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High temperature membrane bioreactor treating kraft evaporator condensate under steady and transient… Jen, Ruey-chiu 2002

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High Temperature Membrane Bioreactor Treating Kraft Evaporator Condensate Under Steady and Transient Conditions by Ruey-chiu Jen National Chiao Tung University, Taiwan, ROC, 1999 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED SCIENCE in THE FACULTY OF GRADUATE STUDIES Department of Civil Engineering We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA August 2002 © Ruey-chiu Jen, 2002 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, 1 agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia Vancouver, Canada • a t e AwyyAH W ^V0O^ • DE-6 (2/88) A B S T R A C T Research results from Berube (2000) have shown that the treatment of kraft evaporator condensate for reuse using a high temperature membrane bioreactor (MBR) is not only technically feasible, but can also be economically attractive. However, dynamics in daily operating conditions at kraft mills would result in non-steady state loadings to such a treatment system. Hence, the influence of transient operating conditions on an M B R system requires investigation before the system could be considered for full-scale plants. Two bench-scale, high temperature MBRs (called RI for Reactor 1 and R2 for Reactor 2) were operated under conditions proposed by Berube (2000) to examine system performance under steady state operation. The operating parameters selected were as follows - 38-day sludge retention time (SRT), 9-hr hydraulic retention time (HRT), and evaporator condensate that contained 1,200 mg methanol /L . During the steady state experiment, the MBRs exhibited stable removal of the main contaminants. Removal efficiencies of 95 % for methanol and 64 % for organic components expressed as total organic carbon (TOC) were observed. Observed growth yields as low as 0.037 for RI and 0.025 for R2 were found. Effects of methanol shock loadings, black liquor spills, and pulp mill shutdown on a high temperature M B R treating condensate were the focus of the present research project. The reactors were subjected to four shock loadings to investigate long-term effects, and one shock loading to identify short-term effects. i i Results showed that the high temperature MBRs were reasonably stable and able to achieve the same removal efficiency when the load was increased by 1.5 and 2 times instantaneously. Overload of methanol was observed during the methanol shock loading test with 2.5 times the regular methanol concentration. However, the system recovered 4 hours after the short-term shock loadings, and two days after the long-term shock loadings. The MBRs started to shown inhibitory effects after the long-term black liquor carryover test with 8 mL black liquor per litre condensate. During the black liquor carryover test with 16 mL black liquor per litre condensate, methanol removal efficiency was greatly decreased and this negatively influenced TOC and chemical oxygen demand (COD) removal efficiencies. However, the system recovered 4 hours after the short-term shock loadings, and two days after the long-term shock loadings. During the tests, the colour of the M B R permeates remained relatively constant while the dissolved solids concentrations of the permeates increased slightly. Methanol, TOC, and COD utilization coefficients decreased during the shutdown period. However, the M B R system recovered along with resumption of loading fairly well. The M B R was capable of handling the 10-day shutdown period and recovered in 4 days to full capacity. No deleterious effects from 10-day shutdown were observed. in T A B L E OF CONTENTS ABSTRACT ii TABLE OF CONTENTS iv LIST OF TABLES ix LIST OF FIGURES x LIST OF PICTURES xii ABBREVIATIONS xiii ACKNOWLEDGEMENT xiv CHAPTER 1 Introduction 1 1.1 Problem Definition 1 1.2 Outline of Thesis 3 CHAPTER 2 Background and Literature Review 4 2.1 Kraft Condensates , 4 2.1.1 Source of Kraft Condensates 5 2.1.2 Characteristics of Kraft Condensates 7 2.2 Requirements and Regulations for Treatment of Kraft Condensates.. ..8 2.2.1 Closed-cycle Concept in Pulp and Paper Industry 8 2.2.2 Regulation Requirements 9 iv 2.3 Alternatives for Treatment of Kraft Condensates 11 2.3.1 Steam Stripping 11 2.3.2 Aerobic Biological Treatment 13 2.3.3 Anaerobic Biological Treatment 13 2.4 Background of the Bioreactor used in this study 14 2.4.1 Membrane Bioreactor 14 2.4.2 High Temperature Membrane Bioreactor Treating Kraft Condensates 17 2.4.3 Effects of High Temperature 18 2.4.4 Effects of Long Sludge Retention Time 19 2.4.5 Transient Conditions 20 CHAPTER 3 Objectives of the Research 22 CHAPTER 4 Experimental Methods and Apparatus 25 4.1 Experimental Setup 25 4.1.1 Membrane Bioreactor 25 4.1.2 Controlled operating conditions 27 4.1.2.1 pH 27 4.1.2.2 Temperature 28 4.1.2.3 Mixing and Aeration 28 4.1.2.4 Permeate Flow 29 4.1.2.5 Trans-membrane Pressure and Crossflow Velocity 29 4.1.2.6 Sludge Retention Time (SRT) 29 4.1.2.7 Hydraulic Retention Time (HRT) 30 4.1.2.8 Nutrients 32 4.1.2.9 Sources of Sludge and Kraft Condensates 32 4.2 Experimental Design 33 4.2.1 Steady-state Tests 34 4.2.2 Methanol Shock Loading Tests '. 35 4.2.3 Black Liquor Carryover Tests 35 4.2.4 M i l l Shutdown Tests 37 4.3 Experimental and Analytical Methods 37 4.3.1 Biomass Acclimatization 37 4.3.2 Membrane Cleaning 38 4.3.3 Sampling and Sample Preparation 39 4.3.4 Analytical Methods 40 4.3.4.1 Chemical Oxygen Demand (COD) 40 4.3.4.2 Conductivity 41 4.3.4.3 Colour 41 4.3.4.4 Methanol Concentration 41 4.3.4.5 pH 42 4.3.4.6 Total Organic Carbon (TOC) Concentration 42 4.3.4.7 Solids 42 CHAPTER 5 Results and Discussions 43 5.1 Characteristics of Condensate 43 5.2 M B R Operating Parameters 44 vi 5.3 Start-Up and Steady-State Operation 44 5.3.1 Methanol Removal ...46 5.3.2 Total Organic Carbon (TOC) Removal 50 5.3.3 Mixed Liquor Volatile Suspended Solids (MLVSS) Concentrations 52 5.3.4 Summary 55 5.4 Methanol Shock Loading Tests 56 5.4.1 Methanol and TOC Removal 57 5.4.2 Colour Removal 62 5.4.3 M L V S S Concentrations 63 5.4.4 Summary 64 5.5 Black Liquor Carryover Tests 65 5.5.1 Characteristics of Condensate with Black Liquor Carryover 66 5.5.2 Methanol, COD, and TOC Removal 67 5.5.3 Colour Removal 73 5.5.4 Solids Removal and Permeate Flux 74 5.5.5 M L V S S Concentrations 75 5.5.6 Summary 76 5.6 M i l l Shutdown Test 78 5.6.1 pH and Temperature of M B R 78 5.6.2 Methanol, TOC, and COD Removal 80 5.6.3 M L V S S concentrations 81 5.6.4 Summary 82 5.7 Membrane Performance 83 vii 5.7.1 Initial Membrane Flux 83 5.7.2 Permeate Flux 83 CHAPTER 6 Conclusions and Recommendations 87 6.1 Conclusions 87 6.2 Recommendations 91 REFERENCES 94 APPENDIX 1 Characteristics of Kraft Condensate 105 APPENDIX 2 Data Collected During Steady State Experiment 107 APPENDIX 3 Data Collected During Methanol Shock Loading Experiment 116 APPENDIX 4 Data Collected During Black Liquor Carryover Experiment 124 APPENDIX 5 Data Collected During Mill Shutdown Experiment 139 APPENDIX 6 Data of Permeate Flux and Membrane Cleaning Procedure 143 v i n L I S T O F T A B L E S Table 2.1 Examples of Condensates from a Kraft Mill 5 Table 2.2 Typical Characteristics of the Kraft Condensates 7 Table 2.3 Advantages and Disadvantages of Treatment Technologies for Kraft Condensate 12 Table 2.4 Comparisons of Two Configurations of MBRs 15 Table 4.1 Composition of Nutrient Solution 32 Table 4.2 Summary of Design Parameters : 34 Table 4.3 Schedules of Methanol Shock Loading Tests 35 Table 4.4 Schedules of Black Liquor Carryover Tests 36 Table 5.1 Characteristics of Evaporator Condensate from Western Pulp Ltd. 43 Table 5.2 Characteristics of Combined Condensate from Howe Sound Pulp Ltd. 44 Table 5.3 Summary of Methanol Shock Loading Tests Results 57 Table 5.4 Characteristics of Condensate used for Black Liquor Carryover Tests 67 Table 5.5 Summary of Black Liquor Carryover Tests Results .68 Table 5.6 Temperature and pH Conditions in MBR during Mill Shutdown Test 79 Table 6.1 Summary of the results of the steady state experiment of the present study and Berube's (2000) research 87 ix L I S T O F F I G U R E S Fig. 2.1 Typical Kraft Liquor Cycle and Sources of Kraft Condensates 6 Fig. 2.2 Configurations of Conventional MBR and MBR with Immersed Membrane 14 Fig. 4.1 Schematic of Bench Scale High Temperature MBR 26 Fig. 4.2 Membrane Unit Used for Rl and Partly for R2 (Membralox IT-70) 39 Fig. 4.3 Membrane Unit Used for R2 (Membralox IT-70) 40 Fig. 5.1 Methanol Removal Efficiencies of MBRs 46 Fig. 5.2 Methanol Concentration of Influent (Condensate Feed) 46 Fig. 5.3 Methanol Concentration of Effluent 47 Fig. 5.4 Concentrations of Methanol and Total Organic Carbon in MBR During a Typical Feed Batch Cycle 49 Fig. 5.5 MLVSS Concentrations Throughout the Steady State (After Day 151) 52 Fig. 5.6 Initial Methanol Concentrations in Feed during the Methanol Shock Loading Tests 56 Fig. 5.7 Contaminants Removal Efficiencies of the MBRs over the Methanol Shock Loading Tests Period 58 Fig. 5.8 Methanol and TOC Utilization Coefficient Profiles during the First Methanol Shock-Loading Test '. 59 Fig. 5.9 Methanol and TOC Utilization Coefficient Profile during the Second Methanol Shock-Loading Test 60 Fig. 5.10 Methanol and TOC Utilization Coefficient Profile during the Third Methanol Shock-Loading Test 61 Fig. 5.11 Colour of the MBRs Permeate and Condensate (Influent) over the Methanol Shock Loading Tests Period 63 Fig. 5.12 MLVSS Concentrations during the Methanol Shock Loading Tests 64 Fig. 5.13 Black Liquor Concentrations during the Black Liquor Carryover Tests 66 Fig. 5.14 (a) (b) Methanol and TOC Concentrations Profiles during the Black Liquor Carryover Tests 69 Fig. 5.15 Methanol, TOC, and COD Utilization Coefficients Profiles during the First Black Liquor Carryover Test 70 Fig. 5.16 Methanol, TOC, and COD Utilization Coefficients Profiles during the Second Black Liquor Carryover Test 70 Fig. 5.17 Methanol, TOC, and COD Utilization Coefficients Profiles during the Third Black Liquor Carryover Test 71 Fig. 5.18 Methanol, TOC, and COD Utilization Coefficients Profiles during the Fourth Black Liquor Carryover Test 72 Fig. 5.19 Colour of the MBRs Permeate and Condensate (Influent) over the Period of Methanol Shock Loading Tests 73 Fig. 5.20 Volatile and Total Solids Concentrations of the MBR Permeates over the Black Liquor Carryover Testing Period 74 Fig. 5.21 MLVSS Concentrations Profiles during Black Liquor Carryover Tests 76 Fig. 5.22 Temperature Profile during the Mill Shutdown Test 79 Fig. 5.23 pH Profile during the Mill Shutdown Test 80 Fig. 5.24 Methanol, TOC, and COD Utilization Coefficients Profiles over the Mill Shutdown Test Period 81 xi Fig. 5.25 MLVSS Concentration in the MBR during the Mill Shutdown Test Period 82 Fig. 5.26 Permeate Flux ofRl 84 Fig. 5.27 Permeate Flux of R2 85 L I S T O F P I C T U R E S Picture 4.1 Bench Scale High Temperature MBR 27 xii A B B R E V I A T I O N S ACGDH American Conference of Government and Industrial Hygienists BOD Biochemical oxygen demand B O D 5 Biochemical oxygen demand (5 day) C H 3 S H Methyl mercaptan COD Chemical oxygen demand DMDS Dimethyl disulfide DMS Dimethyl sulfide DO Dissolved oxygen EPA Environmental Protection Agency FTOC Filtered total organic compound H 2 S Hydrogen sulfide HAP Hazardous air pollutant HRT Hydraulic retention time M A C T Maximum achievable control technology M B R Membrane bioreactor MLSS Mixed liquor suspended solids MLTSS Mixed liquor total suspended solids M L V S S Mixed liquor volatile suspended solids NCASI National council of the Paper Industry for Air and Stream Improvement RSC Reduced sulphur compound SRT