,1196 0. ,1626 2560 217. .33 226.43 86, .5 86, .5 197, .451 202, .449 0. ,1063 0. ,1599 2580 216. .67 226, .55 87, .0 86, .5 197, .159 202, .469 0. ,1013 0. ,1604 2600 217. .00 226, .00 86, .5 85, .0 197, .159 202, .556 0. .1055 0. ,1648 2620 217. .67 225. .86 86, .5 85, .5 197, .159 202, .620 0. ,1089 0. .1614 2640 217. .67 226.26 87, .5 84, .0 196, .576 202, .596 0. ,1058 0, ,1709 2660 218. .00 226. .52 88, .0 84, .0 196, .576 202, .594 0. ,1050 0. .1722 2680 218. .67 226. .65 87. .5 84. .5 197, .159 202, .614 0. ,1089 0. ,1703 2700 219. .00 226. .91 88, .5 85, .5 195, .409 202. .613 0. ,1115 0. .1666 2720 215. .00 227, .73 83. .5 85, .5 195, .409 202, .523 0. ,1166 0. .1710 2740 213. .33 228. .82 81. .0 85, .5 195, .993 202, .390 0. ,1188 0. .1768 2760 214. .00 228. .12 81. ,0 85, ,0 193, ,076 202.541 0. ,1325 0. . 175" 2780 216. .00 228. ,80 81, ,0 86. .0 193, .659 202, .432 0. ,1407 0. .1742 2800 214. .33 226. ,89 82, ,0 86, ,0 197. .159 202, .696 0. ,1148 0. ,1638 2820 214. .67 229. .94 82, .5 86. .0 192. .493 202. .173 0. ,1302 0. ,1806 2840 217. .33 230. ,34 83, ,0 86, ,0 192. .493 202. .149 0. .1415 0. ,1827 2860 216. .67 232. ,27 83, .5 86, ,5 198, ,326 201, ,885 0. ,1151 0. ,1907 2880 217. .33 232. ,67 83, ,5 86, ,5 197. .159 201. ,861 0. ,1224 0. ,1928 2900 217. ,33 234. .05 84, .5 85, ,5 195. .409 201, ,684 0. ,1234 0. ,2053 2920 212. .67 235. ,44 79, ,5 85, ,5 192. .493 201. ,465 0. 1354 0. ,2130 2940 214. .00 226. .83 77, ,0 86, ,0 192. .493 202, ,906 0. 1554 0. ,1628 2960 212. .00 228, ,88 76, ,5 86, ,0 198. ,326 202. .619 0. 1269 0. ,1739 2980 211. .33 229. .42 75, .5 86, ,5 192. .493 202, ,574 0. 1493 0. ,1743 Appendix D. DATA AND RESULTS RUN 11, INDENE HIGH HEAT FLUX DEOXYGENATED INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU QHWP 2.622 2.611 198.00 198.67 84.0 82.0 298.94 302.86 AVERAGE CONDITIONS: TBPFRU TBHWP QPFRU 87.18 82.46 299.02 QHWP VFP REP VFH REH 299.33 0.81 9760 0.04 4.9 TIME PTEMP HTEMP PTB HTB PFH HHF HFR PFR 0 195 .7 202 .9 86. ,5 81, .0 293, .114 292, .199 -0, .0083 0, .0342 20 193 .3 193 .8 82. ,0 81, .5 294, .572 294, .960 -0, .0034 -0. .0024 40 194 .7 194 .3 83. ,0 81, .5 295, .156 298, .918 -0. .0030 -0, .0058 60 194 .7 195 .3 82. ,0 81, .0 293, .114 298, .619 0, .0030 -0, .0002 80 196, .3 194 .3 82. ,0 82, .0 293, .989 298, .918 0, .0076 -0, .0075 100 196, .3 195 .2 84. ,0 83, .5 294, .281 299, .153 0, .0004 -0, .0095 120 198 .0 198 .1 86, .0 85, .5 296, .031 299, .834 -0. .0030 -0, .0076 140 201 .0 199 .3 86, ,0 84, .0 294, .572 299, .581 0, .0091 0, .0019 160 201 .0 198 .2 90. ,0 80, .0 297, .489 299, .858 -0, .0082 0, .0110 180 201 .0 198 .4 88, .0 80, .0 297, .489 299, .905 -0. .0015 0, .0116 200 202 .0 197 .2 89. .0 81, .0 297.489 300, .181 -0, .0015 0, .0041 220 198 .7 198 .5 84. ,0 81, .5 298, .947 299. .952 0, .0022 0, .0072 240 199 .0 198 .5 84. .0 82, .5 297.489 299, .952 0, .0052 0, .0039 260 200 .7 198 .5 86. .0 83, .5 297, .489 299. .952 0 .0041 0, .0006 280 200 .7 199 .8 84, .0 83, .0 298, .947 300, .815 0 .0089 0, .0054 300 200 .7 198 .7 84. .5 81, .5 298, .947 301, .092 0, .0072 0, .0062 320 201 .0 198 .9 84.0 83, .0 296, .905 301, .139 0, .0127 0, .0018 340 203 .0 198 .9 88.0 83, .0 296 .031 301, .139 0, .0071 0, .0018 360 203 .3 199 .9 85, .0 81, .5 298, .947 300, .839 0, .0145 0, .0107 380 205 .3 198 .9 89, .5 81, .0 296, .905 301, .139 0, .0088 0, .0085 400 207 .0 200 .1 89, .5 82, .0 297, .489 300, .886 0, .0136 0, .0096 420 208 .3 200 .2 90, .5 82, .5 297.489 300, .910 0, .0147 0, .0082 440 210 .0 200 .2 93, ,0 81, .5 298, .655 300, .910 0, .0104 0, .0116 460 209 .3 201 .5 91, ,0 81, .0 296, .905 300, .656 0, .0172 0, .0177 480 209 .7 201 .6 90. .0 81, .0 298, .947 300. .680 0, .0189 0, .0180 500 206 .3 200 .4 87, .0 80, .0 296, .905 300, .957 0, .0206 0. .0171 520 208 .3 200 .4 87. .5 80, .0 296, .905 300. .957 0, .0256 0. .0171 540 209 .3 200 .3 88, .0 81, .0 298, .947 300, .933 0, .0245 0. .0135 560 210 .3 199 .3 89. .0 79, .5 298, .947 301. .234 0, .0245 0, .0146 580 209 .7 199 .4 88. .0 80, .5 298, .947 301, .257 0, .0256 0. .0116 600 211 .0 200 .5 90. ,0 81, .0 298, .947 300, .980 0, .0234 0, .0141 620 211 .7 201 .1 91, .0 81, .0 298, .947 301, .121 0, .0223 0. .0159 640 211 .3 202 .2 90, .5 81, .5 297.489 301. .380 0, .0248 0, ,0174 660 212 .0 201 .3 90, ,0 81, .0 298, .947 301. .728 0, .0268 0, ,0158 680 210 .3 201 .3 89, ,5 81, .0 298, .947 301. .728 0, .0229 0, ,0158 700 209 .7 201 .3 89. ,0 81, .0 298, .947 301. .728 0, .0223 0, ,0158 Appendix D. DATA AND RESULTS 720 209 .7 201 .4 87 .0 80, .5 298.947 301, .751 0, .0290 0, .0177 740 205, .3 201 .6 82 .5 79, .0 301.864 301, .799 0, .0256 0, .0233 760 209, .0 204 .1 88 .0 81, .0 300.405 301, .291 0, .0214 0, .0256 780 211, .0 200 .7 89 .5 80, .0 300.405 302, .123 0, .0231 0, .0164 800 211, .7 200 .8 90 .5 79, .5 298.947 302, .146 0, .0240 0, .0183 820 213, .7 201 .2 92 .0 80, .0 300.405 302, .264 0, .0237 0, .0181 840 214, .0 202 .2 93 .5 80. .0 299.822 302, .500 0, .0206 0, .0210 860 214, .3 202 .7 93 .0 81, .0 300.405 302, .618 0, .0226 0, .0192 880 214, .3 203 .8 90 .5 82, .0 300.405 302, .316 0, .0309 0, .0197 900 215, .0 202 .8 93 .0 82. .0 300.405 302, .641 0, .0248 0, .0162 920 215, .3 202 .9 94 .0 82, .0 301.864 302, .665 0, .0206 0, .0164 940 215, .3 203 .0 94 .0 81, .5 300.405 302, .688 0, .0226 0, .0184 960 215, .0 204 .7 92 .0 83. .0 301.864 302, .552 0, .0261 0, .0193 980 216, .0 204 .4 93 .0 84, .0 300.405 302, .481 0, .0281 0, .0152 1000 216, .0 204 .3 92 .0 83, .5 300.405 302, .994 0, .0314 0, .0156 1020 215, .7 205 .5 92 .0 84, .0 300.405 303, .301 0, .0303 0, .0177 1040 215, .3 207 .1 92 .0 86, .0 302.739 303, .116 0, .0260 0, .0164 1060 216, .0 207 .3 93 .5 85. .5 300.405 303, .164 0, .0264 0, .0186 1080 215, .7 206 .2 93 .5 84. .0 300.405 303.466 0, .0253 0, .0197 1100 212, .3 205 .2 90 .5 84. ,0 301.864 303, .768 0, .0223 0, .0158 1120 208, .3 205 .3 87 .5 84. .0 300.405 303, .792 0, .0209 0, .0161 1140 207, .7 206 .4 86 .5 84, .0 300.405 303, .513 0, .0220 0, .0203 1160 207, .7 206 .4 87 .5 84, .0 298.947 303, .513 0, .0206 0, .0203 1180 209, .0 206 .4 89 .0 84, .0 301.864 303, .513 0, .0162 0, .0203 1200 209, .3 205 .3 89 .0 84, .0 298.947 303, .792 0, .0212 0, .0161 1220 208, .7 205 .3 88 .0 84. ,0 297.489 303, .792 0, .0243 0, .0161 1240 209, .7 205 .3 88 .5 84, ,0 297.489 303, .792 0, .0260 0, .0161 1260 210, .0 203 .6 87 .0 82, ,0 296.031 303, .391 0, .0342 0, .0178 1280 212, .7 203 .6 90 .5 82, ,0 301.864 303, .391 0, .0234 0, .0178 1300 212, .0 203 .6 92 .0 82. .5 300.405 303, .391 0, .0181 0, .0161 1320 210, .0 204 .8 86 .0 84. ,0 300.405 303, .136 0, .0314 0, .0156 1340 208, .7 204 .8 85 .5 84. .0 300.405 303, .112 0, .0287 0, .0154 1360 208. .3 204 .8 86 .0 84. .0 298.947 303, .136 0, .0279 0, .0156 1380 209, .3 204 .8 85 .0 84. ,0 301.864 303, .136 0, .0305 0, .0156 1400 209, .7 204 .9 87 .0 84. .0 298.947 303, .159 0, .0290 0, .0159 1420 