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

T H E ROLE OF OLEFINS IN FOULING OF HEAT E X C H A N G E R S By Samuel Asomaning M . Sc. (Eng.) Lvov Polytechnic Institute  A THESIS SUBMITTED IN PARTIAL FULFILLMENT T H E REQUIREMENTS FOR T H E D E G R E E OF M A S T E R OF A P P L I E D SCIENCE  in T H E FACULTY OF GRADUATE STUDIES CHEMICAL  ENGINEERING  We accept this thesis as conforming to the required standard  T H E UNIVERSITY OF BRITISH COLUMBIA  May 1990 © Samuel Asomaning, 1990  OF  In  presenting  this  degree at the freely  thesis  in  partial fulfilment  of  University of  British Columbia,  I agree  available for reference  copying  of  department  this or  publication of  and study.  this  his  or  her  representatives.  OLt^M.C'Ji  ^T^fti»ilflr(  The University of British Columbia Vancouver, Canada  DE-6 (2/88)  that the  may be It  for  an  advanced  Library shall make it  that permission for extensive granted  is  thesis for financial gain shall not be  permission.  Department of  requirements  I further agree  thesis for scholarly purposes by  the  by the  understood  that  allowed without  head  of  my  copying  or  my written  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/m . 2  Only minor differences were noted between the extent or rate of fouling on the two different probes. Runs at heat fluxes below 180 kW/m  2  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  INTRODUCTION  1  2  LITERATURE  7  REVIEW  2.1  FOULING TYPES AND CATEGORIES  2.2  STAGES IN F O U L I N G A N D THEIR C O R R E S P O N D I N G M O D E L S . .  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  7  E F F E C T OF PROCESS V A R I A B L E S ON C H E M I C A L R E A C T I O N FOULING  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 A N D 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 F O U L I N G  37  2.6  MITIGATION A G A I N S T C H E M I C A L R E A C T I O N F O U L I N G  41  2.6.1  Chemical mitigation  42  2.6.2  Cleaning  43  2.7  T H E F O U L I N G 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 TO T H E PRESENT W O R K  49  4  W O R K I N G FLUIDS  52  4.1  KEROSENE  52  4.1.1  53  4.2 5  Hygroscopicity of kerosene  UNSATURATED HYDROCARBONS  56  EXPERIMENTAL APPARATUS  61  5.1  FLOW LOOP  61  5.2  Supply tank  62  5.3  T E S T 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 6.1  6.2  PROCEDURE  73  M E A S U R E M E N T OF FLUID P R O P E R T I E S  73  6.1.1  Measurement of density of test  fluids  73  6.1.2  Determination of viscosity  73  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 F O R F O U L I N G RUNS  77  6.5  CHEMICAL ANALYSES  81  6.5.1  Analysis for peroxides  81  6.5.2  Determination of Bromine Number  84  7 RESULTS AND DISCUSSION 7.1  7.2 ' 7.3  86  PRELIMINARY EXPERIMENTS  86  7.1.1  Heat Transfer Correlation Experiments  86  7.1.2  Preliminary Fouling Experiments  89  S O L U B I L I T Y OF A I R IN K E R O S E N E - O L E F I N M I X T U R E S  92  DISCUSSION OF F O U L I N G 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  8  7.3.8  Deposit characterization  126  7.3.9  Fouling Mechanism  135  CONCLUSIONS A N D RECOMMENDATIONS  139  8.1  CONCLUSIONS  139  8.2  RECOMMENDATIONS  140  Nomenclature  142  Bibliography  146  Appendices  156  A DATA COLLECTION  B  A N D CALCULATIONS  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 O F P E R T I N E N T DATA  163  M A X I M U M F O U L I N G R E S I S T A N C E S A N D INITIAL R A T E S  C P R O G R A M LISTINGS C. l  169 174  COMPUTER PROGRAMS  174  D DATA A N D RESULTS  180  D. l N O M E N C L A T U R E F O R D A T A A N D RESULTS  vii  180  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 N A T O 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]  2.6  Economic Effects of Antifoulant Use on Crude Unit for for Hypothetical  34  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 H W P 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 H W P  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 H W P Initial Fouling Rates  173  ix  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  xi  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 determining 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. Moreover, 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 N A T O countries. 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 N A T O Countries [2]  Country  1985 refining capacity (tonne/day)  Estimated fouling related expenses (millions $/year )  Denmark Norway Portugal Greece Turkey Belgium Netherlands United Kingdom Canada West Germany France Italy USA Luxemborg Iceland Spain  23,000 33,000 40,000 53,000 63,000 89,000 200,000 253,000 253,000 264,000 266,000 374,000 2,082,000 N/A N/A N/A  17 24 30 39 47 66 148 130 187 195 197 277 1,540 N/A 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. fouling.  This is the effective design of heat exchangers to minimize the effects of 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  = UAAT  (1.1)  m  where  Q  —  heat flow, (W)  U  —  overall heat transfer coefficient,  A  —  area of heat transfer, (m )  —  mean temperature difference, (K)  AT  m  (W/m K) 2  2  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  =  U  1 h  |  r ln(r /rj) 0  0  ^ 1 r  0  k  0  hi Ti  w  In the design approach, a fouling resistance Rj given by: Rj  — Rj -T 0  RjiA /Ai 0  (1.3)  Chapter 1.  INTRODUCTION  5  is selected from the Tubular Exchangers Manufacturers Association ( T E M A ) [4] recommended values, and added to the sum of the other resistances. Thus  1  Utotal  Udirty  U  + Rf  (1.4)  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 antioxidant 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 effectiveness 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 precipitation 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 CaCOz, MgSi0 , 3  CaSiO , z  CaS0  4  Mg(OH)2,  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 hydrocarbon 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 formation 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 production 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 exchanger 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 consisting 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 appreciable 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:  m  d  = k (C -C ) t  b  a  (2.5)  where k is the transport coefficient. In cases where the transport is dominated by t  diffusion, k, b ecomes k  m  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 C —> 0. For particles, the mass deposition flux is given by: B  — ktSpCb  (2.6)  Chapter 2. LITERATURE  REVIEW  11  where S is the sticking probability or the probability that any particle reaching p  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:  m  d  = K{C -C T t  (2.7)  sat  where k is the attachment rate constant and C t is the saturation concentration T  ta  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:  _ m  d  -  Cfe — C, (i/k ) + m  r  =  d  =  s  —  C t) , n_1  therefore  5a  k (C -C. ) m  When surface attachment controls, l/k  m  at  r  When mass transfer controls, (l/k ) 3> l/k (C  d  m  b  <C l/k (C r  b  (2.9)  at  k (C -C, ) T  .  i/k (c,-c. r-\  m  m  .  at  at  n  — C t) ~ n  3  ta  l  and C ~ C , thus b  t  (2.10)  In the case of chemical reaction fouling, the same approach can be taken with C t — 0 in Equation 2.8 giving: sa  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 and inversely proportional to 5  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 = m -m =m -— d  T  (2.13)  d  where  m m  m' rh  T  ip f3r  d  a  If rh is assumed to be constant, that is the deposition goes on unabated, then d  integration of Equation 2.13 with the initial conditions 6 = 0, m — 0 yields:  m  = m " ( l - e- <) e/e  And since  dR  f  dm = - p kj T  s  (2.14)  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:  R  = R}(1 - e- <) 6/e  f  (2.15)  Here 8 is the average residence time of an element of fouling deposit on the heat C  transfer surface, or the time it will take to accumulate the asymptotic fouling deposit given a linear fouling process and an initial deposition rate rhd- No removal occurs until 8 becomes less than some critical value, i.e. C  Oc  <  {Qc)crit.  Or  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.  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 reactions 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 solution, the insoluble products precipitate on the heat exchanger wall with particulate fouling as the deposition mechanism. Products of corrosion might either serve as catalysts or deposit on the surface by particulate fouling.  For organic fluids, oxidation  processes are important contributors to fouling.  2.3.1  O x i d a t i o n 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 metals and their compounds, for example, platinum, palladium, vanadium, manganese, manganese 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 containing 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. Molecular 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 oxidation 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 unfavourable, 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  2.3.2  REVIEW  16  Autoxidation  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  R-2.2  —• R00-  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 + 0  2  R-2.6  The initiation step involves a free radical of high reactivity, Z', attacking the hydrocarbon 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  Mn  +0  +2  2  — • Mn  RH + (0 ) 2  + Mn+  RH + (H0 ) 2  17  + (0 )  +3  R-2.7  2  R+  2  (0 H)-  REVIEW  (0 H)~  R-2.8  2  —> Mn+ +• 0 H  3  R-2.9  2  2  —> R+  H0 2  R-2.10  2  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 H 0 2  2  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 + 0  2  —> R + R0 H 2  —> 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 - CH - CH + 1/202 —> R-CH 2  3  = CH + H 0 2  R-2.12  2  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. Moreover, 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 intermediate products and decompose or undergo rearrangement of primary oxidation products.  easily with the formation  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 oxidation 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, R + RCH = CH —> R - CH - (R) C H 1  R-2.13  1  2  2  R - CH - (R) C H  R - CH CH(R)CH  1  — (R) C H etc.  1  2  2  2  R-2.14  and olefin-oxygen copolymerization R-2.15.  R CH 1  2  — (R) C H  —> R - CH RCHOOCH 1  2  2  u  ^  n  R 1  — (R) C H etc.  CH RCHOO2  R-2.15  The copolymerization reaction eventually results in the formation of polymeric peroxides [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 copolymerization 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  Polymerization  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. Chain Polymerization 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  = CH + X- —> R- C H - CH X 2  R-2.17  2  2. Chain propagation.  R- C H(CH X)  + R-CH  2  —>R-  CH{CH X) 2  - {-CH  2  = CH  2  —•  - CH{R)-) CH ~ n  R-2.18  2  3. Chain termination  R - CH(CH X) 2  —> RCH(CH X) 2  - (CH - CH) R 2  - R{CH  2  n  - CHR-)  n  - CH - (R) C H + H- —• 2  - CH - {R)CH 2  2  R-2.19  The chain termination occurs in several ways. It can result from a reaction between 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 — water, 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-  dimer  +  monomer  —>  trimer  +  LW  dimer  - f dimer  —>  tetramer  +  LW  trimer  +  monomer  —•  tetramer  -j- LW  trimer  +  dimer  —>  pentamer  +  LW  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: Aliphatic hydrocarbons  cracking, cyclization dealkylation, polycondensation —> 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 VARIABLES ON C H E M I C A L  REACTION  FOULING 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, disulphides 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 formation 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]. many ways similar to the effects of sulphur compounds.  These effects are in  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  2.4.3  REVIEW  27  T h e role of oxygen i n 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 autoxidation 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  containers, much more gum was formed.  28  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 0  2  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  REVIEW  29  Table 2.4: Effects of Oxygenated Species Addition To Jet Fuel on Mass Deposition [21]  Class of compound added  Dissolved 0 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  2  Compounds added at 100 ppm 0 level, Temperature in kinetic unit: zone 1 = 371°C, zone 2 = 427°C zone 3 = 482°C, zone 4 = 538°C,P = 6989 kPa 2  Chapter 2. LITERATURE  REVIEW  30  Metal ions have also been shown [15] to increase the rate of oxygen uptake by hydrocarbons. 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 polymerization 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^, MgCl ,CaCl 2  2  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 contradictory. 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 reduce 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 p a r t i c u l a t e s  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  2.4.7  REVIEW  Effect of hydrocarbon  32  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 intermediates which undergo condensation and cyclization ultimately forming coke as represented below. paraffins  organic acids coke  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 weight ones. Thus deposition rates increase with increasing carbon number. This fact 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 storage. 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  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 compounds. 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 radicals. 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 condensation (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 alkylaromatics 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, isoparaffins, 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 )/4hr.x 10 2  6  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  9.0  1.0  n-Decane  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 temperature 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 between 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 naphthenic 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 condensation 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 resulted 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. Obviously, much has to be done to investigate the role of condensation reactions in chemical reaction fouhng.  Chapter 2. LITERATURE  2.4.8  REVIEW  37  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.  (i /de) , Rl  e 0  = H^ (-i20,ooo/* r.) e  u  9  ( 2 1 6 )  b  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  KINETICS A N D MODELLING OF CHEMICAL REACTION  FOUL-  ING 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  500 \  o\ \  \  \ o  I00h  00  X7  \  50  \  x  cr  o c  \ \  a _z  \  ^ x  o  10  \ \  \  \ W lb /sec \ \ V A Oil B 0-242 0-1 7 8 Oil B ^ 0-362 Oil A (100% Q \ recirculated) m  O  A V  N  118  126 IOOO/T  Wc  1-34 •R-'XIO  3  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 n  th  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 n  th  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: dR  f  — aiJS-p  (2.17)  Chapter 2. LITERATURE  REVIEW  40  where J is the flux of the foulant given by: J  — k (Cb m  C) w  and S is the sticking probability factor. p  S, Thus for k  m  a,e(-E/R.T.) ^  -  (2-18)  assumed proportional to U , and for rough surfaces (f=constant) the b  intial fouhng rate is given by:  {  -dT =°  -  )e  °  u  3  ( 2 b  -  1 9 )  This equation agrees, to a large extent, with the results obtained from the gas oil experiments. For a chemical reaction controlled first order reaction, independent of velocity and with a low S , the initial fouhng rate becomes: p  (^),=„  =  (2.20)  *<C A- IW.) E  h  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±  de  =  J _ r Pfk i/k f  i  9l  [  t  + i/k  l  T  K  (221) ' '  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- l/k +l/K[  f  C  kDCDi]  ( 2  t  -  2 2 )  where k the reaction rate constant follows an Arrhenius type relationship. Paterson and T  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 reaction kinetics, they derived for the initial fouhng rate, the equation,  =  jf- exp{-EIR T ) b  where, (3 is a constant for a given system. S  g  8  (2.23)  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  2.6  REVIEW  42  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, surface 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 agglomeration 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 entirely 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. According 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  REVIEW  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  THE FOULING RIG  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  T h e annular probe  The annular probe or the Portable Fouhng Research Unit (PFRU) was designed, constructed 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 distance 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  Hydrochloric,  Caustic soda,  Nitric,  Ammonia,  Sulphuric,  Complexing Agents  Oxidants  Solvents  Others  EDTA,  Potassium permanganate,  Aromatics,  Inhibitors,  Gluconates,  Sodium Bromate,  Aliphatic,  Surfactants,  Trisodium,  Sodium Nitrate,  Chlorinated,  Antifoams,  Hydrofluoric,  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 T  — U  as:  w  =  c  — — Q/A  (2.24)  {  V  where Q is the electrical power input to the probe. After fouhng, the overall heat transfer coefficient becomes:  w, - n § 7 ^  (2  '  26)  hence, the fouhng resistance is given by:  R  2.7.2  > - wrk wr =hl  < > 226  T h e hot wire probe  The Hot Wire Probe (HWP) is based on the U O P 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 D C 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  48  REVIEW  r. = ( | - ^ - - i ) / a + r  0  where  Rext  —  is the resistance of the external circuit  R  —  is the resistance of the wire at time zero  —  is the temperature at which R is determined  R  —  is the resistance of the wire at time t  a  —  is the temperature coefficient of the resistance  D  T  0  D  Two thermocouples located immediately above and below the hot wire, measure the bulk temperature of the fluid. Knowing T and T . The heat transfer coefficient is calculated t  b  from  rp h  f  = W  (2  '  27)  Knowing the heat transfer coefficient under clean h and fouled hf conditions, the 0  fouhng resistance is calculated from:  (2.28)  Chapter 3 B A C K G R O U N D TO T H E PRESENT WORK  Most papers which have appeared in the literature on organic fouhng have been concerned 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 reported 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 cracking 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 fouling, 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 thoroughly 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 polymerization, or autoxidation induced polymerization or both. Therefore, this work will concern itself with examining the effects of the fluid chemistry 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  H y g r o s c o p i c i t y of kerosene  A knowledge of the hygroscopicity of kerosene is important because under high temperature 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 ( A S T M D156-64)  +30  Odor  Mild  A P I G r a v i t y 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]  Solubility of water Hydrocarbon  Compound  Formula  (% weight)  25°C  55°C  Paraffin  Iso-octane  C's His  0.0037  0.0055  Naphthene  Cyclohexane  CeH 12  0.0049  0.0087  Aromatic  Benzene  CH  0.0400  0.0570  6  6  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. Generally 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  Temperature  Kerosene with-  Aviation  Aviation  out aromatics  kerosene  kerosene  JP-5  JP-1  (°c)  -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 dicyclopentadiene (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 inhibitor 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 formulas 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 dicyclopentadiene), 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  CH - {CH )  Octene-1  CH% — (CH )s — CH — CH  Hexadecene—1  CHZ - [CH )  4-Vinyl-lcyclohexene  3  2 7  -CH  2  2 1Z  Indene  Dicyclopentadiene  2  2  -CH  9  CH=CH  1,5-Cyclooctadiene  = CH  CO  = CH  2  Co  2  Chapter 4.  WORKING  60  FLUIDS  Table 4.13: Physical Properties of Olefins Used  Compound  Molecular Formula  4-Vinyl-Icy clohexene 1,5-Cyclooctadiene  C&H12  Octene-1  Molecular Mass  Boihng point °C  108.18  Density kg/m  Freezing point °C  Refractive index  127  834  -73.4  1.4640  108.18  150.8  882  -56.4  1.4905  112.22  121.6  714  -101.7  1.4087  3  Indene  CgH  116.60  182.6  996  -1.8  1.5768  Dicyclopentadiene  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  s  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  fluid temperature.  APPARATUS  62  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 H W P 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  63  APPARATUS  a cn. PUMP  OPM  DIFFERENTIAL  PRESSURE  TC4  PFRU SURFACE  TC  THERMOCOUPLE  PR  PRESSURE  IH  IMMERSION HEATER  MANOMETER  THERMOCOUPLES  RELIEF  VALVE  '  Sm  STIRRER MOTOR  MC  MIXING CHAMBER  HT  HEATING TAPE  ®  PRESSURE GAGE  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 G T 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  Miliivoltmeter.  