Sludge retention time TDCS Total dissolved and colloidal solids TOC Total organic carbon TS Total Solids TVDCS Total volatile dissolved and colloidal solids TVS Total volatile solids V O C Volatile organic compound xii i A C K N O W L E D G E M E N T I would like to acknowledge the following individual for their contributions to the completion of this work and my Master degree: • For initiating and funding the research project, I would like to thank my advisor, Dr. Eric Hall. Especially, I would like to express my appreciation for the guidance and moral support throughout this study. • For his careful review and insightful suggestions, Jim Atwater, Civi l Engineering, U B C . • I would like to thank Dr. Pierre Berube for his patient guidance and helpful suggestions for the operation of the reactors and the direction of my research. • For their technical support and expertise, I would like to thank Paula Parkinson and Susan Harper in UBC's Environmental Engineering Laboratory. Especially, their creative solutions for my experimental problems have helped me survive through many difficult times. • I would like to thank Scott Jackson, Douglas Hudniuk, Harald Schrempp, and Peter Taylor for their assistant and their abilities to bring my draft ideas to reality. • For assisting in the tedious task, providing company in the lab, and being there when things did not go as smoothly as expected in the lab, I would like to thank Worapol, Rahul, Mete, and Ar i . • Finally, to my love, friends, and family, a huge thank-you for putting up with me (especially during the experimental period), listening to me ramble about my project, and encouraging or comforting me whatever needed. xiv Chapter 1 Introduction 1.1 Problem Definition Under the driver of stricter regulations and public concern on environmental issues, the pulp and paper industry is looking for solutions to achieve the goal of zero effluent discharge with requirements as follows. First, the technology must be able to treat a large volume of selected waste stream and diminish the use of fresh water, and thus minimize the volume of liquid effluent. Second, the system has to be able to reduce air pollutant emissions to the ambient environment. Third, the treatment process should be cost-effective and be able to attain the required efficiency under various operating conditions. Fourth, reuse of the treated wastewater should not significantly decrease the quality of the pulp mill products. Therefore, reuse of selected process waters with separate treatment is considered as one of the solutions and has been practiced in many mills. For kraft mills, condensate, the condensed vapours produced through the chemical recovery process, is one of the potential process waters for recycle and reuse. Kraft condensates are typically divided into foul condensate and clean condensate. Under current operation, kraft mills typically reuse the 30 to 50% of clean condensate and sewer the remaining portion to be treated in a combined mill effluent treatment system (NCASI, 1995). Some mills also steam strip foul condensate before treatment to minimize potential hazards to ambient air quality (NCASI, 1994a). 1 Steam stripping is the technology most commonly used to treat the foul condensate (NCASI 1994a). However, the associated high expense for energy encourages the industry to consider alternative technologies that can minimize the presence of organic and particulate material in the process water, maximize the energy recovery, and significantly reduce the cost (Farr et al, 1993). Among the potential treatment technologies for kraft condensate, the high temperature aerobic membrane bioreactor (MBR) has been identified as one of the most promising novel technologies (Berube, 2000). An M B R is a modified activated sludge system whose clarifier is replaced by an ultrafiltration membrane unit and thus is able to achieve a zero-suspended solids effluent. For treatment of kraft condensates, a high temperature M B R has the advantages of good effluent quality, compact footprint, good energy recovery, and potentially low operating cost. However, an industrial biological treatment system usually suffers from frequent and severe variations in influent, both by volume and organic loads. Therefore, it's important to investigate the performance under transient conditions that a high temperature M B R may face. The present research project continues the research effort initiated by Berube (2000) at the University of British Columbia's Pulp and Paper Centre. It was aimed to examine further the performance of an M B R under steady and transient conditions while treating kraft evaporator condensate. 2 1.2 Outline of the Thesis This thesis consists of six chapters. Background literature review related to treatment of kraft condensate, membrane bioreactor technology, and shock loading research, is discussed in the Chapter 2. Chapter 3 outlines the objective of the present research project. A complete description of the experimental program and methods is provided in Chapter 4. Chapter 5 presents a summary of the experimental results and discussions, while detailed results are provided in the Appendix. Conclusions and recommendations for further work are given in Chapter 6. 3 Chapter 2 Background and Literature Review 2.1 Kraft Condensates Pulping refers to the process by which wood is reduced to fibrous material (Smook, 1992). Generally, pulping methods can be divided into mechanical, chemical, and semi-chemical methods. The kraft pulping process is a chemical process that cooks the wood chips in a solution of sodium hydroxide and sodium sulfide at elevated temperature and pressure, and it has been dominant in North America since the 1950s. In the kraft pulping process, condensed vapours, referred to as condensate, are produced mainly from the digester and the evaporator. From the sources, kraft condensates are simply classified into digester condensate and evaporator condensate. According to the chemical content, condensates are typically also segregated into clean condensates and foul condensates. Clean condensates contain fewer volatile organic compounds (VOCs) and are typically clean enough to reuse without treatment. Foul condensates typically represent 30 % - 40 % of the total evaporator process condensate flow, but contain 80 % of the methanol and 98 % of the reduced sulphur compounds (RSCs) (Blackwell, 1979). In some literature, condensates fall into three levels depending on chemical oxygen demand (COD) content: fairly clean, medium strength, and contaminated. Average volume and COD concentrations of condensates are shown in Table 2.1 (Danielsson and Hakansson, 1996). 4 Table 2.1 Examples of Condensates from a Kraft M i l l (Adapted from Danielsson and Hakansson, 1996) Fraction Condensate (mVADT*) COD (mg/L) Fairly Clean 5.0 200-400 Medium strength 4.0 1,500-2,000 Contaminated 1.1 10,000-15,000 * ADT - air-dried tonne pulp 2.1.1 Sources of Kraft Condensates The typical kraft pulping process and sources of condensate are illustrated in Figure 2.1. During the cooking process, white liquor, which contains sodium sulphide (Na2S) and sodium hydroxide (NaOH), are mixed with wood chips in the digester to dissolve the lignin from individual wood fibers. VOCs released by the chemical oxidation reactions are condensed and form condensates in the turpentine decanter and blow tank, depending on the cooking methods (batch or continuous). The cooked pulp mixtures are subsequently divided into pulp and spent cooking liquor, referred to as weak black liquor. The pulp is further processed into various paper products. To recover the cooking chemicals to be reused, the weak black liquors are concentrated by evaporation and condensates are produced throughout the recovery process. 5 BLACK LIQUOR - Alkali Lignin - Hydrolysis Salts - Sulphonation Products WHITE LIQUOR - N a O H - N a 2 S Heat GREEN LIQUOR w - Na2C03 - N a 2 S Makeup Chemicals CaO Figure 2.1 Typical Kraft Liquor Cycle and Sources of Kraft Condensates (Adapted from Smook, 1992, and Mimms, 1993) 6 2.1.2 Characteristics of K r a f t Condensates Condensates are mainly water, but contain a number of volatile and semi-volatile compounds. Some non-volatile compounds, such as resin acids and salts, are present in the condensates usually as a result of physical entrainment of weak black liquor (Blackwell, 1979). Typical values for the concentrations of the main contaminants of concern are listed in Table 2.2. Table 2.2 Typical Characteristics of the Kraft Condensates (Adapted from Blackwell, 1979) Compounds (mg/L) Evaporator Batch combined Digester condensate Condensate Methanol 180-700 250-9100 Reduced Sulphur Compounds Hydrogen Sulphide (H2S) 1-90 1-230 Methyl Mercaptan (CH 3SH) 1-30 40-340 Dimethyl Sulphide (DMS) 1-15 40-190 Dimethyl Disulphide (DMDS) 1-50 2-210 Total Organic Content (as BOD5) 60-1,100 720-9,200 Suspended Solids 30-70 PH 9.2-9.6 6.0-11.1 Depending on the wood species, pulping process and equipment configuration (digester, evaporator, and the presence of turpentine recovery system), the characteristics of Kraft condensates vary. However, methanol and reduced sulphur compounds (RSCs) are always the main contaminants of concern of all. 7 Methanol (CH 3 OH) contributes more than 80 % of the condensate B O D 5 and 95 % of the organic material (Blackwell, 1979; Hrutfiord et al, 1973). One gram of methanol accounts for 1.5 g of chemical oxygen demand (COD) and approximately 1.1 g of biochemical oxygen demand (BOD) (Gay, 1974). Hydrogen sulphide (H2S), methyl mercaptan (CH3SH), dimethyl sulphide ((CH 3) 2S or DMS), and dimethyl disulphide ((CH3)2S or DMDS) are the four major volatile sulphur compounds in Kraft condensates. They are responsible for most of the strong odour and 75 % to 95 % of the toxicity of condensates (Environment Canada, 1979; Blackwell, 1979). Other alcohols, ketones, small quantities of phenolic substances, and turpenes are the remainders. Turpenes are a problem in softwood cooking. They can represent a substantial portion of the condensate BOD i f a turpentine recovery system is not used (NCASI, 1995). 2.2 Requirements and Regulations for Treatment of Kraft Condensates 2.2.1 Closed-cycle Concept in Pulp and Paper Industry The closed-cycle concept was initially proposed by Rapson (1967). It refers to a pollution control practice that minimizes the liquid effluent by recycle and reuse of the process water. While a closed cycle mill minimizes the impact on the surrounding environment, it 8 also faces a number of challenges, including process operation and maintenance, product quality, and technical and economic feasibility. Increased heat content, contaminant concentrations, changes in pH and microbial growth in the process lines may result in a variety of detrimental process and product effects (Johnson et ah, 1996; Kotila and Estes, 1994). Therefore, research regarding closed cycle generation currently focuses on separation technology to remove trace contaminants from process water in order to reduce the effects of reusing process water on the pulp and paper industry. 2.2.2 Regulation Requirements Ambient air quality in and around pulp and paper mills has gained increasing attention and has been controlled by standards recommended by the American Conference of Government and Industrial Hygienists (ACGIH, 1999). For the pulp and paper industry, methanol, H 2 S, and C H 3 S H concentrations should be lower than 200, 10 and 0.5 ppm respectively. According to the Cluster Rule promulgated by the U.S. Environmental Protection Agency (EPA), air emissions and effluent discharges from the pulp and paper industry are under stricter control (Vice and Carroll, 1998). Based on the maximum achievable control technology (MACT), the Cluster Rule offers several alternatives for the control of kraft condensate listed below. • Recycle condensates to a controlled process equipment. 