210, .0 204 .9 87 .0 84, ,0 300.405 303, .159 0, .0281 0, .0159 1440 210, .7 204 .9 88, .0 84, ,5 300.405 303, .159 0, .0270 0, .0143 1460 210, .0 204 .8 86, .5 • 83, ,0 301.864 303, .112 0, .0278 0, .0187 1480 211, .3 207 .1 88 .0 85, ,0 300.405 302, .556 0, .0292 0, .0204 1500 211, .7 206 .6 89, .5 84. .0 300.405 302, .438 0, .0253 0, .0222 1520 209. .7 205 .1 88, .5 84, .0 297.489 302, .646 0, .0260 0, .0172 1540 210, .0 204 .5 88, .5 82. .0 297.489 302, .505 0, .0271 0, .0221 1560 210, .3 204 .2 87 .5 81, .5 296.031 302.434 0, .0336 0, .0228 1580 211, .0 204 .1 87, .5 82. ,0 297.489 301, .850 0, .0338 0, .0216 1600 211, .7 203 .9 88, .5 81, .5 298.947 301, .803 0, .0307 0, .0227 1620 211, .7 204 .9 89, .0 83. ,0 298.947 301, .479 0, .0290 0, .0213 1640 211, .7 204 .9 89, .0 82, ,0 298.947 301, .479 0, .0290 0, .0246 1660 211. .3 204 .9 88, .0 82, ,0 298.947 301, ,479 0, .0312 0, .0246 1680 210, .0 204, .2 88, .0 82, .0 298.947 301, .314 0, .0268 0, .0226 1700 210. .7 204, .2 88, .0 82, .0 298.947 301, ,314 0. .0290 0. .0226 1720 210. ,7 204, .9 88, .5 82, ,0 298.947 301, ,479 0. .0273 0, .0246 1740 211. ,0 203, .7 87, .5 82, ,0 298.947 301. ,756 0. .0318 0. .0204 1760 210. ,3 203, .7 88, .0 83. ,0 297.489 301. .756 0. .0299 0. .0171 1780 211, ,3 203, .7 87, .5 82, ,0 298.947 301. ,756 0. .0329 0. .0204 1800 212. ,0 204, .2 88, .5 82. .0 300.405 301, ,314 0. ,0298 0. .0226 1820 212, ,7 203, .7 89. .5 82, ,5 301.864 301. .197 0. .0267 0. .0195 1840 212. ,3 203, .5 90, .5 82. ,0 297.489 301, ,150 0. ,0282 0, ,0205 1860 213, .3 203, .2 91, .5 83. ,0 301.864 301. ,079 0. .0223 0, ,0163 1880 213, .7 204, .4 92, .0 82. ,0 300.405 300, ,802 0. ,0237 0, ,0239 1900 212, .0 204, .4 89. .0 82. ,5 301.864 300. ,802 0, .0261 0, ,0222 1920 210, .0 204, .4 86, .0 82. ,5 297.489 300. ,802 0. .0355 0, ,0222 1940 210, .7 204, .5 86. .0 82. ,5 300.405 300, ,825 0, ,0337 0. ,0225 1960 210, .7 204, .5 86. .0 82. ,5 300.405 300, ,825 0, ,0337 0. ,0225 1980 211. ,0 203, .9 87. .0 82. ,5 297.489 300. ,126 0, .0355 0. .0214 2000 213. .0 204, .5 88. .0 82. ,0 301.864 299, .174 0, .0327 0. ,0265 2020 213. ,0 202, .9 90. .5 81. ,5 301.864 298. ,776 0. .0245 0. ,0232 2040 214. ,0 204, .0 90, ,5 82. ,5 301.864 298. .500 0. .0278 0. ,0241 Appendix D. DATA AND RESULTS 2060 213 .7 202, .4 91 .0 82, .0 301 .864 298, .103 0. .0250 0, .0207 2080 209 .3 203, .5 89 .0 83, .0 296 .031 297, .827 0. .0251 0, .0216 2100 209 .3 203, .5 89 .0 83, .0 297 .489 297 .827 0, .0232 0, .0216 2120 209 .3 203, .5 89 .0 83, .0 297 .489 297, .827 0, .0232 0, .0216 2140 211 .3 203, .5 89 .0 83, .0 301 .864 297, .827 0. .0239 0, .0216 2160 211 .3 204, .2 88 .0 84, .5 301 .864 296 .879 0.0272 0, .0200 2180 212 .0 204, .8 88 .5 85, .5 301 .864 295, .933 0, .0278 0, .0201 2200 213 .7 204, .8 91 .0 84, .5 301 .864 295, .933 0. .0250 0, .0235 2220 213 .3 204, .3 92 .0 84, .0 300 .405 295, .262 0, .0226 0, .0244 2240 213 .3 203, .1 87 .0 83, .0 301 .864 295, .537 0, .0372 0, .0235 2260 213 .3 203, .1 87 .5 82, .5 301 .864 295, .537 0, ,0355 0, .0252 2280 213 .3 203, .1 87 .5 82, .5 301 .864 295, .537 0. ,0355 0, .0252 2300 213 .0 203, .1 87 .5 83, .0 301 .864 295, .537 0. .0344 0, .0235 2320 212 .7 202, .6 87 .5 83, .0 301 .864 294, .867 0. ,0333 0, .0227 2340 213 .0 203. .2 88 .0 82, .5 301 .864 295, .560 0. ,0327 0, .0255 2360 213 .3 202, .1 88 .0 82, .5 301 .864 294, .198 0. .0339 0, .0235 2380 213 .7 202. .1 88 .0 82, .5 301 .864 294, .198 0, ,0350 0, .0235 2400 212 .7 202, .1 87 .0 82. .5 301 .864 294, .198 0. ,0350 0, .0235 2420 203 .3 201, .6 82 .5 82, .5 297, .489 293, .529 0, .0248 0, .0227 2440 203 .3 202, .8 84 .0 82. .5 291, .656 293, .255 0, ,0278 0, .0271 2460 203 .0 201. .7 83 .5 82, .0 291 .656 293, .552 0, ,0284 0, .0247 2480 203 .0 201, .8 84 .0 82. .0 291, .656 293, .575 0. ,0267 0, .0250 2500 203 .0 201, .8 86 .0 82, .0 297 .489 293, .575 0, ,0119 0, .0250 2520 204 .3 201, .8 79 .0 82. .0 303, .322 293, .575 0, ,0319 0, .0250 2540 203 .3 203, ,0 78 .5 82, .5 303, .322 293, .302 0, ,0302 0, .0277 2560 203 .7 203, .1 79 .0 82. .0 303, .322 293, .325 0. .0297 0, .0297 2580 204 .0 201. .9 80 .5 82, .0 297.489 293, .598 0, ,0338 0. .0253 2600 204 .0 201, .9 81 .0 83, ,0 300.405 293, .598 0, ,0281 0. .0219 2620 205 .0 200, ,7 81 .0 83. ,0 300.405 293, .872 0, ,0314 0. .0176 2640 203 .7 200, .7 83 .0 83. .0 300, .405 293, .872 0, .0203 0, .0176 2660 203 .3 201, .9 81 .5 83. ,0 300, .405 293, .598 0. .0242 0. .0219 2680 203 .3 203, .1 80 .5 83. ,0 297, .48? 293, .325 0, ,0316 0, .0263 2700 203 .7 203, .2 80 .5 83, .0 297, .489 293. .348 0, .0327 0, .0266 2720 203 .3 203. .1 80 .5 83, .0 297, .489 293. .325 0. .0316 0. .0263 2740 205, .7 201. .9 81 .5 83, .0 301, .864 293, .598 0. .0300 0. .0219 2760 204, .7 201. .9 81 .5 83, .0 297.489 293, .598 0. .0327 0, .0219 2780 204 .7 203. .1 82 .5 83, ,5 297, .489 293, .877 0. .0293 0, .0239 2800 204 .3 203. .1 82 .5 83, .5 297.489 293, .877 0. .0282 0, .0239 2820 204, .3 203. .1 82, .5 83, .5 297, .489 293. .877 0. .0282 0, ,0239 2840 205 .3 201. .9 82, .0 83. .5 297, .489 294, ,151 0. .0332 0, ,0195 2860 205, .3 201. .9 82, .5 82. .5 297. .489 294, ,151 0. .0316 0, ,0229 2880 205, .0 201. .9 82, .0 82, .5 297, .489 294, .151 0. .0321 0, .0229 2900 205, .3 201. ,9 81, .5 82. .5 297. .489 294, .151 0. ,0349 0. ,0229 2920 205, .0 203. .1 82, .0 82, .5 297, .489 293, .877 0. ,0321 0, ,0273 2940 205, .3 203. ,1 82, .0 82. .5 297. .489 293, .877 0. ,0332 0. .0273 2960 206, .3 203. ,1 82, .5 82. .0 297, .489 293, .877 0. ,0349 0, .0290 2980 206, .3 201. .9 82, .5 82. .5 297. .489 294, .151 0. ,0349 0, .0229 Appendix D. DATA AND RESULTS ROT 12, DICYCLOPENTADIENE MEDIUM HEAT FLUX INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU - TBHWP QPFRU QHWP 2.763 2.576 187.00 185.00 85.0 82.0 281.84 265.30 AVERAGE CONDITIONS: TBPFRU 81.33 TBHWP 80.61 QPFRU 258.03 qHWP 254.41 VFP REP 0.81 9760 VFH 0.04 REH 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 184. .3 187 .0 85. ,0 86 .0 282. ,906 256, .577 -0. ,0108 0. .0054 20 185. .3 188 .2 85. .0 85 .0 281. .739 256, ,820 -0. .0058 0, .0135 40 186. .3 188 .2 85. ,5 85 .0 282, .323 256, .820 -0. .0048 0, .0135 60 188. .0 188 .3 84. .0 85 .0 282, .906 256, .844 0, .0057 0, .0139 80 187. .0 188 .4 84. .0 83 .0 281.448 256. .821 0, .0041 0, .0222 100 188. .7 188 .4 84. .0 84 .0 282, .906 256, ,821 0, .0081 0. .0183 120 188. .7 188 .4 84. .0 84 .0 285. ,823 256. .821 0, .0043 0, .0183 140 190. .0 188 .5 83. .5 82 .5 288, ,739 256, .845 0, .0069 0, .0245 160 191. .0 188 .4 83. .0 82 .0 291. ,656 256. .868 0, .0084 0, .0260 180 191. ,0 188 .4 83, ,0 83 .0 291, ,656 256. .868 0, .0084 0. .0221 200 198. .3 188 .2 82. .5 85 .0 314. ,988 256. .820 0, .0058 0. .0135 220 204. .3 200 .4 85. ,5 85 .0 314. ,988 254. .633 0, .0154 0. .0651 240 205. .0 210 .3 85. .5 84 .0 320. ,821 253. ,156 0, .0106 0, .1108 260 204. ,0 205 .0 82. ,5 83 .0 320. ,821 254. .186 0. .0168 0. .0917 280 