APPARATUS  65  The Power to the supply tank's immersion heater is controlled by a  Superior Electric Company powerstat model 3 P N 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 Transfer 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 U O P 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. N P T 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 H W P 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  BACK PLATE  68  APPARATUS  MIDOLE PLATE  SILVER SOLOEREO FRONT PLATE o o  0  0  0  0  o  0  0  ?  Yl TUBE FIATTENEO  SIOE VIEW OF ASSEMBLY 0  3o 3P  *•  f ¥  0  o  o  0  o  0  o  0  0  0  o  0  o  o  0  0  0  0  0  0  0  0  4  SEALED WITH 0.5 mm TEFLON GASKET  af  -—80.0— mm  TO 15.5x7.8 mm  ELLIPSE Malarial: SS304  Figure 5.5: Hot Wire Probe Flow Channel [80]  Bolt holes not shown in side view.  i n  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 D C 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  TO DATALOGGER TEMP. EQUALIZER HEATING TAPE  PERU A PFRU B PFRU C PFRU ENTER PFRU EXIT HWP ENTER HWP EXIT  POWERSTAT OATALOGGER RELAY SWITCH MULTIMETER  OMV OT TC SS  DIGITAL MIILIVOLTMETER DIGITAL THERMOMETER TEMPERATURE CONTROLLER SAFETY SWITCH ITEMP. CONTROLLER)  Figure 5.6: Control Circuit [80]  Chapter 5. EXPERIMENTAL  APPARATUS  50 VPIV DIODE BRIOGE Rj  75 _yv  R  2  2 k.-n- M A X .  R  3  12.4  R  4  4.99 k_a_  R  g  2 k^x.  R  6  8.66 k_n_  R  ?  16.2  T  t  6.3  MAX.  k^_  VCT. 8 A to 115 V VCT. 0.3 A to 115 V VCT 0.3 A to 115 V  TL  20  T3  20  C, C,  33  DL  DATALOGGER  22  (I? p.? Figure 5.7: A C / D C Conversion Circuit [80]  71  Chapter 5. EXPERIMENTAL  APPARATUS  72  + 14  +  DC ANALOG  K> — VOLTAGE TO B E  V  m  ~  MEASURED  REDUCED V O L T A G E (TO  DATALOGGER)  R = 70 kOhms. 1  Figure 5.8: Voltage Scaling Circuit  R = 6 kOhms. 2  Chapter 6  EXPERIMENTAL PROCEDURE  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 where U — a speed factor inversely related to the rpm.  73  (6.29)  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  CALIBRATION OF T H E EQUIPMENT  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:  ra — mi 2  mass now rate  =  (6.30)  where  ?Ti2  —  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^  where  Vi  —  volumetric flow rate  Crf  —  discharge coefficient  Ap,.  —  cross sectional area of orifice meter  g  —  conversion factor, gravitational to absolute units  c  -  (6 3i)  Chapter 6. EXPERIMENTAL  PROCEDURE  76  Ap  pressure drop across the orifice meter, gravitational units  P  the density of the fluid  di  orifice diameter  d  pipe diameter  2  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  C a l i b r a t i o n of Thermocouples  The thermocouples were calibrated using a Hewlett Packard Model 2801 quartz thermometer. 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  PREPARATION OF CHEMICALS  Three of the olefins used — 1,5-cyclooctadiene, 4-vinyl-l-cyclohexene, and dicyclopentadiene, 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) solvent. Then pure kerosene is pumped around the test rig for several hours at temperatures 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 M I B K 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 thermocouple 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 are pushed into the H W P test section and secured in place by means of swagelok 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: % Weight of Olefin where  =  Wolef  + (V  ayet  -  V l f).p 0  e  .100 k l  (6.32)  Chapter 6. EXPERIMENTAL  PROCEDURE  Wotej —  Weight of olefin.  Vif  —  Volume of olefin.  V t  —  Volume of system.  pker  —  density of kerosene.  0  e  eyt  79  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 R is determined. The bulk temperature is measured and the wire is Q  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 R at the given bulk temperature. D  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 minutes. 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 M I B K 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  CHEMICAL  6.5.1  ANALYSES  A n a l y s i s 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 D102276 [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  (-C -C -O I |  I  -0-)  + 2FeS0  4  + H SO 2  A  —• -COH I  I  - COR + i  Fe (S0 ) 2  4  3  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 i C / 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:  ZV M D  M  t  =  D  ~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:  (6.34) where  Chapter 6. EXPERIMENTAL  84  is the peroxide number(milhequivalent active 02/liter)  P V  PROCEDURE  is the volume of titanous chloride in milhlitres  T  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 D183265 was used to confirm the value of the peroxide number.  6.5.2  D e t e r m i n a t i o n of B r o m i n e N u m b e r  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.  Na S203 2  EXPERIMENTAL  PROCEDURE  85  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  R E S U L T S A N D DISCUSSION  7.1  PRELIMINARY EXPERIMENTS  7.1.1  Heat Transfer Correlation Experiments  Experiments were conducted on the fouhng rig to compare the values of the convective 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.  Nu  = 0.023 Re Pr 0S  c  0A  2. The Wiegand equation [118] for turbulent flow in annuli.  86  (7.36)  Chapter 7. RESULTS  AND  DISCUSSION  Nu  87  = 0.023Re - Pr (d /di) 0  c  8  OA  (7.37)  OA5  0  3. The Morand and Pelton equation [119] for turbulent flow in annuli.  Nu  = 0.02Re Pr - (d /di) 0S5  c  0  5  0  ( 7.38)  53  o  4. The Taborek equation [120] for turbulent flow in pipes.  Nu  = 0.0143 Re  Pr  085  c  (7.39)  05  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.  Nu  c  =  0.664#e°- Pr 5  a33  (7.41)  Chapter 7. RESULTS  AND DISCUSSION  88  2. The Ulsamer equation [123] for laminar flow over tubes and wires.  Nu  c  CRe Pr 0.31  =  (7.42)  n  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 ird /2 was used [71]. w  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:  z =  T -  ^-Q/A  w  where A is the thermal conductivity of the metal. The resistance s/\ TO  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, Q  =  I (V/I-R ) 2  ext  and  z =  (  R — R'ext t  -l)/a  Ro ~ Ri•ext.  Chapter 7. RESULTS  AND  DISCUSSION  89  The calculated convective heat transfer coefficient was evaluated from:  Nu  c  =  (7.44)  where L h is the characteristic length of the heated sections of the probes, and Ay is the c  thermal conductivity of the fluid, and  Nu  c  =  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 P F R U , 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 solvent — 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  h  h  Calculated  Measured  W/m K  W/m K  5114  5835  12  7492  5835  28  6607  5835  13  Taborek  5715  5835  2  Gnielinski  6131  5835  5  Author  2  1.Turbulent flow in pipes Nu =  .023Re°- Pr 8  % Deviation from measured value  2  Dittus/ Boelter  OA  2. Turbulent flow in annuli Wiegand Nu =  0.023Re°- Pr (d /di) 8  OA  OA5  0  Monrad/  3. Turbulent flow in annuli Nu = . 0 2 i ? e ° - P r ° - ( i / d ) 8  33  0  t  o  53  l  Pelton  4.Turbulent flow in pipes Nu = .0143.Pe°- Pr ' 85  0  5  5.Turbulent flow in pipes £ = (l.MLogRe N  u  _  ?/8(fie-iooo)p  - 1.64) r  f l  (  d  /  L  )  ]  er 7. RESULTS AND DISCUSSION  Table 7.15: Experimental Heat Transfer Correlations for Coiled Wire.  h Correlation  Calculated W/m K  Measured W/m K  % Deviation from measured value  Leveque  5021  4863  3  Ulsamer  6654  4863  36  Author  h  2  Nu = 0.664fle°- Pr°5  Nu =  33  0.9lRe°- Pr 5  0 385  2  Table 7.16: Parameters of Heat Transfer Correlation Run V m /hr 3  U  Re  Pr  m/5  T °C  T °C  Heat Flux kW/m  142  82  349.98  136  83  259.49  t  b  2  PFRU  0.94  0.654  26650  2.16  HWP  0.0125  0.0066  3.7  2.16  Chapter 7. RESULTS  AND  DISCUSSION  92  runs were carried out using only kerosene under 375 kPa pressure and air saturated conditions. The first run was carried out at a heat flux of 200 kW/m , 2  a surface temperature  of 180°C, and a bulk temperature of 7 5 ° C The second run was at a heat flux of 250 kW/m , 2  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/m , 2  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. A l 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 autoxidation 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 reactions 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  93  DISCUSSION  - 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 is calculated as: a  S = 5.88/3 + 3.60 t  The solubility parameter S °f the gas is obtained from a table of solubility parameters 2  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  ((0.165(5 - 5 ) - 2.66)(1 - 273/T) - 0.625a - 0.101(8.6 - 5 ) + 5.73) 2  =  e  a  2  2  2  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  94  Table 7.17: Calculated Solubilities of Air and Oxygen in Kerosene Concentration ppmw at 293 K , 410 kPa  Ostwald Coefficient L cm /cm  Bunsen Coefficient B cm /cm atm.  Air  0.162  0.615  997  o  0.233  0.880  1575  0.140  0.528  827  Component  3  2  N  2  3  3  =  3  273 L T P  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:  p = p[l - 0.000595(r - 288.2)/p ] 121  T  and the concentration in ppmw from: G =  U.6BM /  2 PT  where M is the molecular mass of the gas. The calculation yielded the solubilities for 2  air, oxygen and nitrogen shown in Table 7.17.  Chapter 7. RESULTS  7.3  AND  DISCUSSION  95  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. All but two runs — Runs 11 and 14 — were held under oxygenated conditions. The flow rates were constant at 0.8 m /hr. for the P F R U and 0.04 m /hr. for the hot wire 3  3  probe. These correspond to Reynolds numbers of about 9800 for the P F R U and 5 for the H W P . 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  PFRU Run  HWP  T °C 70  U kW/ {m K) 1.803  q kW/m 198.32  T. °C 140  T °C 70  U kW/ {m K) 2.010  q kW/m 140.71  # 1  Foulant Decene-1  T, °C 180  2  Decene-1  185  70  2.232  256.66  160  70  2.038  183.47  3 4  Octene-1 1,5-Cyclooctadiene  190  70  2.236  268.32  175  70  1.959  205.75  190  70  2.236  268.32  170  70  1.956  195.66  Decene-1 4-Vinylcyclohexene Dicyclopentadiene  204  90  3.070  349.99  206  85  2.932  354.78  198  82  2.565  297.49  198  78  2.456  294.77  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 11  Indene Indene deoxygenated Dicyclopentadiene Dicyclopentadiene Dicyclopentadiene deoxygenated Hexadecene-1  180  85  2.087  198.33  180  85  2.090  198.57  198  84  2.622  298.94  198  82  2.611  302.86  187  85  2.763  281.84  185  82  2.5757  265.30  183  82  2.063  208.37  180  82  2.0504  200.94  198  84  2.602  297.48  197  81  2.549  296.91  198  82  2.5689  297.99  198  82  2.6393  306.16  5 6 7  12 13 14  15  b  0  2  2  b  0  2  2  Chapter 7.  RESULTS• AND  DISCUSSION  97  Table 7.19: Average Operating C onditions  Run  #  Foulant  Initial Heat Transfer Coefficient kW/m K  Initial Surface Temperature  Average Bulk Fluid Temperature  °c  °C  2  Average Heat Flux kW/m 2  1  Decene-1  PFRU 1.803  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-Cyclooctadiaene Decene-1 4-Vinylcyclohexene Dicyclopentadiene  2.236 3.070  1.956 2.932  190 204  170 206  74 88  73 85  270.42 357.41  193.29 360.45  2.565  2.456  198  198  84  82  298.86  293.81  2.521  2.497  198  198  80  81  293.61  296.21  5 6 7  HWP 2.010  PFRU 180  HWP 140  PFRU 72  HWP 72  PFRU 196.34  HWP 150.82  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 11  Indene Indene deoxygenated Dicyclopentadiene Dicyclopentadiene Dicyclopentadiene deoxygenated Hexadecene-1  2.087  2.090  180  180  82  83  196.57  198.90  2.622  2.611  198  198  87  82  299.02  299.33  2.763  2.575  187  185  81  80  258.03  254.41  2.063  2.050  183  180  83  81  215.51  201.19  2.602  2.549  198  197  84  81  301.80  297.58  2.59  2.639  198  198  84  82  297.73  307.28  12 13 14  15  Chapter 7. RESULTS  7.3.1  AND  DISCUSSION  98  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/m , 2  and an average H W P heat flux of 150.8 kW/m .  The average bulk fluid  2  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/m  2  for the annular probe and 183.5 kW/m  2  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/m  2  and the average bulk temperature was 74°C. The average H W P heat flux and  bulk temperature were 199.9 kW/m  2  no measurable fouhng.  and 73°C respectively. The octene run also showed  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. conducted using decene—l at an average heat flux of 357.4 kW/m  2  kW/m  2  Thus Run 5 was  for the P F R U , and 360  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 (rn K)/kW 2  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 H W P showed a similar fouhng rate. The thermal fouhng resistance was higher on the H W P 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 (m K)/kWh. 2  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 autoxidation 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/m  2  and a bulk temperature of about 84°C. The average H W P  heat flux was 307 kW/m  and the average bulk fluid temperature was 82°C. Fouhng  2  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 H W P . Over a period of 49 hours, fouhng resistances of 0.27 and 0.19 (m K)/kW 2  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  100  0.090  RUN 5 DECENE-1  • = PFRU Tb=8a?C A - HWP Tb=85 C  0.075 H  U  PFRU: q=357kW/m? HWP: q=360kW/m o.oeoH  A A  0.045 AA  0.030H  A A  ^ A  A A  A  AAfi 5  A  A  A " A A A A A A A A  AA  A  A  A  »AAA  A CP C  0.015H  A ADl  AD  B  •  •  AD  0.000 $000  0.0  !  7.0  14.0  21.0  28.0  35.0  42.0  TIME (HOURS) Figure 7.9: Fouling resistance versus time for Run 5, decene-1  49.0  Chapter 7.  RESULTS AND DISCUSSION  101  0.34-1  RUN 15 HEXADECENE 0.3CH  • = PFRU Tb=84TC A = HWP T b = 8 2 ° C 0.26H  PFRU: q=298 kW/m£ HWP: q=307 kW/m"  riBI  1  0.22 H CO  £, w o  3  •  • •  0.18  A'  CP 00 00  BS  0.14H  0 0  w  S  0.10H  E> O 0.08  ELo "4 0.02  •0.02-f—r—r— 0.0 7.0  I  14.0  '  1  21.0  '  I  1  28.0  1  35.0  '  1  42.0  TIME (HOURS) Figure 7.10: Fouling resistance versus time for Run 15, hexadecene-1  1  I  49.0  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/m , 2  and 74° C respectively for the P F R U , and 200 kW/m  2  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/m , 2  for the P F R U probe, and 294 kW/m  2  for the HWP. The average bulk fluid  temperatures were 84°C and 82°C for the P F R U and H W P 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 (m K)/kW 2  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 (m K)/kW 2  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 (m K)/kW, 2  a change of about 0.03 (m K)/kW 2  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 H W P 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 H W P fouhng rate was also lower than that of the P F R U . The H W P also showed a hnear thermal fouhng resistance with time for the first 21 hours, and reached a value of about 0.11 (m K)/kW 2  during that time. The fouhng rate then fell, exhibiting a sawtooth  nature. The maximum H W P thermal fouhng resistance over the period of the run was about 0.13 (m K/kW). 2  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 dicyclopentadiene containing the inhibitor. The average P F R U heat flux was 294  kW/m  2  and the average bulk fluid temperature was 80°C. The average H W P heat flux was 296 kW/m  2  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 (m K)/kW 2  for the P F R U and about 0.02 (m K)/kW 2  for the H W P .  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  RUN 6 4-VINYL-1-CYCL0HEXENE 0.16  •  o  •  •  0.14  °  cftj  A * ^ A A  ^  0.12  A  JgsBBi •  A  LB B  o  ?s  CO  CO  W  A  N  O.IOH • • 0.08  « S  & A  A  A  A  H  0.06  o  • = PFRU. Tb=84?C A - HWP, Tb=82 C u  • 0.04  PFRU: q=299kW/m| HWP: q=294 kW/m*  H A *  0.02 ^ AA  0.00^ 7.0 A  14.0  21.0  28.0  TIME (HOURS)  I 35.0  •  I 42.0  Figure 7.11: Fouling resistance versus time for Run 6, 4-vinyl-l-cyclohexene  1  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/m  2  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 (m K)/kW 2  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 H W P showed relatively less fouhng. Its thermal fouhng resistance peaked at about 0.3 (m K)/kW 2  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/m  2  and that of the H W P at 201 kW/m . 2  The  average bulk fluid temperature was 83°C for the P F R U and 81°C for the H W P . The  Chapter 7. RESULTS  106  AND DISCUSSION  0.14  RUN 7 DICYCLOPENTADIENE WITH INHIBITOR 0.12  s  AA  • = PFRU Tb=8l"C A = HWP T b = 8 0 ° C  0.10-  • •  PFRU: q=293 kW/m| HWP: q=296 kW/m  8° • • B~ A  •  •  ft  •BA  CO  •  J, H O  0.08•  OQ »—i  00  w «  A  g  AS  •  0.06  A ^  f—(  O  0.04-  IQ A  0.02  0.00  I  0.0  7.0  14.0  21.0  28.0  35.0  42.0  49.0  TIME (HOURS)  Figure 7.12: Fouhng resistance versus time for Run 7, dicyclopentadiene with inhibitor  107  Chapter 7. RESULTS AND DISCUSSION  1.05 R U N 12  0.90-  • = PFRU.  A = HWP, PFRU: 0.75-  HWP:  DICYCLOPENTADIENE  Tb=81°C Tb=80°C  q=258 k W / m ^ q=255kW/nr  0.60-  0.45-  0.30-  A  ^ A B A A  S  *  A  A A  0.15-  A  • AA  0.00-f! 0  7.0  14.0  21.0  28.0  35.0  42.0  TIME (HOURS) Figure 7.13: Fouling resistance versus time for Run 12, dicyclopentadiene  49.0  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 (m K)/kW. 2  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  (m K)/kW 2  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 and that of the H W P was 295.3 kW/m . 2  kW/m , 2  The average bulk fluid temperatures were 81°C  and 80°C for the P F R U and H W P 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 R U N 13  0.24-  DICYCLOPENTADIENE  Tb=83~C Tb=8rC  • = PFRU.  A = HWP,  goo  q=216 kW/rru H W P : q=201 kW/m^ PFRU: 0.20-  • 0.16-  A  A  A  A " A A A  A  A  A A  z  A  A  A. 0.12A  If  DO  •  •  CP  0.08S  A AA  • AA A  0.04-  A  A  A  A A AA  : A A  AAZ  AA AAAA A  A  . A  QAA^  0.00 ^ 0.0  7.0  14.0  21.0  28.0  35.0  42.0  TIME (HOURS) Figure 7.14: Fouhng resistance versus time for Run 13 dicyclopentadiene  49.0  Chapter 7. RESULTS AND DISCUSSION  110  0.7-T  DICYCLOPENTADIENE HEAT F L U X E F F E C T S  0.6 H  • = q=258 kW/m£ A = q=216 kW/rrT 0.5 H  off  •  -  « H  £, w o  •  0.4 H  •  p  •  CO  — tI CO  0.3  A  w  • an  o •-3  0.2-  O A A  OH  0.0 14.0  21.0  i  1 —  28.0  1  35.0  42.0  49.0  TIME (HOURS) 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 {rn K)jkW.  After  2  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/m  2  was used. For about 4 hours after the reduction in  heat flux, the thermal fouhng resistance fell to about 0.5 (m K)/kW 2  and then started in-  creasing again until it reached a maximum thermal fouhng resistance of 0.75  (m K)/kW 2  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 H W P 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 disruption 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/m  2  and the H W P heat flux was 249 kW/m . 2  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 (m K)/kW 2  until! the 17  th  after which the first decline occured. The dechne went on  hour, when it began rising again. The thermal fouling resistance reached  Chapter 7. RESULTS  112  AND DISCUSSION  1.20  RUN 8 INDENE 1.05-  O, • = PFRU Tb=8rC A  = HWP Tb=80°C  PFRU: q=299 k W / m | HWP: q=295 kW/m^  0.90  q reduced  0.75-  A\  to 240 kW/m  z  1  *  *  0.60  0.45  0.30-  0.15-  0.00 0.0  7.0  14.0  21.0  28.0  35.0  TIME (HOURS) Figure 7.16: Fouling resistance versus time for Run 8, Indene  42.0  49.0  Chapter 7. RESULTS  AND  DISCUSSION  113  a maximum value of about 0.225 (m K)/kW  after 40 hours. The H W P thermal fouhng  2  resistance increased rapidly at values almost equivalent to the P F R U ' 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 (m K)/kW. 2  It then declined for a while and began rising again till it  reached a maximum fouhng resistance of 0.2 (m K)/kW 2  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/m  2  and 198.9 kW/m  2  for the P F R U and H W P 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/m  2  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/m . 2  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  114  DISCUSSION  0.35 RUN 9 INDENE  0.30H  I  • = PFRU, Tb=83 C A = HWP, T b = 8 3 ° C PFRU: q=246 k W / m f HWP: q = 2 4 9 k W / r r T  0.25 H  C\2  • So 0.20  o 55  A  CO I—I  CO  0.15H AA  o i  O  0.10-J • a  4  0.05 A  H" 0.00 .0  4  -1 7.0  r  14.0  21.0  28.0  —i  1  35.0  TIME (HOURS) Figure 7.17: Fouling resistance versus time for Run 9, indene  1  42.0  1  49.0  Chapter 7. RESULTS  115  AND DISCUSSION  0.28 RUN  0.24-  I  10  INDENE  • = P F R U , Tb=82°C A = H W P , Tb=83°C P F R U : q=196 kW/rru H W P : q=198 k W / i r T  0.20-  CV  o CO CO  0.16-  *  A  A  A A  A A  A  o  AA A A  0.12  B  Bo  O g A  o  A  A  0.08-  A  A  A-  §  A  A A A^A A A A A  A  •  A  0|  <=»'  A  AA  0.04 A  •  • og  °§_ oo«B s  0.00 .0  7.0  14.0  21.0  28.0  35.0  TIME (HOURS) Figure 7.18: Fouling resistance versus time for Run 10, indene  42.0  49.0  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 induced 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 kWjm  2  for both the P F R U and H W P 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/m , 2  and that of the hot wire was 297.6  kW/m . 2  The average bulk fluid temperatures for this run were 84°C and 81°C for the P F R U and H W P 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 (m K)/kW 2  and 0.02 (m K)/kW 2  for the P F R U probe  for the H W P during the first 10 hours and then levelled off. It then  Chapter 7. RESULTS  AND DISCUSSION  117  1.0 INDENE HEAT F L U X E F F E C T S 0.9H  0.8H  • A O  q=299 kW/mp q=246 k W / m p q=196 kW/rri ff  0.7 H  • •  q reduced 0.6H  to 240  kW/  2 m  ^  o CO  •  0.5 H  CO  w « O  0.4  JZ> O fe  0.3  i—t •-3  • •  14.0  21.0  28.0  35.0  42.0  TIME (HOURS) Figure 7.19: Indene oxygenated runs at different heat fluxes for P F R U  49.0  Chapter 7. RESULTS  AND DISCUSSION  118  0.08 R U N 11 I N D E N E 0.07 H  DEOXYGENATED  • = P F R U , Tb=85°C A = H W P , Tb=83°C PFRU: q=299 k W / m | HWP: q=299 k W / m ^  0.06 H  0.05  0.04 H  B  0.03 H d  8D  § •• A  DD  3A  0.02 H 6?  