9 • Steam stripping the condensates and destroy the hazardous air pollutants (HAPs) by incineration. Or other control devices can achieve the same requirement. • Transport the condensate by a sealed pipe and a submerged inlet to a properly monitored combined mill effluent biological treatment system. The steam stripping (or other devices) option has to achieve a removal efficiency that will result in: (1) removal of at least 92 % of the methanol (or total HAPs) by weight, (2) reduction of methanol (or total HAPs) to 330 mg/L for bleached mills and 210 mg/L for unbleached mills, (3) removal to 5.1 kg and 3.3 kg methanol (or total HAPs) per tonne of pulp produced for bleached mills and unbleached mills. For the option of treatment by the combined mill effluent biological treatment system, 82 % of methanol (or total HAPs) removal by weight has to be attained. In addition, the "Clean Condensate Alternative" of the Cluster Rule offers the mills another option. To qualify for this alternative, a mill must demonstrate that the same level of methanol (or HAPs) reduction as described above will be achieved by reusing the condensate with pre-treatment. The baseline emissions, emission reductions, and test procedures are determined on a case-by-case basis. Reusing the condensates under the Clean Condensate Alternative may require the methanol concentration in the treated condensate to be 20 mg/L based on rough estimation since it's site-specific (Barton et al, 1998). The National Council of the Paper Industry for Air and Stream Improvement (NCASI, 1994a) recommends the 10 concentrations of methanol and suspended solids in the condensates should be less than 20 mg/L for reuse purpose. 2.3 Alternatives for Treatment of Kraft Condensates Steam stripping, aerobic biological treatment, and anaerobic biological treatment are the three main methods investigated for treatment of Kraft condensates. The advantages and disadvantages of the three treatment methods are summarized in Table 2.3. 2.3.1 Steam Stripping Steam stripping is the main technology currently used in the treatment of kraft condensate in North America (NCASI, 1994b). The efficiency of steam stripping on methanol removal depends on the steam to condensate ratio, condensate hydraulic retention time, and methanol transfer rate from the liquid phase to the vapour phase that is proportional to the methanol concentration in the condensate. However, the steam to condensate ratio and the associated cost increase significantly i f more than a 75 % methanol removal efficiency is required (Zuncich et al, 1993). In addition, steam stripping is less effective for methanol removal from clean to moderate strength condensate. 11 Table 2.3 Advantages and Disadvantages of Treatment Technologies for Kraft Condensate Treatment Methods Advantages Disadvantages Steam Stripping • achieve 75 % methanol removal and 95 % of RSC removal by a steam to condensate ratio of 8 % by weight (McCance and Burke, 1980). • system performance is well understood at full-scale treatment of kraft condensate. • pre-cooling isn't required before treatment. • can use waste heat from the blow heat recovery system as an alternative steam source. (Fair et al, 1993). • is not able to remove non- or semi-volatile contaminants or particulate material (Berube, 2000). • may need significant modifications to existing mill configuration (Fair et al., 1993;NCASI 1994b). • cost increases significantly if more than 75 % of methanol removal efficiency is required. (NCASI 1994b). • 20 % of Kraft mills which use a steam stripper exceed the EPA methanol concentration limit (NCASI, 1994b). Aerobic Biological Treatment • achieve higher contaminant removal efficiencies. • potentially lower operating cost. • aeration of system is able to oxidize and strip RSCs. Emission can be minimized if designed as a closed system. • Pre-cooling is required for most of the systems. • generally higher solids content in the effluent and poor sludge settling characteristics at higher operating temperature (Barton et al., 1998; Milet, 1998) Anaerobic Biological Treatment • moderate contaminant removal efficiencies. • potentially lower operating cost than aerobic biological system since aeration is not needed. • unstable removal efficiency and a long lag period after shutdown (Pipyn et al., 1987;Qiue/a/., 1988). • may require pre-stripping to ensure stable performance (Pipyn et al., 1987; Yamaguchi et al, 1990) • limited information concerning the removal of RSCs. • varied solids concentrations in the effluent were observed in different systems and fluctuated with system performance (Barton et al, 1998; Yamaguchi et al, 1990; Qiu et al, 1988). 12 2.3.2 Aerobic Biological Treatment Aerobic biological treatment systems have been considered as a potential treatment method for kraft condensate. Barton et al. (1998) reported that higher methanol and COD removal efficiencies were observed in a completely mixed activated sludge system than in an the anaerobic up-flow sludge blanket system, when the two systems were subjected to 0.88 BOD/g mixed-liquor volatile suspended solids (MLVSS) • day. However, higher RSC and trace HAP removal efficiencies reported in the aerobic system may be mostly due to stripping and abiotic oxidation (Milet, 1998; Mahmood et al., 1999; Berube, 2000). Another main benefit of aerobic biological treatment systems is their resistance to toxic substances or shock loads, which is very beneficial to full-scale operation (Sierra-Alrarez etal, 1994). 2.3.3 Anaerobic Biological Treatment A number of anaerobic biological systems treating kraft condensate have been investigated. Up-flow sludge blanket system, fluidized bed system, fixed bed system, and suspended carrier system are the representative systems (Qiu et al, 1998; Norman, 1983; Pipyn et al, 1987; Yamaguchi et al, 1990; Welander et al, 1999). Generally, aerobic systems showed better contaminant removal efficiency than anaerobic systems. 13 2.4 Background of the Bioreactor used in this study 2.4.1 Membrane Bioreactor The membrane bioreactor (MBR) was first developed in the 1970s (Smith et al., 1969) because activated sludge systems often suffered from problems with poor sludge settlement and high solids contents in the effluent. Therefore, the clarifier in a conventional activated sludge system was replaced with an ultrafiltration membrane to improve liquid-solid separation. Bioreactor Membrane Permeate Conventional MBR Membrane Permeate —9r Bioreactor MBR with Immersed Membrane Figure 2.2 Configurations of Conventional M B R and M B R with Immersed Membrane As presented in Figure 2.2, there are two general configurations of MBRs, conventional M B R or M B R with immersed membranes. Either approach has advantages and disadvantages, as shown Table 2.4. In a conventional M B R , mixed liquor is pumped to an external membrane unit at high velocities and trans-membrane pressures. In an M B R 14 with an immersed membrane, a vacuum pump is used to draw permeate from the membrane unit that is immersed in the reactor tank. Table 2.4 Comparisons of Two Configurations of MBRs (Adapted from Cho and et al, 1999) Characteristic Conventional M B R M B R with immersed membrane Flux Moderate Low Fouling Control Less Difficult Difficult Energy use High to low Moderate Retrofit Easy Less easy Flexibility Good Limited A n M B R has a number of advantages over conventional aerobic biological treatment systems, summarized below. • M B R achieves complete retention of biomass and suspended solids. As a result, very high biomass concentrations ranging from 10,000 to 30,000 mg M L V S S / L can be maintained in an M B R (Krauth and Staab, 1993; Dufresne et al, 1998; Sato and Ishii, 1991; Magara and Itoh, 1991). • High M L V S S concentration in a M B R allows the system to perform well under high organic loading rates. Therefore, a relatively small system size is needed. Moreover, the absence of the clarifier further reduces the footprint of an M B R required (Zaloum et al, 1994; Thomas et al, 2000). • Separate control of the hydraulic retention time (HRT) and the sludge retention time (SRT) allows the system to be operated under better control to reduced sludge production and to achieve greater contaminant removal (Dufresne et al, 1998; Trouve etal, 1994). 15 • Retention of particulate and high molecular weight organics provides increased opportunity for biodegradation and good removal efficiency (Onysko, 1992). • The high shear environment found in the recirculation line of the MBRs can lower the average particle size in the MBRs (Bailey et al, 1994), and is believed to enhance the mass transfer to the biomass and improve the contaminant removal rate. • A n M B R is flexible to various operating parameters, such as high temperature and long SRT, without the need of concern for possible poor sludge settling (Onysko, 1992). • Expansion or retrofit of the M B R system is relatively easy and flexible (Onysko, 1992). However, a major concern with M B R technology is fouling control (Berube, 2000; Ragona, 1998). Under liquid-solid operation of a M B R , permeate (primary solute and dissolved materials) pass through the membrane, and rejected materials, including microorganisms and particulates, accumulate at the membrane surface as a "gel layer". Since the layer increases the resistance to permeation, the permeate flux decreases as the thickness of the layer increases, and finally fouling of the membrane unit occurs (Sato and Ishii, 1991; Yamamoto et al, 1989; Shimizu et al, 1993; Rebsamen et al, 1987). Membrane type, operating conditions (trans-membrane pressure, crossflow velocity, turbulence, and etc.), and solution characteristics are the main factors affecting the rate of fouling (Fane, 1987). High M L V S S concentration in the M B R is considered to increase 16 the fouling problem since high solids concentration in the solution may result in higher rate of solids transfer from the solution to the membrane surface and further decrease the permeate flux (Magara and Itoh, 1991; Reismeier et al, 1987). However, some research has indicated that the M L V S S concentration may have no effect on the permeate flux i f turbulent conditions are maintained over a membrane surface (Lubbecke et al., 1995; Ben Aim, 1999; Nagaoka et al, 1996; Sato and Ishii, 1991; Magara and Itoh, 1991). 2.4.2 High Temperature Membrane Bioreactor Treating Kraft Condensates The ability of aerobic biological treatment to treat kraft condensate has been proven (Milet, 1999; Berube, 2000). Among all the aerobic treatment systems, Berube (2000) suggested that high temperature M B R has the highest potential for treatment of kraft condensate for reuse. Over 99 % of the methanol and approximately 93 % of the organic contaminants contained in the influent evaporator condensate, measured as TOC were removed by a high temperature M B R during the experimental period. However, reduced sulphur compounds were removed mostly due to stripping (Milet, 1999; Berube, 2000). From the experimental results, Berube (2000) suggested that the combined capital and operating costs for a high temperature M B R were estimated to be 40 % to 50 % less than those for a steam stripping system, while an M B R is capable of achieving a higher contaminant removal efficiency than a steam stripping system. This indicates that high temperature M B R is technically feasible, more effective, and more economical than steam stripping for the treatment of kraft condensate for reuse. 