210. .0 208 .5 83, .0 84 .0 320, .821 253, ,570 0, .0339 0, .1028 300 214, .3 206 .5 86, ,5 84 .0 314, .988 253, .982 0. .0439 0, .0940 320 221, .3 207 .4 91, ,5 84 .5 314. .988 253, .799 0, .0503 0, .0959 340 230, .7 207 .1 95, ,5 82 .0 320, .821 254, .008 0, .0594 0, .1041 360 238. .3 207 .2 95, ,5 84 .5 320. .821 253, .985 0, .0833 0, .0948 380 237, .0 208 .5 84, ,5 82 .0 320, .821 253, .710 0, .1134 0, .1105 400 245, .3 210 .8 79, ,0 83 .0 323, .738 260, .179 0, .1519 0, .1031 420 263. .3 214 .8 78, ,5 85 .0 323. .738 259, .461 0, .2090 0, .1120 440 263. .3 200 .9 79, ,5 77 .0 323, ,738 262. .103 0, .2059 0. .0844 460 267. .0 203 .2 80. .5 77 .0 323. ,738 261. ,663 0. .2142 0, .0942 480 269. .7 205 .1 82. ,0 77 .0 320. ,821 261, .268 0. .2230 0. .1021 500 273. ,0 207 .2 83. .0 76 .5 323. ,738 260. ,827 0. ,2250 0, .1130 520 276. ,0 210 .8 84. ,5 80 .5 320. ,821 260, ,131 0. .2350 0. .1128 540 279. .7 214.8 85. .5 81 .0 326.654 259.413 0.2325 0, .1275 560 280, .0 218 .9 86. ,0 84 .5 317, .905 258, .530 0, .2483 0, .1315 580 284, .7 223 .6 87, ,0 84 .0 323, .738 257, .672 0, .2487 0, .1533 600 276. .0 212 .3 80, ,5 78 .0 303. .322 259, .498 0, .2826 0, .1291 620 276. .7 215 .7 78, .5 77 .0 298, ,947 259, .275 0, .3010 0, .1467 640 278. .7 216 .4 79, ,5 78 .0 303, ,322 259, .135 0, .2947 0, .1457 660 281. .3 218 .6 80. ,5 78 .0 303, .322 258, .671 0, .3002 0, .1555 680 284. .0 219 .4 82. .5 79 .0 303, ,322 258, .555 0, .3024 0. .1549 Appendix D. DATA AND RESULTS 700 286 .0 220 .2 84, .5 82, .0 303, .322 258.440 0, .3024 0, .1467 720 286 .3 222 .6 86, .0 81, .0 303, ,322 257, .905 0, .2986 0, .1610 740 288 .0 226 .8 87, .0 81, .5 303. ,322 257, .352 0, .3008 0, .1763 760 288 .7 222 .8 87. .5 80, .0 303, .322 258, .118 0, .3013 0, .1649 780 267 .0 215 .0 73, .0 78, .0 262.490 259, .509 0, .3772 0. .1398 800 268 .3 219 .3 75, .0 77, .0 262, ,490 258, .721 0, .3746 0. .1619 820 269 .0 219 .6 77. .0 76, .0 262, ,490 258, .532 0, .3695 0, .1670 840 269 .7 222 .6 78. .5 78, .0 262.490 257, .905 0, .3664 0, .1726 860 269, .7 220 .1 80, .5 77, .0 256, ,657 258, .227 0, .3751 0, .1660 880 272, .0 222 .1 82, .0 76, .5 262, ,490 257, .832 0, .3619 0, .1763 900 272, .7 220 .9 82. ,0 76, .0 262, .490 257, .970 0, .3645 0, ,1735 920 272 .3 226 .0 83. ,0 79, .0 262.490 257, ,090 0, .3594 0, .1834 940 272 .0 226 .5 83, .5 81 .0 262, .490 256.879 0 .3562 0 .1783 960 273 .7 226 .5 84. .0 80 .0 256, .657 256 .926 0, .3771 0, .1821 980 274 .7 229 .2 84, .5 80 .0 262, .490 256, .580 0, .3626 0, .1932 1000 263 .0 228 .2 78, .5 79, .5 262, .490 256, .695 0, .3410 0, .1909 1020 262 .3 226 .8 72. .5 80, .0 233, .325 256, .927 0, .4517 0, .1830 1040 261 .3 227 .9 71, .5 80, .0 233, .325 256, .789 0, .4517 0, .1878 1060 263 .0 228 .8 71, .5 80, .5 233, .325 256, .603 0, .4588 0, .1899 1080 263 .7 230 .2 72, .0 81, .0 239. .158 256, .277 0, .4395 0, .1941 1100 265, .7 231 .5 73, .0 81, .5 239. .158 255, .975 0.4437 0, .1978 1120 264, .7 231 .5 74. .5 80, .0 242, ,074 255.880 0.4237 0, .2038 1140 267, .0 231 .6 75. .0 80, .5 239, .158 255, .904 0, .4409 0. .2023 1160 268, .0 230 .4 76. ,0 81, .5 242. .074 255, .807 0.4312 0. ,1940 1180 268, .7 232 .0 76. .5 80, .5 244, .991 255, .599 0, .4225 0. .2043 1200 264, .3 231 .4 76. .5 81, .0 244, .991 255, .621 0, .4048 0. .2000 1220 267 .7 231 .5 76, .5 81 .0 233, .325 255.692 0 .4574 0, .2003 1240 268 .7 232 .0 77, .0 81 .5 244. .991 255 .646 0 .4204 0, .2003 1260 268 .7 231 .4 77, .5 82, .0 244. .991 255 .857 0 .4184 0, .1956 1280 269 .0 231 .5 77, .5 82, .5 244. .991 255, .598 0, .4198 0, .1946 1300 269 .0 231 .6 77, .5 82, .5 244, .991 255, .528 0, .4198 0, .1952 1320 269 .3 230 .5 78, .0 81, .5 244, .991 255, ,737 0 .4191 0, .1946 1340 269 .0 231 .2 78, .5 81, .0 244. .991 255, .504 0 .4157 0, .1998 1360 270 .0 231 .1 78. .5 81, .0 239. .158 255, .433 0, .4388 0, .1995 1380 268 .7 231 .4 79. .5 80, .5 244. .991 255.480 0.4102 0, .2022 1400 269 .7 231 .1 79. .5 81, .0 239, ,158 255, .621 0.4332 0, ,1991 1420 268, .3 232 .1 79. .5 80, .0 240, .616 255, .388 0, .4229 0. ,2071 1440 268, .0 232 .4 79. ,5 80, .5 239, .158 255, .318 0, .4263 0, .2067 1460 266 .3 230 .7 76. .5 81, .0 239. .158 255, .714 0, .4318 0. ,1970 1480 266 .7 227 .8 73. ,0 81. .5 233, .325 256. .153 0, .4681 0. ,1828 1500 266, .3 227 .9 72. .5 80, .5 233. .325 256, .223 0, .4688 0. ,1870 1520 269 .7 230 .8 73, .5 79 .0 233, .325 255, .737 0.4788 0, .2053 1540 269 .0 230 .7 74, .0 79, .0 239. .158 255, .714 0, .4534 0, .2049 1560 269 .0 230 .5 74, .5 79, .5 239, .158 255, .690 0, .4514 0, .2025 1580 269 .3 230 .9 75, .0 79, .0 233, .325 255, .620 0, .4710 0, .2060 1600 270 .3 231 .6 76, .5 79, .0 239, .158 255, .669 0.4486 0.2086 1620 270, .3 232 .5 76, .5 81, .0 239, .158 255, ,624 0, .4486 0. .2046 1640 270, .0 238 .4 77. .5 81, .0 239, ,158 254, .510 0.4430 0, .2302 1660 270, .7 247 .5 78, ,0 80, .5 239, .158 252, .675 0, .4437 0, ,2726 1680 270, .7 235 .3 78, ,5 79, .5 239, .158 254, .785 0.4416 0, .2233 1700 271, .3 254 .2 79. .5 80, .0 239, .158 251, .095 0, .4402 0, .3054 1720 270, .7 251 .9 79. ,5 80, .0 239, .158 251, .583 0, .4374 0, ,2950 1740 272, .3 243 .8 80, ,5 79, .5 239. .158 253, .395 0. .4402 0, ,2602 1760 272, .3 243 .0 80. ,5 79. .5 239. .158 253. .558 0, ,4402 0, ,2565 1780 272, .7 254 .1 81. .0 80. ,5 233. .325 251. .398 0. ,4595 0. .3022 1800 273 .3 250 .0 81, .0 78, .5 233, .325 252.234 0.4624 0.2917 1820 273 .0 248 .9 81. .0 80, .5 233, ,325 252, .443 0, .4610 0, ,2789 1840 273, .7 255 .3 81, .5 80, .0 233, ,325 251, .259 0.4617 0, .3093 1860 273, .0 252 .3 81, .5 77, .5 239, ,158 251, ,793 0.4388 0, .3058 1880 274, .0 245 .2 81, .5 78, .0 239. ,158 253, ,163 0.4430 0, .2723 1900 274, .3 245 .5 82, ,5 78. .0 239. ,158 253, .164 0.4402 0, ,2733 1920 274, .3 244 .9 82, ,5 78. .0 239. .158 253. ,233 0.4402 0, .2707 1940 274, .7 246 .9 82, .5 79, ,0 239. ,158 252. .791 0, ,4416 0, .2759 1960 275, .0 248 .3 83. .0 79, .0 239. .158 252. .513 0.4409 0, ,2823 1980 275, .3 248 .8 83, .5 78. ,0 239. ,158 252.467 0.4402 0, ,2883 2000 276, .0 251 .1 83. ,5 78, .5 239. ,158 252. ,025 0.4430 0, .2965 2020 276, ,7 254 .1 83. ,0 76, ,5 239. ,158 251.445 0.4479 0. ,3180 Appendix D. DATA AND RESULTS 2040 277, .0 255 .4 82, .5 78, .5 236. .241 251, .143 0, .4614 0. ,3161 2060 277, .0 248 .9 83, .5 79, .0 236, .241 252, .397 0, .4572 0. .2850 2080 276, .3 247 .4 85, .0 78, .5 236. .241 252 .698 0.4480 0. ,2800 2100 277, .7 248 .7 85, ,0 80, .0 236. .241 252.443 0.4536 0. .2799 2120 278, .7 258 .2 85, .5 81, .0 236, .241 250 .609 0.4558 0. .3187 2140 279, .0 259 .6 84. ,5 80, .5 236. .241 250, .330 0, .4614 0, .3273 2160 280, .0 259 .9 83, .0 81, .0 233. .325 250, .330 0, .4824 0. .3263 2180 280, .7 258 .9 82, .5 81, .0 233. .325 250, .516 0, .4874 0, .3219 2200 280, .3 257 .6 82, .5 81, .0 233, .325 250, .771 0, .4860 0, .3158 2220 281, .7 254 .9 82, .5 81, .0 236.241 251, .329 0, .4812 0, .3037 2240 283, .3 257 .1 82, .5 81, .0 236. .241 250 .864 0, .4882 0, .3137 2260 283, .0 252 .3 82. .5 81, .0 239. .158 251, .840 0, .4764 0, .2918 2280 283, .7 257 .6 82, .0 81, .0 239. .158 250 .818 0, .4813 0, .3157 2300 284, .0 253 .5 82. .0 80, .5 239, .158 251 .561 0.4827 0, .2993 2320 285, .0 257 .3 82, .0 80, .5 239. .158 250 .864 0, .4869 0, .3166 2340 285, .3 259 .6 82, .0 81, .0 239, .158 250 .376 0, .4883 0, .3252 2360 284, .7 252 .3 83. .0 82, .0 239. .158 251, .793 0, .4813 0.2880 2380 284, .7 258 .4 83. .0 81, .5 239, .158 250, .702 0, .4813 0, .3174 2400 285, .7 259 .7 83, .5 82, .0 239. .158 250, .446 0, .4834 0, .3215 2420 285, .7 258 .9 84. .0 81, .5 239. .158 250, .516 0, .4813 0, .3199 2440 286, .7 260 .6 84. .5 81, .0 239. ,158 250 .284 0, .4834 0, .3293 2460 287, .3 253 .6 84, .5 81, .0 239. .158 251 .584 0.4862 0, .2978 2480 287, ,7 253 .7 84. .5 81, .5 239. .158 251 .654 0, .4876 0, .2961 2500 288, .7 253 .5 84, .5 82, .0 236, .241 251 .607 0, .5023 0, .2933 2520 289. .3 258 .5 83. .5 82, .0 236, .241 250 .725 0, .5094 0, .3159 2540 288, .7 258 .4 82. .5 82, .0 236. .241 250, .655 0, .5108 0, .3156 2560 289. .0 259 .1 82. .5 82, .0 236. .241 250, .469 0, .5122 0, .3190 2580 289. .7 258 .0 82. ,5 81, .0 236. .241 250, .725 0, .5150 0, .3179 2600 289, .7 253 .5 82, .5 81, .0 236. .241 251, .561 0, .5150 0, .2973 2620 289. .7 254 .8 82, .5 80, .5 236. .241 251, .399 0, .5150 0, .3050 2640 290, .7 255 .5 83. .0 80, .5 239. .158 251, .259 0, .5064 0, .3083 2660 290, .7 253 .7 83. .0 81, .0 236. .241 250, .795 0, .5171 0, .3201 2680 290, .7 260 .0 83, .5 81, .0 239. .158 250, .586 0, .5043 0. .3260 2700 291. .3 260 .6 83. .0 79, .5 237. .699 250, .470 0, .5145 0. .3348 2720 291. ,3 260 .5 82. .5 80. .5 237. .699 250, .400 0, .5166 0. .3305 2740 291, .3 262 .4 82. .5 80, .0 237. .699 250, .028 0, .5166 0. .3414 2760 292. ,0 260 .0 81. .5 79, .5 237, .699 250, .446 0, .5237 0. .3324 2780 292, .0 261 .0 81. ,5 79, .5 237. .699 250, .167 0, .5237 0, ,3371 2800 292. ,3 256 .0 82. .0 80, .5 236, .241 251, .400 0, .5284 0, ,3098 2820 291, .3 257 .3 82. ,5 80. .0 236, ,241 251, .144 0, .5221 0, ,3178 2840 291, ,7 256 .2 81. .5 80, .0 236, ,241 251, .027 0, .5277 0, ,3138 2860 291. .7 255 .2 81, ,5 80, .0 236, .241 251, .282 0, .5277 0, ,3088 2880 291. ,3 257 .2 82. ,0 80. ,0 236, ,241 251, .121 0, .5242 0, ,3174 2900 291, .7 257 .3 82, .0 81, .0 237, .699 251, .097 0, .5202 0. .3140 2920 292. .0 257 .1 82, ,0 81. .0 237, .699 251, .144 0, .5216 0, ,3129 2940 291, .3 256 .7 83. .0 81, .0 237, .699 251, .027 0, .5145 0. ,3118 2960 291. .3 257 .8 83, ,0 80, .5 239, .158 251, .144 0, .5092 0, ,3178 2980 291. ,7 257 .9 83, ,0 80, ,0 239, ,158 251, .121 0, .5106 0. ,3203 Appendix D. DATA AND RESULTS 205 DICYCLOPENTADIENE LOW HEAT FLUX INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU QHWP 2.063 2.050 183.0 180.0 82.0 82.0 208.37 200.94 AVERAGE CONDITIONS: TBPFRU TBHWP QPFRU QHWP VFP REP VFH REH 82.79 81.55 215.51 201.19 0.81 9760 0.04 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 182. .00 180. ,04 82 .0 83. .0 202, ,701 199. .125 0, ,0086 -0, .0004 20 183. .00 180. .04 82 .0 82. ,5 202. ,701 199. .125 0. ,0136 0, .0021 40 183. .00 179. .19 82 .0 82. .0 204, .159 199. .262 0.0100 0, .0000 60 184. .00 180, .04 82 .0 82, .5 207, .076 199, .125 0, ,0079 0, .0021 80 184, .00 179, .38 82 .0 82, .0 205, .617 199, .292 0, ,0114 0, .0009 100 185. .00 179, .86 82 .5 82, .5 209. .992 199, .095 0, .0034 0, .0013 120 186. .00 179, .01 83 .0 82, .0 209. .992 199, .233 0, ,0058 -0. .0008 140 187, .00 179. .01 83 .5 81. .5 209. .992 199, .233 0, .0082 0, .0017 160 188, .00 180. .04 84 .0 82. .0 209, .992 199, .125 0. .0105 0, .0047 180 188, .00 179. .19 83 .5 81. .0 208, .534 199.262 0. .0164 0, .0051 200 187, .00 180. .04 82 .5 81. .0 213. .492 199, .125 0, .0048 0, .0097 220 200, .67 178. .83 92 .5 79, .5 213.492 199.203 0. .0219 0, .0109 240 192, .00 180. .29 83 .0 80, .0 213. .492 199, .440 0. .0259 0, .0151 260 191, .67 180.29 77 .5 79, .5 212. .909 199.440 0. .0515 0, .0177 280 196, .00 179. .26 76 .0 78. .5 214. ,367 199, .547 0. .0751 0, .0172 300 192, .67 182, .54 77 .0 81, .0 215, .825 199, .253 0, .0512 0, .0219 320 197, .67 183, .58 79 .0 83, .0 215, ,825 199, .145 0, .0651 0, .0174 340 198, .67 184, .80 81 .0 83, .0 215. .825 199, .067 0, .0605 0, .0237 360 200, .67 183, .95 83 .5 84, .0 215. .825 199, .204 0, ,0582 0, .0140 380 202, .00 184. .99 86 .0 85, .5 215, .825 199, .096 0, .0528 0, .0120 400 203, .33 184, .31 85 .0 84, .0 218, .742 199, .263 0, .0563 0, .0157 420 203, .33 184. .13 84 .5 82, .0 218, .742 199, .234 0. .0586 0, .0249 440 203, .33 184. ,01 85 .0 82, .0 215. ,825 199, .489 0. .0636 0, .0236 460 206. .33 185. ,17 84 .0 82, .5 215. ,825 199, .126 0. ,0821 0, .0279 480 205, .00 189. ,83 82 .5 83. .5 215. ,825 198, .496 0. ,0829 0, .0480 500 204, .33 190. ,70 83 .0 83. ,0 218, ,742 198. .359 0. ,0700 0, .0552 520 201, ,33 189. .46 76 .0 82. ,0 218, ,742 198. ,438 0, ,0883 0. .0538 540 201, .67 189, .28 72 .0 82, .0 215, .825 198, .408 0, ,1161 0, .0530 560 202, .00 183, .76 72 .0 80. .0 218, .742 199, .175 0, .1096 0, .0333 580 203, .00 184, .13 72 .5 80. .0 218, .742 199, .234 0, .1119 0, .0349 600 202, .33 184, .74 73 .0 80. .0 218, .742 198, .782 0, .1066 0, .0392 620 203, .33 184. .44 74 .0 79. .0 218. .742 199, .008 0, ,1066 0, .0421 640 203, .33 183, ,76 75 .0 80. .0 215, .825 199, .175 0, ,1099 0, .0333 660 203, .33 183. ,76 76 .0 80, .0 218, .742 199, .175 0. ,0974 0, .0333 680 202. .33 184, ,13 76 .0 80, ,0 218, ,742 199, .234 0, ,0928 0, .0349 700 204, ,33 184, ,50 76 .5 80, ,0 214, ,367 199, ,293 0. ,1116 0, .0366 Appendix D. DATA AND RESULTS 720 204 .33 185.72 77 .0 81 .0 218 .742 199 .214 0, .0974 0 .0380 740 204 .00 185 .60 77 .5 81 .5 218 .742 199 .470 0. .0936 0 .0342 760 204 .33 184 .01 78 .0 81 .5 218 .742 199 .489 0, .0928 0 .0261 780 204 .67 185 .41 78 .0 82 .0 218 .742 199 .440 0, .0944 0 .0308 800 204 .67 185 .41 78 .0 81 .0 218 .742 199.440 0, .0944 0 .0358 820 205 .00 187 .31 78 .0 82 .0 218 .742 199 .194 0. .0959 0 .0410 840 205.33 186 .82 78 .5 81 .0 218 .742 199 .391 0, .0951 0 .0430 860 204 .33 185 .60 78 .5 80 .0 218 .742 199 .470 0, .0906 0 .0417 880 203 .33 184 .92 78 .0 80 .0 214 .367 199 .637 0, .1000 0 .0379 900 204 .00 184.44 78 .5 80 .0 207 .076 199 .834 0, .1214 0 .0349 920 204 .67 184 .62 79 .0 79 .0 212 .909 199 .863 0. .1055 0 .0407 940 205, .33 184 .62 79 .0 79 .0 214 .367 199 .863 0, .1046 0 .0407 960 206 .00 185 .84 79 .5 79 .5 218 .742 199 .785 0, .0936 0 .0446 980 206, .00 186 .70 80 .0 81 .5 218 .742 199 .647 0, ,0913 0 .0392 1000 206, .00 186 .88 80 .0 80 .5 215 .825 199 .676 0. .0991 0 .0451 1020 206, .67 187 .92 80 .0 81 .0 218 .742 199 .568 0. ,0944 0 .0481 1040 207, .00 186 .57 80 .0 81, .5 218 .742 199 .903 0. .0959 0 .0379 1060 207, .67 186 .39 80 .0 82 .0 220 .200 199 .873 0, .0951 0 .0346 1080 206, .67 186 .57 80 .0 81 .0 220 .200 199 .903 0. ,0905 0 .0404 1100 207, .33 187 .43 80 .5 82 .0 214 .367 199 .765 0. .1070 0 .0401 1120 208, .00 189 .33 81 .0 81, .5 215 .825 199 .518 0. ,1037 0 .0527 1140 207, .33 187 .61 81 .0 82 .0 218 .742 199 .794 0, ,0928 0, .0409 1160 207, .67 189 .51 79 .5 81, .5 214 .367 199 .548 0, ,1132 0 .0536 1180 207, .33 187 .80 81 .0 82, .0 215, .825 199 .824 0, ,1006 0, .0417 1200 207, .67 188 .84 81 .0 82, .5 215, .825 199 .715 0. ,1022 0, .0447 1220 208, .00 189 .88 81 .0 82, .0 215 .825 199 .607 0. ,1037 0, .0528 1240 207, .67 191 .11 81 .5 81, .5 215 .825 199 .527 0. .0999 0, .0616 1260 208, .00 190 .74 81 .5 82, .5 215, .825 199 .469 0. ,1014 0 .0549 1280 208. .33 191 .11 82 .0 83, .0 215, .825 199.527 0. .1006 0, .0541 1300 208, .33 192 .15 82 .0 83, .0 215, .825 199 .419 0. .1006 0, .0597 1320 208. .00 193 .02 82 .0 83, .0 215, .825 199, .281 0. .0991 0, .0644 i340 208.00 194, .07 82, .0 83, .0 215, .825 199 .172 0. ,0991 0, .0699 1360 207. .00 193, .39 82, .0 83, .5 215, .825 199, .340 0, .0945 0, .0635 1380 208, ,67 193, .20 81, .5 83, .5 214, .367 199, .310 0. ,1085 0, .0627 1400 208. .67 194, .25 82, .0 83. .0 215, .825 199, .201 0. .1022 0, .0708 1420 209. ,00 195, .12 82, .0 83, .0 215, .825 199, .063 0. .1037 0, .0755 1440 209. .33 196, .17 82, .0 82. .5 215, .825 198, .954 0. .1053 0, .0836 1460 208. ,33 196, .17 82, .5 83, .0 215, .825 198, .954 0. ,0983 0, .0811 1480 209. .00 196, .35 83, .0 83. .0 215, .825 198, .984 0. .0991 0, .0820 1500 209. ,33 192, .34 83, .5 83. .0 214, .367 199, .448 0. .1023 0, .0605 1520 211. .33 193, .20 84, .5 81. .5 209, .992 199, .310 0. ,1193 0. .0727 1540 212. ,33 193, .39 85, .5 80. .5 218, .742 199, .340 0. ,0951 0. .0786 1560 212. ,67 193, .39 86, .5 81, ,5 220, .200 199, .340 0. .0883 0, .0736 1580 213. ,00 194, .25 85, .0 81. ,0 218. .742 199, .201 0. ,1005 0. .0808 1600 213. ,00 193, .57 86, .5 82, .0 218. .742 199, .369 0. ,0936 0. .0719 1620 213. .67 195.49 87, .5 82. .5 215. .825 199, .122 0. ,0999 0. .0797 1640 216. .00 194, .62 86, .0 83, .0 215, .825 199, .260 0. ,1176 0. .0725 1660 219. ,00 194, .80 82, .0 82, .5 214. .367 199, .290 0. ,1544 0. .0758 1680 217. .00 194, .80 80. .0 82, ,0 215. .825 199.290 0. ,1501 0. .0783 1700 214. .67 194. .99 80, .0 82, .0 215. .825 199, .319 0. ,1393 0, ,0792 1720 215. ,00 194. .99 80, ,0 82, ,0 214, ,367 199. ,319 0. ,1451 0, ,0792 1740 216. ,33 196, ,04 81, ,0 82. .5 214, ,367 199, .210 0. ,1466 0, ,0822 1760 217. ,33 196. ,22 81, ,0 82, ,5 214, ,367 199, ,239 0. 1513 0, ,0831 1780 217. ,33 194. .67 81. .5 82. .0 214, .367 199, ,545 0. ,1489 0, ,0769 1800 218. ,00 196, ,01 82, ,0 81, ,5 214. ,367 200. ,037 0. 1497 0, ,0848 1820 217. ,67 196. .88 82. ,5 81. .5 214, .367 199, ,898 0. 1458 0, ,0895 1840 219. ,00 196, ,88 83, .0 82. .5 214. ,367 199. ,898 0. 1497 0. .0845 1860 219. ,00 196. .99 82. ,5 81. .5 214. ,367 200, .469 0. 1521 0. .0884 1880 219. ,67 199, ,69 82. .5 81. ,5 214. ,367 200.625 0. 1552 0. ,1014 1900 219. ,33 197. .20 83, ,0 82. ,5 214. ,367 201, .615 0. 1513 0. .0812 1920 220. ,33 196. ,33 83. ,0 81. ,5 214. ,367 201. ,754 0. 1559 0. .0815 1940 220. ,67 195.47 83, ,0 81. ,0 214. ,367 201. .893 0. 1575 0. ,0793 1960 221. ,67 197. .30 83. ,5 82. ,0 214. ,367 202, ,189 0. 1598 0. ,0826 1980 221. ,67 197. ,41 84. ,0 82. ,0 214. ,367 202, ,763 0. 1575 0. .0815 2000 222. ,00 197. ,41 84. ,5 82. ,0 214. ,367 202. ,763 0. 1567 0. ,0815 2020 222. ,67 197. ,51 84. ,5 82. ,0 214. ,367 203. .339 0. 1598 0. ,0804 2040 223. 00 196. ,65 85. ,0 81. ,0 214. ,367 203.479 0. 1590 0. ,0807 Appendix D. DATA AND RESULTS 2060 224, .00 197 .51 85 .5 81 .5 214. .367 203, .339 0, .1614 0. .0828 2080 224, .67 197, .61 86 .0 81 .5 214, .367 203, .915 0, .1622 0, .0817 2100 225, .33 197 .51 86 .0 80 .5 214, .367 203, .339 0, .1653 0, .0877 2120 225, .67 197 .51 86 .5 80 .0 214, .367 203, .339 0, .1645 0, .0902 2140 226, .67 198, .47 87 .0 81 .0 214, .367 203, .775 0, .1668 0, ,0888 2160 227, .33 198, .47 87 .0 82 .0 214. .367 203, .775 0, .1699 0, ,0839 2180 227, .67 199, .44 87 .0 81 .0 215, .825 204, .212 0, .1671 0, ,0923 2200 228, .00 199.44 87 .0 80 .5 215, .825 204, .212 0, .1686 0, ,0947 2220 228, .00 200, .30 87 .0 80 .5 215, .825 204, .072 0. .1686 0, ,0993 2240 228, .00 202, .12 86 .5 81 .0 215. .825 204, .369 0. .1709 0, ,1049 2260 229, .00 199, .44 86 .5 80 .5 214, .367 204, .212 0, .1800 0, ,0947 2280 228, .33 202, .12 86 .0 79 .5 214. ,367 204, .369 0. .1793 0. ,1123 2300 229, .00 202, .98 86 .5 79 .5 214, .367 204, .228 0, .1800 0, ,1169 2320 230, .00 203, .94 86 .5 79 .5 214, ,367 204, .665 0. .1847 0, ,1203 2340 230, .33 206, .63 86 .5 80 .5 215. .825 204. .821 0. .1817 0. ,1281 2360 230, .67 206, .63 87 .0 80 .0 215. .825 204, .821 0, .1810 0, .1305 2380 231. .00 205, .67 87 .5 79 .5 215, .825 204. .384 0, .1802 0, ,1296 2400 231, .33 206, .63 87 .5 79 .0 215, .825 204. .821 0, .1817 0, ,1354 2420 231. .33 205, .77 87 .5 78 .5 215, ,825 204. .962 0, .1817 0, ,1332 2440 231, .00 206, .72 86 .5 79 .0 218, ,742 205, .399 0, .1759 0, ,1341 2460 239, .33 207, .59 81 .0 79 .5 218, ,742 205. .258 0, .2391 0, ,1363 2480 235, .00 210, .28 81 .0 80 .0 218. ,742 205. .414 0, .2193 0, ,1465 2500 235, .67 212, .10 82 .0 82 .5 218. .742 205, ,710 0, .2178 0, ,1423 2520 236, ,00 212, .97 82 .5 81 .0 220, ,200 205, .569 0, .2124 0, .1543 2540 235, .00 210, .28 83 .5 81 .5 220, .200 205, .414 0, .2033 0, .1392 2560 235, ,00 209, .41 84 .0 81 .0 214. ,367 205, .555 0, .2197 0, .1370 2580 236, ,00 209, .32 85 .0 81 .5 214, .367 204, ,976 0, .2197 0, .1359 2600 236, ,00 212, .02 85 .5 81 .5 215, ,825 205. ,131 0, .2126 0, .1486 2620 237. .00 210, .19 86 .0 81 .5 215, .825 204, ,835 0, .2149 0. .1406 2640 236, ,67 212, .02 86 .5 82 .5 215, .825 205. .131 0, .2111 0. .1437 2660 237, .33 211, .06 87 .0 83 .5 215, .825 204, .694 0, .2118 0, .1355 2680 237, ,33 211, .06 87 .5 83 .5 215, .825 204, .694 0. .2095 0, ,1355 2700 237, ,67 213, .77 87 .5 82 .5 218, .742 204, ,849 0, .2018 0. .1531 2720 237, .00 212, .89 87 .0 82 .5 218, .742 204, .990 0, .2010 0, ,1484 2740 238, .33 211, .06 86 .5 83 .0 218, .742 204, .694 0, .2094 0. .1379 2760 237, .33 211, .94 89 .5 83 .0 218.742 204, ,554 0, ,1911 0. ,1426 2780 237, .00 213, .77 89 .5 83 .0 212. .909 204, .849 0. ,2081 0. ,1506 2800 238, ,67 213, ,77 88 .0 81 .5 218, ,742 204. .849 0. ,2041 0. ,1580 2820 238. .00 211, ,94 88 .0 82 .0 218. .742 204. .554 0. ,2010 0. ,1475 2840 238. .33 211. ,06 88 .0 82 .0 218. .742 204, .694 0. .2026 0. ,1428 2860 237. ,00 211, ,06 87 .5 82 .5 215. .825 204. .694 0. ,2080 0. ,1404 2880 237. .33 212, ,89 87 .5 82 .5 215. .825 204. .990 0. .2095 0. , 1484 2900 236. ,67 213, ,77 87 .5 82 .5 215. .825 204. .849 0. ,2064 0. ,1531 2920 236. .33 213, ,77 89 .0 81 .5 215. ,825 204, .849 0, .1979 0. ,1580 2940 236. ,33 214, .72 88 .5 81 .5 215. .825 205, .286 0. .2003 0. ,1612 2960 236. .67 215, ,59 87 .5 81 .5 215. ,825 205. ,145 0. .2064 0. ,1659 2980 