a — r,  a  _ „ J °  °g A A -A " ^ V A H  A. A A  A  D  W A  ° AA  A  A  A  AA  t A AA ^ A  A AAAA A A A •  ^ A  AA  AA  A AAQAAAA A  A *  A  A *  O.OH  • •  • o.oo H  ° ° 1 0  H  •  g  A  £  A °  0  A  >  A  D  7.0  14.0  21.0  28.0  35.0  42.0  TIME (HOURS)  Figure 7-20: Fouling resistance versus time for Run 11, indene deoxygenated  49.0  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 (m K)/kW 2  for the P F R U and 0.1  (m K )/kW for the HWP. The P F R U showed a higher initial fouhng rate but the fouhng 2  resistance fell off considerably to a value lower than that of the H W P after 30 hours of the run. The H W P 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 evidence 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 polymerization. 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 H W P at equivalent heat fluxes. For the dicyclopentadiene, the maximum fouhng resistance for the deoxygenated run at about 260 kW/m  was 5.5 times that of the deoxygenated run  at a much higher heat flux of 298 kW/m .  In the case of the HWP, the equivalent ratio  2  2  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  0.22-  120  AND DISCUSSION  RUN 14 DICYCLOPENTADIENE DEOXYGENATED • = PFRU T b = 8 4 ° C * = HWP Tb=81°C  0.18-  PFRU: q=301 kW/m? HWP: q=293 kW/m' ::  0.14-  ~  0.10-  0.06-  0.02-  -0.020.0  7.0  14.0  21.0  28.0  35.0  42.0  49.0  TIME (HOURS) Figure 7.21: Fouling Resistance versus time for Run 14, Dicyclopentadiene deoxygenated  Chapter 7. RESULTS AND DISCUSSION  121  1.0-  EFFECTS OF DISSOLVED OXYGEN 0.9-  0.8-  • = OXYGENATED A = DEOXYGENATED ff  0.7-  q reduced  • •  to, 240 kW/m  CO  2  0.8-  g  CO  0.5  1—1  CO K O  t-J  ID O  C?  • •  w  0.4-J • 0.3-  •  0.2  0.1  0.0 7.0  14.0  21.0  28.0  35.0  42.0  TIME (HOURS) Figure 7.22: Comparison of F F R U oxygenated and deoxygenated runs for indene  49.0  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/m  2  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/m  2  heat flux was 248.4 kW/m  2  and a bulk temperature of about 80°C. The H W P  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/m . 2  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/m . 2  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. A n 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  7.3.7  DISCUSSION  123  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/m , 2  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/m . 2  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 dicyclopentadiene, 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 H W P 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/m  R at 40 hr. {m K)/kW  Rf ratio relative to decene-1  2  f  2  Rf ratio relative to indene  5  Decene-1  357  0.015  1  0.02  6  4-Vinyl-1cyclohexene  298  0.16  10  0.21  Dicyclopentadiene (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  Dicylopentadiene deoxygenated  298  0.085  5.5  0.11  15  Hexadecene-1  298  0.25  16  0.33  12  Dicyclopentadiene *  260  0.45  30  0.6  7  14  * 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 dicyclopentadiene 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 H W P Fouhng Resistances at High Heat Flux  Run  Heat Flux kW/m  R at 40 hr. (m K)/kW  Rf ratio relative to decene—l  f  Rf ratio relative to indene  #  Compound  5  Decene—l  360  0.03  1  0.03  6  4-Vinyl-1cyclohexene  294  0.13  4  0.14  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  Dicyclopentadiene *  254  0.032  2.8  0.35  7  2  2  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]  Ratio of Deposition Rate Relative to n-decane  Ratio of Deposition Rate Relative to decene-1  Decene—l  4  1  4- Vinyl-Icy clohexene  22  5.5  Indene  40  10  Unsaturated Species  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  Figure 7.23: Photograph of fouled P F R U probe  130  Chapter 7. RESULTS  AND  DISCUSSION  Figure 7.24: Photograph of fouled coiled wires  131  Chapter 7. RESULTS  AND  DISCUSSION  132  H OO  H  O-O  Figure 7.25: Polymeric Indene Peroxide  1 H-  r-CH  \  - C H - CH-0-O-  I Cf4-0-O-  /  CH  X  -H  CH-  2  1,4-STRUCTURE  1,2-STRUCTURE  Figure 7.26: Polymeric Cyclopentadiene  Peroxide  Chapter 7. RESULTS AND  DISCUSSION  133  Table 7.23: Analysis of Fluids and Deposits  Source  c%  H %  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  63.82  4.87  31.05  0.26  Dicyclopentadiene (deposit from Run 13)  0 %  Amount of oxygen obtained by a difference  N %  Chapter 7. RESULTS AND DISCUSSION  134  aldehyde and acid units. A unit represents the amount of oxidation product in 10 c m  3  of oil. The units are calculated from the peroxide, aldehyde and acid numbers. Thus a 1000 c m of oil with a peroxide number of 0.4 will have 40 peroxide units. The results of 3  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 M e c h a n i s m  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  Light distillate (Pennsylvanian crude)  86.1  13.9  Residue (Penn.)  69.8  8.7  Light distillate (W. Texas crude)  85.5  14.3  Residue (W. Texas)  73.6  9.6  % 0  —  21.1  —  16.4  Peroxide Units  —  3196  —  1402  Aldehyde Units  Acid Units  —  —  680  51  —  —  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 credence 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:  20  2  where (CQHS0 )  2 2  + 2CgH  s  —•  (C H 0'2)2 9  8  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 0  2  = (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 ) 10* g liquid 2  =  1-834 g O  a  Thus the number of moles of oxygen is given by: No. of moles 0  2  =  = 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. A n 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 hydroperoxides were detected in the fluid during the kerosene runs. What was detected can at  Chapter 7. RESULTS  AND  DISCUSSION  best be described as trace amounts.  138  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/m  2  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/m , 2  198 °C) fouhng resistances of up to 0.9 m K/kW 2  wall temperature  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, deoxygenation 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 autoxidation induced reactions.  Moreover, the predominance of autoxidation reactions is a  probable indication that there is little contribution from thermal polymerization. Deposit 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 temperatures 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 recommended 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/m  2  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 kWjm  2  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 experiment be repeated using a heat exchanger with a different configuration.  Nomenclature  L a t i n Symbols ttl - a  4  dimensionless constants  A  area of heat transfer surface, (m )  B  Bunsen coefficient, (cm /cm atm.)  C  concentration,  2  3  3  (kg/rn ) 3  C3 dimensionless constants concentration of foulant at the liquid deposit interface, d  diameter of pipe, (m)  E  activation energy,  f  friction factor  G  concentration in ppmw  h  convective heat transfer coefficient,  I  current, (Amperes)  k  thermal conductivity,  k  (J/mol.K)  (W/mK)  mass transfer coefficient  D  (m/s)  attachment rate constant  K  transport coefficient,  (m/s)  (m/s)  kf  foulant thermal conductivity,  L  Ostwald coefficient  L  length of P F R U heated section, (m)  m  d  mass deposition flux,  (W/m K)  (W/mK)  (cm /cm ) 3  3  (kg/m s) 2  142  2  (kg/m ) 3  Nomenclature  removal flux, (kg/'m s) 2  m"  asymptotic mass per unit surface area, (kg/m )  P  partial pressure of gas,  P  peroxide number  Pd  dimensionless probability function  Q  heat flow, (Watts)  q  heat flux,  R  electrical resistance, (Ohms)  Rext  electrical resistance of the external circuit, (Ohms)  Rj  thermal fouhng resistance,  R}  asymptotic thermal Fouhng Resistance,  Rg  universal gas constant,  R  electrical resistance of coiled wire at zero power, (Ohms)  Rw  thermal resistance of tube wall,  s  distance between thermocouple location and heating surface, (  St  solubihty parameter of liquid, ( ( J / m ) / )  S  solubility parameter of gas, ( ( J / m ) / )  S  sticking probability  T  temperature, (K, °C)  t  time, (s)  U  overall heat transfer coefficient,  0  2  (Njm ) 2  (Watts/m ) 2  (m KjkW) 2  p  u  b  (m K/kW) 2  3  bulk fluid velocity,  (m/s)  V  voltage, (volts)  V  volume, (m )  X  deposit thickness (m)  3  2  (J/mol.K)  3  2  (m K/kW)  1  1  2  2  (W/m K) 2  Nomenclature  UA  G r e e k Symbols j3  dimensionless contact angle  r  shear stress,  xj)  deposit strength  6  time, (s)  9  C  (N/m ) 2  time constant, (s)  pf  foulant density, (kg/m )  p  density of liquid at temperature T, (kg/m )  2  3  t  a  temperature coefficient of resistance,  A  thermal conductivity,  /A  viscosity, (kg/m.s)  (K~ )  (W/mK)  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  1  Nomenclature  Superscripts n  order of reaction  *  asymptotic Dimensionless G r o u p s  Nu  Nusselt number,  Pr  Prandtl number,  Re  Reynolds number,  (hD/k) (C fi/k) p  (U^D/v)  Bibliography  Van Nostrand, W . L . , S. H . Leach, and J . L . Haluska, "Economic Penalties Associated 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. N A T O 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 ( T E M A ) 6 tion, 140-142, T E M A , New York, (1978).  th  edi-  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 Phenomenon! in the Petroleum Industry. Paper 76-CSME/CSCHE-23, 16 National Heat Transfer Conference, St. Louis, MO., Aug. (1976). th  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 Petrochemical Reactors", in Fouhng of Heat Transfer Equipment 441-435, eds Somerscales, 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." A P I Division of Refining 40 mid year meeting Chicago. Preprint No. 06-75, May (1975). th  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, 12651268, (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. A P I section III (Refining) vol. 43, 106114, (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, S A E Aeronautics and Space Eng. Meeting, Los Angeles, October (1968). Eaton, P. and R. Lux, "Laboratory Fouhng Test Apparatus for Hydrocarbon Feedstocks." A S M E H T D 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 Chemical 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 Oxidation 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. 7 Int. Heat Transfer Conf, vol. 6, 391-396, (1982). th  [41] Palen, J . W., and J . W . Westwater, "Heat Transfer and Fouhng During Pool Boiling of Calcium Sulphate solutions". A I C h E 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 Exchangers", 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 . A m . 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 Publishing 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 Publishing 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 Convective 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, 42, (1915). P  [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 Decomposition 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 4 Conf. on Ocean Thermal Energy. New Orleans, VII-15 to VII-24 March (1977). th  [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 Stability 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. symposium series, vol. 1, No.86 (1984). [80] Fetissoff, P. E., "Comparison of Two Fouhng Probes.", M.A.Sc. Thesis, The University 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 . A m . 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 Cyclohexene", 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 Methylstilbenes", J . Am. Chem. Soc, 83, 3440-3444, (1961).  a-  [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. Li, 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. E F C 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 Procesing 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, A C S Symposium Series No 32, 345-372, (1976). [103] Brill, W . F., "The Isomerization and Rearrangement of Pure Acychc Hydroperoxides." 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 . A m . 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 . A m . 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 Sulphides, 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: Thermolysis." 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. 7 Intern. Heat Transfer Conf. vol. 5 2555-2560, Hemisphere Publishing (1986). th  [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 temperatures, the entry and exit bulk fluid temperatures, the power supphed to the probe and the manometer A z reading. The wall temperatures were converted to the surface temperature using the formula:  T.  =  T -jQ/A w  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 P F R U 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:  _ ~  K  T  —T (Q/A)  so  bo  a  and that of the fouled surface from:  J_ h  T -T Q/A  =  a  f  b  Knowing the heat transfer coefficients under clean and fouled conditions, the thermal fouhng resistance was calculated from:  hj 156  h  c  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  Q  V  = I (y — R t) ex  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. JX — /t t ex  0  where R  a  is the resistance of the wire at zero power and at a temperature T . a  resistance is determined before each run. R . ext  This  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  A.l  AND  CALCULATIONS  158  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 T \ — 199.3 °C, w  T 2 — 200.5 ° C , and T $ = 204.0 °C. The local surface temperature is calculated from W  w  the wall temperatures as:  where ( f )  = 7.Q92A0~ (m K)/kW, 3  r c i  1.667.lO- {m K)/kW. 2  Thus, T  2  (f )  2  = S.3Z3.10- {rn K)/kW, 3  TC2  = 197.01, T  Sl  S2  = 198.021, T  2  S 3  and  )  T C 3  =  = 199.04 and the average  value is given by T  to  = (197.01 + 198.02 + 199.04)/3 = 198.02°C  The heat flow and area are given by: Q = 1020 W A = 0.0034287m  2  From whence the heat flux is calculated as: q  =  0  ^ = 297.48  kW/m  2  The bulk fluid temperature under clean surface conditions is evaluated as the average of the entry and exit bulk fluid temperatures. T  bl  T  b2  T  bo  = 78°C  = 84°C7  = {T +T )/2 bl  b2  = 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 g  h  0  (m K)/kW 2  0  P F R U U N D E R F O U L E D CONDITIONS: A sample of three of the wall temperatures, under fouled conditions, read by the thermocouples are T  Wl  = 215°C, T 2 W  = 216.3°<7, and T  W3  = 220°C.  The surface  temperatures are calculated from the wall temperatures as: T. =  T -jQ/A w  Thus, T  = 213.0°C  sl  T  s2  = 214.9°C  T, - 220.0°C 3  and the mean surface and bulk fluid temperatures are given by: T, = ( T + T.2 + r )/3 = 214°C al  j3  T = {T +T )/2 b  Where T i and T b  b2  bi  b2  = 84°C  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/m  2  The heat transfer coefficient under fouled conditions is evaluated from: _L h  T =  f  >~ q  T  b =  0.4349  (m K)/kW 2  The thermal fouhng resistance is calculated as the difference between the reciprocals of the overall heat transfer coefficients under clean and fouled conditions. R  f  =  hf  -  h  = 0.042  (m K)/kW 2  a  H W P 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, R = 9.10 Ohms., R a  T  ext  = 0.038 Ohms, T  bl  = 81°C,  = 85°C, T = 22°C and A = 0.00004918 m . Hence the power to the probe, and heat 2  b2  a  flux are evaluated respectively as: Q = I {V/I 2  - R )  = 14.6507 W  ext  q= Q/A = 297.87 kW/m  2  And the resistance, surface and bulk temperatures are evaluated respectively as: R  T  = V/I = 10.5992 Ohms.  = {*~_ : R  ao  xt  - l) I a + T = 198°C a  where a the temperature coefficient of the electrical resistance is 0.00094 T  =  bo  (T  bl  + T )/2 = 83°C b2  The film heat transfer coefficient under clean conditions is calculated as: 1  _  T  so  T  bo  0.3879  (m^K)fkW  K~ . l  Appendix A. DATA COLLECTION  AND  CALCULATIONS  161  H W P 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., T i — 77°C, and T 0  = 81°C. The relevant parameters are evaluated  b2  from these values as for the initial conditions.  R  =  Q  10.6313 Ohms  =  q =  T  14.4764 W  294.32W/m  2  = 201.76°C7  s  T  =  b  79°C  and the heat transfer coefficient under fouled conditions is calculated as:  =  0.4171  m K/kW 2  The thermal fouhng resistance is calculated from: R  s  =  hf  h  = 0.0292 c  m K/kW 2  Appendix A. DATA COLLECTION  A.2  AND  CALCULATIONS  162  CALCULATION OF VOLUMETRIC FLOW RATES  The volume flow rates are calculated as follows. Using the P F R U as a sample, the orifice discharge coefficient C = 0.6102, the orifice diameter d = 0.0158 m , the manometer d  2  differential pressure AZ = 6.5 in., fi = di/d , hence d\ = fid . Therefore, the ori2  2  fice cross-sectional area A„ = f3 ird /4 = 4.9488.10- m . 2  test fluid is p = 792.4 kg/rn 3  5  2  The density of the flowing  and the density of the mecury in the manometer p  3  13643 kg/m .  2  m  =  The difference between the densities of the mercury and flowing fluid  8p = Pm — P — 12850 kg/m , and the pressure drop A p = AzAp = 2121.63 kg/m . Thus 3  2  the volumetric flow rate is calculated as:  2gc(Ap) The bulk fluid velocity and Reynolds number are calculated as follows: The equivalent diameter of the annulus d  is given by:  eg  (d - d ) = 0.025 - 0.0107 = 0.0143 m  d, •eg  0  {  where d is the annulus outer diameter and d{ is the annulus inner daimeter. The crossa  sectional area of the annulus is given by  Thus the bulk fluid velocity is given as U  =  V (3600)(0.000401)  0.56 m/s  The Reynolds number is calculated from: Re  =  Ud p _ (0.5611)(0.0143)(792.4) = 9781 a ~ 0.00065 eq  Appendix A. DATA COLLECTION  A.3  AND  CALCULATIONS  163  CALCULATION OF T H E R M A L 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 If  =  1 . dx. 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 presented 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 H W P 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  Dicyclopentadiene  0.31  0.69  Dicyclopentadiene  0.14  0.67  4-Vinyl-1cyclohexene  0.07  0.44  13 6  Table A.26: Viscosity of Kerosene  Temperature °C Measured Viscosity x 10 cP 6  44  54  64  74  84  94  1.067  0.936  0.830  0.726  0.652  0.588  Appendix A. DATA COLLECTION  AND  CALCULATIONS  165  Table A.27: Densities of Test Fluids at Room Temperature  Test Fluid  Density at beginning of run kg/m 3  Density at end of run kg/m 3  Kerosene  803.4  Indene/Kerosene  807.2  809.9  Dicyclopentadiene/Kerosene  810.7  811.4  4-Vinylcyclohexene / Kerosene  795.6  795.9  Hexadecene/ Kerosene  790.6  791.2  Cyclooctadiene/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  0.604  0.751  0.8  0.854  0.905  1.087  0.613  0.613  0.609  0.608  0.610  0.608  Volume flow rate m / h r . 3  Orifice Meter Discharge Coefficient  Table A.29: Discharge coefficients determined from cahbration of H W P  Manometer Ah reading (in Volume flow rate m /hr. 3  Orifice discharge coefficient  4.0  6.0  8.0  10.0  12.0  15.0  0.015  0.018  0.021  0.024  0.025  0.029  0.689  0.689  0.701  0.698  0.700  0.689  Appendix A. DATA COLLECTION  AND  CALCULATIONS  167  1.20  RUN 8B INDENE 1.05  • = PFRU Tb=79°C A - H W P Tb=?2°C  0.90-  C\2  PFRU: q=292 kW/mjr HWP: q=237 kW/m q reduced to 230 kW/m  0.75  1  o  55 0.60CO  t—I  CO  «  o 55  0.45  »—i  5D  o fe  q reduced t o 175 kW/m  0.30-  7  0.15  0.00 14.0  21.0  28.0  35.0  TIME (HOURS) Figure A.27.: Repeat of Run 8, indene at high heat flux  42.0  49.0  Appendix A. DATA COLLECTION  AND  CALCULATIONS  168  0.08  RUN 11B INDENE DEOXYGENATED II 0.07  ow ,  • = PFRU, Tb=83 C A = HWP, Tb=83°C PFRU: q=301 kW/m^ HWP: q=292kW/m^  0.06  0.05-  0.04-  "AA  A 4§> p AA  UP  0.03-  ED'  rtP A J H  • A  Q A\  0.02  A  •  • •  0.000*  £  •P • A  0.01  Cf^  A  •  A A  A  \  <  A •  A  AA=I_^ AAV  A'  AA  •  •  *  A  4£>  AA A A A A  7.0  14.0  21.0  28.0  35.0  TIME (HOURS) Figure A.28: Repeat of Run 11, indene deoxygenated  42.0  49.0  Appendix B M A X I M U M FOULING RESISTANCES AND INITIAL RATES  Tables B.30 and B.31 show the maximum fouhng resistances for the P F R U and H W P 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 H W P 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  #  Compound  Atmosphere  Heat Flux kW/m  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  Run  2  at 40 hours (m K)/kW 2  Appendix B. MAXIMUM  FOULING  RESISTANCES  AND INITIAL  RATES  171  Table B.31: Maximum Thermal Fouling Resistances after 40 Hours for H W P Probe  Run  #  Compound  Atmosphere  1  Decene-1  oxygenated  2  Heat Flux kW/m  2  at 40hours m K/kW 2  150  No measurable fouhng  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  Table B.32: P F R U Initial Fouling Rates  Initial Fouling Rate Run #  (m K)/kWhr. 2  Range of time data fitted in hours  5  0.0027  3-10  6  0.0139  1 - 11  8  0.0406  4-20  9  0.0154  0 - 11  10  0.0051  1 - 11  11  0.0032  2-14  12  0.0399  3-18  13  0.0110  2-10  14  0.0030  2-24  15  0.0073  3-24  RATES  172  Appendix B. MAXIMUM  FOULING  RESISTANCES  AND INITIAL  Table B.33: H W P Initial Fouling Rates  Initial Fouling Rate Run #  (m K)/kWhr. 2  Range of time data fitted in hours  5  0.00382  3-10  6  0.00574  1 - 21  • 8  0.05177  14 — 28  9  0.00779  2-17  10  0.00776  1 - 11  11  0.00219  2-14  12  0.0206  3-14  13  0.0031  3-26  14  0.00220  3-21  15  0.00610  3-17  RATES  173  Appendix C P R O G R A M LISTINGS  C.l C  C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C  COMPUTER  PROGRAMS  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) This i s a program resistances.  