17 Aeration causes stripping of HAP and foul odorous compounds from the aerobic biological treatment system. An M B R can be designed as a closed system and emissions of HAP and temperature fluctuations can be minimized for system stability (Krauth and Staab, 1993). 2.4.3 Effects of High Temperature The M B R used in the present study was operated at constant 60 °C. High temperature aerobic biological treatment is reported to have higher contaminant removal efficiencies and poor sludge settling ability (Allen and Tripathi, 1998; Flippin and Eckenfelder, 1994; LaPara and Alleman, 1999). However, the drawbacks of high temperature operation can be overcome by an M B R because of the complete retention of suspended solids. In addition, permeate flux increases at high temperature. Moreover, no cooling is required before treatment of kraft condensate and the heat content can be recovered because the temperature of kraft condensate typically ranges from 55 to 70 °C (Zuncich et al, 1993). Research has indicated that a combined effect of an increase of oxygen transfer coefficient and a decrease of oxygen saturation concentration with an increase of temperature resulted in a constant oxygen transfer rate regardless of the operating temperature (Vogelaar et al, 2000; Berube, 2000). 18 Research has indicated that a combined effect of an increase of oxygen transfer coefficient and a decrease of oxygen saturation concentration with an increase of temperature resulted in a constant oxygen transfer rate regardless of the operating temperature (Vogelaar et al, 2000; Berube, 2000). 2.4.4 Effects of Long Sludge Retention Time From previous research, low surplus sludge production and low oxygen uptake rate have been observed for a biological treatment system with long sludge retention time (SRT) (Berube, 2000; Rosenberger et al, 1999). Rosenberger et al. (1999) concluded that the M B R with a highly concentrated sludge is limited by organic carbon, not by oxygen. Nevertheless, it should be noticed that the increasing biomass concentration could influence the oxygen transfer rate of the system. Therefore, it is necessary to select high performance systems with adjustable energy input to maintain oxygen concentration in an M B R system (Wangner et al, 1999). Most MBRs are operated with partial removal of excess sludge. Recently, some researchers have reported that a zero surplus sludge production can be achieved by long, even infinite, SRT and F / M ratios as low as 0.1 kg COD / kg M L V S S • day (Rosenberger, 1999). However, the results published in the literature contradict each other (Chaize and Huyard, 1991; Canales et al, 1994; Muller et al, 1995) and further research needs to be done. A n M B R without removal of excess sludge can largely reduce the costs of sludge disposal and is more economically attractive. 19 2.4.5 Transient Conditions Dynamics in daily operating conditions at kraft mills result in non-steady state loadings to a wastewater treatment plant, with respect to volume, strength, and unexpected incidents such as spills. In addition, mill shutdowns may have deleterious effects on a biological treatment system. Therefore, the ability of a treatment system to cope with shock loads and mill shutdown is an important criterion for evaluating its suitability for full-scale implementation. Rosenberger et al. (1999) concluded that no problems due to shock loading would be considered likely in a M B R that has a long SRT and a high biomass concentration. However, the influence of transient operating conditions on the system hasn't been fully investigated and further research is required prior to applying the system into full-scale plants. Organic shock loads may be of at least two types: either a short-term transient that only lasts a few hours, or a longer-term change of days to weeks before reversion back to the original operating conditions. The microbial responses to short-term and long-term transients are expected to be identical in the first few hours to days; the biomass is expected to reach a new steady state after a long-term shock (Nachaiyasit and Stuckey, 1997a). 20 After discussions with Dr. Barton (Doug Barton, NCASI, 2001) and Ms. Taylor (Taylor J., 2001, Western Pulp Limited Partnership, Squamish, Canada), three scenarios for possible shock loads associated with treatment of kraft condensates are chosen to be investigated in this study. They are methanol shock loads, black liquor carryover, and mill shutdown. 21 Chapter 3 Objectives of the Research Following Berube's research (2000), the main objective of the present study is to improve the understanding of performance of the high temperature M B R treating kraft evaporator condensate and the applicability of the system to full-scale plant operation. The ability of high temperature M B R to treat kraft mill evaporator condensate has been proven by Berube (2000) who concluded: the optimal operating temperature and pH for a high temperature M B R are 60 °C and neutral respectively; 99 % methanol removal and 90 % TOC removal were observed during the treatment of kraft evaporator condensate by M B R . However, the M B R used in his study was operated under low mixed liquor volatile suspended solids (MLVSS) concentration (2500 mg /L while commonly achievable M L V S S concentration in a M B R is 10,000 to 30,000 mg/L) and low methanol loading (900 mg methanol/L condensate and 18-hr hydraulic retention time). Therefore, a steady state experiment was proposed to examine the performance of the high temperature M B R under the operating conditions proposed by Berube (2000) for a full-scale M B R system. Based on the results of Berube's study (2000), the operating parameters for the steady state experiment for the present study were selected as following: 38-day sludge retention time (SRT) and 9-hr hydraulic retention time (HRT) with kraft evaporator condensate that contained 1,200 mg methanol /L condensate. An in-mill process water treatment plant would have to cope with non-steady state loadings resulting from the dynamic operating conditions at kraft mills. The volume and 22 strength of the wastewater, and unexpected incidents such as spills may have deleterious effects on the biological treatment process. In addition, the treatment system may need a long periods of start-up time after mill shutdowns for maintenance. Therefore, the ability of a treatment system to achieve satisfactory removal efficiency following shock loads and after mill shutdown is an important criterion for evaluating its suitability for full-scale implementation. The effects of transient operating conditions on the high temperature M B R system performance are the other main interests of the present study. Considering the possible transient conditions that might cause upset of a treatment system in a kraft pulp mill, the present study proposed to investigate the effects of methanol organic shock loadings, black liquor carryover, and mill shutdown on the performance of high temperature M B R . In summary, the objectives of the present research are listed below. 1. Investigate the performance of a bench-scale, high temperature M B R treating kraft mill evaporator condensate, with respect to removal efficiencies of methanol and total organic carbon (TOC), and biomass concentration in the M B R . 2. Identify the effects of methanol shock loadings on the performance of the high temperature M B R . 23 3. Determine the effects of black liquor carryover on the performance of the high temperature M B R . 4. Evaluate the capability of the high temperature M B R to cope with a mill shutdown and to recover in a reasonable time frame. 24 Chapter 4 Experimental Methods and Apparatus 4.1 Experimental Setup 4.1.1 Membrane Bioreactor A schematic of the two MBRs used for the study is presented in Figure 4.1. Each membrane bioreactor consisted of an aerated reactor tank and a ceramic tubular ultrafiltration membrane. A progressive cavity pump (Moyno Model SP 33304) continuously circulated the mixed liquor through the membrane module and forced solid-liquid separation under trans-membrane pressure (30 psi, 200 kPa). Permeate from the membrane unit, controlled by level control devices, was wasted or recycled back to the reactor to maintain liquid volumes. Two bench scale reactor tanks, both with 1.8 litre working volumes, were used and are shown in Picture 4.1. They were constructed of stainless steel and insulated to minimize temperature fluctuations. Ceramic ultrafiltration membrane units (Membralox 1T1-70 bench scale filtration unit: 7mm ID, 0.0055 m surface area, 500 angstrom pore size) were selected because of their proven sustainability under extreme operating conditions such as high temperature (Berube, 2000). 25 Solenoid Valve Treated Effluent Recycling Pump Heating Plate Temperature Controller Recycle Line — Permeate Electrical Line — " Fluid (Feed, Nutrient, and NaOH) Line Figure 4.1 Schematic of Bench Scale High Temperature M B R 26 Picture 4.1 Bench Scale High Temperature M B R 4.1.2 Controlled operating conditions 4.1.2.1 p H The pH of the mixed liquor in the M B R was controlled by a pH controller that added 2% sodium hydroxide solution automatically when pH was lower than the set point, 6.5. 27 4.1.2.2 Temperature The temperature of the mixed liquor was maintained at 60 °C by a temperature controller and a heating plate. The reactor tank and the heating plate were placed inside a box constructed of insulation board to further minimize the temperature fluctuations. Moreover, before feeding, evaporator condensate was pre-heated until the temperature was equal to that of the operating temperature of the M B R . Therefore, the temperature fluctuation of the mixed liquor was controlled within ± 2 °C of the set point. 4.1.2.3 Mixing and Aeration According to Berube (2000), to maintain non-limiting dissolved oxygen (DO) conditions, an aeration rate of 0.5 L/minute in the bench scale M B R was required as used for the present study. Non-limiting dissolved oxygen (DO) conditions were assumed when the zero order coefficients for the biological methanol removal were relatively constant. Due to the instability of the available DO probe at elevated temperatures, the DO concentrations in the M B R could not be continuously monitored. Hence, the DO probe was used only during the setup period to ensure non-limiting DO conditions in the MBRs. A 0.5 L/minute of airflow was chosen and provided through a fine bubble diffuser in each reactor tank. 28 Mixing was provided by high the circulation rate between the reactor and the membrane component, and through aeration. 4.1.2.4 Permeate Flow The permeate flow rate from both systems was monitored daily by collecting permeate in a graduated cylinder and calculating the volume filtered as a function of time. 4.1.2.5 Trans-membrane Pressure and Crossflow Velocity The trans-membrane pressure on each system was maintained at 200 kPa (30 psi) and volumetric flow through the filter cartridge was controlled at 7 L/min to provide a crossflow velocity of 3 m/s at the membrane surface. The pump motor speed and the flow restriction valve on the downstream end of the recycling line of each M B R were adjusted daily to maintain these constant operating conditions. 4.1.2.6 Sludge Retention Time (SRT) Commonly biomass concentrations in an M B R range from 10,000 to 30,000 mg/L (as mixed-liquor suspended solids, abbreviated as MLSS), and these high biomass concentrations allow high loading rates to MBRs. Therefore, relatively small reactor volumes wil l be required. During Berube's (2000) study, an observed growth yield of 0.2 and a biomass concentration of 2500 mg mixed-liquor volatile suspended solids 29 (MLVSS) per litre were measured when the sludge retention time was maintained at 20 days. Based on the result of Berube's (2000) research, a 38 day SRT was chosen for the present study, in order to achieve a M L V S S concentration of 10,000 mg/L. However, the effect of increasing the SRT on the observed growth yield wasn't considered in this calculation. The solids retention time in each reactor was controlled by the wastage rate under steady state conditions. A 38-day SRT corresponded to 47 mL of daily wastage from the mixed liquor in each reactor. 