238. ,00 213, .77 88 .0 82 .0 212. ,909 204. .849 0. .2198 0. ,1555 Appendix D. DATA AND RESULTS DICYCLOPENTADIENE DEOXYGENATED. INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU qHWP 2.602 2.549 198.33 197.47 84.0 81.0 297.48 296.91 AVERAGE CONDITIONS: TBPFRU TBHWP qPFRU qHWP VFP REP VFH REH 84.58 81.34 301.80 297.58 0.81 9760 0.04 4.9 TIME PTEMP HTEMP PTB HTB PHF HHF PFR HFR 0 197 .7 195 .3 84.0 80 .0 297.489 300. .449 -0. .0022 -0. .0085 20 199 .0 194 .1 81 .5 79 .0 298. .947 300. .741 0. .0087 -0. ,0095 40 198 .0 196 .9 81 .5 80 .0 298. .947 300, .828 0, .0054 -0. .0038 60 198 .3 196 .9 81 .5 79 .0 298. .947 300, .828 0, .0065 -0. .0005 80 197 .3 199 .3 80 .0 79 .0 297. .489 300, .245 0, .0101 0, .0083 100 197 .0 197 .7 80 .0 78 .5 297. .489 299, .867 0, .0090 0, ,0053 120 197 .3 196 .2 80 .5 81 .5 297. .489 299, .489 0, .0084 -0. .0095 140 198 .3 197 .4 80 .5 80 .5 300, .405 299, .198 0, .0079 -0. ,0017 160 199 .0 198 .6 81 .5 80 .5 300, .405 298, .907 0, .0068 0, .0027 180 198 .3 198 .6 80 .0 80 .5 297, .489 298, .907 0, .0134 0, .0027 200 199 .0 198 .2 81 .5 80 .5 298, .947 298. .240 0. .0087 0, .0023 220 200 .3 198 .2 80 .0 80 .0 297, .489 298, .240 0, .0202 0, .0040 240 201 .3 199 .4 79 .0 80 .0 300, .405 297, .949 0, .0229 0, .0084 260 201 .7 199 .0 79 .5 79 .5 285, .823 297, .283 0, .0431 0, .0098 280 202 .7 198 .7 81 .5 79 .0 298, .947 296, .617 0, .0210 , 0, .0112 300 202 .0 195 .1 81 .5 78 .0 297, .489 297.486 0, .0207 0, .0013 320 202 .3 198 .7 81 .0 77 .5 301, .864 296, .617 0, .0176 0, .0163 340 203 .3 197 .1 82 .0 77 .0 293, .114 296, .241 0, .0296 0, .0132 360 203 .0 195 .6 81 .5 76 .0 301, .864 295, .865 0, .0182 0, .0118 380 204 .3 194 .0 82 .0 77 .5 300, .405 295, .489 0, .0229 0, .0019 400 205 .3 196 .4 83 .0 77 .5 301.864 294.912 0, .0209 0, .0109 420 206 .3 199 .2 84 .5 78 .5 300.405 294, .998 0, .0212 0 .0168 440 207 .7 194 .1 84 .0 79 .5 300, .405 293, .211 0, .0273 -0. .0015 460 209 .7 198 .5 86 .5 80 .0 300, .405 293, .672 0, .0257 0, .0110 480 210 .3 198 .5 86 .0 79 .5 300, .405 293, .672 0, .0296 0, .0128 500 211 .3 199 .7 86 .0 80 .5 301, .864 293, .384 0, .0309 0, .0139 520 210 .7 199 .7 86 .0 81 .0 300, .405 293, .384 0, .0307 0, .0122 540 213 .0 200 .9 87 .5 81 .5 301, .864 293. .096 0, .0314 0, ,0150 560 212 .0 202 .0 88 .0 81 .0 300, .405 300. .332 0, .0284 0. ,0107 580 212 .0 203 .2 86 .0 81 .5 301, .864 300. .040 0, .0331 0, .0134 600 210 .7 201 .7 85 .0 81 .0 300, .405 299. .662 0, .0340 0, .0104 620 211 .0 204 .4 86 .0 82 .0 301, .864 299, .748 0, .0298 0, .0162 640 211 .7 202 .4 84 .0 81 .0 304, .780 301, .002 0, .0345 0, .0110 660 210 .3 202 .4 84.0 78 .0 297, .489 301, .002 0, .0403 0, .0209 680 212 .7 201 .2 84 .0 78 .0 303, .322 301, .294 0, .0399 0, .0165 700 214 .0 205 .5 85 .5 79 .0 303, .322 301.758 0, .0393 0, .0269 720 216 .0 205 .1 87 .5 79 .5 303, .322 301, .087 0. .0393 0, ,0250 740 216 .3 206 .4 88 .5 79 .0 303. .322 300. .795 0, .0371 0, .0311 760 216 .3 206 .4 87 .5 79 .0 301, .864 300, .795 0, .0425 0, .0311 Appendix D. DATA AND RESULTS 780 217 .3 208 .8 88 .0 80 .5 301 .864 300.209 0 .0441 0, .0350 800 217 .0 208 .8 88 .5 80 .0 301 .864 300 .209 0 .0414 0, .0366 820 217 .0 210 .0 89 .0 80 .5 303 .322 299 .917 0 .0377 0, .0395 840 217 .7 209 .1 88 .5 81 .5 303 .322 300 .879 0 .0415 0, .0319 860 218 .3 209 .1 88 .5 82 .0 300 .405 300 .879 0 .0479 0, .0302 880 218 .7 209 .1 89 .5 82 .5 300 .405 300 .879 0. .0456 0, .0285 900 218 .3 211 .9 90 .0 83 .0 300 .405 300 .963 0. .0429 0, .0360 920 219 .3 210 .3 90 .0 83 .0 300 .405 300 .586 0. .0462 0, .0313 940 219 .3 210 .3 90 .0 82 .0 301 .864 300 .586 0 .0441 0, .0347 960 220 .0 210 .3 90 .5 81 .5 300 .405 300 .586 0 .0467 0, .0363 980 220 .0 209 .1 91 .0 81 .5 300 .405 300 .879 0. .0451 0, .0319 1000 220 .3 210 .3 91 .0 82 .0 300 .405 300 .586 0 .0462 0, .0347 1020 220 .3 210 .3 91 .0 82 .5 300.405 300 .586 0 .0462 0, .0330 1040 220, .7 210 .3 91 .0 82 .5 301 .280 300 .586 0 .0461 0, .0330 1060 220 .7 211 .9 91 .5 83 .5 304 .780 300 .963 0 .0395 0, .0343 1080 221, .3 211 .6 91 .5 83 .5 301 .864 300 .293 0 .0458 0, .0341 1100 221, .0 211 .6 91 .0 83, .5 301 .864 300 .293 0 .0463 0, .0341 1120 220, .3 211 .6 91 .0 83 .0 300 .405 300 .293 0 .0462 0, .0358 1140 222, .3 210 .3 92 .5 82 .5 300 .405 300 .586 0, .0479 0, .0330 1160 221, .7 211 .6 90 .0 83 .0 301 .864 300 .293 0, .0518 0, .0358 1180 222, .0 213 .1 89 .0 83 .5 301 .864 300 .669 0. .0563 0, .0388 1200 222, .7 213 .1 90 .0 84 .5 304 .780 300 .669 0. .0510 0 .0355 1220 224, .0 211 .9 90 .0 84 .5 300 .405 300 .963 0 .0617 0, .0310 1240 223, .7 214 .3 90 .0 85, .0 300 .405 300 .376 0 .0606 0, .0383 1260 223, .3 214 .3 89 .0 86, .0 304 .780 300 .376 0 .0564 0, .0349 1280 222, .7 214 .3 89 .0 85, .5 303 .322 300 .376 0 .0563 0, .0366 1300 223, .0 214 .3 90 .0 86, .0 304 .780 300 .376 0 .0520 0, .0349 1320 220, .3 212 .4 88 .5 85, .5 300 .405 299 .332 0 .0545 0. .0317 1340 221, .7 212 .1 88 .5 84, .5 303 .322 298 .664 0, .0547 0, .0349 1360 220. .7 214 .5 87 .0 84, .5 294 .572 298 .080 0, .0694 0, .0439 1380 222, .0 213 .3 86 .5 83, .5 303 .322 298 .372 0, .0624 0, .0427 1400 221, .3 213 .3 85 .5 83, .0 303 .322 298, .372 0, .0635 0, .0444 1420 220, .0 215 .8 83 .5 82, .5 303, .322 297, .787 0, .0657 0, .0552 1440 221, .3 215 .8 84 .5 82, .0 304, .780 297, .787 0, .0646 0. .0569 1460 220, .7 217 .0 84 .0 82, .0 303, .322 297 .495 0, .0662 0, .0614 1480 221, .7 217 .0 84 .0 81, .0 303, .322 297, .495 0, .0695 0. .0648 1500 221, .3 217 .0 84, .5 82, .0 304, .780 297, .495 0, .0646 0, .0614 1520 221, ,7 217 .0 85, .5 83, .0 304, .780 297, .495 0, .0624 0, ,0581 1540 222, .3 218 .2 86, .0 83, .0 304, .780 297, .203 0, .0630 0. ,0627 1560 222. ,7 218 .2 87, .0 83, .5 304, .780 297, .203 0, .0608 0, ,0610 1580 222, ,3 218 .2 88, .5 84. .5 293, .114 297, .203 0, .0723 0, ,0576 1600 223. ,0 219 .5 89, .0 85, .0 303, .322 296, .910 0, .0574 0, ,0605 1620 222, .3 219 .5 89, .5 84, .5 294, .572 296, .910 0, .0666 0, ,0622 1640 224, .3 219 .5 90, .5 84, .0 300.405 296, .910 0, .0612 0, ,0639 1660 223. ,3 221 .0 90, .5 83, .0 303, .322 297, .283 0, .0536 0, .0720 1680 224, ,3 221, .0 91, .5 83, .0 300, .405 297, .283 0, .0578 0, .0720 1700 224, ,3 221 .0 90, .0 82, .5 304, .780 297, .283 0. .0564 0. .0737 1720 224, ,3 221, .0 90, .0 82, ,0 304, .780 297, .283 0, .0564 0. .0754 1740 219, ,7 222, .3 81, .0 83, ,0 303, .322 296, .991 0, .0728 0, ,0766 1760 217, ,7 222 .3 81, .0 83, ,0 303, .322 296, .991 0, .0662 0, .0766 1780 218, ,0 223, .2 80, .0 84, ,0 303, .322 296. .034 0, .0706 0, .0778 1800 218. .7 221, .6 80, .0 84, ,0 304. .780 295. .662 0, .0706 0. .0731 1820 219, .7 221, .9 80, .5 83, ,5 304, .780 296, .326 0. .0723 0. ,0748 1840 219, .7 221, .9 81, .0 83, .0 304. .780 296, ,326 0, .0706 0. .0765 1860 220. .3 221, .9 82, .0 82, .5 300. .405 296, ,326 0, .0762 0. ,0782 1880 221, ,0 221, .9 82, .5 82. .0 301. .864 296, ,326 0, .0745 0. ,0799 1900 