to calculate  and p l o t the thermal  NOMENCLATURE TS1 TS2 TBI TB2 TT RO REXT ALPH Al A2 U01 U02 Ul U2 R V RI QF1 QF2 RFI RF2  the average surface temperature of the PFRU probe. the average surface temperature of the HWP. i s the bulk f l u i d temperature of the PFRU probe. i s the bulk f l u i d temperature of the hot wire probe. i s time i n minutes. i s the r e s i s t a n c e of the hot wire at zero power. i s the r e s i s t a n c e of the e x t e r n a l c i r c u i t . i s the temperature c o e f f i c i e n t of the s t a i n l e s s s t e e l 302 wire. i s the surface area of the PFRU probe. i s the surface area of the hot wire probe. i s the o v e r a l l heat t r a n s f e r c o e f f i c i e n t of the clean PFRU surface i s the o v e r a l l heat t r a n s f e r c o e f f i c i e n t of the clean hot wire surface. i s the o v e r a l l heat t r a n s f e r c o e f f i c i e n t of the PFRU probe i s the o v e r a l l heat t a n s f e r c o e f f i c i e n t of the hot wire probe. i s the r e s i s t a n c e of the hot wire. i s the voltage across the hot wire. i s the current through the hot wire. i s the PFRU heat f l u x . i s the hot wire probe heat f l u x . i s the thermal f o u l i n g r e s i s t a n c e of the PFRU probe. i s the thermal f o u l i n g r e s i s t a n c e of the hot wire probe.  READ(5,*)M,N READ(5,*)R0 T0,REXT,ALPH,A1,A2,U01,U02 READ(5,*)TS11,TS22,TB11, TB22.QF11,QF22 1  C C C C  fouling  Read i n the surface temperatures. READ(5,*)((X(I,J),I=i,M),J=l,N)  174  Appendix C. PROGRAM  C C  Average PFRU surface  LISTINGS  temperatures.  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. CONTINUE  20 C C C a l c u l a t e 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 C a l c u l a t e the PFRU heat f l u x e s , heat t r a n s f e r c o e f f i c i e n t s and C thermal f o u l i n g r e s i s t a n c e s 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 C a l c u l a t e the PFRU heat f l u x e s , heat t r a n s f e r c o e f f i c i e n t s , and C thermal f o u l i n g r e s i s t a n c e s 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 C a l c u l a t e the averages over the run of the heat f l u x e s , 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 P r i n t out the i n i t i a l and average c o n d i t i o n s , data and r e s u l t s . 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) 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 $,F9.4) 440  C C C C  P l o t f o u l i n g r e s i s t a n c e versus time curves. Scale values of time f o r the x-coordinate.  10 C  DO 10 11=1,N TT(II)=TT(II)/60. CONTINUE CALL DSPDEV('PLOT') CALL NOBRDR CALL COMPLX  C C C  Define s i z e of page and area of p l o t  C C C  Label  C C C  C C C  C  CALL PAGE(8.5,11.0) CALL AREA2D(5.2,6.8) axis  CALL CALL CALL CALL CALL CALL CALL CALL  MIXALF('INSTR') YNAME('FOULING RESISTANCE (Qm(E0.7)2 XNAME('TIME (()H0URS())$',100) YAXANG(O.O) XTICKS(2) YTICKS(2) GRAF(0.0,7.0,50.0,0.00,0.150,1.2) THKFRM(0.04)  Plot f o u l i n g resistances CALL CALL CALL CALL CALL  against  (EX)K())/kW$»,100)  time  FRAME MARKER(O) CURVE(TT,RFI,126,-1) MARKER(2) CURVE(TT,RF2,126,-1)  Draw Legend MAXLIN=LINEST(IPAK,500,50) CALL MIXALF('INSTR') CALL LINESCPFRU T(L0.3)b(EX)=81(E0.8)o(EX)C$'.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  Appendix C. PROGRAM  c  LISTINGS  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 C  Calculate  heat fluxes  DO 10 1=1,N  C  QF1(I)=X(6,I)/A1/1000.  C C C C  Calculate  heat t r a n s f e r  coefficient.  U1(I)=QF1(I)/(TS1(I)-TB1(I))  C C C  Calculate 10  C C  thermal f o u l i n g  resistance.  RF1(I)= 1/UKD-1/U01 CONTINUE RETURN END 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 C  Calculate  C C C  Calculate  C C C  Calculate  heat fluxes  QF2(I)=X(7,I)*X(8,I)/A2/1000. heat t r a n s f e r  coefficient  U2(I)=QF2(I)/(TS2(I)-TB2(D)  10  thermal f o u l i n g  RF2(I)=1/U2(I)-1/U02 CONTINUE RETURN END  resistance  Appendix C. PROGRAM  C C C C C C C C C C C C C C C C C C C C C C  LISTINGS  IMPLICIT REAL*4(A-H,L,0-Z) NOTATION This program was used i n c a l c u l a t i n g the s o l u b i l i t y of a i r oxygen and n i t r o g e n i n kerosene, the flow r a t e s of the Hot Wire and PFRU probes and the corresponding Reynolds numbers. P — SI S2 F M2 L B D DT T G  P a r t i a l pressure of gas i n atmospheres. S o l u b i l i t y parameter of of l i q u i d Equivalent s o l u b i l i t y parameter of gas. Fuel f a c t o r Molecular weight of gas. Ostwald c o e f f i c i e n t . Bunsen c o e f f i c i e n t . Density of l i q u i d at 15 degrees C e l s i u s . Density of l i q u i d at s p e c i f i e d temperature. Temperature at which s o l u b i l i t y i s c a l c u l a t e d . S o l u b i l i t y i n parts per m i l l i o n by weight.  Calculation  of S o l u b i l i t i e s .  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 C C ZP C CDP C BETAP C D C GC C DM C DL C A0P C VFP C REP C PR C DO C Dl C UP C DEQP C VIS C VISK C RH0 C ADUCT C  c  of PFRU Flow  rates.  Pressure drop across PFRU o r i f i c e meter i n inches. PFRU o r i f i c e discharge c o e f f i c i e n t . Dimensionless contact angle of PFRU o r i f i c e meter. Diameter of o r i f i c e A c c e l e r a t i o n due t o g r a v i t y . Density of mercury. Density of t e s t f l u i d . C r o s s e c t i o n a l area of PFRU o r i f i c e meter. Volume flow r a t e of PFRU probe PFRU Reynolds number. P r a n d t l number Outer diameter of annulus Inner diameter of annulus. Bulk v e l o c i t y of t e s t f l u i d . Equivalent diameter of annular probe Dynamic v i s c o s i t y of t e s t f l u i d . Kinematic v i s c o s i t y of t e s t f l u i d . Density of t e s t f l u i d . HWP duct c r o s e c t i o n a l area.  ZP=6.5 CDP=0.6102 BETAP=0.5024  Appendix C. PROGRAM  C C C C C C  C C C C  C C C C C C  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. Calculate  flow  rate.  VFP=3600.*CDP*A0P*SqRT(2*GC*DELP/DL/(l.-BETAP**4)) Calculate  PFRU Reynolds number.  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 a l c u l a t i o n of HWP flow r a t e and Reynolds number. Nomenclature i s the same as f o r the PFRU with the 'P' denoting PFRU replaced by 'H' f o r HWP. ZH=24. CDH=0.6928 BETAH=0.0748 DZ=ZH*2.54/100. DELH=DRH0*DZ Calculate  flow  rate.  A0B=BETAH*BETAH*PI*D*D/4 VFH=3600*CDH*AOH*SORT(2*GC*DELH/DL/(1-BETA**4)) Calculate  HWP Reynolds number.  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 A N D RESULTS  D.l  N O M E N C L A T U R E FOR DATA AND RESULTS  HTEMP—  H W P average surface temperature (°C)  PTEMP—  P F R U average surface temperature (°C)  HHF  Hot wire heat flux (kW/m )  —  2  P F R U heat flux (kW/m )  PHF  2  I ('IF,  —  Hot wire probe's bulk fluid temperature (°C)  PTB  —  PFRU's bulk fluid temperature (°C)  HFR  —  H W P thermal fouhng resistance  ((m K)/kW)  PFR  —  P F R U thermal fouhng resistance  ((m K~)/kW)  2  THWP —  H W P surface temperature (°C)  TPFRU —  P F R U surface temperature (°C)  TBHWP—  H W P bulk fluid temprtaure (°C)  QHWP —  H W P heat flux (kW/m )  QPFRU—  P F R U heat flux (kW/m )  UHWP —  H W P initial heat transfer coefficient  UPFRU —  P F R U initial heat transfer coefficient  VFP  —  P F R U volume flow rate  VFH  —  H W P volume flow rate  REP  —  P F R U Reynolds number  REH  —  H W P Reynolds number  2  2  2  180  (m /hr) 3  (m /hr) 3  (kW/(m K)) 2  (kW/(m K)) 2  Appendix D. DATA AND RESULTS  181  RUN 5, DECENE-1 INITIAL CONDITIONS: UPFRU  UHWP  TPFRU  THWP  TBPFRU  TBHWP  qPFRU  QHWP  3.070  2.932  204.00  206.00  90.0  85.0  349.99  354.78  AVERAGE CONDITIONS: TBPFRU  TBHWP  QPFRU  QHWP  VFP  REP  VFH  REH  88.00  85.00  357.41  360.45  0.81  9760  0.04  4.9  TIME  PTEMP  HTEMP  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780 800 820 840  205 .00 205,.00 208,.33 206,.00 206,.33 204,.33 198 .67 201 .00 201,.00 200,.33 202,.67 202,.67 203,.00 204,.33 205,.00 207 .00 208,.33 209,.33 211,.33 208,.33 206,.00 207,.33 210..33 211..33 210,.33 211,.33 210,.67 209,.33 208,.33 210,.33 212..67 215..67 209,.00 208,.00 207,.67 208,.00 207,.33 207,.00 207,.00 210..33 206.,67 206,.33 206,.33  205,.50 205,.32 205.42 203,.40 195,.95 205,.62 206,.64 206,.83 208,.60 207,.76 208,.68 205..16 205..35 213..85 219,,22 224,.90 226,.43 213,.99 213,.25 210,.84 208,.62 207,.97 207,,14 207,.87 208,.33 210,.56 212,.32 211,.39 212,,79 217,,09 216,,83 217..29 218..62 219,.54 220.49 219,.48 220,,70 221,,00 221..66 222.,04 217.,23 218,,64 215.45  PTB 89 .0 91 .5 92 .0 92 .5 96 .0 91 .0 84 .0 90 .0 87 .5 87 .0 87 .0 87 .0 85 .5 85 .0 85 .0 86 .5 88 .0 89 .0 90 .0 89 .5 88 .5 88 .5 88 .5 89 .0 89 .5 90 .0 90 .0 90 .0 89 .0 90 .5 91 .0 90 .5 87 .0 84 .0 84 .0 82 .5 83 .0 82 .5 83 .0 83 .0 80 .5 80 .0 79 .5  HTB 86,.5 90,.0 93..5 89..0 87,.0 87,,0 84,.5 82,.0 80,.0 78,.5 77,.5 77..0 77,.0 85,,5 92,,0 96,.0 97,.0 91,.5 84,.5 79,,0 76,,0 73,,5 72,.0 72,.0 72,.5 78,.5 81,,5 84,,0 85,,5 86,,5 87,.5 87.,5 87,.5 87,.5 85,,5 85.,5 84..5 88.,0 83.,5 83.,5 83.,5 83.,0 82.,0  PHF  HHF  PFR  352,.903 347,.070 352,.903 347,.070 347,.070 341,.237 344 .154 344,.154 349,.987 347,.070 352,.903 352,.903 347,.070 349,.987 349..987 352,.903 354,.362 354,.362 358,.736 352,.903 347,.070 349,.987 358..736 358,.736 352,.903 355,.820 352,.903 352,.903 354,.362 354,.362 355..820 355..820 349,.987 355,.820 354..362 358,.736 352,.903 354,,362 349,,987 358,,736 357,,278 354,.362 358,,736  371,.213 371,.216 371,.132 371,.760 373,.878 370,,910 370,.541 370,.484 369,.832 370,.144 369,.914 371,.052 370,.995 369,.275 367.,374 365,.662 365,.150 368,.863 369..037 369,.723 370..354 370.,608 370..865 370,.637 370,.549 369,.809 369,.322 369,.607 369..179 367.,812 367..788 367.,645 367,,191 367,,015 366,.675 366,,824 366,,508 366,,313 366,.114 366.,000 367.,454 367,,027 367,.996  0,.0000 0,.0000 0,.0000 0,.0000 0,.0000 0,.0000 0.0000 0.0000 0,.0000 0.0000 0,.0023 0,.0020 0,.0120 0,.0149 0,.0171 0,.0151 0,.0134 0,.0134 0,.0120 0,.0109 0,.0129 0,.0143 0,.0137 0,.0151 0,.0163 0,.0151 0,.0163 0,.0129 0..0106 0,,0120 0.,0163 0..0257 0,.0229 0..0223 0..0229 0,,0243 0,,0266 0.,0257 0..0289 0..0294 0.,0272 0,,0309 0,,0277  HFR -0..0072 -0.,0171 -0.,0262 -0.,0200 -0.,0363 -0.,0079 0,.0019 0..0092 0,.0200 0,.0215 0,.0269 0..0177 0..0182 0,,0198 0,,0186 0,.0248 0,.0267 0..0044 0,,0212 0.,0289 0..0304 0.,0351 0.,0367 0,,0389 0,.0388 0,,0294 0..0265 0..0169 0..0171 0.,0273 0.,0239 0.,0253 0,.0294 0..0321 0..0404 0.,0375 0.,0439 0.,0354 0.,0496 0.0508 0.0362 0.0418 0.,0349  Appendix D. DATA AND  860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100 2120 2140  204,.67 207,.33 207,.67 207 .33 207 .00 206 .00 205 .67 204,.67 205,.67 204,.67 207,.67 207,.67 207 .67 206 .67 207,.67 205,.33 206,.67 205,.33 205,.33 204,.00 205 .33 204,.67 205 .67 207 .33 206,.00 208,.33 206,.00 205,.33 205,.33 206 .33 207,.33 210,.67 211..33 209,.33 209,.33 208,.67 209.67 210..33 208,.67 210,.67 211,.33 211..67 212,.33 212,.00 213,.00 216,.00 213.,33 215,.67 215,.67 214,.67 216.67 215,.67 216..67 216..67 216..33 215,.67 215,.67 217..00 217..67 217..67 216..33 217..33 215..00 215.,33 215.,67  215,.44 215,.45 214,.52 215 .36 215.44 214 .60 215,.07 214,.52 214,.52 215,.36 215,.18 215,.54 215 .26 214 .25 214 .34 214,.16 214,.06 215,.08 215,.36 215,.28 219 .24 217 .37 217 .36 217,.54 216,.61 216,.51 215,.39 215,.76 216,.05 214,.09 217,.92 218,.47 218,.00 218,.10 219,.42 218,.38 217,.82 218,.30 218,.20 218,.39 218,.12 218,.31 218,.39 218,.57 216,.93 216,.15 217..75 217,.70 217.43 216,.76 215,.94 215..38 216,,69 214,,82 217,,71 216.69 215,.67 216,.32 216..60 217,,07 215,,95 211,,38 215,.75 216..97 218,.28  RESULTS  80 .5 81 .0 81 .0 81 .0 81 .0 81 .0 80 .5 80 .5 80 .5 81 .5 82 .0 82 .0 83 .0 83 .0 83 .0 83 .5 82 .5 83 .5 83 .0 83 .5 84 .0 84 .5 84 .5 86 .0 86 .5 86 .0 86 .5 86 .5 86 .5 87 .0 87 .5 88 .5 88 .5 88 .5 88 .5 87 .5 88 .5 88 .5 88 .5 89.0 90 .0 90 .0 89 .5 89 .5 89 .5 91 .5 91 .5 93 .0 93 .0 93 .5 93 .5 93 .0 93 .5 93 .5 94 .0 94 .0 94 .0. 93 .5 94 .5 95,.0 93,.5 93,.5 93,.0 93,.5 93 .5  82 .0 • 349.,987 81 .5 355,,820 81 .5 357,,278 81 .5 357..278 81 .5 357..278 82 .0 352,.903 82 .0 354,.362 81 .5 349,,987 81 .5 352,,903 81 .5 349.,987 82 .0 354.,362 357..278 81..5 82 .5 355,.820 82 .5 355,.820 83 .0 352,,903 83 .5 349,.987 82 .5 354,,362 83 .5 347.,070 83 .0 349,,987 84,.5 344.,154 84 .5 347,.070 86 .5 347,.070 85 .0 349..987 84 .0 352,.903 83 .5 347..070 85 .0 352,,903 85 .5 349.,987 86 .0 347,,070 87 .0 347,,070 87 .5 347,.070 87 .5 349,.987 88 .5 354..362 88 .5 354..362 89 .0 352..903 88 .5 352,,903 88 .5 354.,362 88,.5 352,,903 89,.0 354.,362 89 .0 349..987 89 .0 352,,903 89 .5 354,.362 89 .0 354.,362 89 .5 354,.362 88,.5 354,,362 89,.5 358,,736 89,.0 358.,736 88,.0 349,.987 87 .0 352.,903 86 .0 354,,362 85 .0 354,,362 84,.5 354.,362 84,.5 358,,736 84,.0 358,,736 84,.5 358..736 84,.0 354.,362 84 .0 354,,362 84 .0 354,,362 84,.5 355..820 84,.5 355,.820 84,.5 352,,903 84,.0 358.,736 84,.0 358.,736 84,.5 358.,736 83,.5 354.,362 84,.5 354..362  368,.051 367,.996 368,.281 368 .025 368,.051 368,.308 368,.165 368,.281 368,.227 367,.970 367,.972 367,.968 368,.053 368,.257 368,.284 368,.286 368,.314 368,.055 367,.970 367,.944 369,.153 369,.725 369 .780 369,.778 370,.064 370,.092 370,.436 370,.376 370,.235 370 .837 369 .663 369,.546 369,.689 369,.661 369,.205 369,.575 369,.746 369,.494 369,.577 369,.520 369,.496 369,.439 369,.465 369,.518 369,.018 368,.781 369,.556 369,.254 369,.971 370,.281 370,.374 370.491 370..145 370..718 369..885 370,.090 370,.405 370,.205 370,.119 369,.976 370,.264 371,,776 370..431 370,,004 369,.658  0,.0294 0,,0294 0,,0294 0,.0274 0,.0271 0,.0280 0,.0274 0..0292 0,.0286 0..0257 0..0294 0..0257 0,.0249 0,.0223 0,.0280 0,.0223 0,.0249 0..0252 0,,0237 0,.0243 0,.0234 0,.0209 0,.0206 0,.0180 0,.0186 0,.0203 0,.0157 0..0163 0.,0166 0,.0177 0,.0166 0,.0186 0,.0206 0,.0169 0,.0169 0,.0160 0,.0177 0..0177 0,.0177 0,.0186 0,.0161 0..0180 0,.0209 0..0199 0,.0187 0,.0215 0..0219 0,.0223 0,.0209 0,.0163 0,.0214 0,,0166 0,,0171 0..0169 0,,0194 0,.0172 0,,0177 0,,0214 0,,0209 0.,0214 0,,0166 0,,0192 0..0149 0.,0177 0,.0194  0.0348 0.0363 0.0335 0.0360 0.0362 0.0323 0.0337 0.0335 0.0335 0.0361 0.0342 0.0366 0.0330 0.0300 0.0289 0.0270 0.0295 0.0298 0.0320 0.0277 0.0373 0.0262 0.0302 0.0334 0.0320 0.0276 0.0229 0.0226 0.0208 0.0136 0.0251 0.0240 0.0226 0.0215 0.0269 0.0237 0.0220 0.0222 0.0219 0.0224 0.0204 0.0223 0.0211 0.0243 0.0176 0.0171 0.0234 0.0262 0.0275 0.0281 0.0272 0.0256 0.0307 0.0238 0.0338 0.0308 0.0277 0.0284 0.0292 0.0306 0.0287 0.0149 0.0266 0.0330 0.0342  Appendix D. DATA AND  2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880 2900 2920 2940 2960 2980  218,.33 217 .33 215 .67 216 .00 216 .67 217,.33 217,.00 217,.33 217,.33 218 .67 217 .00 217.67 215 .67 216,.67 216,.00 217,.00 214,.67 215.00 216 .00 216,.33 216,.00 217,.00 216.00 218,.33 216,.67 216,.33 214,.67 212,.33 213,.33 215,.00 212,.33 220..33 216.,00 207,.67 209,.67 211,.33 211,,00 212,,67 212,.67 214.,67 217,,67 214..33  216,.32 215 .48 216 .89 217 .74 218 .12 217,.84 217,.55 218,.58 218,.21 219,.23 218 .00 217 .53 218,.19 217,.54 217,.92 217,.55 211,.77 211 .86 211 .02 212,.41 211,.39 213,.07 212,.69 212,.14 214..08 214,.73 213,.83 213,.82 214,.38 215,.12 215,.87 217,.46 217..26 215,.31 216,.05 218.47 217,.45 219,,34 224,.23 222..51 222..33 222,.79  RESULTS  93 .5 93 .5 93 .5 93 .5 93 .5 93 .5 93 .5 94 .0 93 .5 93 .5 93 .5 93 .5 93 .5 93 .5 93 .5 93 .5 93 .5 94 .5 94 .5 94 .5 94 .5 95 .0 94 .5 95 .0 94,.5 94 .5 95 .0 95 .0 95 .5 96 .0 96 .5 97 .0 92,.5 86 .5 89 .0 91 .0 92 .0 93 .5 94,.0 95,.0 95,.5 91,.5  84.,5 84,.0 84,.0 84,.5 84,.0 84,,0 84..5 84,,5 84.,5 85,.0 85,.0 84,.5 84,.5 84,,5 83..0 83.,0 83..5 82,.5 82,.5 82,.5 83,.0 83,.5 83..0 83.,5 85,,0 85,,0 86,.5 85,,5 85,.5 86.,5 88.,0 88.,5 87.,5 86,.0 84,.0 83,.0 83,.0 83.,5 84,.0 84.,5 85.,0 85,.0  358.736 358,.736 354,.362 358,.736 358.736 358,.736 357,.278 354,,362 358,,736 358,.736 358,.736 358,.736 354,.362 355,.820 355,.820 355..820 355,.820 352.903 355,.820 355,.820 352,.903 354,.362 354,,362 358.,736 355,,820 355.820 349,.987 344,.154 347,.070 349,,987 341,,237 354,.362 354,.362 352,.903 352,.903 352,.903 349,.987 352,.903 349,.987 349,.987 349..987 347,.070  370,.205 370 .462 369,.978 369,.665 369,.496 369,.582 369,.722 369.408 369..522 369,.262 369,.689 369,.833 369,.632 369,.778 369,.663 369,.722 371,.552 371,.523 371,.781 371,.351 371,.667 371,.151 371..266 371..438 370..892 370,.691 370,.757 370,.813 370,.696 370,.466 370,.183 369..751 369,.864 370,.409 370,.235 369,.546 369,.806 369..124 367,,746 368..370 368.,373 368,.285  0,.0214 0 .0192 0,.0194 0 .0157 0,.0177 0,.0194 0,.0200 0,.0223 0,.0206 0 .0214 0 .0186 0,.0206 0,.0196 0,.0200 0,.0186 0,.0214 0,.0149 0,.0157 0 .0157 0 .0166 0,.0180 0,.0186 0,.0173 0,.0180 0,.0179 0 .0165 0,.0158 0,.0149 0,.0136 0,.0142 0,.0139 0,.0223 0..0229 0,.0171 0,.0163 0,.0157 0,.0139 0,.0123 0..0129 0,,0157 0.,0229 0,.0280  0,.0284 0,.0272 0,.0315 0,.0327 0,.0353 0,.0344 0,.0321 0,.0352 0.,0341 0.0358 0,.0320 0,.0320 0,.0340 0,,0321 0,.0373 0,,0362 0,.0175 0,.0205 0,.0180 0,.0221 0,.0177 0,.0214 0.,0216 0,,0186 0,.0203 0,.0223 0,.0157 0,.0183 0,.0199 0..0195 0.,0177 0,,0210 0,.0231 0,.0214 0,.0289 0..0389 0,.0358 0,,0403 0,.0536 0,,0469 0..0451 0..0464  Appendix D. DATA AND RESULTS  184  RUN 6, 4-VINYL-l-CYCLOHEXENE INITIAL CONDITIONS: UPFRU  UHWP  2.565  2.454  TPFRU  THWP  198.00  198.00  TBPFRU  TBHWP  82.0  78.0  QPFRU  qHWP  297.49  294.77  AVERAGE CONDITIONS: TBPFRU  TBHWP  84.00  82.00  QPFRU  QHWP  298.86  293.81  TIME  PTEMP  HTEMP  PTB  HTB  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780 800 820  205,.0 204,.3 206,.3 215..0 221.,0 220.,3 220.,7 208.,3 216.,0 219,.7 222,.0 219..3 219..3 215..7 220.,0 221.,0 222.,0 223,.7 227..0 229,.7 231,.0 235,.3 240..7 239,.3 239,,0 239,.3 241,.7 241,.3 243,.3 243,.0 243,.3 242..7 246,,0 247,,3 247..7 247,.0 245..7 248,.3 246.,0 245.,7 247,.0 249.,7  195 .5 196 .3 197 .8 199 .0 201 .4 202 .9 203 .4 201 .9 202 .2 212 .1 209 .7 207 .1 207 .1 209 .1 208 .9 208 .5 209 .4 209 .5 210 .3 213 .5 212 .3 212 .3 210 .5 213 .2 215 .9 214.0 214 .1 215 .0 216 .9 213 .0 214 .3 216 .3 217 .0 217 .2 221 .5 220 .3 216 .2 216 .3 222 .5 224 .7 226 .9 227 .0  81,.5 80,.0 81,.0 87,.0 89,.0 90..5 93,,0 80,.0 78,.0 79,.0 80,.0 80,.5 81,.5 78..0 81,.5 82,.0 82,,0 83,.0 85,.5 86,.0 86,.0 87,.0 82,.5 83,.0 82,,5 82,.0 82,.0 82,.5 81,.0 80,.0 80..0 80..0 80.,5 81.,0 81,.0 81,.0 81,.5 82,,0 81,,0 82,,0 82,,0 82..5  78 .0 79 .0 79 .0 78 .0 78 .5 78 .5 79 .0 79 .5 80 .5 86 .5 85 .5 84 .0 84 .5 85 .5 86 .5 83 .5 86 .0 86 .0 83 .5 82 .0 80 .5 79 .0 79 .5 80 .0 81 .5 80 .0 82 .0 83 .0 83 .5 83 .0 84 .0 83 .0 83 .5 84 .0 84 .5 84 .0 83 .5 83 .0 83 .0 83 .5 84 .0 84 .5  VFP 0.81  REP 9760  PHF  HHF  320.821 320.821 326.654 320.821 326.654 320.821 323.738 326.654 326.654 326.654 326.654 320.821 320.821 320.821 320.821 323.738 323.738 326.654 326.654 326.654 320.821 320.821 329.571 320.821 323.738 320.821 326.654 320.821 326.654 323.738 326.654 323.738 326.654 326.654 326.654 326.654 323.738 326.654 323.738 320.821 323.738 328.113  293,.158 295,.268 295,.154 294,.474 294,.070 293,.466 293,.591 294,.195 294,.270 292,.263 293,.156 293,.976 293,.976 293.496 293,.935 293..835 293.,570 293,.595 293,.281 292 .585 292,.801 292,.801 293,.330 293,.000 292..205 292,.710 292 .734 292,.470 291,.940 292,.950 292..296 291,.816 291,,964 292,.014 291,.078 291,.294 292..254 292..279 290.,838 290,,382 289,,927 289,,951  VFH  REH  0.04  4.9  PFR -0,.0050 -0,,0024 -0,.0062 0,.0091 0..0142 0..0148 0..0044 0..0029 0,,0325 0,.0407 0,,0448 0..0428 0,.0397 0..0392 0,,0418 0.,0394 0,,0425 0,,0407 0,,0433 0,,0499 0,.0620 0.,0724 0.,0900 0.,0974 0.,0935 0,.1005 0,.0989 0,.1052 0,.1070 0,,1136 0.,1101 0,,1125 0.,1167 0..1193 0,,1203 0,,1183 0,,1172 0,,1193 0.,1197 0,,1202 0.,1197 0,,1196  HFR -0,.0090 -0,.0096 -0,.0044 0,.0030 0,.0092 0,.0143 0,.0144 0,.0077 0 .0053 0,.0184 0.0138 0,.0100 0,.0083 0,.0118 0,.0078 0,.0166 0,.0112 0.0116 0,.0224 0,.0384 0,.0396 0,.0447 0,.0367 0,.0442 0,.0485 0,.0470 0,.0405 0,.0403 0,.0449 0,.0333 0,.0344 0..0448 0,.0453 0..0443 0,.0571 0,.0549 0,.0425 0,.0445 0,.0657 0,,0715 0,,0773 0.,0760  Appendix D. DATA AND  840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100 2120 2140 2160  247 .0 248,.3 247,.3 248,.7 250,.7 251,.7 252,.7 253..0 254,.3 255,.0 258,.3 255,.7 253,.7 243,.7 243,.7 242,.3 246,.0 245,.3 244,.3 242,.3 243,.7 251..7 247,.0 247,.3 247,.0 249,.0 250,.7 249,.0 252..0 247,.0 251,.3 252,.7 254,.7 253,.0 255..3 261,.3 260..7 259,.3 251,.3 249,.0 250..7 250..0 248..7 247,.3 246,,7 244,.3 246,.7 244..7 247..7 250,.7 252,,7 248,,7 247,.3 249,.7 253..7 252,,7 249..7 252,,3 251,.7 256,.7 257,.0 251,.3 251,,0 251,.7 255.,0 250.,0 251.,7  229 .3 228 .1 228 .1 229 .4 226 .1 227 .1 229 .1 232 .4 225 .0 231 .5 227 .3 231 .3 235 .7 230 .6 235 .6 229 .3 230 .1 228 .9 236 .2 234 .0 232 .8 232 .2 232 .5 230 .5 230 .1 234 .3 235 .8 235 .9 234 .6 235 .6 235 .8 236 .9 237 .0 237 .1 236 .9 236 .4 234 .4 235 .0 234 .5 234 .6 235 .8 235 .6 234 .9 235 .0 236 .8 236 .8 237 .5 236 .5 237 .7 237 .7 237 .8 237 .9 238 .1 237 .3 237 .8 238 .0 238 .5 237 .4 237 .5 239 .4 239 .6 239 .8 240 .2 239,.2 240,.1 243,.1 240,.1  RESULTS  83 .0 83,.5 84,.0 85,.5 87,.0 88,.0 89,.0 89,.5 90,.5 92,.0 93,.0 91,.0 88,.0 76,.5 77,.0 78,.0 79,.0 79,.5 79,.5 80,.0 80,.0 80,.0 80,.5 81,.0 82,.0 83,.0 83,.0 83,.0 84,.0 83,.0 85,.0 86,.5 87,.0 88,.0 88,.0 89,.0 90,.0 86,.0 80,.0 79,.0 79,.0 79,.0 79..5 80..0 80.,0 80,.0 80,.5 80,.0 81,.0 81,.5 82,.0 81,,5 81,.5 80,.5 80,.0 80,.0 80.,0 81,.5 82,,5 85.0 85,.0 85,.0 84,,0 83,,0 86,,0 83..0 83.,0  85,.0 84,.0 83,.0 83,.5 83,.0 82,,5 82,,0 81,,5 81,.0 79,.5 80,.5 82,.5 82,,5 81,.0 78,,5 78,.0 77,.0 78,.0 79,.5 80,.0 80..0 80..5 81,.0 80,.0 81,.0 81,.0 81,.0 81..5 82,,0 82.,0 82,.5 83,.0 83,.0 83..0 82..0 82,,5 82,,0 82,.5 83,.0 83,.5 83,.0 83.,0 83,,0 83,.5 84,,0 84,.0 84..5 84,,0 83,.5 83,,5 84,.0 84..0 84..5 85,.0 85,.5 86,.0 86,.5 86..0 86.,0 86,.5 86,,0 86..0 86.,5 87.,0 87.,5 87.,0 86.,5  320,.821 323,.738 320,.821 320.821 320,.821 320.,821 320.,821 320,,821 320,.821 317,.905 320..821 317,.905 317.,905 320..821 320.,821 320,.821 320,.821 320,.821 320..821 316.446 317..905 320.,821 317.905 320,.821 317,.905 320,.821 320..821 320..821 320..821 317.,905 320,.821 320,.821 320..821 320,,821 323..738 326.,654 320.,821 323.738 320,.821 320,.821 323.,738 323,,738 323.,738 320,,821 320.,821 317,.905 320,.821 323..738 323,,738 326,,654 328,,113 323,,738 326,.654 326,.654 328,.113 328,.113 326,.654 328..113 326.,654 328,.113 328,.113 320..821 320..821 323.,738 323.,738 320.,821 320.,821  289,.495 289,.711 289,.711 289,.520 290,.216 289..976 289..471 288.,774 290,.456 289,.039 290,.000 289,.962 289,.024 290..276 288..999 290,.468 290,.178 291,.343 289,.631 290..089 290..305 290..645 290,.718 291,.225 291,.126 290,.163 290,.020 290..044 290.,236 289.,970 290,.020 289,.778 289,.803 289,.827 289,.778 290.,142 290.,187 290,.310 289,.240 289,.264 289,,048 288..999 289..338 289.,362 288..807 288,.807 288,.954 289,.219 289,.003 289..003 289,,027 289,,052 289,.101 289,,391 289,.027 289,.076 289..174 289..415 289.439 288.909 288,.958 289,.467 289..565 289..831 289.,541 288.,768 289.,541  0,,1213 0,.1192 0,,1192 0,,1187 0,.1202 0,.1202 0..1202 0..1197 0,.1207 0,,1228 0,,1254 0,.1281 0,,1312 0,.1311 c..1296 0..1223 0,.1306 0..1270 0,.1239 0,.1231 0,.1249 0..1452 0,.1338 0,.1285 0,,1291 0..1275 0,,1327 0,,1275 0..1337 0..1260 0..1285 0,,1280 0.,1327 0..1244 0,,1270 0,.1376 0,.1420 0,.1455 0,,1441 0,,1400 0,.1403 0,.1383 0..1326 0.,1317 0..1296 0.,1270 0,.1280 0,.1187 0..1249 0..1280 0.,1302 0.,1264 0,,1177 0,.1280 0.,1394 0.,1363 0.,1295 0.,1307 0.,1280 0..1333 0.,1343 0.,1285 0.,1306 0.,1311 0.,1321 0.,1306 0. 