4.1.2.7 Hydraulic Retention Time (HRT) Because semi-continuous operation can provide more information about removal kinetics than experiments performed under strict continuous flow conditions, the MBRs were operated in a semi-continuous mode by feeding a mixture of evaporator condensate and nutrient, once every two hours. The feeds of evaporator condensate and nutrient were pumped by Masterflex pumps to a 2-litre stainless steel tank. Then, the mixture was pre-heated for approximately 30 minutes with a stainless steel heating coil until the temperature was approximately equal to 60 °C. Subsequently, a solenoid valve, located at the bottom of the pre-heating tank, opened automatically to allow the mixture to flow into the M B R . 30 A hydraulic retention time of 9 hours was selected to achieve 95 % methanol removal efficiency, according to the specific methanol utilization coefficient estimated by Berube (2000). To maintain the selected HRT, a level control switch maintained a constant mixed liquor volume in each reactor tank. It directed the treated effluent (permeate) to a drain when the liquid volume in the reactor tank was above the setpoint, and recycled permeate back to the reactor tank when the setpoint liquid level had been reached. The level control switch was not activated until 30 to 60 minutes after the addition of the evaporator condensate in each feed cycle. During this period, permeate was recycled back to the reactor tank. The delayed wastage of permeate was designed to allow the bioreactor to have enough contact time with evaporator condensate to ensure maximal methanol removal. The start time of wasting at each cycle was controlled by a time delay box and was adjusted daily according to the permeate flow rate. During experiments involving black liquor spill tests and the mill shutdown test, condensate was obtained from Howe Sound Pulp and Paper Limited (Port Mellon, BC, Canada). The Howe Sound condensate contained about 3-fold higher methanol concentrations than the condensate from the Western Pulp Limited Partnership bleached kraft mill (Squamish, Canada). To maintain an equivalent organic loading rate, the HRT was decreased four-fold. 31 4.1.2.8 Nutrients Evaporator condensate contains some of the nitrogen required for the growth of microorganisms (Welander et al, 1999), but lacks the metal ions necessary for healthy biological growth (Milet, 1998). Therefore, supplementation of nutrients may be necessary for achieving stable M B R operation when treating evaporator condensate. The composition of the nutrient solution used in the present study (Table 4.1) remained constant throughout the study and was selected to ensure non-nutrient limiting conditions (Berube, 2000). To reduce the volume of nutrient solution added, the nutrient solution was concentrated 10-fold and 100 mL nutrient solution was added in the MBRs for every litre of condensate feed. Table 4.1 Composition of Nutrient Solution Nutrients Nutrient Concentration per Litre of Condensate (Methanol Concentration = 1,200 mg/L) (mg/L) NH4N03 112.5 KH2P04 76.5* (153) MgS04-lH20 25 CaCl2 32.8 FeCl, -6H20 20 * According to Berube (2000), the amount ofKH2P04was doubled to maintain required KH2P04 concentration. 4.1.2.9 Source of Sludge and Evaporator Condensate During the period of steady state testing and the methanol shock loading tests, the evaporator condensate was shipped from the Western Pulp Limited Partnership bleached 32 kraft mill (Squamish, BC, Canada) to U B C . Due to a shutdown of the Western Pulp mill, combined condensate was collected from Howe Sound Pulp and Paper Limited Partnership (Port Mellon, B C , Canada) during the black liquor spill tests and mill shutdown test. When received, kraft condensate was immediately sampled and characterized. Then, the condensate were acidified to a pH of approximately 4 with HCl , stored at temperature of 4 °C, and typically used within one week. The kraft condensate was transferred to a smaller 4 L sealed feed container, which was stored at 4 °C. Throughout the study, the evaporator condensate received from Western Pulp Ltd., Squamish, was sampled and analyzed for methanol, TOC, pH, and conductivity. COD was characterized for the condensate from Howe Sound Pulp and Paper, Port Mellon. Condensate that had conductivity greater than 800 uS was discarded. A high conductivity indicated the possible presence of black liquor entrainment in the evaporator condensate (personal communication, Pierre Berube, 2000) and that might affect M B R performance and consistency of experimental results. 4.2 Experimental Design The intention of the study was to improve the understanding of process efficiency of the high temperature M B R and its applicability to full-scale plant operation. The experimental plan was divided into two phases. Phase I investigated the performance of the high temperature M B R treating condensate under the design conditions proposed by Berube (2000) for a full-scale plant. Phase II evaluated the effects of transient operating 33 conditions, which included methanol shock loadings, black liquor carryover, and mill shutdown, on the high temperature M B R system. 4.2.1 Steady-state Tests According to research results reported by Berube (2000), a high temperature M B R treating evaporator condensate was designed to be operated under the conditions summarized in Table 4.2. Table 4.2 Summary of Design Parameters (Berube, 2000) Design Parameters Value Methanol Concentration (mg/L) 1,200 Operating temperature (°C) 60 PH 6.5 Sludge Retention Time (day) 38 Hydraulic Retention Time (hour) 9 Cross-flow velocity (m/s) 3 Trans-membrane pressure (atmosphere) 2 Time span of a batch cycle (hour) 2 By increasing the sludge retention time, a biomass concentration of 10,000 mg/L was expected to be reached in the M B R . Thus, the ability of the M B R to remove contaminants from evaporator condensate was anticipated to be maintained. M L V S S , the biological removal efficiency of methanol and TOC, growth yield, membrane permeate flow rate and colour removal efficiency were monitored throughout the test period. 34 4.2.2 Methanol Shock Loading Tests The purpose of this test was to examine the response of the high temperature M B R to transients in organic loading rate, at constant HRT. Since real evaporator condensate was used as feed, the methanol concentration was adjusted by addition of exogenous methanol, to achieve different methanol loading rates. In order to investigate the response to short-term and long-term shock loadings, Reactor 1 was subjected to four shock loadings to investigate long-term effects and Reactor 2 was subjected to one shock loading, to show short-term effects (Refer to Table 4.3). Condensate with concentrations of 150%, 200%o and 250% of the steady-state methanol concentration (1200 mg/1) were used to generate the different shock loadings applied to the MBRs. Table 4.3 Schedules of Methanol Shock Loading Tests Date Influent Concentrations Reactor 1 Reactor 2 (mg/L) (Number of Feed Cycles with Shock Loading) (Number of Feed Cycles with Shock Loading) Test 1 June 25, 2001 1800 4 (8 hrs) 1 (2 hrs) Test 2 June 28, 2001 2400 4 (8 hrs) 1 (2 hrs) Test 3 July 2, 2001 3000 4 (8 hrs) 1 (2 hrs) 4.2.3 Black Liquor Carryover Tests The potential toxic effects of a black liquor entrainment to a high temperature M B R treating evaporator condensate were studied by these tests. The conductivity of 35 evaporator condensate increases dramatically with black liquor entrainment into the evaporator condensate and it can be used as an indicator. Volumes of 4 mL, 6 mL, 8 mL and 16 mL of black liquor in one litre of kraft condensate resulted in around 1000, 2000, 3000, and 6000 pS conductivity and these black liquor concentrations were chosen as the intensities of the black liquor shocks to be investigated. During every black liquor carryover test, one reactor was subjected to four cycles of feed with black liquor addition to investigate long-term effects and the other was subjected to one cycle of feed with black liquor addition, to show short-term effects. However, among the four sets of black liquor carryover tests, each reactor received two long-term tests and two short-term tests to reduce the correlation between the test results to the extent possible (Refer to Table 4.4). Table 4.4 Schedules of Black Liquor Carryover Tests Date Influent Reactor 1 Reactor 2 Concentrations (Number of Feed (Number of Feed (mL black liquor Cycle with Shock Cycle with Shock addition/L) Loading) Loading) Test 1 August 4, 2001 4 4 (8 hrs) 1 (2 hrs) Test 2 August 7, 2001 6 1 (2 hrs) 4 (8 hrs) Test 3 August 10, 2001 8 1 (2 hrs) 4 (8 hrs) Test 4 August 16, 2001 16 4 (8 hrs) 1 (2 hrs) 36 4.2.4 Mill Shutdown Test A kraft pulp mill is often shut down for 7 to 10 days for maintenance every year (personal communication, Jeanne Taylor, 2000, Western Pulp Limited Partnership, Squamish, B.C., Canada). To simulate the situation that a membrane bioreactor may face during mill shutdown, a 10-day-shutdown test was applied to reactor 2. Feeding and heating of the M B R system were terminated. Aeration and circulation rates through the membrane were reduced to one half of the normal values to maintain aerobic conditions in the reactor. During this 10 day period, a batch test was performed every two days to monitor the activity of reactor biomass. After the 10-day-shutdown test, the temperature was increased 10 °C every day until the original operating temperature of 60 °C was reached. Aeration and circulation rates through the membrane were returned to the original levels to maintain non-limiting dissolved oxygen (DO) conditions and mixing. During this re-start period, the M B R feed rate was increased from 25% of the original operating value to 100%>, in 25 % steps every day. Reactor activity was monitored during these four days. 4.3 Experimental and Analytical Methods 4.3.1 Biomass Acclimatization During the start-up phase of the program, each M B R was inoculated with sludge from a full-scale activated sludge system treating kraft pulp mill effluent (Western Pulp Ltd. 37 Partnership, Squamish, B.C., Canada) and sludge from a pilot scale activated sludge system (UBC-Civi l Engineering Pilot Plant, Vancouver, Canada). Approximately 500 mL of inoculum from each location were added directly to each M B R at approximately the same time and the reactor tank was topped-off with tap water. Since methanol is the most abundant compound in condensate, methanol was added to tap water to make up feed with a 1200 mg/L methanol concentration. When the systems were acclimatized to synthetic feed after two weeks, the MBRs were switched to 25% real evaporator condensate, 50% and finally 100% real evaporator condensate for a week respectively. The composition of feed was based on calculations to maintain constant methanol concentration. To reintroduce microorganisms that might not be able to grow under the previous conditions during the acclimatization, 250 mL of activated sludge from Western Pulp Ltd. was added into each M B R whenever the feed ratio of real evaporator condensate was changed. 4.3.2 Membrane Cleaning The permeate flow rate through the membrane decreased with time. When the permeate flow rate was close to the rate that was just sufficient to accommodate the influent flow rate, membrane cleaning was performed based on the recommendation of the supplier and Berube (personal communication, 2000). The cleaning procedure required approximately 2 hours, and membrane runs lasted 1 to 9 weeks, depending on the nature of the membrane and the experiments. 