220. ,7 223, .2 83, ,5 81. .5 300.405 296, ,034 0, .0723 0. ,0863 1920 220. ,0 223, .2 83, .5 81. .5 300, .405 296, .034 0, .0701 0. ,0863 1940 220. ,7 223, .2 84, ,5 81. ,0 301, .864 296, ,034 0, ,0668 0. ,0879 1960 220. ,0 223, .2 84. ,5 81. ,0 304, .780 296, .034 0. .0602 0. ,0879 1980 221. ,0 223, .2 85, ,5 81. ,0 300, .405 296, ,034 0. ,0667 0. ,0879 2000 221. ,0 223, .2 84, ,5 81. ,0 300. .405 296.034 0. .0701 0. ,0879 2020 221. ,0 224, ,4 83, ,5 80. ,0 303. .322 295. ,741 0. ,0690 0. ,0960 2040 220. ,3 224, ,4 83. ,0 80. ,5 304. .780 295. .741 0. ,0663 0. ,0943 2060 220. ,7 224, .4 82. ,0 79. ,5 304. .780 295. .741 0. .0706 0. ,0977 2080 221. ,3 224, ,4 81, ,0 78. ,5 303. .322 295. ,741 0. ,0783 0. ,1011 Appendix D. DATA AND RESULTS 2100 221 .3 224 .4 80, .0 78 .5 303 .322 295, .741 0, .0816 0, ,1011 2120 221, .3 224 .4 80, .0 79 .0 303 .322 295, .741 0, .0816 0, ,0994 2140 221, .0 225 .7 79, .5 79, .0 303 .322 295, .449 0, .0822 0, .1041 2160 221, .7 225 .7 79, .5 79, .5 303 .322 295.449 0, .0844 0, .1024 2180 221, .3 225 .7 80, .0 79, .5 303, .322 295.449 0, .0816 0, .1024 2200 222 .0 225 .7 80. .5 80, .0 301, .864 295, .449 0, .0844 0, .1007 2220 222 .0 225 .7 81, .5 80, .5 303 .322 295.449 0, .0789 0. ,0990 2240 222 .7 226 .9 80, .5 81, .0 301, .864 295, .157 0, .0866 0. .1020 2260 220, .7 226 .9 80. .5 80, .5 304 .780 295, .157 0, .0756 0. .1037 2280 221, .0 226 .9 80, .5 81, .0 303 .322 295, .157 0, .0789 0. .1020 2300 221, .0 226 .9 80, .5 81, .0 304 .780 295, .157 0, .0767 0, .1020 2320 221, .0 226 .9 80. .5 81, .0 304, .780 295, .157 0, .0767 0, .1020 2340 220, .7 226 .9 80, .5 81, .5 304, .780 295, .157 0, .0756 0, ,1003 2360 220, .7 228 .2 . 78, .5 82, .0 303, .322 294, .865 0, .0844 0. .1034 2380 220, .7 228 .2 77. .5 82, .0 303, .322 294, .865 0, .0877 0, .1034 2400 219, .7 228 .2 78, .0 82, .5 304, .780 294, .865 0, .0805 0, .1017 2420 221, .0 228 .2 78. .5 83, .0 303, .322 294, .865 0, .0855 0, .1000 2440 220, .7 228 .2 79, .5 82, .5 303, .322 294, .865 0, .0811 0, .1017 2460 221, .0 228 .2 79. .5 82, .5 303, .322 294, .865 0, .0822 0, .1017 2480 221, .0 226 .9 79, .5 82, .0 306, .238 295. .157 0, .0777 0, .0987 2500 220, .3 226 .9 80, .5 81, .5 303, .322 295, .157 0, .0767 0. ,1003 2520 220, .3 226 .9 80, .5 81, .5 304, .780 295, .157 0, .0745 0, .1003 2540 222, ,3 225 .7 80, .5 80, .5 301, .864 295. .449 0, .0855 0, ,0990 2560 221, .7 225 .7 81, .5 80, .0 301, .864 295. .449 0, .0800 0. ,1007 2580 221, .7 225 .7 82, .5 80, .0 301, .864 295, .449 0, .0767 0, ,1007 2600 221, .7 225 .7 82, .5 79, .5 300, .405 295.449 0, .0789 0. .1024 2620 221. ,3 225 .7 82, .5 79, .5 304, .780 295, .449 0, .0712 0, ,1024 2640 220, ,7 225 .7 83, .5 80. .0 303, .322 295, .449 0, .0679 0, ,1007 2660 221, ,7 225 .7 83, .5 80, .5 304, .780 295, .449 0, .0690 0, ,0990 2680 221, .3 225 .7 84, .5 80, .5 304, .780 295. .449 0, .0646 0. ,0990 2700 221, ,0 225 .7 85, .0 81. .0 303, .322 295. .449 0, .0640 0. .0973 2720 221. ,3 225 .7 85, .5 81, .5 303, .322 295, .449 0, .0635 0, ,0956 2740 220. .7 225 .7 85. .5 82. .0 303, .322 295, .449 0. .0613 0. ,0939 Appendix D. DATA AND RESULTS 211 RUN 15, HEXADECENE-1 INITIAL CONDITIONS: UPFRU UHWP TPFRU THWP TBPFRU TBHWP QPFRU QHWP 2.569 2.639 198.00 198.00 82.0 82.0 297.99 306.16 AVERAGE CONDITIONS: TBPFRU 83.89 TBHWP 81.70 QPFRU 297.73 QHWP 307.28 VFP 0.81 REP 9760 VFH 0.04 REH 4.9 TIME PTEMP HTEMP PTB HTB 0 197, .0 198 .5 86 .5 82, .0 20 197, .7 198 .3 85, .0 82, .0 40 197, .7 198 .5 85, .5 82, .0 60 198, .3 198 .7 86, .0 82, .0 80 198, .7 198 .7 85, .0 82, .0 100 199, .3 198 .7 84, .5 82, .5 120 200, .0 199 .0 84, .0 83, .0 140 202, .7 199 .5 84, .5 83, .0 160 202, .3 200 .3 83, .5 83, .0 180 203, .7 200 .4 82, .5 83, .0 200 204, .3 200 .6 81, .5 82, .5 220 206, .3 201 .3 81, .0 81, .0 240 208, .3 201 .9 82, .5 82. .0 260 209, .7 202 .3 82, .5 81, .5 280 211, .0 201 .7 86, .5 81. .0 300 210, ,7 203 .9 79, .0 81. .0 320 209, .3 202 .8 80, .0 81, .0 340 211. .3 203 .4 86, .0 82. ,0 360 214, .0 204 .3 92, .5 82. .0 380 218. .0 203 .8 96, .5 83, .0 400 221, .0 205 .2 94, .5 82, .0 420 222. .7 205 .3 93, .5 82, ,0 440 221, ,7 205 .9 91, .5 81. .0 460 220, ,0 205 .8 80, .5 81, ,5 480 214. ,7 207 .4 79, .0 81. .5 500 .215, ,3 207 .6 79, .5 81, ,5 520 215. ,7 208 .3 80. .5 80. .5 540 216, .0 209 .6 81. .5 83, ,0 560 215, .7 210 .3 82, .5 83, ,0 580 216, ,3 211 .2 83. .0 83, ,0 600 217, .7 211 .9 84, .0 81, ,0 620 218. .7 213 .0 85, .5 82, ,0 640 237, ,3 213 .3 78, ,5 82, ,0 660 228. ,3 214 .7 87, ,5 81, .0 680 228. ,3 215 .3 94, ,0 80, ,5 700 229. ,3 215 .8 95. .5 80. ,5 PHF HHF PFR HFR 298 .947 300, .969 -0, .0196 0 .0081 297 .489 300, .925 -0, .0105 0 .0076 297 .489 300, .969 -0, .0122 0, .0081 297 .489 300, .999 -0, .0117 0 .0089 298 .947 300, .999 -0, .0090 0, .0089 298, .947 300, .999 -0, .0051 0, .0072 297.489 301, .102 0 .0007 0, .0064 297, .489 301, .175 0, .0080 0, .0078 297, .489 301, .336 0 .0102 0 .0102 297.489 301, .307 0 .0180 0, .0107 298, .947 301, .351 0 .0216 0, .0129 297.489 301.438 0 .0320 0, .0202 297, .489 301, .556 0 .0337 0, .0187 297, .489 301, .644 0 .0382 0, .0215 298, .947 301, .689 0 .0272 0, .0213 298, .947 301, .524 0, .0512 0, .0286 296, .031 301, .865 0, .0476 0, .0247 296, .031 302, .174 0, .0341 0, .0228 296, .031 302, .394 0, .0212 0, .0255 279, .989 302.424 0, .0447 0, .0206 298, .947 302, .792 0, .0339 0, .0280 298, .947 303, ,560 0, .0428 0, .0273 297, .489 303, .500 0, .0483 0, .0327 297.489 303, .708 0, .0797 0, .0304 298, .947 303, .764 0, .0646 0, .0356 298, .947 304, .075 0, .0651 0, .0357 300, .405 304. .163 0, .0607 0, .0413 300, .405 304.383 0, .0585 0, .0370 300.405 304. .752 0, .0540 0. .0387 294, ,572 304, .958 0. .0634 0, .0417 297, .489 305, ,164 0, .0601 0, .0499 297, .489 305. .429 0, .0584 0, .0499 298, .947 305.443 0. .1420 0, .0509 303, .322 305, ,618 0, .0750 0, .0587 303, .322 305, ,839 0, .0536 0, ,0618 303, .322 305, .882 0. .0520 0, ,0636 Appendix D. DATA AND RESULTS 212 720 231 .0 215 .8 95, .0 81, .5 304, .780 305, .882 0, ,0570 0, ,0603 740 231 .0 216 .6 94, .0 82, .0 304, .780 306, .059 0, .0602 0. ,0608 760 233 .0 217 .4 93, .0 82, .5 303, .322 306, .205 0, .0723 0. ,0618 780 233 .3 217 .9 92, .5 83, .0 303.322 306. .264 0, .0750 0. ,0617 800 222 .7 218 .1 85, .5 83 .5 303, .322 306. .397 0, .0630 0. ,0604 820 224 .3 218 .4 79, .5 83, .0 303. .322 306. .500 0, .0882 0. ,0629 840 226 .7 219 .6 80 .5 82 .0 303, .322 306. .482 0 .0926 0, .0700 860 227 .3 219 .3 82, .0 81 .5 303, .322 306, .736 0 .0899 0, .0703 880 228 .7 219 .6 84, .0 80 .5 301, .864 306, .839 0, .0900 0. .0744 900 230 .3 219 .6 86, .5 81 .5 300, .405 307, .107 0, .0895 0, .0707 920 228 .7 220 .2 83, .5 80, .5 303, .322 307, .209 0, .0893 0, .0760 940 229 .7 220 .3 80, .5 79 .5 303, .322 307, .283 0, .1025 0, .0793 960 230 .0 220 .8 81, .0 80, .5 304, .780 307, .342 0, .0996 0. .0776 980 231 .7 220 .6 81, .5 80, .0 303, .322 307, .476 0, .1058 