1358  0,.0818 0,.0813 0..0847 0,.0873 0..0779 0,,0831 0,,0916 0..1045 0,.0811 0,.1080 0,.0903 0..0973 0..1120 0,.0999 0.,1252 0,.1057 0,.1120 0,.1044 0,.1241 0,.1148 0.,1109 0.,1070 0,.1064 0,.1030 0,.0982 0,.1125 0,,1176 0,.1163 0.,1103 0..1135 0,.1125 0,.1145 0,.1148 0,.1152 0..1178 0,.1144 0..1095 0,.1097 0,.1064 0,,1050 0..1107 0..1100 0,.1078 0..1065 0,.1109 0,.1109 0,.1115 0,.1099 0,.1156 0.,1156 0..1143 0.,1146 0,.1137 0,.1091 0..1092 0,.1082 0,.1080 0.,1061 0,.1064 0,.1112 0,,1137 0,.1141 0..1139 0..1089 0.,1101 0.,1220 0.,1135  Appendix D. DATA AND  2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840  251 .0 251 .0 251 .0 257 .7 256 .7 259,.3 261,.7 252,.7 252 .0 252,.3 253,.0 252,.7 255,.7 254,.3 254,.7 254,.0 257,.7 252..0 259,.3 256..0 264,.0 255..3 257,.3 255,.3 255,.3 253..0 257..3 254..7 257.,0 258,.3 257,,3 259..3 262..0 260..3  242 .5 240 .3 242,.6 239 .2 243 .4 242 .2 241,.5 240,.4 242,.6 242,.6 242,.7 241,.7 241,.6 238,.4 240,.6 240,.6 241,.6 240,.6 242,.5 241,.0 241..1 241,.6 241,.5 241,.3 241,.5 240,.3 240,.3 241,.4 241,,3 241,.4 240.,3 243..2 244..3 244..4  RESULTS  83 .0 82.0 81.0 81 .0 81 .0 82,.0 82,.0 78 .0 78,.0 81,.0 81,.0 81,.5 83,.0 83,.0 83,.5 84,.0 84,.0 84,.0 85,.0 85,.0 87,.0 83,.5 82,.0 82,.0 83,.5 84,.0 85,,0 85,,0 85,.0 86,.0 86,.0 86,.5 86..5 86.,5  86 .5 86 .0 86 .0 85 .5 85 .0 85 .0 85,.5 85,.0 84,.5 84,.0 84,.0 84,.0 84,.5 84,.5 85,.0 85,.5 86,.0 86,.0 85,.5 85,.0 84.0 84..0 84..0 83,.5 83,,0 83,.0 83,.5 82,,0 82,.0 82,,5 83,.0 83.,0 83..5 84..0  320 .821 320 .821 320 .821 328 .113 328 .113 326 .654 328 .113 323 .738 323,.738 320 .821 320,.821 323,.738 323,.738 320,.821 320,.821 320,.821 320,.821 317,.905 320,.821 317,.905 323,.738 317..905 323,.738 323,.738 320,.821 317..905 320,.821 317..905 320,.821 320,.821 317.,905 317,.905 320,.821 320..821  289 .107 289,.590 289,.131 289,.831 288,.841 289,.058 289,.373 289,.614 289,.131 289,.131 289,.156 289,.422 289,.397 290,.121 289,.663 289,.663 289..397 289,.663 289,,107 289.,736 289,.761 289,,883 289,.858 289,,810 289,,858 290..076 290..076 289,.834 289..810 289..834 290.,076 289..278 289.,036 289.,061  0,,1337 0..1368 0,,1400 0,.1485 0,.1455 0,,1530 0,,1577 0,,1496 0,,1475 0,,1441 0,.1462 0,.1388 0.,1434 0..1441 0.,1436 0..1400 0..1514 0.,1385 0.,1535 0.,1480 0..1568 0.,1506 0.,1517 0.,1455 0.,1457 0.,1417 0.,1472 0.,1438 0.,1462 0.,1472 0. 1490 0.,1537 0. 1571 0. 1519  0,.1215 0,.1159 0,.1236 0,.1140 0,.1299 0,.1259 0,.1216 0..1197 0,.1287 0,.1304 0..1307 0.,1275 0,.1254 0..1145 0,,1204 0,.1187 0..1203 0,.1170 0,.1249 0,.1215 0,,1253 0.,1271 0.,1268 0.,1277 0,.1302 0.,1262 0.,1245 0.,1332 0.,1328 0.,1315 0.,1262 0.,1360 0.,1379 0. 1366  Appendix D. DATA AND RESULTS  187  RUN 7, DICYCLOPENTADIENE  WITH INHIBITOR  INITIAL CONDITIONS:  UPFRU  UHWP  2.521  2.497  TPFRU  THWP  198.00  198.54  TBPFRU  TBHWP  QPFRU  QHWP  80.0  79.0  297.49  298.43  AVERAGE CONDITIONS:  TBPFRU 80.00  TBHWP  QPFRU  81.00  293.61  QHW P  VFP  296 .21  REP  0.81 9760  VFH  REH  0.04  4.9  TIME  PTEMP  HTEMP  PTB  HTB  PHF  HHF  PFR  HFR  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780  198,,3 199,.0 200.,0 201,.0 201,.3 201,.3 201,.7 202,.3 202..3 202..0 202,.0 202,.3 202,.7 202,.7 201,.3 201..0 201,.0 201..0 201,.0 201,.0 201,.0 200,.7 200,.7 200,.7 201,,0 199,.0 201,.7 200,.7 202..7 202..3 202..7 202,,0 202,.3 202,.3 202..3 203,.0 203,,3 204,,0 198..3 198.,0  198.5 200.1 202.5 203.2 204.2 204.6 205.4 205.6 205.9 206.5 206.2 206.5 206.1 206.6 206.6 206.8 206.7 207.0 206.9 207.1 207.1 207.1 207.3 206.9 207.5 207.8 207.4 207.9 207.8 207.7 207.7 207.9 207.8 207.9 207.8 207.5 207.9 208.1 208.0 208.1  81.5 81.5 81.5 81.5 79.0 78.5 78.5 81.0 81.0 80.0 81.0 81.0 81.5 81.0 80.0 80.0 79.5 80.0 79.0 80.5 80.0 78.0 78.0 78.0 76.5 77.0 77.5 78.5 79.5 80.5 81.5 82.0 82.5 82.5 83.5 84.5 82.0 82.0 78.0 78.0  79.0 79.0 79.5 80.0 80.0 81.0 80.0 80.0 80.0 79.0 79.0 79.5 79.0 78.0 78.0 78.0 78.0 78.0 79.5 79.0 79.0 80.0 81.0 80.0 81.0 81.0 81.5 82.0 82.0 81.0 81.0 81.0 80.5 80.0 80.5 80.5 80.0 80.0 80.0 79.0  286..989 288..156 290.,197 297,.780 297,.489 297..489 297,.489 282,,031 282.,323 284.,656 283.489 284,.656 284..948 284..656 286..989 286.,698 289..031 286..114 288,.447 287,.864 289,.031 293..697 292,.531 293,.697 297.,489 295,.156 297,.780 294..864 297..489 294.,572 292.,531 290.,197 289,.322 289,.322 286,,698 284,,948 293,,114 294.,572 290..489 286..698  299,.385 298,.972 298,.348 298 .167 297 .784 297 .714 297.482 297,.452 297,.291 297,.190 297,.301 297,.260 297,.351 297,.934 297,.713 297,.682 297,.662 297,.552 297,.531 297,.451 297,.401 297.451 297,.391 297,.481 297,.380 297,.270 297,.411 297,.290 297,.320 297,.300 297,.229 297,.169 297,.149 297,.219 297,.199 297,.139 297,.099 296,.968 296..998 296..968  0.,0075 0.,0082 0.,0088 0,.0017 0..0117 0..0133 0.,0145 0.,0306 0.,0302 0..0290 0..0273 0..0267 0.,0257 0.,0278 0.,0232 0..0225 0.,0208 0..0233 0..0234 0,.0190 0,.0191 0,,0181 0,,0198 0,,0181 0..0189 0,,0138 0,,0174 0,,0147 0,,0145 0,.0140 0.,0146 0.,0139 0..0146 0,,0146 0.,0149 0.,0163 0,,0144 0,.0146 0.,0147 0,,0190  0,,0001 0,.0052 0,,0117 0,,0125 0,.0156 0,.0138 0..0199 0,.0203 0,,0214 0..0268 0,.0258 0,,0252 0,,0256 0,,0304 0,,0307 0,,0311 0,,0308 0,.0318 0,.0265 0,.0287 0,.0289 0,.0254 0,,0229 0,,0249 0,,0236 0,.0246 0,,0215 0..0215 0,,0211 0.,0241 0..0240 0,,0249 0,.0262 0,.0281 0,,0261 0,.0253 0,,0281 0,.0288 0.,0284 0.,0321  Appendix D. DATA AND  800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100 2120  202,.0 199,.7 200,.7 201,.0 201,.3 201,.3 201,.7 201,.7 203,.0 203,.0 204,.0 201,.7 202,.3 202,.7 203 .0 202,.7 204,.3 205,.3 206,.0 203,.7 203,.0 202,.3 203,.0 204,.0 204 .0 204 .0 204,.7 205,.0 204,.7 205,.3 205,.0 204,.7 204,.7 203,.3 204,.7 205,.7 206,.0 205,.7 207,.0 207,.3 208,.0 209,.0 209..0 209,.7 210,.0 207,.7 208,.3 209,.3 209,.7 210..0 210,.3 210..7 210,.7 211,.0 211,.3 211,.7 211,.7 212..3 213..0 213..3 213..7 214..3 215..0 215..0 215..7 216..7 217.,0  207 .8 207 .8 207 .7 208 .0 208 .3 208 .3 208 . 5 208 .4 208 .3 208 .4 208 .6 208 .6 208 .6 208 .7 208 .6 208 .6 208 .4 208 .5 208 .8 208 .9 208 .8 208 .9 208 .9 209 .0 208 .9 209 .1 208 .9 209 .0 208 .8 208 .9 208 .9 208 .9 208 .7 209 .2 209 .2 209 .0 209 .1 209 .2 209 .2 201 .6 209,.2 209,.5 209,.5 209 .5 209 .6 209 .7 209 .6 209 .8 209 .9 209,.9 210,.7 210,.3 210,.3 210 .3 210 .3 210 .3 210 .5 210,.3 210,.6 210,.6 210,.9 210,.9 212,.2 212,.2 212,.6 212,.6 212,.8  RESULTS  78 .0 78 .0 74 .5 77 .0 77 .5 78 .5 78 .5 79 .0 80 .5 82 .0 83 .0 82 .5 82 .5 83 .0 83 .0 84 .0 83 .5 86 .0 82 .0 79 .5 79 .5 79 .5 79 .5 80 .5 80 .5 80 .5 80 .5 80 .5 80 .0 80 .5 80 .5 79 .0 77 .5 76 .5 77 .5 79 .5 80 .5 80 .5 81 .0 81 .5 81 .5 83 .0 84 .0 84 .5 85 .0 84 .5 83 .5 84 .0 84 .5 85 .0 85 .5 85 .5 85 .5 85 .5 85 .5 85 .5 85 .5 85 .5 85 .5 86 .0 86 .5 87 .5 88 .0 88 .5 89 .0 89 .5 89 .5  79 .0 78 .0 78 .0 78 .0 79 .0 79 .0 79 .0 79 .0 78 .5 78 .5 78 .5 78 .5 78 .0 78 .0 78 .0 78 .0 78 .5 79 .0 79 .0 79 .5 79 .0 79 .0 80 .0 80 .0 80 .0 80 .0 80 .0 80 .0 80 .5 80 .0 80 .0 80 .0 79 .5 79 .5 79 .5 79 .0 79 .0 79 .0 79 .0 79 .0 79 .0 79 .5 79 .5 79 .5 79 .5 80 .0 80 .0 80 .0 81 .0 81 .0 82 .0 81 .0 81 .5 81 .0 81.0 81 .0 81 .0 80 .0 80 .0 80 .0 79 .0 79 .5 79,.0 78 .0 78 .0 78 .0 78 .5  293,,114 286..698 297.,489 298.,655 296,.614 295,.156 296,.322 294,.864 295,.156 291..364 291..364 287,.864 287..864 285..531 285,.531 273,.573 285,.531 285,.531 296,.905 293,.989 286,.698 289..614 297..489 297,.489 297,.489 295,.739 296,.614 296,.905 297,.197 298,.364 294,.572 293,.989 296..905 296,.614 299,.822 298,.947 298,.072 295,.447 298,.072 296..031 330..154 299,.822 296..905 297.780 299,.239 293,.697 297,.489 297..780 297,.780 298.,072 296.,614 297..489 296.,614 296,.905 296..031 296..031 296..031 296..031 298.,655 298.,655 298,,947 298..655 298,,655 296..905 296..322 296.,614 300.,697  297..029 297,,029 297..059 297.,018 296,.908 296,.908 296,.877 296..928 296,.958 296..928 296..847 296.,797 296.,797 296.,747 296,.847 296,.847 296,.807 296,.827 296,.717 296.687 296,.767 296,.737 296..687 298..516 298,.546 298,.536 298,.616 298,.586 298,.647 298,.616 298,.667 298,.616 298.,677 298.556 298,.576 298,.637 298,.606 298,.556 298,.576 300..425 298..506 298.,465 298.,465 298,.395 298,.364 298,.384 298,.485 297..680 297..288 298..253 297.,830 298.404 298..474 298,.354 298,.333 298..354 298,,323 298..404 298,,243 298,,243 298,.182 298,.182 297.,879 297,.829 297,,808 297,.808 297.,727  0,,0235 0,,0248 0..0245 0,,0156 0..0179 0,,0166 0.,0161 0,,0164 0,,0155 0,,0157 0,,0157 0,,0144 0..0167 0.,0195 0,.0207 0,.0342 0..0236 0..0184 0..0181 0..0228 0,.0312 0,,0246 0.,0156 0,.0156 0..0156 0,.0180 0..0190 0..0198 0..0199 0..0188 0..0231 0.,0279 0..0287 0,.0280 0,.0246 0..0225 0..0215 0,.0241 0.,0231 0,.0255 -0.,0164 0,,0207 0.,0214 0,.0208 0..0182 0,.0198 0..0201 0,,0213 0.,0208 0,,0198 0.,0213 0.,0212 0..0224 0..0231 0..0255 0,,0266 0,,0266 0.,0289 0..0273 0.,0268 0..0258 0.,0251 0.,0257 0..0265 0..0279 0.,0292 0..0244  0,.0313 0..0346 0.,0342 0.,0353 0,.0330 0,,0330 0,.0334 0,.0333 0,.0345 0,.0349 0,.0355 0,.0356 0,.0373 0..0375 0,.0372 0,.0372 0,.0349 0,.0335 0,.0345 0,.0333 0,.0344 0,.0348 0,.0316 0,.0318 0 .0314 0,.0321 0,.0315 0,.0320 0,.0294 0,.0315 0,.0314 0,.0315 0,.0324 0 .0341 0,.0343 0,.0352 0,.0356 0,.0357 0,.0360 0,.0103 0..0359 0..0353 0..0353 0,.0352 0,.0356 0,.0342 0,.0339 0,.0345 0,.0316 0..0316 0..0308 0.,0328 0..0313 0,.0330 0..0327 0..0330 0.,0334 0..0362 0.,0373 0,,0373 0,.0415 0,,0399 0.,0458 0,,0493 0,.0507 0,,0507 0,.0496  Appendix D. DATA AND  2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880 2900 2920 2940 2960  215..7 217.,7 218..0 218,.0 219,.7 221,.3 222,.0 223,.7 224,.7 225..7 227..3 230,.0 231,.7 236,.3 246,.3 240,.0 238,,3 240..3 239.,7 238..7 242,.3 242,.7 247,.3 244,.7 242,.7 241,.7 239..7 240.,0 238..7 238,.7 236,.7 233,.3 233,.3 235..7 236..3 236,.7 236.,7 237,,3 234,.7 235,.0 237,.7 238,,0  212 .8 212 .9 212 .8 213 .0 213 .0 213 .7 213 .8 214 .2 214 .7 214 .9 215 .0 215 .1 215 .5 216 .0 216 .4 216 .6 216 .6 216 .8 217 .2 218 .0 218 .0 218 .5 218 .4 218 .6 218 .7 218 .8 220 .0 220 .4 220 .5 220 .8 226 .2 227 .2 229 .6 229 .8 231 .1 231 .5 232 .3 233 .3 235 .6 237 .0 237 .4 237 .6  RESULTS  89 .5 89 .0 88.0 88 .0 87 .5 88 .0 88 .0 88 .0 88 .5 88 .5 86 .0 86 .0 86 .0 86 .5 87 .0 87 .5 88 .0 88 .0 88 .5 88 .5 88 .5 88 .5 89 .0 89 .5 88 .0 88 .0 88 .0 86 .5 86 .0 84 .0 84 .5 82 .5 82 .0 83 .0 83 .0 84 .0 84 .0 84 .5 84 .0 83 .0 84 .0 84 .0  78 .5 78 .5 79 .0 79 .0 79 .0 79 .0 78 .0 78 .5 78 .5 78 .0 78 .0 78 .5 78 .5 79 .0 79 .0 79 .0 79 .0 79 .0 80 .0 80 .0 80 .0 80 .5 80 .5 81 .0 81 .0 81 .0 81 .0 81 .5 81 .5 81 .5 81 .5 82 .0 82 .0 82 .0 82 .0 82 .0 81 .5 81 .5 81 .5 81 .5 82 .0 82 .0  291,.656 294,.572 297 .489 292,.531 294,.864 296,.031 291,.656 298,.655 295,.156 288,,739 291.,947 293,.989 301,.280 282,.614 318,.488 298,.072 291,.072 292,.531 293,.989 288..156 296 .031 295,.447 318,.780 312,.947 308,.280 311,.488 304,.780 309,,155 309.,738 312,.655 303,.322 296,.614 293,.697 297,.197 298,.655 297.,489 297.,197 300,.989 295,.739 294,.281 297,.489 300,.989  297,.778 297,.697 297,.727 297,.647 297,.596 297,.395 297,.364 297,.324 297,.202 297,.142 297..162 297,.182 297,.091 296,.970 296,.828 296,.798 296,.748 296,.738 296,.647 296,.465 296,.465 296,.344 296,.374 296,.313 296,.283 296,.303 296,.030 295.769 295..789 295,.748 294,.505 294,.213 293,.717 293,.707 293..354 293..313 293..151 292..888 292,.273 292,.040 292,.019 291,.938  0,.0330 0.,0372 0,.0374 0,.0448 0,.0487 0,.0508 0,.0599 0,,0547 0.,0618 0..0755 0.,0845 0,.0902 0,.0839 0,.1306 0,.1007 0,.1121 0,.1169 0..1212 0,.1146 0..1216 0,.1201 0,.1222 0,.0971 0,.0963 0,.1021 0,.0938 0,.0981 0,.0969 0..0933 0,.0951 0,.1021 0,.1089 0,.1157 0,.1141 0,.1138 0,,1136 0.,1141 0.,1082 0,.1099 0,.1169 0,.1170 0,.1121  0.,0495 0..0500 0,.0479 0..0485 0,.0487 0,.0509 0..0547 0..0542 0,,0559 0,.0584 0,,0587 0,.0573 0,.0586 0,.0586 0..0601 0..0605 0..0606 0..0614 0..0593 0.,0619 0,.0619 0,.0619 0,.0615 0,.0607 0,.0611 0..0614 0..0653 0,.0651 0.,0653 0,.0665 0,.0843 0,.0863 0,.0940 0..0947 0..0993 0,,1004 0.,1050 0,,1083 0,,1161 0,.1207 0,,1205 0,.1211  Appendix D. DATA AND RESULTS  ROT 8, INDENE  190  AT HIGH HEAT FLUX  INITIAL CONDITIONS:  UPFRU  UHWP  2.542  2.578  TPFRU  THWP  TBPFRU  198.00  198.54  81.0  TBHWP 83.0  QPFRU  QHWP  297.48  297.87  AVERAGE CONDITIONS:  TBPFRU  TBHWP  81.08  79.45  QPFRU 299.24  TIME  PTEMP  HTEMP  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740  203,.33 203..67 202..33 205..33 208,.33 205,.33 206,.67 206,.67 206,.67 206,.67 205.,67 207..00 207,.33 205,.00 206,.00 209..00 214..00 216,,33 220.,00 221,.00 221,.00 223..00 224,.33 231.,00 234,.33 238,,00 241,.00 245,.67 248,.33 252,,33 257,,00 270,,33 277,,33 287..33 302,.33 303..67 307,.67 307,,33  193,.60 192,.67 193..30 193..31 193,.54 194,.18 194,.29 194,.42 194,.51 194..52 199.,19 199..63 201,.33 200,.68 200,.68 200,.99 201..11 201..33 201..54 201,.77 201,.88 201,.89 202..93 203,.57 208.,32 206,,08 205,.74 207..15 206,.92 206,.29 206,.30 207.,60 207,,76 207..91 208,.00 208.,05 208..27 207,.95  PTB 87 .5 88 .0 84 .0 87 .5 92 .0 86 .0 79 .0 78 .5 80 .0 80 .5 81 .0 82 .0 83 .0 83 .0 84 .0 85 .5 84 .0 83 .0 82 .0 82 .0 83 .0 81 .0 83 .0 83 .5 84 .0 84 .0 85 .0 85 .5 86 .5 87 .0 87 .0 86,.0 85,.0 82 .0 81 .5 80 .0 80 .0 79,.0  QHWP  VFP  REP  VFH  REH  295.32  0.81  9762  0.04  4.9  HTB 79,.0 79,.0 79,.5 80,.0 80 .0 81 .0 80,.0 80,.0 80,.0 79,.0 79,.0 79,.5 79 .0 78,.0 78,.0 78,.0 78,.0 78,.0 79,.5 79 .0 79,.0 80,.0 81,.0 80,.0 81,.0 81,,0 81,.5 82,.0 82,.0 81,.0 81,.0 81,.0 80,.5 80,.0 80,.5 80,.5 80,.0 80,.0  PHF  HHF  297.489 302,.155 303,.322 302,.739 300 .989 301,.572 305 .655 296 .322 296,.322 295,.739 296,.031 303,.322 307 .988 296 .322 293 .989 297,.489 298,.947 299,.822 300,.989 303 .322 300 .989 302,.155 300,.989 305,.655 306,.238 310,.322 296,.322 296,.905 298,.655 293,.989 298,.655 297,.489 305,.655 306,.238 305,.655 299,.822 299,.822 300,.989  294,.306 294,.536 294,,386 294,.388 294..343 294,.195 294,.170 294,.153 294,.123 294,.125 293,.027 292,.929 292,.529 292,.677 292,.677 292,.599 292,.576 292,.529 292..479 292,.431 292.408 292,.411 293,.104 292,.954 291..859 292..387 292,.460 292,.137 292,.184 292,.337 292.,340 292,.041 292.,479 292,.917 292,.887 293,.350 293,.302 293..378  PFR -0.,0034 -0,,0100 -0,,0027 -0,,0036 -0,.0063 0,.0029 0,.0249 0,.0397 0,.0346 0,.0338 0,.0283 0,.0193 0 .0109 0,.0189 0,.0222 0,.0223 0,.0420 0,.0519 0,.0657 0,.0654 0,.0657 0,.0771 0,.0767 0,.0898 0..0981 0..1034 0,.1336 0,.1466 0,.1491 0,.1696 0,.1764 0,.2268 0..2364 0,.2777 0,.3297 0,.3532 0,.3665 0..3658  HFR 0,.0015 -0,,0020 -0,.0013 -0..0030 -0,.0022 -0.,0032 0,.0006 0,.0011 0,.0014 0,.0049 0..0223 0,.0222 0,.0303 0,.0313 0,.0313 0,.0324 0,.0329 0,.0337 0..0294 0,.0319 0,.0324 0,.0290 0,.0281 0,.0339 0.,0484 0..0399 0,.0369 0,.0405 0..0397 0..0407 0,.0407 0,.0456 0,,0472 0,.0488 0,.0474 0,.0469 0..0494 0,.0482  Appendix D. DATA AND  760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080  308..00 315..33 322.,00 331..00 328.,00 337.,00 337.,00 342,.33 346,.33 351,.00 353,.33 355,.33 364,.33 363,.33 363,.33 366,.00 369,,00 373,.33 376,,33 375,.33 365.67 353,.00 356,.67 356,.67 363.,00 369..00 361,.67 356,.67 354,,67 352,,33 352.,33 351,,00 355,,67 352,,00 357,,00 341..33 346.,67 352,.33 356.,67 358,,67 358,,00 358.,33 360,,67 361,.00 362,.00 364,.67 368.,33 371,.00 370,,33 373,,67 373,,33 372,,67 369,,67 369.,33 370,.67 371..67 370..67 371.,67 371.,33 370.,33 371,,00 371,,33 369..67 369..33 367..33 377.,67 368.,33  210.21 217.52 219.08 221.39 223.97 228.73 232.05 233.26 240.75 241.96 242.86 243.74 244.19 244.87 246.44 247.78 263.33 270.96 276.53 282.81 286.47 302.39 310.97 316.90 333.82 324.55 340.43 344.84 349.94 356.01 358.68 364.96 367.28 372.02 376.45 384.57 386.66 387.33 393.88 395.20 400.24 406.89 406.90 411.75 416.22 417.46 421.01 422.74 426.27 549.64 428.09 437.90 440.89 443.37 444.32 445.17 446.11 447.20 449.12 451.09 456.22 459.58 462.52 463.52 453.07 453.63 441.41  RESULTS  79,.0 80,.0 80,.0 81,.0 81,.0 81,.5 82,.0 82,.5 83,.0 84,.0 85,.0 86,.0 85,.5 85,.5 84,.0 83,.5 82,.0 81,.0 81,.0 80,.0 80.0 80,.0 79,.0 78 .0 80,.0 80,.5 81,.0 81,.0 82,.0 83,.0 84,.0 85,.0 85,.5 86 .0 87 .0 88,.0 89,.0 87,.0 87,.5 87,.0 87,.0 85,.0 85,.5 85,.0 85,.0 83,.0 82..0 81,.0 80,.0 80,.0 78,.0 77,.0 77,.0 76,.0 76,.0 77,.5 78,.0 78,.0 79,,0 79,,5 79,.5 80,.0 80,.5 80,.0 79,,0 78,,0 77,,0  80 .0 79 .0 79 .0 78 .0 78,.0 78,.0 79 .0 79 .0 79 .0 79 .0 78 .5 78 .5 78 .5 78 .5 78 .0 78 .0 78 .0 78 .0 78 .5 79 .0 79 .0 79 .5 79 .0 79 .0 80 .0 80 .0 80 .0 80 .0 80 .0 80 .0 80 .5 80 .0 80 .0 80 .0 79 .5 79 .5 79 .5 79 .0 79 .0 79 .0 79 .0 79 .0 79 .0 79,.5 79 .5 79 .5 79,.5 80 .0 80 .0 80 .0 81 .0 81 .0 82,.0 81 .0 81,.5 81,.0 81,.0 81,.0 81,.0 80,.0 80 .0 80,.0 79,.0 79,.5 79,.0 78,.0 78,.0  300,.989 296..322 297..489 298..072 296..322 300..989 300.405 299,.822 300,.989 299,.822 305,.655 302,.155 300,.989 296,.905 296..322 296,.322 296..322 298..655 297.,489 296..322 296..322 298,.072 298,.655 298,.947 298,.655 299,.239 299,.239 299,.822 299,.239 300.405 299,.822 302..739 303..322 305,.655 303,.322 304,.489 305,.072 299,.822 300,.405 300,.989 300,.989 299,.822 296,.322 299..239 293..989 299..822 297..489 297.489 297.489 297..489 297.489 297,.489 297..489 297.,489 297,,489 297.,489 297.489 297,.489 297,,489 297..489 297,.489 297.489 297,.489 297.489 297.489 297,.489 297.489  292,.850 291,.631 291,.286 291,.213 290,,648 289,,569 290,,172 294,.549 294,.232 297,.219 297,.017 296,.809 296,.707 296,.555 296,.199 295,.892 292.384 295,.274 294,.037 292,.638 291,.840 289,.294 287,.917 287,.616 284,.040 288,.189 285,.243 288,.401 291,.780 294,.963 294,.406 293,.105 292,.628 300,.920 299,.586 297,.881 297,.450 297,.317 295,.968 295,.697 294.672 293,.318 293.321 292..350 291..460 291,.218 290..518 298,.873 298,.162 275,.116 306,.605 304.568 303,.956 303,.459 303,.262 303..045 302,.903 302..677 302,.288 301,.851 300,.821 300.,155 299..572 299,,379 301.469 301,,358 303,,838  0,.3680 0,.4014 0,.4207 0,.4459 0,.4407 0.4561 0.4560 0,.4738 0,.4821 0,.4977 0,.4851 0,.4986 0,.5336 0,.5429 0,.5498 0,.5605 0,.5757 0,.5860 0,.5999 0,.6038 0 .5712 0 .5231 0 .5369 0 .5393 0 .5548 0 .5713 0,.5451 0 .5266 0,.5184 0,.5037 0,.5022 0.4858 0,.4979 0 .4774 0 .4973 0,.4392 0,.4518 0,.4922 0,.5032 0,.5098 0,.5075 0,.5188 0,.5358 0,.5295 0,.5494 0..5466 0..5697 0,.5820 0,.5831 0,.5943 0,.5999 0,.6011 0,.5910 0,.5932 0..5977 0..5960 0..5910 0..5943 0,.5899 0.,5848 0,.5871 0,.5865 0,.5792 0,.5798 0,.5764 0,,6145 0,,5865  0,.0567 0,.0871 0,.0930 0,.1045 0,.1143 0,.1326 0,.1395 0,.1358 0,.1618 0,.1604 0,.1655 0 .1688 0 .1705 0 .1731 0,.1808 0,.1859 0,.2460 0,.2656 0,.2856 0,.3086 0 .3230 0 .3826 0 .4178 0 .4392 0 .5057 0.4607 0,.5251 0,.5304 0,.5372 0,.5478 0,.5570 0,.5843 0,.5938 0 .5825 0 .6033 0,.6362 0,.6448 0,.6491 0,.6760 0,.6814 0,.7022 0,.7300 0,.7300 0,.7486 0.,7674 0..7726 0..7876 0,.7589 0..7734 1,.3192 0,.7441 0,.7839 0,.7928 0,.8062 0.,8085 0..8138 0,,8175 0,,8220 0,.8299 0,,8415 0,.8628 0..8767 0,,8923 0,,8948 0,,8529 0,,8585 0,,8082  Appendix D. DATA AND  2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500  366 .67 364,.33 364,.33 365,.67 365,.33 362,.67 363,.00 362,.67 361,.33 360,.00 347,.67 354..67 355..00 355..00 370..00 370..67 389,,67 396.,67 412..00 417.,33 420..33  442,.23 442,.38 442,.52 442,.64 442,.66 454,.39 454..54 454..83 454,.97 455..11 454,,86 456..38 446,,13 449,,08 448,,80 449.,36 449,,51 451.,07 447.,32 452..34 447.,34  RESULTS  77 .0 76 .0 76 .0 77 .0 78 .0 77,.0 76,.0 75,.0 74,.0 74,.0 74,.0 72,.0 70,.0 70,.0 68,.0 66,.5 72,.5 74,.5 76,.5 77,.5 77,.5  78 .0 78 .5 78 .5 78 .5 79 .0 79 .0 79 .0 79 .0 78 .0 78 .5 78 .5 78 .0 78 .0 78 .5 78 .5 79 .0 79 .0 79 .0 79 .0 79 .0 80 .0  297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489 297.489  303,.673 303,.647 303,.620 303,.590 303,.592 301,.178 301,.153 301,.099 301,.071 301,.043 295..231 294,.979 297..088 296.,516 296,.571 296,.463 296,.437 296,,138 296,,885 295,.892 296,,887  0..5809 0,.5764 0,.5764 0,.5775 0,.5730 0,.5674 0,.5719 0,.5742 0,.5730 0,.5686 0,.5271 0..5574 0,.5652 0.,5652 0,,6223 0.,6296 0,,6733 0.,6901 0,,7350 0,.7495 