38 4.3.3 Sampling and Sample Preparation Mixed liquor samples were taken directly from the reactor and analyzed immediately. Feed samples were obtained from the pre-heat tanks just before introduction into the reactor. Permeate samples were collected from the membrane cartridge permeate port (See Figure 4.2 and Figure 4.3). The membrane casing was drained before sampling to minimize the dilution effect that can occur in the membrane casing. Since permeate samples were already filtered through the membrane unit (0.05 urn), they did not require filtration before analysis and therefore, simplified analytical methods were applied. Permeate Port ( 5 M R U U 1 : ! \ °!! a ,' fHO C A P Sampling Port / Permeate port Figure 4.2 Membrane Unit Used for RI and Partly for R2 (Membralox IT-70) 39 Sampling Port / Permeate port Sampling Port / -1 1/2" Sanitary Clamp P e r m e a t e P ° r t u > (By Customer) ^""^ P O o o 1 1/4" NDP Coupling (By Customer) 1 1/2" Sanitary Butt-Weld Ferrule (By Customer) Figure 4.3 New Membrane Unit Used for R2 (Membralox IT-70) 4.3.4 Analytical Methods 4.3.4.1 Chemical Oxygen Demand (COD) Condensate and feed samples were analyzed for total COD (TCOD) and dissolved COD (DCOD). Samples for DCOD analysis were filtered through 0.45 /mi cellulose nitrate membrane filters. Because the pore size of the membrane unit (0.05 um) was smaller than that of the cellulose nitrate membrane filters, TCOD was assumed to be equivalent to DCOD for effluent samples. Then, samples were diluted to fall into the range 0 ~ 900 mg/L COD according to an estimation of sample strength. Samples were prepared and analyzed using a closed reflux colorimetric procedure with mercuric chloride addition as per Standard Methods 5220D (APHA/AWWA/WEF, 1995). After digestion in a Hach COD block digester, the absorbance of the samples and standards was measured at 600 40 nm using a Hach DR-2000 spectrophotometer. According to the standard curves and absorbance of the samples, COD in the samples were determined. 4.3.4.2 Conductivity After the samples were acclimatized to ambient temperature (approximately 20 °C), the conductivity was measured using a Radiometer Copenhagen CDM3 conductivity meter. 4.3.4.3 Colour True colour and apparent colour of permeate and feeds were evaluated using Standard Methods 2120B (APHA/AWWA/WEF, 1995). Colour readings were made using a Hach colour comparator. Because the colour and the pH of samples were highly related, both were recorded. 4.3.4.4 Methanol Concentration Before analysis, feed and condensate samples were filtered through 0.45 /mi cellulose nitrate membrane filters. The concentration of methanol was measured by direct injection of samples into a gas chromatograph (HP6890, Hewlett Packard Co.) with a 30 m long wide bore capillary column (Berube, 2000) and flame ionization detector, using 1-butanol as an internal standard. 41 4.3.4.5 pH The pH was measured using a Beckman Model PHI 44 pH meter. 4.3.4.6 Total Organic Carbon concentration (TOC) Condensate samples were analyzed for total organic carbon (TOC) and filtered TOC (FTOC). FTOC was assumed to be equivalent to TOC for permeate samples. Samples were filtered through a 0.45 um cellulose nitrate syringe membrane filter cartridge before analysis of FTOC. The concentrations of TOC and FTOC were measured by combustion-infrared methods using the TOC analyzer (Shimadzu TOC-500) according to Standard Methods 5310B (APHA/AWWA/WEF, 1995). 4.3.4.7 Solids Solids analyses followed Standard Methods 2540 (APHA/AWWA/WEF, 1995). Feed samples during black liquor tests were analyzed for total solids (TS), total volatile solids (TVS), total dissolved and colloidal solids (TDCS), and total volatile dissolved and colloidal solids (TVDCS). The permeate samples during black liquor tests were analyzed for TDCS. Samples from the mixed liquor of the membrane bioreactor were analyzed for total suspended solids (MLTSS) and volatile suspended solids (MLVSS). 42 Chapter 5 Results and Discussions In this section, data and results obtained under steady and transient operating conditions are presented and discussed. 5.1 Characteristics of Condensate During the period of steady state testing and methanol shock testing, evaporator condensate shipped from the Western Pulp Limited Partnership bleached kraft pulp mill in Squamish, British Columbia, Canada, was used. Due to a long period of Western Pulp mill shutdown, combined condensate was sampled from Howe Sound Pulp and Paper Limited (Port Mellon, BC, Canada) and used during the period of the black liquor carryover tests and the mill shutdown test. The characteristics of condensate used throughout the study were monitored and are summarized in Table 5.1 and Table 5.2 (Raw data are presented in Appendix 1). Table 5.1 Characteristics of Evaporator Condensate from Western Pulp Ltd. Measurement Uni ts Average 9 0 % * (+/-) N u m b e r o f samples Conductivity uS 381 44 39 PH 7.7 0.2 39 Methanol mg/L 380 31 39 TOC mgC/L 326 25 39 Filtered TOC mgC/L 297 24 39 TOC solids** % 9.3 2 39 Methanol as TOC % 45.4 3 39 COD mg0 2/L 1027 126 39 * 90% confidence interval TOC in the form of suspended solids 43 Table 5.2 Characteristics of Combined Condensate from Howe Sound Pulp Ltd. Measurement Uni ts Average 9 0 % * (+/-) N u m b e r o f samples Conductivity US 483 27.4 3 PH 8.4 0.19 3 Methanol mg/L 4953 108.0 3 TOC mgC/L 2085 95.0 3 Filtered TOC mgC/L 1923 48.7 3 TOC solids % 7.6 4.1 3 Methanol as TOC % 89 6.0 3 COD mg0 2/L 9303 114.1 3 * 90% confidence interval TOC in the form of suspended solids Since the methanol concentration in the Western Pulp condensate was much lower than the design conditions (1200 mg/L), the Western Pulp evaporator condensate was spiked with methanol to a concentration of approximately 1200 mg/L before use. 5.2 MBR Operating Parameters Temperature, trans-membrane pressure, crossflow velocity, pH, and SRT were independently controlled for this experiment, except for the mill shutdown test. These operating parameters can significantly influence the performance of the membrane bioreactors and were maintained as constant as possible. 5.3 Start-Up and Steady-State Operation Two bench scale MBRs (called RI for Reactor 1 and R2 for Reactor 2), described in Section 4.1.1, were used to investigate the performance of MBRs treating kraft evaporator condensate under steady state conditions. Based on Berube's (2000) research 44 results, the operating conditions for a high temperature membrane bioreactor were selected (referred to Table 4.2). HRT and SRT were maintained as 9 hours and 38 days respectively. After approximately 6 weeks of acclimatization, the methanol removal kinetics, total organic carbon removal kinetics, and suspended solids concentrations in the systems were monitored for 34 weeks. The performance of the MBRs under steady state conditions was compared with the predictions from Berube (2000) and details are discussed below. A steady state condition was assumed to have been achieved when the concentration of mixed liquor volatile suspended solids (MLVSS) and the rate of the methanol removal in the MBR were relatively constant. Various incidents occurred during the first 150 days while operating the membrane biological reactor and these are listed in Appendix 2. Mostly, they were due to spills caused from foaming problems and the breakdown of equipment. Excessive foaming was initially observed during the experimental period To reduce foaming, a shower head on the return line and an insulation box around the reactor unit were installed for each MBR system. The foaming problem was well controlled after these changes. Due to several serious upsets during the first 150 days of the experimental period, the performance of the two MBRs was significantly affected and the resulting data can't realistically represent the performance of an MBR under steady state conditions, as presented in Figure 5.1. Hence, only the data collected after day 150 for Reactor 1 (Rl) and Reactor 2 (R2) were used in assessing MBR performance at steady state. 45 5.3.1 Methanol Removal * 100 i ^ o 90 80 70 60 50 -R1 -R2 i 1 r 0 20 40 60 80 100 120 140 160 180 200 220 240 Time (day) Figure 5.1 Methanol Removal Efficiencies of MBRs 0 50 100 150 200 Day Figure 5.2 Methanol Concentration of Influent (Condensate Feed) As shown in Figure 5.2, methanol concentration in the influent (condensate) was maintained relatively constant at a level of about 1,200 mg/L. However, various incidents, including high methanol concentration of influent, resulted in fluctuating 46 average effluent concentration and methanol removal efficiency before Day 151, shown respectively in Figure 5.3 and Figure 5.1. in E 450 | 400 350 13' 300 fthnol Cone MBRs (mg 250 200 fthnol Cone MBRs (mg 150 S 100 50 0 100 150 200 Day Figure 5.3 Average Methanol Concentration of Effluent During a typical batch cycle, a volume of 400 mL condensate with a methanol concentration of 1,200 mg/L was added to the reactor containing a liquid volume of 1.8 L at the beginning of each feed cycle. This resulted in approximately 260 mg/L of methanol in the reactor. The concentration of methanol in the M B R was then reduced from approximately 260 mg/L to below the analytical method detection limit of 0.5 mg/L, as illustrated in Figure 5.4. Notably, before methanol in the reactor was fully biodegraded, part of the methanol was wasted with the permeate. Therefore, the average methanol concentration in the effluent was not zero, although all methanol in the reactor was removed by the end of the batch cycle. The average methanol concentration in the effluent was determined for the total volume of effluent collected from a feed cycle. 47 Methanol removal kinetics similar to those reported by Berube (2000) and Milet (1998) were observed throughout the steady state experimental period and the methanol removal rate achieved by the membrane bioreactor was estimated by using a zero-order relationship as presented in Equation 5.1. PMeOH = ^MeOH ' ^ = ^MeOH (5-1) where RMeOH is the rate of biological removal of methanol (mg/L-min), UMeOH is the specific methanol utilization coefficient (/min), KMeOH is the zero-order coefficient for the biological removal of methanol (mg/L-min), and X is the concentration of MLVSS of MBR (mg/L) The zero-order removal rate indicated that the uptake of methanol by the mixed microbial culture was not limited or inhibited by the concentrations of methanol in the range of concentrations examined (from approximately 260 mg/L (100 mg/L expressed as TOC) to below the detection limit of 0.5 mg/L). In addition, according to Berube (2000), stripping of methanol is a first order reaction and methanol removal due to stripping of the aeration system only accounted for less than 1% of the mass of methanol removed from the MBR. 48 • Methanol (expressed as TOC) • TOC 20 40 60 Time (min) 80 100 Figure 5.4 Concentrations of Methanol and Total Organic Carbon in M B R During a Typical Feed Batch Cycle (Methanol expressed as TOC) During the steady state period of operation, the average methanol removal efficiency for R l was 94.9 ± 0.94 % and for R2 was 94.8 ± 0.8 %, based on mass balance calculations for each the system (based on the data of Table A2-1 to A2-24 in Appendix 2). The average initial bioreactor methanol concentration in batch feed cycles for R l and R2 was 257.3 ± 5.9 mg/L and the average effluent concentration was 12.9 ± 2.4 mg/L. Due to the different calculation methods used in Berube^ s (2000) research and in the present study, the removal efficiency estimated from this study