0. .0784 1000 233 .0 221 .2 82, .5 80, .5 304, .780 307, .057 0, .1045 0. .0794 1020 231 .0 222 .0 82. .0 81, .0 288, .739 307. ,145 0, .1268 0, .0801 1040 230 .0 222 .6 81, .0 80, .5 296. .031 307. ,172 0, .1141 0. ,0837 1060 231 .7 222 .5 81, .5 81 .0 296, .031 307, .381 0 .1180 0, .0813 1080 232 .0 222 .4 82, .0 82, .0 296, .031 307. .218 0 .1174 0, .0781 1100 233 .0 223 .3 83, .0 82 .5 296, .031 307, .274 0 .1174 0, .0792 1120 234 .0 223 .5 83, .5 82, .5 296, .031 307, .319 0, .1191 0, .0798 1140 234 .7 224 .1 84, .0 83, .5 296, .031 307, .331 0, .1197 0. .0787 1160 235 .3 224 .1 84, .0 83, .5 296, .031 307, .346 0, .1219 0, .0785 1180 236 .3 224 .4 84, .0 83, .5 296, .031 307, .345 0, .1253 0, .0797 1200 237 .0 224 .7 84, .5 83, .0 297, .489 307, .374 0, .1234 0. ,0821 1220 238 .0 224 .8 84, .5 82, .5 297. .489 307, .359 0, .1267 0. ,0839 1240 239 .3 224 .6 84, .5 81, .5 297. ,489 307, .494 0, .1312 0, ,0863 1260 240 .0 225 .6 84. .5 80, .5 297. .489 307. .327 0, .1334 0. ,0933 1280 242 .0 225 .6 85, .0 79 .5 297, .489 307, .342 0 .1385 0. .0964 1300 242 .7 225 .4 85. .5 79 .0 297, .489 307, .372 0 .1390 0, .0975 1320 242 .7 225 .5 85, .5 79 .5 297, .489 307, .267 0, .1390 0, .0963 1340 243 .7 225 .4 85, .5 80, .0 297.489 307, .387 0 .1424 0, ,0940 1360 243 .7 226 .2 85, .5 80, .0 296, .031 307, .444 0, .1450 0, ,0968 1380 243 .7 226 .4 86. .0 80, .5 294. .572 307, .503 0, .1460 0, ,0954 1400 244 .3 226 .7 86, ,5 81, .0 294. .572 307. .517 0, .1465 0, ,0948 1420 246 .3 227 .0 87, .0 81, .0 296. .031 307.441 0, .1490 0. ,0959 1440 245 .7 227 .5 89, ,0 81, .5 296, .031 307. ,573 0, .1400 0. .0959 1460 246 .3 227 .5 90. ,0 82, .0 290, .197 307. .499 0, .1495 0. ,0942 1480 245 .7 227 .4 90. ,0 82, .0 296. .031 307. .514 0, .1366 0. ,0940 1500 248 .7 227 .9 91, .5 83, .0 291, .656 307, .572 0, .1496 0, .0922 1520 249 .3 228 .7 93, .0 84, .0 290. .197 307, .480 0, .1495 0. .0916 1540 251 .0 230 .2 91, .5 84, .0 290. .197 307. .206 0, .1604 0. .0969 1560 247 .3 232 .3 88, .0 84, .5 288. .739 306.797 0, .1626 0, .1027 1580 246 .0 233 .1 82. .0 85, .0 290. .197 306. .600 0, .1759 0, ,1041 1600 245 .0 233 .8 78, ,0 86, .0 290. .197 306. ,508 0, .1862 0, .1035 1620 246 .7 234 .8 78, .5 86, .0 288. .739 306. .281 0, .1932 0, ,1069 1640 246 .7 236 .4 78, ,5 85, .5 287. .281 305, ,992 0, .1961 0. .1142 1660 247 .7 235 .6 79, .0 85. .0 288, .739 306. ,189 0, .1949 0. .1128 1680 249. .7 235 .6 78, ,0 84. .0 288.739 306. ,174 0, ,2053 0. ,1163 1700 250, .0 235, .7 79. .0 83. .0 288, .739 306. .233 0, ,2030 0. ,1199 1720 251 .3 235 .8 79, .0 82, .5 288, .739 306. .307 0.2076 0, .1216 1740 248 .0 235 .4 79. .0 81, .5 279, .989 306, ,323 0, .2143 0. .1234 1760 252 .3 235 .6 80, ,0 81, .5 288, ,739 306, ,352 0, .2076 0. .1242 1780 252 .0 236 .0 80, ,0 81, .0 288, ,739 306, .172 0, .2064 0. ,1274 1800 252, .7 235 .5 81, ,0 80, .5 288, ,739 306, ,293 0, .2053 0. ,1271 1820 253, .7 237 .1 82, .0 82, ,0 290. ,197 306. .093 0, ,2023 0. ,1277 1840 254, .7 237, .1 82. ,0 81, ,5 290. ,197 306. .093 0, ,2057 0. ,1294 1860 255, .0 236, .3 83. .0 81. .5 290. .197 306. ,275 0. .2034 0. ,1266 1880 254, .0 236, .0 84. ,0 81, ,0 290. ,197 306.440 0, ,1965 0. ,1269 1900 255, .3 236, .2 84. ,0 81, ,0 288. ,739 306.483 0. ,2041 0. ,1274 1920 256, .3 236, .0 84. ,0 80. ,5 288. ,739 306. ,514 0. ,2076 0. ,1286 1940 258. .0 236, .4 85. .0 80. ,0 290. .197 306. .527 0. ,2069 0. ,1312 1960 257, .0 236, .2 79. .5 79, .5 290. .197 306. .573 0, ,2224 0. ,1321 1980 257, .7 236, .7 79. ,0 80, .0 298. ,947 306.452 0.2084 0. ,1324 2000 258, .3 237, .0 79. ,0 81, .0 298. ,947 306. ,450 0, ,2106 0. ,1303 2020 261, .3 237, .0 80. ,0 81. .0 298. ,947 306. .465 0. .2173 0. 1301 2040 261. .0 236, .8 80. ,0 81. .5 304. ,780 306. ,585 0, .2046 0. 1278 Appendix D. DATA AND RESULTS 2060 262, .3 236 .9 80, .0 82, .0 298 .947 306, .480 0, .2207 0. .1266 2080 261, .7 237 .0 79, .0 82, .0 304 .780 306, .465 0, .2101 0, ,1268 2100 261, .7 234 .7 79, .0 82, .5 296 .031 308, .142 0, .2278 0, .1151 2120 261, .3 242 .4 79, .5 83, .0 297.489 310, .796 0, ,2220 0, .1340 2140 262, .3 247 .7 79, .0 82, .5 298 .947 312, .342 0, .2240 0, .1501 2160 266, .0 249 .4 79, .0 83, .0 298 .947 312, .813 0, .2363 0, ,1531 2180 266, .3 249 .5 79, .0 83, .0 300 .405 312, .963 0, .2343 0. .1532 2200 267, .0 249 .0 79, .0 82, .0 296 .031 313, .086 0.2458 0, ,1546 2220 268, .3 249 .9 80, .0 82, .0 296 .031 312.960 0.2469 0, ,1576 2240 269, .3 249 .8 78, .5 81, .0 300.405 313, .066 0. .2460 0. .1604 2260 269, .0 250 .5 79, .5 80, .0 300.405 313, .003 0, .2416 0. .1657 2280 270, .7 251 .9 81, .0 80, .0 300 .405 312, .844 0. .2421 0. .1705 2300 272, .0 252 .0 82, ,5 79, .0 300 .405 312, .904 0. .2416 0. ,1739 2320 272, .3 252 .3 83, .5 79, .0 300, .405 312, .827 0. .2393 0. .1751 2340 273, .3 253 .2 84, .5 80, .0 303, .322 312, .957 0. .2333 0. ,1747 2360 274, .0 253 .2 85, .0 81, .0 303, .322 312. .792 0. .2338 0. .1716 2380 275, .3 253 .2 85, .5 81, .0 303, .322 312. .702 0. .2366 0. .1718 2400 272, .3 253 .2 86, .0 81, .5 306, .238 312. .792 0.2192 0. .1700 2420 277, .0 255 .2 87, .0 81, .5 306, .238 312, .585 0, .2312 0. .1767 2440 279. .3 256 .6 87, .5 82, .5 306, .238 312. .411 0. .2372 0. .1785 2460 274. .3 257 .4 85, .0 83. .0 300, .405 312, .046 0, .2410 0. ,1801 2480 275. ,3 257 .8 82. .0 83. .0 300, .405 312. .134 0. .2543 0. .1811 2500 275. .0 257 .9 81. .5 83, .0 300, .405 312. ,013 0, .2549 0, ,1818 2520 277, ,0 257 .9 81. .5 82. .5 301, .864 312. ,013 0, ,2584 0. ,1834 2540 278. ,0 258 .6 82. .5 82. .0 303, .322 311. .949 0, ,2553 0, ,1872 2560 278. ,3 259 .0 82, .5 82, .0 303, .322 311, ,857 0, .2564 0, ,1886 2580 278, ,7 259 .4 83. ,0 81. ,5 303, .322 311. ,929 0, ,2558 0, ,1914 2600 278, ,7 259 .0 83, ,0 81, ,0 301, .864 311, ,931 0, ,2589 0, ,1918 2620 278, ,7 259 .0 83. ,5 81. ,0 301, .864 311. ,931 0, ,2573 0, ,1918 2640 278. .7 259 .9 83. ,5 81, .0 301, .864 311. .731 0. .2573 0, .1949 2660 279, .3 259 .8 83. .5 80. .5 301, .864 311. .836 0.2595 0, ,1961 2680 280. .0 260 .4 83. .5 81, .0 301, .864 311. .862 0. ,2617 0, ,1964 2700 280. .3 260 .7 84. .0 80. ,0 301, .864 311. .891 0. .2611 0, ,2004 2720 281. ,0 260 .9 84. .0 79, .5 301. .864 311. ,410 0. ,2634 0. ,2035 2740 280, .3 261 .0 84. ,5 79. .0 298. .947 311. ,379 0. ,2658 0. .2056 2760 281. ,3 260 .9 84. .5 80. .0 301. .864 311.484 0. ,2628 0. .2019 2780 282. .0 261 .4 85. .0 81. .0 301, .864 311. ,361 0. ,2634 0. ,2006 2800 282. .3 261 .8 85. .0 82. ,0 301. ,864 311. .359 0. .2645 0. ,1986 2820 283, .0 261 .6 85. .5 80. .0 300, ,405 311.405 0. ,2682 0. ,2043 2840 284. ,7 261 .4 86. .0 81. .0 303. ,322 311. ,451 0. ,2657 0. ,2004 2860 283. ,3 261 .4 86. ,0 82. ,0 300, ,405 311.467 0. ,2676 0. ,1970 2880 284. .3 260 .9 86. .5 81. .0 300.405 311. ,230 0. ,2693 0. ,1991 

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
https://iiif.library.ubc.ca/presentation/dsp.831.1-0058696/manifest

Comment

Related Items