0,.7596  0,.8115 0,.8105 0,.8110 0,.8116 0,.8099 0,.8585 0,.8591 0,.8603 0,.8642 0..8631 0,,8869 0,,8948 0,,8512 0,.8619 0,.8607 0,.8614 0,,8620 0,,8685 0.8527 0..8738 0..8494  Appendix D. DATA AND RESULTS  RUN 9 INDENE MEDIUM HEAT FLUX INITIAL CONDITIONS:  UPFRU  UHWP  TPFRU  2.504  2.519 183.00  THWP  TBPFRU  183.00  TBHWP  84.0  84.5  QPFRU  QHWP  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  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720  183..3 183,.7 186..0 186,.3 186..7 189,.3 191..7 193,.0 194..3 195,.7 196,.3 197,.7 198,.0 198,.7 199..3 203,.0 202 .3 201,.7 202,.7 205,.7 205,.0 206,.0 203,.7 205,.0 205,.7 207,.0 207,.3 206..3 206,.3 203,.3 204,.0 205,.3 204,.7 205,.7 206,.0 206,.7 207..0  182,.5 182,.7 184,.7 182 .8 183 .6 184 .1 184,.8 182,.8 183,.8 186,.0 186,.9 191,.1 191,.7 193,.2 195,.4 197,.4 201 .3 198 .8 198,.5 198,.1 197,.0 196,.0 195,.9 195,.9 196,.4 195,.7 198..3 198..1 198,.2 198,.2 198,.5 198,.7 199,.0 200,.4 200,.9 200..8 199,.8  87 .0 88 .5 84 .5 87 .5 88 .5 89 .0 87 .5 88 .0 89 .0 88 .5 88 .5 88 .0 88 .0 87 .5 86 .0 86 .0 80 .0 80 .5 80 .5 80 .5 80 .5 80 .5 79 .0 78 .5 79 .0 79,.5 79,.5 78,.5 76 .0 76 .0 69 .5 71 .5 72 .0 72 .5 73,.0 73,.5 73,.5  83 .0 83 .5 84 .5 82 .0 82 .0 83 .0 83 .0 81 .0 82 .0 83.0 82 .0 79 .5 83 .0 82 .0 82 .0 82 .0 81 .0 82 .0 82 .5 84 .0 86 .0 84 .0 83 .0 82 .0 82 .0 83 .0 82 .5 82 .0 82 .0 81 .0 81 .0 81 .0 82 .5 82 .0 83 .5 82 .5 81 .0  244.,407 239.,158 244.,991 245,.574 247,.324 249,.657 250..241 247..907 247..907 246..449 250.,824 246..157 244.,991 247..324 245.,574 253.,740 253,.740 242,.658 243..241 243..824 250..241 250.,824 247..324 246.,741 247.,324 249.,074 249..657 248.,491 247..907 246..157 245..574 246.,157 246.,741 244.407 244,,991 244.,991 245,,574  246,.580 246,.559 246..147 246,.539 246..379 246,.287 246,.153 246,.588 246,.842 246,.820 247.407 248,.212 248..328 248,.819 249,.311 249..717 250,.556 251,.595 251,.659 251,.731 251,.970 252,.185 252,.206 252,.177 252..081 252,.223 251..710 251..731 251,.706 251,.703 251,.657 251,.564 251,.496 251,.213 251,.121 251..147 251,.360  PFR -0.,0052 -0.,0014 0..0150 0..0031 -0..0024 0,.0025 0..0169 0,.0242 0..0255 0,,0355 0..0306 0.,0462 0.,0497 0.,0501 0,,0622 0.,0618 0,.0828 0,.1000 0..1029 0,.1140 0,.0982 0,,1010 0,.1047 0..1133 0..1128 0..1126 0..1127 0..1151 0..1264 0,,1179 0..1484 0,.1443 0..1383 0..1455 0.,1435 0.,1442 0.,1443  HFR 0,.0067 0,.0052 0,.0103 0.0119 0,.0154 0,.0134 0,.0165 0,.0159 0,.0156 0,.0205 0,.0269 0,.0527 0,.0407 0,.0499 0..0579 0,.0652 0..0833 0,.0674 0,.0638 0,.0564 0,.0435 0,.0471 0..0505 0,.0549 0..0568 0,,0499 0..0629 0,,0643 0,.0648 0,.0687 0,.0697 0,.0709 0,.0664 0,.0744 0,.0705 0,,0740 0,.0755  Appendix D. DATA AND  740 760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060  207 .7 209 .0 208 .7 210 .3 209 .7 209 .3 210 .3 210 .7 210 .7 211 .3 211 .0 211 .0 211 .7 211 .3 211 .3 212 .3 211 .3 212 .0 213 .0 210 .7 210 .0 210 .7 211 .7 212 .3 210 .7 212 .3 213,.3 214 .3 215 .3 216,.7 215,.7 216 .7 216,.0 226,.0 225,.7 224,.3 226,.7 230,.7 231,.0 228,.3 229,.3 229,.3 221,.3 229,.0 229..7 232,.7 230..0 233,,0 232,.3 229,,0 232,,0 236,,3 237,,3 235,.7 234,.7 235..7 234,.3 234..7 235,.0 236.,0 235..7 234.,7 235.,0 233.,7 234.,3 232.,3 234.,3  200 .0 200 .8 201 .1 201 .0 201 .8 201 .7 202 .0 208 .8 208 .9 209 .3 209 .2 207 .7 210 .4 209 .9 210 .1 209 .1 209 .3 209 .2 209 .1 209 .0 209 .2 209 .4 209 .9 213 .1 213 .3 212 .9 212 .2 211 .9 214 .6 213 .3 212 .3 214 .1 215 .5 216 .7 221 .5 223 .2 219 .3 219 .6 220 .3 219 .4 221 .7 222 .7 222 .6 222 .9 223 .4 224 .4 225 .4 226 .9 226 .2 227 .9 221 .0 222 .6 223 .8 223 .7 222,.1 223,.4 222,.2 223,.9 222,.2 223,.5 224,.5 224,.9 223..8 222..9 224..0 224..7 225,.1  RESULTS  74 .5 75 .0 75 .5 76 .5 77 .5 78 .5 79 .0 79 .5 79 .5 80 .5 81 .0 81 .5 82 .5 82 .5 82 .5 83 .5 83 .5 84 .5 84 .5 85,.5 85,.0 80,.5 79,.5 82,.5 83,.5 84,.5 85,.5 85,.5 86,.5 85,.5 83,.0 83,.5 84,.5 87,.0 86,.5 87..5 90..5 92..5 94..5 91,.5 90..0 89,.0 82..0 80,.5 80,.5 84..5 81,,5 83.,0 81.,5 82,,5 85.,5 85,,5 84..5 84..5 84..5 84.,0 83.,5 84.,0 84.,5 84.,5 84.,5 84.,5 84.,5 83.,5 82.,5 82. 5 82. 5  81 .0 82 .0 79 .0 79 .0 78 .0 79 .0 78 .0 79 .0 79 .0 82 .0 83 .0 83 .5 84 .5 84 .5 85 .5 84,.0 83,.0 84,.0 84,.0 84,.5 83,.0 83,.0 83,.5 82,.0 81,.0 80,.0 80,.0 80,.0 80,.0 80,.0 80,.0 80,.5 80..0 80,.0 80..0 81,.5 82,.5 82..5 83,.0 83.,0 83,.0 84,,0 84,.0 84,,0 85,,0 85,.5 86,,0 86..0 86.,0 87.,0 88.,0 88..0 88.,0 89.,0 89.,5 89.,0 88.,0 88.,0 78.,5 86.,5 89.,0 87. 0 87. 0 87. 0 86. 0 86. 0 86. 0  246 .157 244 .991 247 .907 246 .157 242 .658 241.491 246 .157 243 .824 244.407 242 .658 241 .491 242 .074 242 .658 242 .658 243 .824 244 .407 244 .407 243 .824 244 .407 239,.158 244,.407 244,.407 244,.407 241.491 242,.658 243,.824 244,.991 244,.991 247,.324 245,.574 246,.157 245,.574 247..324 245,.574 244..991 247..324 247..907 247..324 243..824 243.,241 240..324 244.,407 244..407 244..407 247..324 245.,282 245.,574 245.,574 246..157 247..324 246..741 245..574 245.,574 246.,741 247.,324 247.,907 251.,990 251.,990 252.,574 247.,907 248.,491 247. 324 250.,824 250. 824 251. 407 250. 241 250. 824  251 .309 251 .147 251 .072 251 .098 250 .936 250 .962 250 .913 249 .528 249 .502 249 .434 249 .410 249 .717 249 .181 249 .276 249 .227 249 .440 249 .396 249 .415 249 .440 249,.466 249,.419 249,.398 249 .281 248 .650 248,.627 248,.699 248,.833 248,.882 248,.369 248,.629 248,.819 248,.467 248,.186 247,.954 247,.021 246,.742 247..532 247..916 248..191 248,.383 247..939 247,.730 247.,751 247,,707 247,.615 247..404 247,,218 246.,938 247.,092 247.,236 248.,704 248.,549 248.,316 248..344 248.,677 248.425 248.,665 248.,337 248.,695 248.,442 248.,256 248. 190 248.402 248. 569 248. 361 248. 246 248. 154  0 .1416 0 .1476 0 .1378 0 .1443 0 .1453 0 .1424 0 .1342 0 .1386 0 .1373 0 .1398 0 .1390 0 .1356 0 .1330 0 .1316 0 .1290 0 .1278 0 .1237 0 .1236 0 .1264 0,.1240 0,.1121 0,.1332 0 .1414 0,.1383 0,.1247 0 .1249 0,.1224 0,.1265 0,.1216 0,.1348 0,.1396 0,.1429 0,.1323 0,.1667 0,.1687 0,.1539 0,.1499 0,.1593 0,.1605 0..1632 0,.1804 0..1748 0,.1707 0..2082 0,.2038 0.,2047 0,,2054 0,,2115 0,,2134 0,,1930 0.,1944 0.,2149 0..2230 0..2133 0.,2078 0.,2124 0.,1992 0.,1986 0.,1965 0.,2118 0.,2090 0.,2078 0.,2007 0. 1993 0. 2046 0. 1994 0. 2060  0,.0764 0,.0760 0,.0894 0,.0890 0..0965 0,.0921 0,.0970 0,.1233 0,.1238 0,.1134 0,.1090 0,.1003 0,.1082 0,.1062 0.,1032 0,.1045 0.,1096 0,,1050 0.,1045 0,,1021 0,,1091 0,,1097 0,,1103 0,,1304 0..1350 0,.1374 0..1342 0,.1332 0.,1448 0,,1390 0.,1349 0,.1407 0.,1491 0,,1544 0.,1759 0.,1774 0.,1559 0.,1562 0.,1563 0.,1521 0. 1623 0. 1631 0. 1625 0.,1636 0.,1618 0.,1646 0. 1669 0. 1735 0. 1705 0. 1730 0. 1378 0. 1446 0. 1500 0. 1455 0. 1361 0. 1441 0. 1429 0. 1504 0. 1807 0. 1545 0. 1487 0. 1585 0. 1536 0. 1500 0. 1589 0. 1616 0. 1638  Appendix D. DATA AND  2080 2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500  233 .7 234 .0 234 .7 234 .7 233 .0 232 .7 228 .3 229 .0 230 .0 229 .7 231 .0 231 .3 231 .3 231 .0 233 .0 232 .3 234.7 235 .0 235 .3 235 .7 235 .3 236 .0  225 .1 226 .2 229 .0 228 .0 228 .6 229 .0 229 .3 230 .5 230 .0 227 .5 229 .8 230 .5 229 .8 229 .8 228 .8 230 .5 230 .8 230 .7 230 .9 230 .9 231 .2 231 .2  RESULTS  83,.5 83,.5 83,.5 84,.5 83,.5 83,.5 84,.5 84,.5 79,.0 79,.5 78,.0 79..5 81..0 82..5 84..5 86..5 87,.5 88,,5 90,,0 91,,5 91,,5 89,,0  86,.0 85,.5 85,.5 86,.0 86,.0 85,.0 85,.0 85,.5 84,.5 84,.5 85,.5 83,.0 82,.0 82,.0 82,.0 82,,0 83,.5 83,.5 84,,5 82,,5 82,,0 82,,0  251,.990 252,.282 247,.907 250,.824 250,.824 246,.449 245,.866 245,.574 245,.574 244,.699 246,.449 247,.324 247,.616 245,.574 244,.407 245,.574 247,.324 244..407 246,.157 242,,074 246,.157 242..658  248,.154 247,.944 247,.405 247,.621 247,.508 247.448 247,.450 247,.226 247,.354 247,.960 248,.679 248,.539 248..685 248..687 248.,876 248,.548 248.,501 248,.527 248.,481 248.484 248.,439 248.,443  0,.1966 0,.1972 0,.2104 0,.1993 0,.1967 0,.2059 0,.1857 0..1891 0,.2155 0..2143 0..2215 0,.2146' 0..2078 0,.2054 0..2082 0,.1945 0,.1957 0,.2001 0,,1911 0,,1962 0,.1850 0,,2064  0.,1638 0,.1707 0.,1831 0.,1763 0,,1791 0.,1850 0,,1860 0.,1896 0,,1911 0.,1798 0,,1831 0.,1964 0,,1973 0,.1973 0..1930 0,.2006 0,.1957 0,.1952 0,,1923 0,,2004 0,.2035 0,,2036  Appendix D. DATA AND RESULTS  RUN  10, INDENE LOW HEAT FLUX  INITIAL CONDITIONS:  UPFRU  UHWP  2.087  TPFRU  2.090  180.00  THWP  TBPFRU  TBHWP  QPFRU  QHWP  85.0  85.0  198.3  198.57  180.0  AVERAGE CONDITIONS: TBPFRU  TBHWP  QPFRU  82.00  83.00  196.57  QHWP 198.91  VFP 0.81  REP 9760  TIME  PTEMP  HTEMP  PTB  HTB  PHF  HHF  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780 800  190..67 193..33 194..33 196,.00 196,.00 196,.00 195,.00 194,.00 196..00 194..33 190..33 189..33 191,.33 189,.33 189,.67 192,.67 193,.00 194,.00 192,.67 192,.67 192,.33 193,.67 193,.67 194,.67 195,.00 194,.33 195,.33 200,.00 199,.67 197..33 197,.67 199,.33 199,.00 199,.67 202,.67 201,.00 201,.67 202,.33 202 .67 202 .33 202,.67  187,.01 190,.93 192,.66 193,.29 194,.19 195,.36 196,.67 197.41 198,.95 199,.30 200,.34 200,.53 200,.95 201,.09 201,.48 201,.20 201,.60 201,.86 202,.13 202,.13 203,.49 202 .14 202 .41 202,.53 202,.67 202,.53 202,.93 202,.93 202,.94 203,.33 203 .47 203,.47 203,.60 203,.60 203,.87 204,.00 204,.00 203,.99 204.26 204,.67 204,.67  81..0 85,,0 86..0 85,.0 85..0 86,.5 85,.5 82,.0 82,.5 82,.0 79..0 78..0 80,.0 78,.0 78,.5 79,.5 81,.0 80,.5 80,.5 80,.0 79,.0 80,.0 80,.5 81,.0 81,.0 80,.0 81..5 83,.5 82,.0 81..0 81,.0 81,.5 81,.0 81,.0 82,.5 82,.0 82..0 81.,0 80.0 78,.0 78,.5  86,,0 86,,0 86,,5 82,.0 83,.0 84,.0 83..0 83,.0 82,,0 82,.0 81.,0 79,,5 80,.0 82,.0 82,.0 83,.0 83,.0 83,.0 82,.5 82..0 85.,0 80..0 81,.0 80,.0 81,.0 81,.0 81..5 82..0 82.,0 81..0 81..0 81,.0 82,.5 82,.0 80,.5 80..5 80,.0 81,.0 82,.0 83,.0 83,.0  195.,993 195..409 196.,576 198,.326 197..743 191..326 190.,743 197..159 198,.326 198.,909 198,,909 199.,492 193,.659 193,.076 198,.326 198,.326 198..909 193,.076 193.,659 193..076 198.,326 198,.326 195,.993 198,.326 195,.409 198..909 199..492 200..659 198.,326 199..492 195,.993 193,.659 193,.659 198,.326 197,.159 195..993 197,,159 196.,576 195,.409 196,.868 196,.576  198,,099 197.,151 196.,957 197,.016 197,.073 197,.088 197,.082 197,.284 197,.400 197,.584 197.,620 197.,950 198,.403 198,.381 198,.400 198,.484 198.,420 198,.419 198.417 198..417 198..161 198,.334 198,.333 198,.353 198,.331 198,.353 198.330 198,.330 198..289 198..266 198,.244 198,.244 198,.223 198,.223 198..221 198..200 198..200 198,,241 198,.198 198,.134 198,.134  VFH  REH  0.04  4.9  PFR 0,.0032 -0.,0020 -0.,0053 0,.0033 0,.0050 0,.0160 0,.0177 0..0117 0..0159 0,.0084 0.,0034 0..0017 0,.0185 0,.0203 0,.0042 0,.0143 0,.0067 0,.0315 0,.0228 0..0272 0..0151 0..0168 0,.0210 0,.0168 0,.0270 0,.0184 0,.0143 0,.0242 0..0369 0..0268 0,.0389 0,.0521 0,.0530 0..0420 0,.0531 0..0508 0,,0506 0,,0609 0,.0714 0,.0752 0,.0753  HFR -0..0214 0..0009 0.,0077 0,.0336 0,.0329 0,.0337 0,.0455 0..0486 0..0612 0..0624 0.,0726 0.,0801 0,.0783 0,.0690 0,.0709 0,.0642 0,.0664 0,.0678 0.0716 0.,0741 0.,0666 0,.0846 0,.0808 0,.0865 0,.0822 0,.0814 0,.0810 0,.0784 0..0786 0..0857 0,.0865 0,.0865 0,,0797 0,.0822 0,.0911 0,.0918 0..0943 0.,0891 0.0856 0,,0828 0,,0828  Appendix D. DATA AND  820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100 2120  202,.33 205,.33 204,.67 202,.00 202,.00 202,.67 204,.00 204,.00 205,.67 205,.67 207,.67 207,.67 207,.67 208,.00 208,.00 208,.67 210,.67 . 201, .67 201,.00 205,.33 205,.33 206,.33 207,.67 207,.33 207,.67 208,.67 209,.00 209,.67 209,.67 209,.67 210,.67 210,.67 215,.00 214,.00 217,.00 217,.67 218,.00 217,.67 219,.00 210,.67 214,.33 215,.00 216,.33 212,.33 211,.67 214,.67 214,.33 213,.67 212,.67 212,.67 213,.00 211,.67 212,.33 212,.00 212,.00 211,.00 211..00 211..33 211,.33 211,.00 211,.00 211..00 210..00 212,.67 210..00 211,.33  204,.93 205,,74 206,,14 206,,81 208.,03 210,.21 211,.29 211..14 211,.55 211,.41 211,.40 211,.39 212.,05 212..04 212..27 212,.53 212..93 214,.98 213,.05 213,,04 213,.99 213,,83 214,.10 214,,77 214..20 214,,74 214.59 214,.71 216,.21 216,.05 217,.14 216,.86 216..42 216,.54 216.,66 216,.78 216..77 217,.18 217,.16 216,.33 217,,42 217..96 219.,33 218..21 218..20 218.46 218..45 218,.57 218..56 218,.83 218,,82 218.,43 218,,98 219,,38 220,,75 220,,74 221,,00 220.,85 220,.99 221,.12 221,.52 221,.22 221,.90 219..41 222..57 222 .,70  RESULTS  79 .0 80 .0 79 .5 77 .5 78 .5 78 .5 80 .0 79 .0 79 .5 80 .0 81 .0 81 .0 80 .5 81 .0 81 .5 82 .5 82 .5 71 .5 69.0 72 .0 72 .5 73 .5 75 .5 75 .5 76 .5 77 .0 77 .5 77 .5 77 .5 78 .5 80 .0 80 .5 83 .5 83 .0 86 .5 86 .5 87 .0 86 .5 87 .5 80 .5 79 .5 81 .0 82 .0 79 .5 78 .0 80 .5 81 .0 81 .0 79 .5 79 .0 78 .5 77 .0 76 .5 76 .5 76 .0 74 .5 73 .5 72 .5 72 .5 73 .0 73 .0 73 .0 73 .0 73 .5 74 .0 74 .5  83,.0 83,.0 83,.0 83,.0 83,.0 83,.0 83,.0 82,.5 82,.5 81,.5 78,.5 78,.0 78,.0 78,.0 78,.0 79,.5 79,.0 81,.0 79,.5 79,.0 79,.0 80,.0 80,.0 80,.0 80,.0 80,.0 80,.0 80,.5 80,.0 80,.0 80,.0 79,.5 79,.5 79,.5 79,.0 79,.0 80,.0 80,.0 81,.0 83,.0 83,.5 83,.5 84,.5 84,.5 83,.0 83,.0 84,.0 84,.0 85,.0 82,.0 81,.0 83,.5 84,.0 84,.0 85,.0 85,.0 86.,0 86,.0 86..0 89..0 89,.5 89,,0 88,,0 88,,0 88,,0 87,,5  195.409 198,.326 198,.034 195,.409 194,.826 195,.409 195,.409 197,.159 198,.034 196,.576 198,.326 198,.326 198,.326 198,.326 197,.743 197,.743 197,,743 192.493 194,.243 194,.243 194,.826 194,.534 194,.826 194,.826 194,.826 195,.409 195.409 195,.993 195,.993 196,.284 196,.576 196,.576 195,.409 192,.493 199,.492 199,.492 200,.076 199,.492 199,.492 199,.492 200,.076 193,.076 195,.409 197,.159 195,.993 195.409 195.409 195.409 197,.159 197.451 197,.451 197,.159 197,.159 197,.159 197,.159 197..451 195,.993 197,,159 196..868 195,.993 193,,076 199.492 193,,076 197,.159 199,,492 197,.743  198,,133 198.,045 198,,022 197,.957 197,,763 197..462 197.331 197..394 197,.371 197,.392 197.434 197,.475 197,.451 197.492 197,.656 197,.654 197,.631 197,.350 197,.692 197,.734 197.625 197,.729 197,.727 197,.661 197,.830 197,.785 197,.848 197,.910 197.714 197,.819 197,.688 197,.772 197,.920 197,.981 198,.042 198,.062 198,.104 198,.080 198,.122 198,.293 198,.162 198,.117 197,.943 198,.157 198,.198 198,.238 198.279 198,.299 198,.341 198,.339 198.380 198,.321 198..276 198.,253 198.,078 198..120 198.,118 198,,181 198,.159 198,,179 198,,156 198,,282 198,.216 198,.646 198..190 198,.210  0..0748 0,,0756 0,.0757 0,,0808 0,.0775 0..0791 0..0782 0..0776 0,.0807 0..0829 0,.0823 0,.0823 0,.0848 0,.0840 0,.0834 0,.0817 0,.0918 0,.1199 0,.1232 0,.1301 0,.1254 0,.1265 0,.1220 0,.1203 0,.1169 0,.1174 0,.1166 0,.1180 0,.1180 0,.1119 0,.1084 0,.1058 0,.1166 0,.1242 0,.0978 0,.1011 0,.0984 0,.1011 0,.1028 0,.0961 0,.1176 0,.1377 0,.1311 0,.1174 0,.1256 0,.1302 0,.1260 0,.1226 0,.1191 0..1206 0,.1248 0..1267 0..1326 0,.1309 0,.1334 0..1350 0,.1452 0..1478 0,.1489 0,.1477 0,,1584 0,,1354 0,,1532 0,,1495 0,,1254 0,,1356  0.,0841 0..0885 0.,0905 0..0941 0..1009 0.,1129 0..1188 0.,1204 0..1225 0.,1268 0..1418 0.,1442 0..1476 0.,1474 0,,1480 0.,1418 0,.1464 0,,1476 0,.1442 0,,1466 0,.1518 0,.1455 0,.1469 0,,1505 0,.1471 0,,1500 0,.1490 0,,1468 0,.1576 0,,1565 0..1624 0,.1632 0,.1605 0..1609 0,.1638 0,.1644 0,,1591 0,.1612 0,,1560 0..1411 0,.1445 0,.1474 0,.1498 0,.1435 0,.1509 0..1520 0,.1468 0,.1473 0,.1421 0..1586 0,.1634 0,.1491 0..1495 0..1516 0.,1540 0..1538 0..1501 0..1492 0.,1499 0..1354 0.,1350 0.,1356 0..1443 0.,1302 0.,1477 0.,1508  Appendix D. DATA AND  2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880 2900 2920 2940 2960 2980  213,.00 213,.33 213,.00 214,.00 214,.00 214,.00 215,.00 215,.00 208,.00 213,.67 216,.00 215,.33 217,.33 217,.00 217,.67 218,.33 219,.00 220,.67 219,.67 220..33 220..67 217..33 216..67 217..00 217..67 217..67 218..00 218..67 219..00 215..00 213..33 214..00 216..00 214..33 214..67 217..33 216..67 217..33 217.,33 212..67 214..00 212..00 211..33  222 .70 222 .69 222 .82 222 .67 222 .93 223.06 222,.77 222,.77 223,.04 224,.54 225,.36 224,.52 224,.59 224,.86 225,.26 224,.84 225,.10 225,.78 225,.76 226,.04 226,.44 226.43 226,.55 226,.00 225..86 226.26 226..52 226..65 226..91 227,.73 228..82 228..12 228.,80 226.,89 229..94 230.,34 232.,27 232.,67 234..05 235.,44 226..83 228,,88 229..42  RESULTS  75 .5 76 .0 77 .0 77 .5 78 .5 79 .5 81..0 81..5 73,.5 76..5 80,.0 82,.5 84,.5 86,.0 87,.0 86,.0 86,.5 87,.5 87,.0 87,.5 87,.0 86,.5 87,.0 86,.5 86,.5 87,.5 88,.0 87..5 88,.5 83..5 81..0 81.,0 81,,0 82,,0 82,.5 83,,0 83,.5 83,,5 84,.5 79,,5 77,,0 76,,5 75,.5  87 .5 87 .5 86 .0 86 .0 86 .0 86 .0 86 .0 86,.5 86,.5 86,.0 86,.0 87,.5 88,.5 89,.0 89,.0 89,.0 89..0 89,.0 87,.0 87,.0 86,.0 86,.5 86,.5 85,.0 85,.5 84,.0 84,.0 84..5 85,.5 85,.5 85,.5 85,,0 86..0 86,,0 86..0 86,,0 86,,5 86,,5 85,,5 85,,5 86,,0 86,,0 86,,5  197 .451 197 .743 197 .743 197 .159 196 .576 196 .284 197,.159 197,.159 197,.159 197,.159 197,.159 197,.159 197,.743 198,.326 198,.326 198,.909 198,.326 197,.743 197,.159 197,.159 197,.743 197,.451 197,.159 197,.159 197,.159 196,.576 196,.576 197,.159 195,.409 195,.409 195,.993 193,,076 193,.659 197..159 192..493 192..493 198,,326 197..159 195..409 192..493 192..493 198.,326 192..493  198 .210 198 .252 198 .272 198 .335 198 .333 198 .353 198.437 198,.437 198.436 198,.281 198 .192 198,.364 202,.419 202,.418 202,.394 202,.501 202,.500 202,.432 202,.474 202,.430 202,.407 202,.449 202,.469 202,.556 202,.620 202,.596 202,.594 202,.614 202..613 202,.523 202,.390 202.541 202,.432 202,.696 202..173 202..149 201,,885 201.,861 201,,684 201.,465 202,,906 202..619 202,,574  0.,1400 0..1381 0,,1314 0,,1360 0,.1329 0,,1289 0,,1233 0,.1208 0,,1258 0,,1394 0,,1334 0.,1174 0,,1154 0.,1042 0..1025 0.,1089 0..1117 0.,1171 0.,1165 0.,1174 0.,1196 0.,1063 0.,1013 0..1055 0.,1089 0.,1058 0.,1050 0.,1089 0.,1115 0.,1166 0.,1188 0.,1325 0.,1407 0.,1148 0.,1302 0..1415 0.,1151 0.,1224 0.,1234 0. 1354 0. 1554 0. 1269 0. 1493  0,,1508 0,,1506 0,,1588 0,,1578 0,.1591 0,,1597 0,,1580 0.,1554 0,.1568 0..1674 0,,1719 0.,1594 0,.1410 0..1399 0,.1419 0..1395 0,, 1408 0.,1444 0.,1540 0,.1556 0.,1626 0.,1599 0.,1604 0.,1648 0..1614 0,,1709 0..1722 0.,1703 0..1666 0..1710 0..1768 0.. 175" 0..1742 0.,1638 0.,1806 0.,1827 0.,1907 0.,1928 0.,2053 0.,2130 0.,1628 0.,1739 0.,1743  Appendix D. DATA AND RESULTS  RUN  11, INDENE HIGH HEAT FLUX DEOXYGENATED  INITIAL CONDITIONS:  UPFRU  UHWP  2.622  TPFRU  2.611 198.00  THWP 198.67  TBPFRU  TBHWP  QPFRU  QHWP  84.0  82.0  298.94  302.86  AVERAGE CONDITIONS:  TBPFRU  TBHWP  QPFRU  QHWP  VFP  REP  VFH  87.18  82.46  299.02  299.33  0.81  9760  0.04 4.9  TIME  PTEMP  HTEMP  PTB  HTB  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700  195 .7 193 .3 194 .7 194 .7 196,.3 196,.3 198 .0 201 .0 201 .0 201 .0 202 .0 198 .7 199 .0 200 .7 200 .7 200 .7 201 .0 203 .0 203 .3 205 .3 207 .0 208 .3 210 .0 209 .3 209 .7 206 .3 208 .3 209 .3 210 .3 209 .7 211 .0 211 .7 211 .3 212 .0 210 .3 209 .7  202 .9 193 .8 194 .3 195 .3 194 .3 195 .2 198 .1 199 .3 198 .2 198 .4 197 .2 198 .5 198 .5 198 .5 199 .8 198 .7 198 .9 198 .9 199 .9 198 .9 200 .1 200 .2 200 .2 201 .5 201 .6 200 .4 200 .4 200 .3 199 .3 199 .4 200 .5 201 .1 202 .2 201 .3 201 .3 201 .3  86.,5 82.,0 83.,0 82.,0 82.,0 84.,0 86,.0 86,,0 90.,0 88,.0 89..0 84.,0 84..0 86..0 84,.0 84..5 84.0 88.0 85,.0 89,.5 89,.5 90,.5 93,,0 91,,0 90..0 87,.0 87..5 88,.0 89..0 88..0 90.,0 91,.0 90,.5 90,,0 89,,5 89.,0  81,.0 81,.5 81,.5 81,.0 82,.0 83,.5 85,.5 84,.0 80,.0 80,.0 81,.0 81,.5 82,.5 83,.5 83,.0 81,.5 83,.0 83,.0 81,.5 81,.0 82,.0 82,.5 81,.5 81,.0 81,.0 80,.0 80,.0 81,.0 79,.5 80,.5 81,.0 81,.0 81,.5 81,.0 81,.0 81,.0  PFH  HHF  293,.114 294,.572 295,.156 293,.114 293,.989 294,.281 296,.031 294,.572 297,.489 297,.489 297.489 298,.947 297.489 297,.489 298,.947 298,.947 296,.905 296 .031 298,.947 296,.905 297,.489 297.489 298,.655 296,.905 298,.947 296,.905 296,.905 298,.947 298,.947 298,.947 298,.947 298,.947 297.489 298,.947 298,.947 298,.947  292,.199 294,.960 298,.918 298,.619 298,.918 299,.153 299,.834 299,.581 299,.858 299,.905 300,.181 299..952 299,.952 299..952 300,.815 301,.092 301,.139 301,.139 300,.839 301,.139 300,.886 300,.910 300,.910 300,.656 300..680 300,.957 300..957 300,.933 301..234 301,.257 300,.980 301,.121 301..380 301..728 301..728 301..728  REH  HFR -0,.0083 -0,.0034 -0..0030 0,.0030 0,.0076 0,.0004 -0..0030 0,.0091 -0,.0082 -0..0015 -0,.0015 0,.0022 0,.0052 0 .0041 0 .0089 0,.0072 0,.0127 0,.0071 0,.0145 0,.0088 0,.0136 0,.0147 0,.0104 0,.0172 0,.0189 0,.0206 0,.0256 0,.0245 0,.0245 0,.0256 0,.0234 0,.0223 0,.0248 0,.0268 0,.0229 0,.0223  PFR 0,.0342 -0..0024 -0,.0058 -0,.0002 -0,.0075 -0,.0095 -0,.0076 0,.0019 0,.0110 0,.0116 0,.0041 0,.0072 0,.0039 0,.0006 0,.0054 0,.0062 0,.0018 0,.0018 0,.0107 0,.0085 0,.0096 0,.0082 0,.0116 0,.0177 0,.0180 0..0171 0..0171 0..0135 0,.0146 0..0116 0,.0141 0..0159 0,,0174 0,,0158 0,,0158 0,,0158  Appendix D. DATA AND  720 740 760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040  209 .7 205,.3 209,.0 211,.0 211,.7 213,.7 214,.0 214,.3 214,.3 215,.0 215,.3 215,.3 215,.0 216,.0 216,.0 215,.7 215,.3 216,.0 215,.7 212,.3 208,.3 207,.7 207,.7 209,.0 209,.3 208,.7 209,.7 210,.0 212,.7 212,.0 210,.0 208,.7 208..3 209,.3 209,.7 210,.0 210,.7 210,.0 211,.3 211,.7 209..7 210,.0 210,.3 211,.0 211,.7 211,.7 211,.7 211..3 210,.0 210..7 210.,7 211.,0 210.,3 211,,3 212.,0 212,,7 212.,3 213,.3 213,.7 212,.0 210,.0 210,.7 210,.7 211.,0 213..0 213.,0 214.,0  201 .4 201 .6 204 .1 200 .7 200 .8 201 .2 202 .2 202 .7 203 .8 202 .8 202 .9 203 .0 204 .7 204 .4 204 .3 205 .5 207 .1 207 .3 206 .2 205 .2 205 .3 206 .4 206 .4 206 .4 205 .3 205 .3 205 .3 203 .6 203 .6 203 .6 204 .8 204 .8 204 .8 204 .8 204 .9 204 .9 204 .9 204 .8 207 .1 206 .6 205 .1 204 .5 204 .2 204 .1 203 .9 204 .9 204 .9 204 .9 204,.2 204,.2 204,.9 203,.7 203,.7 203,.7 204,.2 203,.7 203,.5 203,.2 204,.4 204,.4 204,.4 204,.5 204,.5 203,.9 204,.5 202,.9 204,.0  RESULTS  87 .0 80,.5 82 .5 79,.0 88 .0 81,.0 89 .5 80,.0 90 .5 79,.5 92 .0 80,.0 93 .5 80..0 93 .0 81,.0 90 .5 82,.0 93 .0 82..0 94 .0 82,.0 94 .0 81,.5 92 .0 83..0 93 .0 84,.0 92 .0 83,.5 92 .0 