was slightly lower than Berube's (2000) results of 99%. However, the observed efficiency was still higher than the 90% removal achieved by the conventional technology, steam stripping. Removal efficiency calculated by Berube (2000) was the total biodegraded contaminant concentration in the reactor (the total mass of biodegraded TOC divided by total volume of the reactor) divided by influent contaminant concentration in the condensate (the total 49 mass of TOC of the feed divided by the total volume of the condensate added during a feed cycle). It should be noticed that the concentrations can't used directly to calculate the removal efficiency since the volume of the reactor (1.8 L) and the volume of the condensate added during a feed cycle (400 ml) are different. Therefore, the contaminant removal efficiencies are higher from Berube's (2000) results. Throughout the steady state period, the specific methanol utilization coefficients were estimated to be 1.03 ± 0.13 /day for RI and 1.47 ± 0.15 /day for R2, which were 75 % and 150 % higher than Berube's result of, 0.59 ±0 .11 /day. The data are presented in Table A2-1 to A2-24 in Appendix 2. The higher specific methanol utilization coefficients of this study possibly indicated the higher methanol-utilization-capacity of the biomass because the biomass concentrations of both experiments were quite close to each other (Berube's (2000) biomass concentration was approximately 2,500 mg/L). Following the start of each batch feed cycle, the pH in the MBR tended to decrease. This was also reported by Berube (2000) and he suggested that it was due to the production of CO2 during the biological oxidation of methanol. This decline of pH was used as a one of the indicators for the removal of methanol from MBR. 5.3.2 Total Organic Carbon (TOC) Removal As illustrated in Figure 5.4, the concentrations of TOC in the MBRs were reduced from approximately 160 mg/L to approximately 50 mg/L during each batch feed cycle (172.1 ± 6.19 to 61.9 ± 3.83 mg/L for RI and 161.92 ± 5.49 mg/L to 57.28 ± 3.16 mg/L). Similar 50 to Berube's observations, there was no significant further reduction in the concentration of TOC after methanol removal was completed (approximately 105 minutes after the start of the batch feed cycle). A relatively high residual concentration of TOC, 59.6 ± 5.9 mg/L, remained in the MBR, and the residual TOC was considered to be non-biodegradable organic matter. Conclusively, 64 % of the organic material, measured as TOC, contained in the evaporator condensate could be removed by a high temperature membrane bioreactor. Comparing with the high TOC removal efficiency observed by Berube (2000) as 91 %, the TOC removal efficiency summarized during the present study was relatively low, but the difference between the results is mainly due to the different calculation methods used for removal efficiency (as mentioned in the last paragraph on page 48). The TOC concentration in the MBR was modeled using two zero order sequential relationships as presented in Equation 5.1. Data from the tests and results from the linear regressions are presented in Appendix 2. The first specific TOC utilization coefficient (the slope of darker dashed line in Figure 5.4) was estimated to be 0.51 ± 0.072 /day for RI and 0.74 ± 0.065 /day for R2. The results were close to 0.66 ± 0.056 /day, reported by Berube (2000). 51 5.3.3 Mixed Liquor Volatile Suspended Solids (MLVSS) Concentrations To maintain a constant SRT, 47 mL of M B R mixed liquor was wasted daily. The resulting M L V S S concentration profiles of the two reactors throughout the steady state experiment are shown in Figure 5.5. 6000 •R1 •R2 Figure 5.5 M L V S S Concentrations Throughout the Steady State Period (After Day 151) The observed growth yield was calculated following Equation 5.2 and details are included in Appendix 2. 1obs ^(Methanol) (5.2) where Yobs: observed growth yield 52 Biomass): Cumulative biomass production; total biomass wasted/sampled from the reactor and accumulated/decumulated in the reactor ^{Methanol): Cumulative methanol removed; [(mass of influent methanol per batch) - (mass of permeate methanol per batch)] x (number of batches) An observed growth yield of 0.2 mg MLVSS produced/mg methanol biologically removed was derived from Berube's (2000) research when treating bleached kraft mill evaporator condensate. An MLVSS concentration of 10,000 mg/L, was expected to be achievable in a high temperature membrane bioreactor with a 9 hr HRT and evaporator condensate with a 1200 mg/L methanol concentration. However, it is known that sludge production from biological aerobic wastewater treatment decreases with decreasing organic loading rates and increasing solids retention time (Henze et al., 1987). The steady state MLVSS concentration observed in the present study was approximately 3000 mg/L in RI and 2500 mg/L in R2. The resulting calculated observed growth yields were 0.0347 forRl and 0.0254 for R2. Due to the nature of the bench-scale reactor set-up, wall growth of biomass in the reactor was observed, which affected the MLVSS concentration during the early stages of the experiment. To limit the wall growth and minimize the disturbance, scraping of the wall every two or three days was carried out throughout the study and it was found to effectively eliminate the wall growth. 53 Ragona (1998) reported that biomass from a membrane bioreactor was able to pass through the filter used for the determination of suspended solids according to Standard Methods (APHA/AWWA/WEF, 1995). As an alternative for suspended solids measurement, she subtracted the total solids concentration (which is equivalent to dissolved solids) in the permeate from the total solids concentration in the mixed liquor of the reactor to obtain the suspended solids concentration in the mixed liquor. Comparing the solids concentrations estimated in the two different ways, she found the MLVSS concentration estimated by the alternative method appeared to be a better indication of biomass. In the present study, dark or gray colour was observed from the liquid passing through the filter and it indicated that fine suspended solids possibly passed through the filter. However, this information was found almost at the end of the present study and since the solids determination followed Standard Methods, there are no appropriate data to confirm the findings of Ragona with the results of the present study. Wouter and Willy (1999) reported that a substantially lower sludge yield (20 - 30 %) was observed in an MBR than in a conventional activated sludge system (CAS) under comparable conditions of influent concentration and volumetric loading rate. In addition, complete sludge retention achieved through membrane filtration may lead to grazing on bacteria by protozoa and metazoa in an MBR, since a higher abundance of flagellates and free ciliates was observed in an MBR than in a CAS (Wouter and Willy, 1999). Uncoupled energy production and corcesponding high maintenance energy for biomass are other possible explanations for the observed low growth yield in MBRs. Under certain conditions, more energy is produced than is required for anabolism and the excess 54 energy must be consumed by non-growth-associated processes. The phenomenon is called uncoupling (Horan, 1990), as the link between energy production and growth has been uncoupled. Low yield would be beneficial since it would reduce the cost of handling and disposal of biomass. 5.3.4 Summary During the steady state period of the experiment, methanol and TOC removal efficiencies were 95 % and 64 % respectively. Compared with Berube's (2000) result (99 % methanol removal and 91 % TOC removal), the MBRs in the present study exhibited stable removal of the main contaminants. However, the difference between TOC removal efficiencies was due to the different calculation methods used for removal efficiency, as explained in 5.3.1. With a long SRT (38 days), the MBRs exhibited a low observed growth yield, 0.0347 for Rl and 0.0254 for R2. Low growth yield is considered as an advantage of the process because of the low biosolids management cost. Throughout the steady state period, the specific methanol utilization coefficients were estimated to be 1.03 ± 0.13 /day for R l and 1.47 ± 0.15 /day for R2, which were 75 % and 150 % higher than Berube's (2000) result of, 0.59 ± 0.11 /day. 55 5.4 Methanol Shock Loading Tests Methanol was identified as one of main contaminants of kraft condensate and methanol concentration fluctuates along with the evaporator operating conditions. To investigate the performance of a high temperature M B R under transient methanol loadings, M B R R l was exposed to "long-term" methanol shock loading (8 hrs), and M B R R2 was exposed to "short-term" methanol shock loading (2 hrs), as described in Table 4.3 and Figure 5.6. 3500 Figure 5.6 Initial Methanol Concentrations in Feed during the Methanol Shock Loading Tests (M: Methanol Shock Loading Test; L: Long-term; S: Short-term) The effects of methanol shock loading on the high temperature membrane bioreactors were investigated by increasing the methanol concentration by factors of 1.5, 2, and 2.5. R l was fed four consecutive batches (8 hours, close to 1 HRT that is 9 hrs) of feed with a higher concentration to study the long-term effect; R2 was fed one batch (2 hour) of high concentration feed to examine the short-term impact. 56 5.4.1 Methanol and TOC Removal Results from the three methanol shock loading tests are summarized in Table 5.3 and details can be found in Appendix 3. Removal efficiencies of a feed cycle during periods of methanol shock-load testing are presented in Figure 5.7. Contaminant utilization coefficient profiles during the first, second, and third methanol shock loading test are shown respectively in Figure 5.8, 5.9, and 5.10 Table 5.3 Summary of Methanol Shock Loading Tests Results Methanol Initial Final Methanol Methanol Initial Final TOC TOC Shock Methanol Methanol Utilization Removal TOC TOC Utilization Removal Loading Cone. In Cone. In Coefficient Efficiency Cone. In Cone. In Coefficient Efficiency Test MBR MBR (mg/L-min) (%) MBR MBR (mg/L-min) (°/ '») (mg/L) (mg/L) (mg/L) (mg/L) Test Batch Rl R2 Rl R2 Rl R2 Rl R2 Rl R2 Rl R2 Rl R2 Rl R2 1 1 398 402 0 6 4.5 3.3 99 98 216 209 61 56 1.7 1.7 70 72 2 405 259 0 0 3.8 2.9 99 99 172 138 64 33 1.1 1.0 61 75 3 401 270 0 0 3.7 3.1 99 99 166 120 60 32 1.1 0.9 58 72 4 388 281 0 0 3.5 3.2 99 99 154 128 60 31 1.1 1.0 60 66 5 265 268 0 0 4.3 3.6 100 100 148 141 43 36 1.23 1.33 70 74 2 1 534 533 0 41 5.6 4.1 99 91 252 263 49 48 2.4 2.6 80 81 2 536 268 0 0 6.0 4.6 99 100 208 95 56 34 1.7 0.9 72 63 3 532 269 0 0 4.5 3.6 99 99 269 106 62 29 1.8 0.9 75 70 4 510 238 90 0 3.5 3.5 81 99 240 106 108 32 1.1 1.0 52 69 5 269 266 0 0 3.7 3.4 99 99 157 158 46 54 1.4 1.32 70 64 3 1 668 670 488 490 1.5 1.5 24 24 273 243 225 207 0.4 0.3 13 11 2 1130 754 806 502 2.7 2.1 26 30 408 267 348 243 0.5 0.2 10 5 3 1353 707 1029 479 2.7 1.9 21 29 540 259 516 199 0.2 0.5 1 19 4 1672 685 1324 421 2.9 2.2 18 36 695 259 623 199 0.6 0.5 6 19 5 1560 642 1188 385 3.1 2.5 21 38 637 191 505 131 1.1 0.5 17 28 57 1 1 I— I ' I — I 1 3 5 7 9 11 Time (day) Figure 5.7 Contaminants Removal Efficiencies of the MBRs over the Methanol Shock Loading Tests Period (L: Long-term; S: Short-term; Time - 1st day: June 24, 2001) As illustrated in Figure 5.8, there were no significant inhibitory effects on the performance of the MBRs, from either the long-term or short-term shock loadings. Methanol utilization coefficients of both MBRs increased as the methanol concentrations of the feed increased and returned to normal after the shock loadings were stopped. Removal efficiencies of both MBRs remained above 95% throughout the first methanol shock loading tests. Because methanol removal accounts for most of the T O C removal, TOC removal coefficients increased along with the methanol removal coefficients. 