84,.0 92 .0 86,.0 93 .5 85..5 93 .5 84..0 90 .5 84.,0 87 .5 84..0 86 .5 84,.0 87 .5 84,.0 89 .0 84,.0 89 .0 84,.0 88 .0 84.,0 88 .5 84,,0 87 .0 82,,0 90 .5 82,,0 92 .0 82..5 86 .0 84.,0 85 .5 84..0 86 .0 84..0 85 .0 84.,0 87 .0 84..0 87 .0 84,,0 88,.0 84,,5 86,.5 • 83,,0 88 .0 85,,0 89,.5 84..0 88,.5 84,.0 88,.5 82..0 87 .5 81,.5 87,.5 82.,0 88,.5 81,.5 89,.0 83.,0 89,.0 82,,0 88,.0 82,,0 88,.0 82,.0 88,.0 82,.0 88,.5 82,,0 87,.5 82,,0 88,.0 83.,0 87,.5 82,,0 88,.5 82..0 89..5 82,,5 90,.5 82.,0 91,.5 83.,0 92,.0 82.,0 89..0 82.,5 86,.0 82.,5 86..0 82.,5 86..0 82.,5 87..0 82.,5 88..0 82.,0 90..5 81.,5 90,,5 82.,5  298.947 301.864 300.405 300.405 298.947 300.405 299.822 300.405 300.405 300.405 301.864 300.405 301.864 300.405 300.405 300.405 302.739 300.405 300.405 301.864 300.405 300.405 298.947 301.864 298.947 297.489 297.489 296.031 301.864 300.405 300.405 300.405 298.947 301.864 298.947 300.405 300.405 301.864 300.405 300.405 297.489 297.489 296.031 297.489 298.947 298.947 298.947 298.947 298.947 298.947 298.947 298.947 297.489 298.947 300.405 301.864 297.489 301.864 300.405 301.864 297.489 300.405 300.405 297.489 301.864 301.864 301.864  301,.751 301,.799 301,.291 302,.123 302,.146 302,.264 302,.500 302,.618 302,.316 302,.641 302,.665 302,.688 302,.552 302,.481 302,.994 303,.301 303,.116 303,.164 303.466 303,.768 303,.792 303,.513 303,.513 303,.513 303,.792 303,.792 303,.792 303,.391 303,.391 303,.391 303,.136 303,.112 303,.136 303,.136 303,.159 303,.159 303,.159 303,.112 302,.556 302,.438 302,.646 302,.505 302.434 301,.850 301,.803 301,.479 301,.479 301,,479 301,.314 301,,314 301,,479 301.,756 301..756 301.,756 301,,314 301..197 301,,150 301.,079 300,,802 300.,802 300.,802 300,,825 300,,825 300.,126 299,.174 298.,776 298..500  0,.0290 0,.0256 0,.0214 0,.0231 0,.0240 0,.0237 0,.0206 0,.0226 0,.0309 0,.0248 0,.0206 0,.0226 0,.0261 0,.0281 0,.0314 0,.0303 0,.0260 0,.0264 0,.0253 0,.0223 0,.0209 0,.0220 0,.0206 0,.0162 0,.0212 0,.0243 0,.0260 0,.0342 0,.0234 0,.0181 0,.0314 0,.0287 0,.0279 0,.0305 0,.0290 0,.0281 0,.0270 0,.0278 0,.0292 0,.0253 0,.0260 0,.0271 0,.0336 0,.0338 0,.0307 0,.0290 0,.0290 0,.0312 0,.0268 0..0290 0..0273 0..0318 0..0299 0..0329 0.,0298 0..0267 0.,0282 0..0223 0.,0237 0,.0261 0..0355 0,,0337 0,,0337 0,.0355 0,.0327 0..0245 0..0278  0,.0177 0,.0233 0,.0256 0,.0164 0,.0183 0,.0181 0,.0210 0,.0192 0,.0197 0,.0162 0,.0164 0,.0184 0,.0193 0,.0152 0,.0156 0,.0177 0,.0164 0,.0186 0,.0197 0,.0158 0,.0161 0,.0203 0,.0203 0,.0203 0,.0161 0,.0161 0,.0161 0,.0178 0,.0178 0,.0161 0,.0156 0,.0154 0,.0156 0,.0156 0,.0159 0,.0159 0,.0143 0,.0187 0,.0204 0,.0222 0,.0172 0,.0221 0,.0228 0,.0216 0,.0227 0,.0213 0,.0246 0,.0246 0,.0226 0..0226 0,.0246 0..0204 0..0171 0..0204 0..0226 0..0195 0,,0205 0,,0163 0,,0239 0,,0222 0,,0222 0.,0225 0.,0225 0..0214 0.,0265 0.,0232 0.,0241  Appendix D. DATA AND  2060 2080 2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880 2900 2920 2940 2960 2980  213 .7 209 .3 209 .3 209 .3 211 .3 211 .3 212 .0 213 .7 213 .3 213 .3 213 .3 213 .3 213 .0 212 .7 213 .0 213 .3 213 .7 212 .7 203 .3 203 .3 203 .0 203 .0 203 .0 204 .3 203 .3 203 .7 204 .0 204 .0 205 .0 203 .7 203 .3 203 .3 203 .7 203 .3 205,.7 204,.7 204 .7 204 .3 204,.3 205 .3 205,.3 205,.0 205,.3 205,.0 205,.3 206,.3 206,.3  202,.4 203,.5 203,.5 203,.5 203,.5 204,.2 204,.8 204,.8 204,.3 203,.1 203,.1 203,.1 203,.1 202,.6 203..2 202,.1 202..1 202,.1 201,.6 202,.8 201..7 201,.8 201,.8 201,.8 203,,0 203,.1 201..9 201,.9 200,,7 200,.7 201,.9 203,.1 203,.2 203..1 201..9 201..9 203..1 203..1 203..1 201..9 201..9 201..9 201.,9 203..1 203.,1 203.,1 201..9  RESULTS  91 .0 89 .0 89 .0 89 .0 89 .0 88 .0 88 .5 91 .0 92 .0 87 .0 87 .5 87 .5 87 .5 87 .5 88 .0 88 .0 88 .0 87 .0 82 .5 84 .0 83 .5 84 .0 86 .0 79 .0 78 .5 79 .0 80 .5 81 .0 81 .0 83 .0 81 .5 80 .5 80 .5 80 .5 81 .5 81 .5 82 .5 82 .5 82,.5 82,.0 82,.5 82,.0 81,.5 82,.0 82,.0 82,.5 82,.5  82,.0 83,.0 83,.0 83,.0 83,.0 84,.5 85,.5 84,.5 84,.0 83,.0 82,.5 82,.5 83,.0 83,.0 82,.5 82,.5 82,.5 82..5 82,.5 82..5 82,.0 82..0 82,.0 82..0 82,.5 82..0 82,.0 83,,0 83.,0 83..0 83.,0 83.,0 83,.0 83,.0 83,.0 83,.0 83,,5 83,.5 83,.5 83..5 82..5 82,.5 82..5 82,.5 82..5 82..0 82..5  301 .864 296 .031 297 .489 297 .489 301 .864 301 .864 301 .864 301 .864 300 .405 301 .864 301 .864 301 .864 301 .864 301 .864 301 .864 301 .864 301 .864 301 .864 297,.489 291,.656 291 .656 291,.656 297 .489 303,.322 303,.322 303,.322 297.489 300.405 300.405 300,.405 300,.405 297,.48? 297,.489 297,.489 301,.864 297.489 297,.489 297.489 297,.489 297,.489 297..489 297,.489 297..489 297,.489 297..489 297,.489 297..489  298,.103 297,.827 297 .827 297,.827 297,.827 296 .879 295,.933 295,.933 295,.262 295,.537 295,.537 295,.537 295,.537 294,.867 295,.560 294,.198 294,.198 294,.198 293,.529 293,.255 293,.552 293,.575 293,.575 293,.575 293,.302 293,.325 293,.598 293,.598 293,.872 293,.872 293,.598 293,.325 293..348 293..325 293,.598 293,.598 293,.877 293,.877 293..877 294,,151 294,,151 294,.151 294,.151 293,.877 293,.877 293,.877 294,.151  0..0250 0..0251 0,.0232 0,.0232 0..0239 0.0272 0,.0278 0..0250 0,.0226 0,.0372 0,,0355 0.,0355 0..0344 0.,0333 0.,0327 0..0339 0,,0350 0.,0350 0,.0248 0,,0278 0,,0284 0.,0267 0,,0119 0,,0319 0,,0302 0..0297 0,,0338 0,,0281 0,,0314 0,.0203 0..0242 0,,0316 0,.0327 0..0316 0..0300 0..0327 0..0293 0..0282 0..0282 0..0332 0..0316 0..0321 0.,0349 0.,0321 0.,0332 0.,0349 0.,0349  0,.0207 0,.0216 0,.0216 0,.0216 0,.0216 0,.0200 0,.0201 0,.0235 0,.0244 0,.0235 0,.0252 0,.0252 0,.0235 0,.0227 0,.0255 0,.0235 0,.0235 0,.0235 0,.0227 0,.0271 0,.0247 0,.0250 0,.0250 0,.0250 0,.0277 0,.0297 0..0253 0..0219 0..0176 0,.0176 0..0219 0,.0263 0,.0266 0..0263 0..0219 0,.0219 0,.0239 0,.0239 0,,0239 0,,0195 0,,0229 0,.0229 0.,0229 0,,0273 0..0273 0,.0290 0,.0229  Appendix D. DATA AND RESULTS  ROT 12, DICYCLOPENTADIENE  INITIAL  UPFRU  UHWP  2.763  2.576  CONDITIONS:  TPFRU  THWP  187.00  185.00  AVERAGE  MEDIUM HEAT FLUX  TBPFRU 85.0  TBHWP  QPFRU  QHWP  82.0  281.84  265.30  CONDITIONS:  TBPFRU  TBHWP  QPFRU  qHWP  VFP  REP  VFH  REH  81.33  80.61  258.03  254.41  0.81  9760  0.04  4.9  TIME  PTEMP  HTEMP  PTB  HTB  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680  184..3 185..3 186..3 188..0 187..0 188..7 188..7 190..0 191..0 191.,0 198..3 204..3 205..0 204.,0 210..0 214,.3 221,.3 230,.7 238..3 237,.0 245,.3 263..3 263..3 267..0 269..7 273.,0 276.,0 279..7 280,.0 284,.7 276..0 276..7 278..7 281..3 284..0  187 .0 188 .2 188 .2 188 .3 188 .4 188 .4 188 .4 188 .5 188 .4 188 .4 188 .2 200 .4 210 .3 205 .0 208 .5 206 .5 207 .4 207 .1 207 .2 208 .5 210 .8 214 .8 200 .9 203 .2 205 .1 207 .2 210 .8 214.8 218 .9 223 .6 212 .3 215 .7 216 .4 218 .6 219 .4  85.,0 85..0 85.,5 84..0 84..0 84..0 84..0 83..5 83..0 83,,0 82..5 85.,5 85..5 82.,5 83,.0 86,,5 91,,5 95,,5 95,,5 84,,5 79,,0 78,,5 79,,5 80..5 82.,0 83..0 84.,5 85..5 86.,0 87,,0 80,,5 78,.5 79,,5 80.,5 82..5  86 .0 85 .0 85 .0 85 .0 83 .0 84 .0 84 .0 82 .5 82 .0 83 .0 85 .0 85 .0 84 .0 83 .0 84 .0 84 .0 84 .5 82 .0 84 .5 82 .0 83 .0 85 .0 77 .0 77 .0 77 .0 76 .5 80 .5 81 .0 84 .5 84 .0 78 .0 77 .0 78 .0 78 .0 79 .0  PHF  HHF  282.,906 281..739 282,.323 282,.906 281.448 282,.906 285.,823 288,,739 291.,656 291,,656 314.,988 314.,988 320.,821 320.,821 320,.821 314,.988 314..988 320,.821 320..821 320,.821 323,.738 323..738 323,,738 323.,738 320.,821 323.,738 320.,821 326.654 317,.905 323,.738 303..322 298,,947 303,,322 303,.322 303,,322  256,.577 256,,820 256,.820 256,.844 256..821 256,,821 256..821 256,.845 256..868 256..868 256..820 254..633 253.,156 254..186 253,,570 253,.982 253,.799 254,.008 253,.985 253,.710 260,.179 259,.461 262..103 261.,663 261,.268 260.,827 260,,131 259.413 258,.530 257,.672 259,.498 259,.275 259,.135 258,.671 258,.555  PFR -0.,0108 -0..0058 -0..0048 0,.0057 0,.0041 0,.0081 0,.0043 0,.0069 0,.0084 0,.0084 0,.0058 0,.0154 0,.0106 0..0168 0,.0339 0..0439 0,.0503 0,.0594 0,.0833 0,.1134 0,.1519 0,.2090 0,.2059 0..2142 0..2230 0.,2250 0..2350 0.2325 0,.2483 0,.2487 0,.2826 0,.3010 0,.2947 0,.3002 0,.3024  HFR 0..0054 0,.0135 0,.0135 0,.0139 0,.0222 0..0183 0,.0183 0,.0245 0,.0260 0..0221 0..0135 0..0651 0,.1108 0..0917 0,.1028 0,.0940 0,.0959 0,.1041 0,.0948 0,.1105 0,.1031 0,.1120 0..0844 0,.0942 0..1021 0,.1130 0..1128 0,.1275 0,.1315 0,.1533 0,.1291 0,.1467 0,.1457 0,.1555 0..1549  Appendix D. DATA AND  700 720 740 760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020  286 .0 286 .3 288 .0 288 .7 267 .0 268 .3 269 .0 269 .7 269,.7 272,.0 272,.7 272 .3 272 .0 273 .7 274 .7 263 .0 262 .3 261 .3 263 .0 263 .7 265,.7 264,.7 267,.0 268,.0 268,.7 264,.3 267 .7 268 .7 268 .7 269 .0 269 .0 269 .3 269 .0 270 .0 268 .7 269 .7 268,.3 268,.0 266 .3 266 .7 266,.3 269 .7 269 .0 269 .0 269 .3 270 .3 270,.3 270,.0 270,.7 270,.7 271,.3 270,.7 272,.3 272,.3 272,.7 273 .3 273 .0 273,.7 273,.0 274,.0 274,.3 274,.3 274,.7 275,.0 275,.3 276,.0 276,,7  220 .2 222 .6 226 .8 222 .8 215 .0 219 .3 219 .6 222 .6 220 .1 222 .1 220 .9 226 .0 226 .5 226 .5 229 .2 228 .2 226 .8 227 .9 228 .8 230 .2 231 .5 231 .5 231 .6 230 .4 232 .0 231 .4 231 .5 232 .0 231 .4 231 .5 231 .6 230 .5 231 .2 231 .1 231 .4 231 .1 232 .1 232 .4 230 .7 227 .8 227 .9 230 .8 230 .7 230 .5 230 .9 231 .6 232 .5 238 .4 247 .5 235 .3 254 .2 251 .9 243 .8 243 .0 254 .1 250 .0 248 .9 255 .3 252 .3 245 .2 245 .5 244 .9 246 .9 248 .3 248 .8 251 .1 254 .1  RESULTS  84,.5 86,.0 87,.0 87..5 73,.0 75,.0 77..0 78..5 80,.5 82,.0 82.,0 83.,0 83,.5 84..0 84,.5 78,.5 72..5 71,.5 71,.5 72,.0 73,.0 74..5 75..0 76.,0 76..5 76..5 76,.5 77,.0 77,.5 77,.5 77,.5 78,.0 78,.5 78..5 79..5 79..5 79..5 79.,5 76..5 73.,0 72..5 73,.5 74,.0 74,.5 75,.0 76,.5 76,.5 77..5 78,,0 78,,5 79..5 79.,5 80,,5 80.,5 81..0 81,.0 81..0 81,.5 81,.5 81,.5 82,,5 82,,5 82,.5 83..0 83,.5 83.,5 83.,0  82,.0 81,.0 81,.5 80,.0 78,.0 77,.0 76,.0 78,.0 77,.0 76,.5 76,.0 79,.0 81 .0 80 .0 80 .0 79,.5 80,.0 80,.0 80,.5 81,.0 81,.5 80,.0 80,.5 81,.5 80,.5 81,.0 81 .0 81 .5 82,.0 82,.5 82,.5 81,.5 81,.0 81,.0 80,.5 81,.0 80,.0 80,.5 81,.0 81..5 80,.5 79 .0 79,.0 79,.5 79,.0 79,.0 81,.0 81,.0 80,.5 79,.5 80,.0 80,.0 79,.5 79..5 80.,5 78,.5 80,.5 80,.0 77,.5 78,.0 78..0 78..0 79,,0 79,.0 78.,0 78,.5 76,,5  303,.322 303,,322 303.,322 303,.322 262.490 262,,490 262,,490 262.490 256,,657 262,,490 262,.490 262.490 262,.490 256,.657 262,.490 262,.490 233,.325 233,.325 233,.325 239..158 239..158 242,,074 239,.158 242..074 244,.991 244,.991 233,.325 244..991 244..991 244..991 244,.991 244,.991 244..991 239..158 244..991 239,,158 240,.616 239,.158 239..158 233,.325 233..325 233,.325 239..158 239,.158 233,.325 239,.158 239,.158 239,,158 239,.158 239,.158 239,.158 239,.158 239..158 239..158 233..325 233,.325 233,,325 233,,325 239,,158 239.,158 239.,158 239..158 239.,158 239..158 239.,158 239.,158 239.,158  258.440 257,.905 257,.352 258,.118 259,.509 258,.721 258,.532 257,.905 258,.227 257,.832 257,.970 257,,090 256.879 256 .926 256,.580 256,.695 256,.927 256,.789 256,.603 256,.277 255,.975 255.880 255,.904 255,.807 255,.599 255,.621 255.692 255 .646 255 .857 255,.598 255,.528 255,,737 255,.504 255,.433 255.480 255,.621 255,.388 255,.318 255,.714 256..153 256,.223 255,.737 255,.714 255,.690 255,.620 255,.669 255,,624 254,.510 252,.675 254,.785 251,.095 251,.583 253,.395 253..558 251..398 252.234 252,.443 251,.259 251,,793 253,,163 253,.164 253.,233 252..791 252..513 252.467 252.,025 251.445  0,.3024 0,.2986 0,.3008 0,.3013 0,.3772 0,.3746 0,.3695 0,.3664 0,.3751 0,.3619 0,.3645 0,.3594 0 .3562 0,.3771 0,.3626 0,.3410 0,.4517 0,.4517 0,.4588 0,.4395 0.4437 0.4237 0,.4409 0.4312 0,.4225 0,.4048 0 .4574 0 .4204 0 .4184 0,.4198 0,.4198 0 .4191 0 .4157 0,.4388 0.4102 0.4332 0,.4229 0,.4263 0,.4318 0,.4681 0,.4688 0.4788 0,.4534 0,.4514 0,.4710 0.4486 0,.4486 0.4430 0,.4437 0.4416 0,.4402 0,.4374 0..4402 0,,4402 0.,4595 0.4624 0,.4610 0.4617 0.4388 0.4430 0.4402 0.4402 0,,4416 0.4409 0.4402 0.4430 0.4479  0,.1467 0,.1610 0,.1763 0,.1649 0..1398 0..1619 0,.1670 0,.1726 0,.1660 0,.1763 0,,1735 0,.1834 0 .1783 0,.1821 0,.1932 0,.1909 0,.1830 0,.1878 0,.1899 0,.1941 0,.1978 0,.2038 0..2023 0.,1940 0..2043 0..2000 0,.2003 0,.2003 0,.1956 0,.1946 0,.1952 0,.1946 0,.1998 0,.1995 0,.2022 0,,1991 0.,2071 0,.2067 0.,1970 0.,1828 0.,1870 0,.2053 0,.2049 0,.2025 0,.2060 0.2086 0..2046 0,.2302 0,,2726 0,.2233 0,.3054 0,,2950 0,,2602 0,,2565 0..3022 0.2917 0,,2789 0,.3093 0,.3058 0,.2723 0,,2733 0,.2707 0,.2759 0,,2823 0,,2883 0,.2965 0.,3180  Appendix D. DATA AND  2040 2060 2080 2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880 2900 2920 2940 2960 2980  277,.0 277,.0 276,.3 277,.7 278,.7 279,.0 280,.0 280,.7 280,.3 281,.7 283,.3 283,.0 283,.7 284,.0 285,.0 285,.3 284,.7 284,.7 285,.7 285,.7 286,.7 287,.3 287,,7 288,.7 289..3 288,.7 289..0 289..7 289,.7 289..7 290,.7 290,.7 290,.7 291..3 291.,3 291,.3 292.,0 292,.0 292.,3 291,.3 291,,7 291..7 291.,3 291,.7 292..0 291,.3 291..3 291.,7  255 .4 248 .9 247 .4 248 .7 258 .2 259 .6 259 .9 258 .9 257 .6 254 .9 257 .1 252 .3 257 .6 253 .5 257 .3 259 .6 252 .3 258 .4 259 .7 258 .9 260 .6 253 .6 253 .7 253 .5 258 .5 258 .4 259 .1 258 .0 253 .5 254 .8 255 .5 253 .7 260 .0 260 .6 260 .5 262 .4 260 .0 261 .0 256 .0 257 .3 256 .2 255 .2 257 .2 257 .3 257 .1 256 .7 257 .8 257 .9  RESULTS  82,.5 83,.5 85,.0 85,,0 85,.5 84.,5 83,.0 82,.5 82,.5 82,.5 82,.5 82..5 82,.0 82..0 82,.0 82,.0 83..0 83..0 83,.5 84..0 84..5 84,.5 84..5 84,.5 83..5 82..5 82..5 82.,5 82,.5 82,.5 83..0 83..0 83,.5 83..0 82..5 82..5 81..5 81.,5 82..0 82.,5 81..5 81,,5 82.,0 82,.0 82,,0 83..0 83,,0 83,,0  78,.5 79,.0 78,.5 80,.0 81,.0 80,.5 81,.0 81,.0 81,.0 81,.0 81,.0 81,.0 81,.0 80,.5 80,.5 81,.0 82,.0 81,.5 82,.0 81,.5 81,.0 81,.0 81,.5 82,.0 82,.0 82,.0 82,.0 81,.0 81,.0 80,.5 80,.5 81,.0 81,.0 79,.5 80..5 80,.0 79,.5 79,.5 80,.5 80..0 80,.0 80,.0 80.,0 81,.0 81..0 81,.0 80,.5 80,,0  236..241 236,.241 236..241 236..241 236,.241 236..241 233..325 233..325 233,.325 236.241 236..241 239..158 239..158 239,.158 239..158 239,.158 239..158 239,.158 239..158 239..158 239.,158 239..158 239..158 236,.241 236,.241 236..241 236..241 236..241 236..241 236..241 239..158 236..241 239..158 237..699 237..699 237..699 237,.699 237..699 236,.241 236,,241 236,,241 236,.241 236,,241 237,.699 237,.699 237,.699 239,.158 239,,158  251,.143 252,.397 252 .698 252.443 250 .609 250,.330 250,.330 250,.516 250,.771 251,.329 250 .864 251,.840 250 .818 251 .561 250 .864 250 .376 251,.793 250,.702 250,.446 250,.516 250 .284 251 .584 251 .654 251 .607 250 .725 250,.655 250,.469 250,.725 251,.561 251,.399 251,.259 250,.795 250,.586 250,.470 250,.400 250,.028 250,.446 250,.167 251,.400 251,.144 251,.027 251,.282 251,.121 251,.097 251,.144 251,.027 251,.144 251,.121  0,.4614 0,.4572 0.4480 0.4536 0.4558 0,.4614 0,.4824 0,.4874 0,.4860 0,.4812 0,.4882 0,.4764 0,.4813 0.4827 0,.4869 0,.4883 0,.4813 0,.4813 0,.4834 0,.4813 0,.4834 0.4862 0,.4876 0,.5023 0,.5094 0,.5108 0,.5122 0,.5150 0,.5150 0,.5150 0,.5064 0,.5171 0,.5043 0,.5145 0,.5166 0,.5166 0,.5237 0,.5237 0,.5284 0,.5221 0,.5277 0,.5277 0,.5242 0,.5202 0,.5216 0,.5145 0,.5092 0,.5106  0.,3161 0..2850 0.,2800 0..2799 0..3187 0,.3273 0..3263 0,.3219 0,.3158 0,.3037 0,.3137 0,.2918 0,.3157 0,.2993 0,.3166 0,.3252 0.2880 0,.3174 0,.3215 0,.3199 0,.3293 0,.2978 0,.2961 0,.2933 0,.3159 0,.3156 0,.3190 0,.3179 0,.2973 0,.3050 0,.3083 0,.3201 0..3260 0..3348 0..3305 0..3414 0..3324 0,,3371 0,,3098 0,,3178 0,,3138 0,,3088 0,,3174 0..3140 0,,3129 0.,3118 0,,3178 0.,3203  Appendix D. DATA AND RESULTS  205  DICYCLOPENTADIENE  LOW HEAT FLUX  INITIAL CONDITIONS:  UPFRU  UHWP  2.063  2.050  TPFRU  THWP  183.0  180.0  TBPFRU  TBHWP  QPFRU  QHWP  82.0  82.0  208.37  200.94  AVERAGE CONDITIONS:  TBPFRU  TBHWP  QPFRU  QHWP  VFP  82.79  81.55  215.51  201.19  0.81  TIME  PTEMP  HTEMP  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700  182..00 183..00 183..00 184..00 184,.00 185..00 186..00 187,.00 188,.00 188,.00 187,.00 200,.67 192,.00 191,.67 196,.00 192,.67 197,.67 198,.67 200,.67 202,.00 203,.33 203,.33 203,.33 206..33 205,.00 204,.33 201,,33 201,.67 202,.00 203,.00 202,.33 203,.33 203,.33 203,.33 202..33 204,,33  180.,04 180..04 179..19 180,.04 179,.38 179,.86 179,.01 179..01 180..04 179..19 180..04 178..83 180..29 180.29 179..26 182,.54 183,.58 184,.80 183,.95 184..99 184,.31 184..13 184.,01 185.,17 189.,83 190.,70 189..46 189,.28 183,.76 184,.13 184,.74 184..44 183,,76 183.,76 184,,13 184,,50  PTB 82 .0 82 .0 82 .0 82 .0 82 .0 82 .5 83 .0 83 .5 84 .0 83 .5 82 .5 92 .5 83 .0 77 .5 76 .0 77 .0 79 .0 81 .0 83 .5 86 .0 85 .0 84 .5 85 .0 84 .0 82 .5 83 .0 76 .0 72 .0 72 .0 72 .5 73 .0 74 .0 75 .0 76 .0 76 .0 76 .5  HTB 83..0 82.,5 82..0 82,.5 82,.0 82,.5 82,.0 81..5 82..0 81..0 81..0 79,.5 80,.0 79,.5 78..5 81,.0 83,.0 83,.0 84,.0 85,.5 84,.0 82,.0 82,.0 82,.5 83..5 83.,0 82.,0 82,.0 80..0 80..0 80..0 79..0 80..0 80,.0 80,,0 80,,0  REP 9760  PHF  HHF  202,,701 202.,701 204,.159 207,.076 205,.617 209..992 209..992 209..992 209,.992 208,.534 213..492 213.492 213..492 212..909 214.,367 215,.825 215,,825 215..825 215..825 215,.825 218,.742 218,.742 215.,825 215.,825 215.,825 218,,742 218,,742 215,.825 218,.742 218,.742 218,.742 218..742 215,.825 218,.742 218,,742 214,,367  199..125 199..125 199..262 199,.125 199,.292 199,.095 199,.233 199,.233 199,.125 199.262 199,.125 199.203 199,.440 199.440 199,.547 199,.253 199,.145 199,.067 199,.204 199,.096 199,.263 199,.234 199,.489 199,.126 198,.496 198..359 198.,438 198,.408 199,.175 199,.234 198,.782 199,.008 199,.175 199,.175 199,.234 199,,293  VFH  REH  0.04  4.9  PFR 0,,0086 0.,0136 0.0100 0,,0079 0,,0114 0,.0034 0,,0058 0,.0082 0..0105 0..0164 0,.0048 0..0219 0..0259 0..0515 0..0751 0,.0512 0,.0651 0,.0605 0,,0582 0,.0528 0,.0563 0..0586 0..0636 0.,0821 0.,0829 0.,0700 0,,0883 0,,1161 0,.1096 0,.1119 0,.1066 0,,1066 0,,1099 0.,0974 0,,0928 0.,1116  HFR -0,.0004 0,.0021 0,.0000 0,.0021 0,.0009 0,.0013 -0..0008 0,.0017 0,.0047 0,.0051 0,.0097 0,.0109 0,.0151 0,.0177 0,.0172 0,.0219 0,.0174 0,.0237 0,.0140 0,.0120 0,.0157 0,.0249 0,.0236 0,.0279 0,.0480 0,.0552 0..0538 0,.0530 0,.0333 0,.0349 0,.0392 0,.0421 0,.0333 0,.0333 0,.0349 0,.0366  Appendix D. DATA AND  720 740 760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 i340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040  204 .33 204 .00 204 .33 204 .67 204 .67 205 .00 205.33 204 .33 203 .33 204 .00 204 .67 205,.33 206 .00 206,.00 206,.00 206,.67 207,.00 207,.67 206,.67 207,.33 208,.00 207,.33 207,.67 207,.33 207,.67 208,.00 207,.67 208,.00 208..33 208,.33 208..00 208.00 207..00 208,,67 208..67 209.,00 209..33 208.,33 209..00 209.,33 211..33 212.,33 212.,67 213.,00 213.,00 213..67 216..00 219.,00 217..00 214..67 215.,00 216.,33 217.,33 217.,33 218.,00 217.,67 219.,00 219.,00 219.,67 219.,33 220.,33 220.,67 221.,67 221.,67 222.,00 222.,67 223. 00  185.72 185 .60 184 .01 185 .41 185 .41 187 .31 186 .82 185 .60 184 .92 184.44 184 .62 184 .62 185 .84 186 .70 186 .88 187 .92 186 .57 186 .39 186 .57 187 .43 189 .33 187 .61 189 .51 187 .80 188 .84 189 .88 191 .11 190 .74 191 .11 192 .15 193 .02 194,.07 193,.39 193,.20 194,.25 195,.12 196,.17 196,.17 196,.35 192,.34 193,.20 193,.39 193,.39 194,.25 193,.57 195.49 194,.62 194,.80 194,.80 194..99 194..99 196,,04 196.,22 194..67 196,,01 196..88 196,,88 196..99 199,,69 197..20 196.,33 195.47 197..30 197.,41 197.,41 197.,51 196.,65  RESULTS  77 .0 77 .5 78 .0 78 .0 78 .0 78 .0 78 .5 78 .5 78 .0 78 .5 79 .0 79 .0 79 .5 80 .0 80 .0 80 .0 80 .0 80 .0 80 .0 80 .5 81 .0 81 .0 79 .5 81 .0 81 .0 81 .0 81 .5 81 .5 82 .0 82 .0 82 .0 82,.0 82,.0 81,.5 82,.0 82,.0 82,.0 82,.5 83,.0 83,.5 84,.5 85,.5 86,.5 85,.0 86,.5 87,.5 86,.0 82,.0 80..0 80,.0 80,,0 81,,0 81,,0 81..5 82,,0 82.,5 83,.0 82.,5 82..5 83,,0 83.,0 83,,0 83.,5 84.,0 84.,5 84.,5 85.,0  81 .0 81 .5 81 .5 82 .0 81 .0 82 .0 81 .0 80 .0 80 .0 80 .0 79 .0 79 .0 79 .5 81 .5 80 .5 81 .0 81,.5 82 .0 81 .0 82 .0 81,.5 82 .0 81,.5 82,.0 82,.5 82,.0 81,.5 82,.5 83,.0 83,.0 83,.0 83,.0 83,.5 83,.5 83..0 83,.0 82..5 83,.0 83..0 83..0 81..5 80..5 81,,5 81.,0 82,.0 82..5 83,.0 82,.5 82,,0 82,.0 82,,0 82..5 82,,5 82..0 81,,5 81..5 82..5 81..5 81.,5 82.,5 81.,5 81.,0 82.,0 82.,0 82.,0 82.,0 81.,0  218 .742 218 .742 218 .742 218 .742 218 .742 218 .742 218 .742 218 .742 214 .367 207 .076 212 .909 214 .367 218 .742 218 .742 215 .825 218 .742 218 .742 220 .200 220 .200 214 .367 215 .825 218 .742 214 .367 215,.825 215,.825 215 .825 215 .825 215,.825 215,.825 215,.825 215,.825 215,.825 215,.825 214,.367 215,.825 215,.825 215,.825 215,.825 215,.825 214,.367 209,.992 218,.742 220,.200 218..742 218..742 215..825 215,.825 214..367 215..825 215..825 214,,367 214,,367 214,,367 214,.367 214.,367 214,.367 214.,367 214.,367 214.,367 214.,367 214.,367 214.,367 214.,367 214.,367 214.,367 214.,367 214.,367  199 .214 199 .470 199 .489 199 .440 199.440 199 .194 199 .391 199 .470 199 .637 199 .834 199 .863 199 .863 199 .785 199 .647 199 .676 199 .568 199 .903 199 .873 199 .903 199 .765 199 .518 199 .794 199 .548 199 .824 199 .715 199 .607 199 .527 199 .469 199.527 199 .419 199,.281 199 .172 199,.340 199,.310 199,.201 199,.063 198,.954 198,.954 198,.984 199,.448 199,.310 199,.340 199,.340 199,.201 199,.369 199,.122 199,.260 199,.290 199.290 199,.319 199.,319 199,.210 199,,239 199,,545 200.,037 199,,898 199.,898 200,.469 200.625 201,.615 201.,754 201..893 202,,189 202,,763 202.,763 203..339 203.479  0,.0974 0..0936 0,.0928 0,.0944 0,.0944 0..0959 0,.0951 0,.0906 0,.1000 0,.1214 0..1055 0,.1046 0,.0936 0,,0913 0..0991 0.,0944 0..0959 0,.0951 0.,0905 0..1070 0.,1037 0,,0928 0,,1132 0,,1006 0.,1022 0.,1037 0..0999 0.,1014 0..1006 0..1006 0..0991 0.,0991 0,.0945 0.,1085 0..1022 0..1037 0..1053 0.,0983 0..0991 0..1023 0.,1193 0.,0951 0..0883 0.,1005 0.,0936 0.,0999 0.,1176 0.,1544 0.,1501 0.,1393 0.,1451 0.,1466 0. 1513 0.,1489 0. 1497 0. 1458 0. 1497 0. 1521 0. 1552 0. 1513 0. 1559 0. 1575 0. 1598 0. 1575 0. 1567 0. 1598 0. 1590  0 .0380 0 .0342 0 .0261 0 .0308 0 .0358 0 .0410 0 .0430 0 .0417 0 .0379 0 .0349 0 .0407 0 .0407 0 .0446 0 .0392 0 .0451 0 .0481 0 .0379 0 .0346 0 .0404 0 .0401 0 .0527 0,.0409 0 .0536 0,.0417 0,.0447 0,.0528 0,.0616 0 .0549 0,.0541 0,.0597 0,.0644 0,.0699 0,.0635 0,.0627 0,.0708 0,.0755 0,.0836 0,.0811 0,.0820 0,.0605 0..0727 0..0786 0,.0736 0..0808 0..0719 0..0797 0..0725 0..0758 0..0783 0,,0792 0,,0792 0,,0822 0,,0831 0,,0769 0,,0848 0,,0895 0..0845 0..0884 0.,1014 0..0812 0..0815 0.,0793 0.,0826 0..0815 0.,0815 0.,0804 0.,0807  Appendix D. DATA AND  2060 2080 2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880 2900 2920 2940 2960 2980  224,.00 224,.67 225,.33 225,.67 226,.67 227,.33 227,.67 228,.00 228,.00 228,.00 229,.00 228,.33 229,.00 230,.00 230,.33 230,.67 231..00 231,.33 231..33 231,.00 239,.33 235,.00 235,.67 236,,00 235,.00 235,,00 236,,00 236,,00 237..00 236,,67 237,.33 237,,33 237,,67 237,.00 238,.33 237,.33 237,.00 238,,67 238..00 238..33 237.,00 237..33 236.,67 236..33 236.,33 236..67 238.,00  197 .51 197,.61 197 .51 197 .51 198,.47 198,.47 199,.44 199.44 200,.30 202,.12 199,.44 202,.12 202,.98 203,.94 206,.63 206,.63 205,.67 206,.63 205,.77 206,.72 207,.59 210,.28 212,.10 212,.97 210,.28 209,.41 209,.32 212,.02 210,.19 212,.02 211,.06 211,.06 213,.77 212,.89 211,.06 211,.94 213,.77 213,,77 211,,94 211.,06 211,,06 212,,89 213,,77 213,,77 214,.72 215,,59 213,.77  RESULTS  85 .5 86 .0 86 .0 86 .5 87 .0 87 .0 87 .0 87 .0 87 .0 86 .5 86 .5 86 .0 86 .5 86 .5 86 .5 87 .0 87 .5 87 .5 87 .5 86 .5 81 .0 81 .0 82 .0 82 .5 83 .5 84 .0 85 .0 85 .5 86 .0 86 .5 87 .0 87 .5 87 .5 87 .0 86 .5 89 .5 89 .5 88 .0 88 .0 88 .0 87 .5 87 .5 87 .5 89 .0 88 .5 87 .5 88 .0  81 .5 81 .5 80 .5 80 .0 81 .0 82 .0 81 .0 80 .5 80 .5 81 .0 80 .5 79 .5 79 .5 79 .5 80 .5 80 .0 79 .5 79 .0 78 .5 79 .0 79 .5 80 .0 82 .5 81 .0 81 .5 81 .0 81 .5 81 .5 81 .5 82 .5 83 .5 83 .5 82 .5 82 .5 83 .0 83 .0 83 .0 81 .5 82 .0 82 .0 82 .5 82 .5 82 .5 81 .5 81 .5 81 .5 82 .0  214..367 214,.367 214,.367 214,.367 214,.367 214..367 215,.825 215,.825 215,.825 215..825 214,.367 214.,367 214,.367 214,,367 215..825 215..825 215,.825 215,.825 215,,825 218,,742 218,,742 218.,742 218..742 220,,200 220,.200 214.,367 214,.367 215,,825 215,.825 215,.825 215,.825 215,.825 218,.742 218,.742 218,.742 218.742 212..909 218,,742 218..742 218..742 215..825 215..825 215..825 215.,825 215..825 215.,825 212.,909  203,.339 203,.915 203,.339 203,.339 203,.775 203,.775 204,.212 204,.212 204,.072 204,.369 204,.212 204,.369 204,.228 204,.665 204..821 204,.821 204..384 204..821 204..962 205,.399 205..258 205..414 205,,710 205,.569 205,.414 205,.555 204,,976 205.,131 204,,835 205..131 204,.694 204,.694 204,,849 204,.990 204,.694 204,,554 204,.849 204..849 204..554 204,.694 204..694 204..990 204..849 204,.849 205,.286 205.,145 204..849  0,.1614 0,.1622 0,.1653 0,.1645 0,.1668 0,.1699 0,.1671 0,.1686 0..1686 0..1709 0,.1800 0..1793 0,.1800 0..1847 0..1817 0,.1810 0,.1802 0,.1817 0,.1817 0,.1759 0,.2391 0,.2193 0,.2178 0,.2124 0,.2033 0,.2197 0,.2197 0,.2126 0,.2149 0,.2111 0,.2118 0..2095 0,.2018 0,.2010 0,.2094 0,,1911 0.,2081 0.,2041 0.,2010 0..2026 0.,2080 0..2095 0.,2064 0,.1979 0..2003 0..2064 0..2198  0..0828 0,.0817 0,.0877 0,.0902 0,,0888 0,,0839 0,,0923 0,,0947 0,,0993 0,,1049 0,,0947 0.,1123 0,,1169 0,,1203 0.,1281 0,.1305 0,,1296 0,,1354 0,,1332 0,,1341 0,,1363 0,,1465 0,,1423 0,.1543 0,.1392 0,.1370 0,.1359 0,.1486 0..1406 0..1437 0,.1355 0,,1355 0..1531 0,,1484 0..1379 0.,1426 0.,1506 0.,1580 0.,1475 0.,1428 0.,1404 0., 1484 0.,1531 0.,1580 0.,1612 0.,1659 0.,1555  Appendix D. DATA AND RESULTS  DICYCLOPENTADIENE DEOXYGENATED. INITIAL CONDITIONS:  UPFRU  UHWP  2.602  2.549  TPFRU  THWP  TBPFRU  TBHWP  QPFRU  qHWP  198.33  197.47  84.0  81.0  297.48  296.91  AVERAGE CONDITIONS:  TBPFRU  TBHWP  qPFRU  qHWP  84.58  81.34  301.80  297.58  TIME  PTEMP  HTEMP  PTB  HTB  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760  197 .7 199 .0 198 .0 198 .3 197 .3 197 .0 197 .3 198 .3 199 .0 198 .3 199 .0 200 .3 201 .3 201 .7 202 .7 202 .0 202 .3 203 .3 203 .0 204 .3 205 .3 206 .3 207 .7 209 .7 210 .3 211 .3 210 .7 213 .0 212 .0 212 .0 210 .7 211 .0 211 .7 210 .3 212 .7 214 .0 216 .0 216 .3 216 .3  195 .3 194 .1 196 .9 196 .9 199 .3 197 .7 196 .2 197 .4 198 .6 198 .6 198 .2 198 .2 199 .4 199 .0 198 .7 195 .1 198 .7 197 .1 195 .6 194 .0 196 .4 199 .2 194 .1 198 .5 198 .5 199 .7 199 .7 200 .9 202 .0 203 .2 201 .7 204 .4 202 .4 202 .4 201 .2 205 .5 205 .1 206 .4 206 .4  84.0 81 .5 81 .5 81 .5 80 .0 80 .0 80 .5 80 .5 81 .5 80 .0 81 .5 80 .0 79 .0 79 .5 81 .5 81 .5 81 .0 82 .0 81 .5 82 .0 83 .0 84 .5 84 .0 86 .5 86 .0 86 .0 86 .0 87 .5 88 .0 86 .0 85 .0 86 .0 84 .0 84.0 84 .0 85 .5 87 .5 88 .5 87 .5  80 .0 79 .0 80 .0 79 .0 79 .0 78 .5 81 .5 80 .5 80 .5 80 .5 80 .5 80 .0 80 .0 79 .5 79 .0 78 .0 77 .5 77 .0 76 .0 77 .5 77 .5 78 .5 79 .5 80 .0 79 .5 80 .5 81 .0 81 .5 81 .0 81 .5 81 .0 82 .0 81 .0 78 .0 78 .0 79 .0 79 .5 79 .0 79 .0  VFP  REP  VFH  REH  0.81  9760  0.04  4.9  PHF  HHF  297.489 298..947 298..947 298..947 297..489 297..489 297..489 300,.405 300,.405 297,.489 298,.947 297,.489 300,.405 285,.823 298,.947 297,.489 301,.864 293,.114 301,.864 300,.405 301.864 300.405 300,.405 300,.405 300,.405 301,.864 300,.405 301,.864 300,.405 301,.864 300,.405 301,.864 304,.780 297,.489 303,.322 303,.322 303,.322 303..322 301,.864  300..449 300..741 300,.828 300,.828 300,.245 299,.867 299,.489 299,.198 298,.907 298,.907 298..240 298,.240 297,.949 297,.283 296,.617 297.486 296,.617 296,.241 295,.865 295,.489 294.912 294,.998 293,.211 293,.672 293,.672 293,.384 293,.384 293..096 300..332 300..040 299..662 299,.748 301,.002 301,.002 301,.294 301.758 301,.087 300..795 300,.795  PFR  HFR  -0..0022 -0..0085 0..0087 -0.,0095 0,.0054 -0..0038 0,.0065 -0..0005 0,.0101 0,.0083 0,.0090 0,,0053 0,.0084 -0..0095 0,.0079 -0.,0017 0,.0068 0,.0027 0,.0134 0,.0027 0..0087 0,.0023 0,.0202 0,.0040 0,.0229 0,.0084 0,.0431 0,.0098 0,.0210 , 0,.0112 0,.0207 0,.0013 0,.0176 0,.0163 0,.0296 0,.0132 0,.0182 0,.0118 0,.0229 0,.0019 0,.0209 0,.0109 0,.0212 0 .0168 0,.0273 -0..0015 0,.0257 0,.0110 0,.0296 0,.0128 0,.0309 0,.0139 0,.0307 0,.0122 0,.0314 0,,0150 0,.0284 0.,0107 0,.0331 0,.0134 0,.0340 0,.0104 0,.0298 0,.0162 0,.0345 0,.0110 0,.0403 0,.0209 0,.0399 0,.0165 0,.0393 0,.0269 0..0393 0,,0250 0,.0371 0,.0311 0,.0425 0,.0311  Appendix D. DATA AND  780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080  217 .3 217 .0 217 .0 217 .7 218 .3 218 .7 218 .3 219 .3 219 .3 220 .0 220 .0 220 .3 220 .3 220,.7 220 .7 221,.3 221,.0 220,.3 222,.3 221,.7 222,.0 222,.7 224,.0 223,.7 223,.3 222,.7 223,.0 220,.3 221,.7 220..7 222,.0 221,.3 220,.0 221,.3 220,.7 221,.7 221,.3 221,,7 222,.3 222.,7 222,,3 223.,0 222,.3 224,.3 223.,3 224,,3 224,,3 224,,3 219,,7 217,,7 218,,0 218..7 219,.7 219,.7 220..3 221,,0 220.,7 220.,0 220.,7 220.,0 221.,0 221.,0 221.,0 220.,3 220.,7 221.,3  208 .8 208 .8 210 .0 209 .1 209 .1 209 .1 211 .9 210 .3 210 .3 210 .3 209 .1 210 .3 210 .3 210 .3 211 .9 211 .6 211 .6 211 .6 210 .3 211 .6 213 .1 213 .1 211 .9 214 .3 214 .3 214 .3 214 .3 212 .4 212 .1 214 .5 213 .3 213 .3 215 .8 215 .8 217 .0 217 .0 217 .0 217 .0 218 .2 218 .2 218 .2 219 .5 219 .5 219 .5 221 .0 221,.0 221 .0 221,.0 222,.3 222 .3 223,.2 221,.6 221,.9 221,.9 221,.9 221,.9 223,.2 223,.2 223,.2 223,.2 223,.2 223,.2 224,,4 224,,4 224,.4 224,,4  RESULTS  88 .0 88 .5 89 .0 88 .5 88 .5 89 .5 90 .0 90 .0 90 .0 90 .5 91 .0 91 .0 91 .0 91 .0 91 .5 91 .5 91 .0 91 .0 92 .5 90 .0 89 .0 90 .0 90 .0 90 .0 89 .0 89 .0 90 .0 88 .5 88 .5 87 .0 86 .5 85 .5 83 .5 84 .5 84 .0 84 .0 84,.5 85,.5 86,.0 87,.0 88,.5 89,.0 89,.5 90,.5 90,.5 91,.5 90,.0 90,.0 81,.0 81,.0 80,.0 80,.0 80,.5 81,.0 82,.0 82,.5 83,,5 83,.5 84,,5 84.,5 85,,5 84,,5 83,,5 83.,0 82.,0 81,,0  80 .5 80 .0 80 .5 81 .5 82 .0 82 .5 83 .0 83 .0 82 .0 81 .5 81 .5 82 .0 82 .5 82 .5 83 .5 83 .5 83,.5 83 .0 82 .5 83 .0 83 .5 84 .5 84 .5 85,.0 86,.0 85,.5 86,.0 85,.5 84,.5 84,.5 83,.5 83,.0 82,.5 82,.0 82,.0 81,.0 82,.0 83,.0 83,.0 83,.5 84..5 85,.0 84,.5 84,.0 83,.0 83,.0 82,.5 82,,0 83,,0 83,,0 84,,0 84,,0 83,,5 83,.0 82,.5 82..0 81..5 81..5 81.,0 81.,0 81.,0 81.,0 80.,0 80.,5 79.,5 78.,5  301 .864 301 .864 303 .322 303 .322 300 .405 300 .405 300 .405 300 .405 301 .864 300 .405 300 .405 300 .405 300.405 301 .280 304 .780 301 .864 301 .864 300 .405 300 .405 301 .864 301 .864 304 .780 300 .405 300 .405 304 .780 303 .322 304 .780 300 .405 303 .322 294 .572 303 .322 303 .322 303,.322 304,.780 303,.322 303,.322 304,.780 304,.780 304,.780 304,.780 293,.114 303,.322 294,.572 300.405 303,.322 300,.405 304,.780 304,.780 303,.322 303,.322 303,.322 304..780 304,.780 304..780 300..405 301..864 300.405 300,.405 301,.864 304,.780 300,.405 300..405 303..322 304..780 304..780 303..322  300.209 300 .209 299 .917 300 .879 300 .879 300 .879 300 .963 300 .586 300 .586 300 .586 300 .879 300 .586 300 .586 300 .586 300 .963 300 .293 300 .293 300 .293 300 .586 300 .293 300 .669 300 .669 300 .963 300 .376 300 .376 300 .376 300 .376 299 .332 298 .664 298 .080 298 .372 298,.372 297,.787 297,.787 297 .495 297,.495 297,.495 297,.495 297,.203 297,.203 297,.203 296,.910 296,.910 296,.910 297,.283 297,.283 297,.283 297,.283 296,.991 296,.991 296..034 295..662 296,.326 296,,326 296,,326 296,,326 296,,034 296,.034 296,,034 296,.034 296,,034 296.034 295.,741 295..741 295..741 295.,741  0 .0441 0 .0414 0 .0377 0 .0415 0 .0479 0..0456 0..0429 0..0462 0 .0441 0 .0467 0..0451 0 .0462 0 .0462 0 .0461 0 .0395 0 .0458 0 .0463 0 .0462 0,.0479 0,.0518 0..0563 0..0510 0 .0617 0 .0606 0 .0564 0 .0563 0 .0520 0 .0545 0,.0547 0,.0694 0,.0624 0,.0635 0,.0657 0,.0646 0,.0662 0,.0695 0,.0646 0,.0624 0,.0630 0,.0608 0,.0723 0,.0574 0,.0666 0,.0612 0,.0536 0,.0578 0..0564 0,.0564 0,.0728 0,.0662 0,.0706 0,.0706 0..0723 0,.0706 0,.0762 0,.0745 0,.0723 0,.0701 0,,0668 0..0602 0.,0667 0..0701 0.,0690 0.,0663 0..0706 0.,0783  0,.0350 0,.0366 0,.0395 0,.0319 0,.0302 0,.0285 0,.0360 0,.0313 0,.0347 0,.0363 0,.0319 0,.0347 0,.0330 0,.0330 0,.0343 0,.0341 0,.0341 0,.0358 0,.0330 0,.0358 0,.0388 0 .0355 0,.0310 0,.0383 0,.0349 0,.0366 0,.0349 0..0317 0,.0349 0,.0439 0,.0427 0,.0444 0,.0552 0..0569 0,.0614 0..0648 0,.0614 0,,0581 0.,0627 0,,0610 0,,0576 0,,0605 0,,0622 0,,0639 0,.0720 0,.0720 0..0737 0..0754 0,,0766 0,.0766 0,.0778 0..0731 0.,0748 0..0765 0.,0782 0.,0799 0.,0863 0.,0863 0.,0879 0.,0879 0.,0879 0.,0879 0.,0960 0.,0943 0.,0977 0.,1011  Appendix D. DATA AND  2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740  221 .3 221,.3 221,.0 221,.7 221,.3 222 .0 222 .0 222 .7 220,.7 221,.0 221,.0 221,.0 220,.7 220,.7 220,.7 219,.7 221,.0 220,.7 221,.0 221,.0 220,.3 220,.3 222,,3 221,.7 221,.7 221,.7 221.,3 220,,7 221,,7 221,.3 221,,0 221.,3 220..7  224 .4 224 .4 225 .7 225 .7 225 .7 225 .7 225 .7 226 .9 226 .9 226 .9 226 .9 226 .9 226 .9 228 .2 228 .2 228 .2 228 .2 228 .2 228 .2 226 .9 226 .9 226 .9 225 .7 225 .7 225 .7 225 .7 225 .7 225 .7 225 .7 225 .7 225 .7 225 .7 225 .7  RESULTS  80,.0 80,.0 79,.5 79,.5 80,.0 80..5 81,.5 80,.5 80..5 80,.5 80,.5 80..5 80,.5 . 78, .5 77..5 78,.0 78..5 79,.5 79..5 79,.5 80,.5 80,.5 80,.5 81,.5 82,.5 82,.5 82,.5 83,.5 83,.5 84,.5 85,.0 85,.5 85..5  78 .5 79 .0 79,.0 79,.5 79,.5 80,.0 80,.5 81,.0 80,.5 81,.0 81,.0 81,.0 81,.5 82,.0 82,.0 82,.5 83,.0 82,.5 82,.5 82,.0 81,.5 81,.5 80,.5 80,.0 80,.0 79,.5 79,.5 80..0 80,.5 80,.5 81..0 81,.5 82..0  303 .322 303 .322 303 .322 303 .322 303,.322 301,.864 303 .322 301,.864 304 .780 303 .322 304 .780 304,.780 304,.780 303,.322 303,.322 304,.780 303,.322 303,.322 303,.322 306,.238 303,.322 304,.780 301,.864 301,.864 301,.864 300,.405 304,.780 303,.322 304,.780 304,.780 303,.322 303,.322 303,.322  295,.741 295,.741 295,.449 295.449 295.449 295,.449 295.449 295,.157 295,.157 295,.157 295,.157 295,.157 295,.157 294,.865 294,.865 294,.865 294,.865 294,.865 294,.865 295..157 295,.157 295,.157 295..449 295..449 295,.449 295.449 295,.449 295,.449 295,.449 295..449 295..449 295,.449 295,.449  0,.0816 0,.0816 0,.0822 0,.0844 0,.0816 0,.0844 0,.0789 0,.0866 0,.0756 0,.0789 0,.0767 0,.0767 0,.0756 0,.0844 0,.0877 0,.0805 0,.0855 0,.0811 0,.0822 0,.0777 0,.0767 0,.0745 0,.0855 0,.0800 0,.0767 0,.0789 0,.0712 0,.0679 0,.0690 0,.0646 0,.0640 0,.0635 0..0613  0,,1011 0,,0994 0,.1041 0,.1024 0,.1024 0,.1007 0.,0990 0..1020 0..1037 0..1020 0,.1020 0,.1020 0,,1003 0..1034 0,.1034 0,.1017 0,.1000 0,.1017 0,.1017 0,.0987 0.,1003 0,.1003 0,,0990 0.,1007 0,,1007 0..1024 0,,1024 0,,1007 0,,0990 0.,0990 0..0973 0,,0956 0.,0939  Appendix D. DATA AND RESULTS  RUN  211  15, HEXADECENE-1  INITIAL CONDITIONS:  UPFRU  UHWP  2.569  2.639  TPFRU  THWP  198.00  198.00  TBPFRU  TBHWP  QPFRU  QHWP  82.0  82.0  297.99  306.16  AVERAGE CONDITIONS:  TBPFRU  TBHWP  83.89  81.70  QPFRU 297.73  TIME  PTEMP  HTEMP  PTB  0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700  197,.0 197,.7 197,.7 198,.3 198,.7 199,.3 200,.0 202,.7 202,.3 203,.7 204,.3 206,.3 208,.3 209,.7 211,.0 210,,7 209,.3 211..3 214,.0 218..0 221,.0 222..7 221,,7 220,,0 214.,7 .215,,3 215.,7 216,.0 215,.7 216,,3 217,.7 218..7 237,,3 228.,3 228.,3 229.,3  198 .5 198 .3 198 .5 198 .7 198 .7 198 .7 199 .0 199 .5 200 .3 200 .4 200 .6 201 .3 201 .9 202 .3 201 .7 203 .9 202 .8 203 .4 204 .3 203 .8 205 .2 205 .3 205 .9 205 .8 207 .4 207 .6 208 .3 209 .6 210 .3 211 .2 211 .9 213 .0 213 .3 214 .7 215 .3 215 .8  86 .5 85,.0 85,.5 86,.0 85,.0 84,.5 84,.0 84,.5 83,.5 82,.5 81,.5 81,.0 82,.5 82,.5 86,.5 79,.0 80,.0 86,.0 92,.5 96,.5 94,.5 93,.5 91,.5 80,.5 79,.0 79,.5 80..5 81..5 82,.5 83..0 84,.0 85,.5 78,,5 87,,5 94,,0 95..5  QHWP 307.28  HTB 82,.0 82,.0 82,.0 82,.0 82,.0 82,.5 83,.0 83,.0 83,.0 83,.0 82,.5 81,.0 82..0 81,.5 81..0 81..0 81,.0 82.,0 82..0 83,.0 82,.0 82,,0 81..0 81,,5 81..5 81,,5 80..5 83,,0 83,,0 83,,0 81,,0 82,,0 82,,0 81,.0 80,,5 80.,5  VFP 0.81  REP 9760  PHF  HHF  298 .947 297 .489 297 .489 297 .489 298 .947 298,.947 297.489 297,.489 297,.489 297.489 298,.947 297.489 297,.489 297,.489 298,.947 298,.947 296,.031 296,.031 296,.031 279,.989 298,.947 298,.947 297,.489 297.489 298,.947 298,.947 300,.405 300,.405 300.405 294,,572 297,.489 297,.489 298,.947 303,.322 303,.322 303,.322  300,.969 300,.925 300,.969 300,.999 300,.999 300,.999 301,.102 301,.175 301,.336 301,.307 301,.351 301.438 301,.556 301,.644 301,.689 301,.524 301,.865 302,.174 302,.394 302.424 302,.792 303,,560 303,.500 303,.708 303,.764 304,.075 304..163 304.383 304..752 304,.958 305,,164 305..429 305.443 305,,618 305,,839 305,.882  VFH  REH  0.04  4.9  PFR -0,.0196 -0,.0105 -0,.0122 -0,.0117 -0,.0090 -0,.0051 0 .0007 0,.0080 0 .0102 0 .0180 0 .0216 0 .0320 0 .0337 0 .0382 0 .0272 0,.0512 0,.0476 0,.0341 0,.0212 0,.0447 0,.0339 0,.0428 0,.0483 0,.0797 0,.0646 0,.0651 0,.0607 0,.0585 0,.0540 0..0634 0,.0601 0,.0584 0..1420 0,.0750 0,.0536 0..0520  HFR 0 .0081 0 .0076 0,.0081 0 .0089 0,.0089 0,.0072 0,.0064 0,.0078 0 .0102 0,.0107 0,.0129 0,.0202 0,.0187 0,.0215 0,.0213 0,.0286 0,.0247 0,.0228 0,.0255 0,.0206 0,.0280 0,.0273 0,.0327 0,.0304 0,.0356 0,.0357 0,.0413 0,.0370 0..0387 0,.0417 0,.0499 0,.0499 0,.0509 0,.0587 0,,0618 0,,0636  Appendix D. DATA AND  720 740 760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200 1220 1240 1260 1280 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1520 1540 1560 1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040  231 .0 231 .0 233 .0 233 .3 222 .7 224 .3 226 .7 227 .3 228 .7 230 .3 228 .7 229 .7 230 .0 231 .7 233 .0 231 .0 230 .0 231 .7 232 .0 233 .0 234 .0 234 .7 235 .3 236 .3 237 .0 238 .0 239 .3 240 .0 242 .0 242 .7 242 .7 243 .7 243 .7 243 .7 244 .3 246 .3 245 .7 246 .3 245 .7 248 .7 249 .3 251 .0 247 .3 246 .0 245 .0 246 .7 246 .7 247 .7 249..7 250,.0 251 .3 248 .0 252 .3 252 .0 252,.7 253,.7 254,.7 255,.0 254,.0 255,.3 256,.3 258..0 257,.0 257,.7 258,.3 261,.3 261..0  215 .8 216 .6 217 .4 217 .9 218 .1 218 .4 219 .6 219 .3 219 .6 219 .6 220 .2 220 .3 220 .8 220 .6 221 .2 222 .0 222 .6 222 .5 222 .4 223 .3 223 .5 224 .1 224 .1 224 .4 224 .7 224 .8 224 .6 225 .6 225 .6 225 .4 225 .5 225 .4 226 .2 226 .4 226 .7 227 .0 227 .5 227 .5 227 .4 227 .9 228 .7 230 .2 232 .3 233 .1 233 .8 234 .8 236 .4 235 .6 235 .6 235,.7 235 .8 235 .4 235 .6 236 .0 235 .5 237 .1 237,.1 236,.3 236,.0 236,.2 236,.0 236,.4 236,.2 236,.7 237,.0 237,.0 236,.8  RESULTS  95,.0 94,.0 93,.0 92,.5 85,.5 79,.5 80 .5 82,.0 84,.0 86,.5 83,.5 80,.5 81,.0 81,.5 82,.5 82..0 81,.0 81,.5 82,.0 83,.0 83,.5 84,.0 84,.0 84,.0 84,.5 84,.5 84,.5 84..5 85,.0 85..5 85,.5 85,.5 85,.5 86..0 86,,5 87,.0 89,,0 90.,0 90.,0 91,.5 93,.0 91,.5 88,.0 82..0 78,,0 78,.5 78,,5 79,.0 78,,0 79..0 79,.0 79..0 80,,0 80,,0 81,,0 82,.0 82.,0 83..0 84.,0 84.,0 84.,0 85..0 79..5 79.,0 79.,0 80.,0 80.,0  81,.5 82,.0 82,.5 83,.0 83 .5 83,.0 82 .0 81 .5 80 .5 81 .5 80,.5 79 .5 80,.5 80,.0 80,.5 81,.0 80,.5 81 .0 82,.0 82 .5 82,.5 83,.5 83,.5 83,.5 83,.0 82,.5 81,.5 80,.5 79 .5 79 .0 79 .5 80,.0 80,.0 80,.5 81,.0 81,.0 81,.5 82,.0 82,.0 83,.0 84,.0 84,.0 84,.5 85,.0 86,.0 86,.0 85,.5 85..0 84..0 83..0 82,.5 81,.5 81,.5 81,.0 80,.5 82,,0 81,,5 81..5 81,,0 81,,0 80.,5 80.,0 79,.5 80,.0 81,.0 81..0 81..5  212  304,.780 304,.780 303,.322 303.322 303,.322 303..322 303,.322 303,.322 301,.864 300,.405 303,.322 303,.322 304,.780 303,.322 304,.780 288,.739 296..031 296,.031 296,.031 296,.031 296,.031 296,.031 296,.031 296,.031 297,.489 297..489 297.,489 297..489 297,.489 297,.489 297,.489 297.489 296,.031 294..572 294..572 296..031 296,.031 290,.197 296..031 291,.656 290..197 290..197 288..739 290..197 290..197 288..739 287..281 288,.739 288.739 288,.739 288,.739 279,.989 288,,739 288,,739 288,,739 290.,197 290.,197 290..197 290.,197 288.,739 288.,739 290..197 290..197 298.,947 298.,947 298.,947 304.,780  305,.882 306,.059 306,.205 306..264 306..397 306..500 306..482 306,.736 306,.839 307,.107 307,.209 307,.283 307,.342 307,.476 307,.057 307.,145 307.,172 307,.381 307..218 307,.274 307,.319 307,.331 307,.346 307,.345 307,.374 307,.359 307,.494 307..327 307,.342 307,.372 307,.267 307,.387 307,.444 307,.503 307..517 307.441 307.,573 307..499 307..514 307,.572 307,.480 307..206 306.797 306..600 306.,508 306..281 305,,992 306.,189 306.,174 306..233 306..307 306,,323 306,,352 306,.172 306,,293 306..093 306..093 306.,275 306.440 306.483 306.,514 306..527 306..573 306.452 306.,450 306..465 306.,585  0,,0570 0,.0602 0,.0723 0,.0750 0,.0630 0,.0882 0 .0926 0 .0899 0,.0900 0,.0895 0,.0893 0,.1025 0,.0996 0,.1058 0,.1045 0,.1268 0,.1141 0 .1180 0 .1174 0 .1174 0,.1191 0,.1197 0,.1219 0,.1253 0,.1234 0,.1267 0,.1312 0,.1334 0 .1385 0 .1390 0,.1390 0 .1424 0,.1450 0,.1460 0,.1465 0,.1490 0,.1400 0,.1495 0,.1366 0,.1496 0,.1495 0,.1604 0,.1626 0,.1759 0,.1862 0,.1932 0,.1961 0,.1949 0,,2053 0,,2030 0.2076 0,.2143 0,.2076 0,.2064 0,.2053 0,,2023 0,,2057 0..2034 0,,1965 0.,2041 0.,2076 0.,2069 0,,2224 0.2084 0,,2106 0..2173 0,.2046  0,,0603 0.,0608 0.,0618 0.,0617 0.,0604 0.,0629 0,.0700 0,.0703 0..0744 0,.0707 0,.0760 0,.0793 0..0776 0..0784 0..0794 0,.0801 0.,0837 0,.0813 0,.0781 0,.0792 0,.0798 0..0787 0,.0785 0,.0797 0.,0821 0.,0839 0,,0863 0.,0933 0..0964 0,.0975 0,.0963 0,,0940 0,,0968 0,,0954 0,,0948 0.,0959 0..0959 0.,0942 0.,0940 0,.0922 0..0916 0..0969 0,.1027 0,,1041 0,.1035 0,,1069 0..1142 0..1128 0.,1163 0.,1199 0,.1216 0..1234 0..1242 0.,1274 0.,1271 0.,1277 0.,1294 0.,1266 0.,1269 0.,1274 0.,1286 0.,1312 0.,1321 0.,1324 0.,1303 0. 1301 0. 1278  Appendix D. DATA AND  2060 2080 2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 2620 2640 2660 2680 2700 2720 2740 2760 2780 2800 2820 2840 2860 2880  262,.3 261,.7 261,.7 261,.3 262,.3 266,.0 266,.3 267,.0 268,.3 269,.3 269,.0 270,.7 272,.0 272,.3 273,.3 274,.0 275,.3 272,.3 277,.0 279..3 274..3 275.,3 275..0 277,,0 278.,0 278.,3 278,,7 278,,7 278,,7 278..7 279,.3 280..0 280..3 281.,0 280,.3 281.,3 282..0 282..3 283,.0 284.,7 283.,3 284..3  236 .9 237 .0 234 .7 242 .4 247 .7 249 .4 249 .5 249 .0 249 .9 249 .8 250 .5 251 .9 252 .0 252 .3 253 .2 253 .2 253 .2 253 .2 255 .2 256 .6 257 .4 257 .8 257 .9 257 .9 258 .6 259 .0 259 .4 259 .0 259 .0 259 .9 259 .8 260 .4 260 .7 260 .9 261 .0 260 .9 261 .4 261 .8 261 .6 261 .4 261 .4 260 .9  RESULTS  80,.0 79,.0 79,.0 79,.5 79,.0 79,.0 79,.0 79,.0 80,.0 78,.5 79,.5 81,.0 82,,5 83,.5 84,.5 85,.0 85,.5 86,.0 87,.0 87,.5 85,.0 82..0 81..5 81..5 82..5 82,.5 83.,0 83,,0 83.,5 83.,5 83..5 83..5 84..0 84..0 84.,5 84..5 85..0 85..0 85..5 86..0 86.,0 86..5  82,.0 82,.0 82,.5 83,.0 82,.5 83,.0 83,.0 82,.0 82,.0 81,.0 80,.0 80,.0 79,.0 79,.0 80,.0 81,.0 81,.0 81,.5 81,.5 82,.5 83..0 83..0 83,.0 82..5 82..0 82,.0 81.,5 81,,0 81.,0 81,.0 80..5 81,.0 80.,0 79,.5 79..0 80..0 81..0 82.,0 80..0 81..0 82.,0 81..0  298 .947 304 .780 296 .031 297.489 298 .947 298 .947 300 .405 296 .031 296 .031 300.405 300.405 300 .405 300 .405 300,.405 303,.322 303,.322 303,.322 306,.238 306,.238 306,.238 300,.405 300,.405 300,.405 301,.864 303,.322 303,.322 303,.322 301,.864 301,.864 301,.864 301,.864 301,.864 301,.864 301..864 298..947 301..864 301,.864 301.,864 300,,405 303.,322 300,,405 300.405  306,.480 306,.465 308,.142 310,.796 312,.342 312,.813 312,.963 313,.086 312.960 313,.066 313,.003 312,.844 312,.904 312,.827 312,.957 312..792 312..702 312..792 312,.585 312..411 312,.046 312..134 312.,013 312.,013 311..949 311,,857 311.,929 311,,931 311.,931 311..731 311..836 311..862 311..891 311.,410 311.,379 311.484 311.,361 311..359 311.405 311.,451 311.467 311.,230  0,.2207 0,.2101 0,.2278 0,,2220 0,.2240 0,.2363 0,.2343 0.2458 0.2469 0..2460 0,.2416 0..2421 0..2416 0..2393 0..2333 0..2338 0..2366 0.2192 0,.2312 0..2372 0,.2410 0..2543 0,.2549 0,,2584 0,,2553 0,.2564 0,,2558 0,,2589 0,,2573 0..2573 0.2595 0.,2617 0..2611 0.,2634 0.,2658 0.,2628 0.,2634 0..2645 0.,2682 0.,2657 0.,2676 0.,2693  0..1266 0,,1268 0,.1151 0,.1340 0,.1501 0,,1531 0..1532 0,,1546 0,,1576 0..1604 0..1657 0..1705 0.,1739 0..1751 0.,1747 0..1716 0..1718 0..1700 0..1767 0..1785 0.,1801 0..1811 0,,1818 0.,1834 0,,1872 0,,1886 0,,1914 0,,1918 0,,1918 0,.1949 0,,1961 0,,1964 0,,2004 0.,2035 0..2056 0..2019 0.,2006 0.,1986 0.,2043 0.,2004 0.,1970 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:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0058696/manifest

Comment

Related Items