58 0 2 4 6 8 10 Time horn the Start of the Teat (hr) Figure 5.8 Methanol and TOC Utilization Coefficient Profiles during the First Methanol Shock-Loading Test (Methanol Cone. = 1,800 mg/L; L: Long-term; S: Short-term) Observed from Figure 5.9, for the second long-term methanol shock loading test, the methanol removal coefficient increased during the first feed cycle of the shock load, then decreased slightly. Since the methanol concentration of the shock load was much higher than that of the regular feed, the removal efficiency decreased even though the methanol removal coefficient remained above the initial value. Throughout the entire test, at least 95 % methanol removal efficiency was achieved in the MBR that received 4 batches of feed with a methanol concentration of 2400 mg/L. No negative effect on the MBR was observed from a short-term shock loading during the second methanol shock loading tests. These results showed that the MBR was reasonably stable to methanol organic shock loadings and maintained the same removal efficiency when the load was increased by 1.5 and 2 times instantaneously. 59 Time after the Start of the Test (hr) Figure 5.9 Methanol and TOC Utilization Coefficient Profile during the Second Methanol Shock-Loading Test (Methanol Cone. = 2,400 mg/L; L: Long-term; S: Short-term) When the feed strength was increased by a factor of 2.5, the methanol utilization coefficient of R l (long-term test) dropped during the first feed cycle of shock load and increased slightly during the following shock loads, as shown in Figure 5.10. The methanol utilization coefficient of R2 (short-term test) decreased during the first feed cycle of shock load and gradually recovered once the shock loading was terminated. However, the MBRs showed distinct signs of overload, and couldn't biodegrade methanol fast enough so that the methanol concentration in MBRs increased after the shock loadings. There was unconsumed methanol present in the permeate and methanol and TOC removal efficiencies decreased to 21 % and 11 % respectively. About four hours after the short-term shock loadings, the methanol concentration in R2 returned to normal levels; the methanol concentration in R l came back to the original concentration two days after the long-term shock loadings (refer to Figure 5. 7). 60 0 2 4 6 8 10 Time from the Start of the Test (hr) Figure 5.10 Methanol and TOC Utilization Coefficient Profile during the Third Methanol Shock-Loading Test (Methanol Cone. = 3,000 mg/L; L: Long-term; S: Short-term) A short-term shock loading didn't impose a serious effect on the high temperature M B R system and the system started to recover once the shock loading was terminated. The long-term shock loadings resulting from increased methanol concentration by factors of 2 and 2.5 times seemed to reduce the methanol removal efficiencies, but the system was still able to recover within 2 days. Higher concentrations of methanol, as high as 4000 mg/L, have been reported by others to be non-inhibitory to a mixed culture (Koh et al., 1989). On the other hand, dissolved oxygen (DO) was indicated as a rate-limiting factor for methanol oxidation (Shuler and Kargi, 1992; Milet, 1998). However, DO was not monitored throughout the present 61 methanol shock loading tests because of a temperature limitation for DO probe usage. Further research is needed to confirm the cause of the inhibitory effect from excess methanol concentration in the feed. Conclusively, a high temperature MBR was stable to a perturbation of excess methanol concentration, and was able to absorb the overload and maintain the performance of the reactor until the loading rate was so high that it overloaded the system. 5.4.2 Colour Removal As illustrated in Figure 5.11, the colour of the condensate was much higher than that of permeate, indicating that the ultrafiltration membrane was effective at rejecting some colour bodies. Since the nominal size of the ultrafiltration membrane (0.05 um) was smaller than that of the membrane filter required for the filtration of the sample for colour determination, the apparent colour of the permeate was equivalent to the true colour of the permeate. Addition of methanol didn't increase the colour of condensate. However, there was a slight increase of permeate colour after the third methanol shock loading test. Overload of methanol seemed to disturb the biomass and the upset reaction of biomass to degrade and oxidize the condensate organic matter probably produced this additional colour. 62 Figure 5.11 Colour of the MBRs Permeate and Condensate (Influent) over the Methanol Shock Loading Tests Period (M: Methanol Shock-Loading Test; A: Apparent Colour; T: True Colour; L: Permeate of M B R 1 (Long-term Shock Loading); S: Permeate of M B R 2 (Short-term Shock Loading); Time - 1 s t day: June 17, 2001) 5.4.3 MLVSS Concentrations MLVSS concentration profiles of R l and R2 are shown in Figure 5.12. Excess methanol from the methanol shock-loading tests seemed to increase the observed growth yields and the M L V S S concentrations in the MBRs. Except after the third methanol shock-loading test, biomass in R l notably decreased and built up slowly in the reactor because of the overload of the system. The observed yield coefficients (0.0415 for R l and 0.0334 for R2) were higher for both the long-term and short-term transient experiments. 63 5.4.4 Summary The MBRs were reasonably stable and able to maintain the same removal efficiency when the feed methanol concentration was increased by 1.5 and 2 times instantaneously. When the feed strength was increased by a factor of 2.5, the MBRs showed distinct signs of overload. However, R l recovered about four hours after the short-term shock loadings, and R2 functioned normally two days after the long-term shock loadings. Overload of methanol seemed to disturb the biomass and the colour of the permeate slightly increased after the methanol shock loading test with 3,000 mg/L methanol concentration. 64 Excess methanol from the methanol shock-loading tests increased the observed growth yields and the MLVSS concentrations in the MBRs. 5.5 Black Liquor Carryover Tests Although Best Management Practices (BMP) programs have been implemented by many mills to reduce the extent and frequency of liquor spills, it's difficult to fully eliminate spills from mill operations. Condensate used throughout the present study sometimes was found to have much higher conductivity than normal, and the high conductivity indicated the presence of a significant amount of black liquor entrainment into the condensate. (Personal communication with Taylor J., 2001, Western Pulp Limited Partnership, Squamish, Canada; Berube, 2000). A significant liquor spill typically increases the COD to an external secondary treatment plant by a factor of 3 to 4 (Personal communication, Doug Barton, NCASI, 2001), and it's important to determine whether a high temperature membrane bioreactor can survive spills or black liquor carryover of a similar magnitude. To simulate black liquor carryover, weak black liquor was collected from Howe Sound Pulp and Paper Ltd. (Port Mellon, Canada) and added into condensate at different ratios. The raw data, on which this discussion is based, are presented in Appendix 4. As shown in Table 4.4 and Figure 5.13, R l and R2 were exposed to long-term and short-term black liquor carryover tests alternately during the black liquor carryover tests. The black liquor shock tests were separated in time by 3 to 6 days of normal operation (See Table 4.4). For the convenience of discussion, the results are presented by long-term and short-term tests. 65 26 22 1 18 I 1 § O o ! OQ 10 ; I 11 A • • J 1 1 • • ' 1 I 11 A M m i 1 i • i If W « A > t • 4 6 Time(hr) 10 -X- - - B1 - S (R2) —B1-L(R1) -©--- B2-S(R1) -m—B2-L(R2) -A B3-S(R1) —B3-L(R2) -O--- B4-S(R2) ——B4-L(R1) Figure 5.13 Black Liquor Concentrations during the Black Liquor Carryover Tests (B: Black Liquor Carryover Test; L: Long-term; S: Short-term) 5.5.1 Characteristics of Condensate with Black Liquor Carryover Black liquor is a complex mixture of water, inorganic salts, and organic matter. The characteristics of black liquor vary considerably with the operating conditions of mills and change significantly throughout different stages of evaporation and burning within a mill (Frederick et al., 1980). Since the focus of the present study was on the effects of black liquor carryover on condensate treatment, not black liquor itself, the characteristics of black liquor weren't studied. Weak kraft black liquor was collected from Howe Sound Pulp and Paper Ltd. (Port Mellon, Canada) and added into condensate in different amounts. The characteristics of condensate with different amounts of black liquor addition are presented in Table 5.4. It is interesting to note that the TOC increased significantly with the volume of black liquor contained in the condensate while COD did 66 not increased accordingly. However, it is highly possible that it is due to experimental error when conducting the COD experiment Table 5.4 Characteristics of Condensate used for Black Liquor Carryover Tests Sample Conductivity TOC COD Filtered Filtered TS TVS TVS GiS) (mgC/L) (mgC/L) COD COD/COD (mg/) (mg/L) /TS (mg C/L) (%) (%) Condensate 480 2085 9303 9205 99.5 1200 780 65 4 * 1000 2785 9671 9254 95.2 1880 1380 73.4 8* 2000 3420 9793 9354 95.5 2380 1620 68.1 12* 3000 4072 9965 9597 96.3 3080 2400 61.9 24* 6000 5896 10014 9840 98.3 4880 2860 58.5 * The number indicates the volume of mL black liquor per L condensate 5.5.2 Methanol, COD, and TOC Removal Results from the four black liquor carryover tests are summarized in Table 5.5. From Table 5.5 and Appendix 4, initial contaminant concentrations and final effluent contaminant concentrations in the MBRs of one batch cycle during the periods of black liquor carryover testing are presented in Figure 5.14. Contaminant utilization coefficient profiles during the first, second, third, and fourth black liquor carryover tests are shown respectively in Figure 5.15, 5.16, 5.17, and 5.18. As shown in Figure 5.15 and Figure 5.16, the first and second black liquor carryover tests didn't have any significant effects on the MBRs, as a result of either the short-term or long-term shocks. The MBRs were able to degrade the excess COD and TOC and the methanol removal efficiency remained above 95 %. 67 COD Utilization Coefficient (mg/Lmin) 2 CM Tf" CM Tf' C O C O C O oq C M C M m C O i n C O C M • V CM T T C O m C O C O rf cn Tf" 0) C O C O C O C D C O 00 C O C O T f COD Utilization Coefficient (mg/Lmin) 2 lO CM o> C M CM co CM CM T f T f •* C O C O C O C O C O C O T f C O C O C O C M T f T f C O co' C M C O C D CM m CM T f CM Final COD Conc; In MBR (mg/L) 2 C O CM C M C M o CM C M C O cn C O C M m CM I C M co i n C D co s CM T f C M C O C M C M T f C O co C O o C M T f oo oo T f o C O T f T f 00 C M T f r~ O C O Final COD Conc; In MBR (mg/L) 2 m T f c -o l O i n s C O T f C O C M C O CM -<* o> C O o C O C O C D C O m o T f m C O CM s O O m T f o T f s T f 00 00 T f a? C O C M oo T f T— o C D C O C M x— Initial COD Conc. In MBR (mg/L) 2 w C O h~ 1— T f m C D co (0 0) O co O O 00 in s co s CM oo 0> C O 00 oo oo C O o oo CM T f 00 C D s 00 o o T— S3 C D 8 C D C M CM C D s co C O CM oo Initial COD Conc. In MBR (mg/L) 2 m v -r>-w C O r-~ T— 00 f -C O C M C O oo r>-oo o o> C M O 00 C M 00 o cn r -m C O h-co CM h-T f C O CO oo T f 00 00 C D m C D o CM C D o s — C D co T f T -C O f » m TOC Utilization Coefficient (mg/Lmin) 2 C O d C O d r--d i n T -C O d o> d T— cq T -q p 1— p in T f T— C O d C D d co d 00 d TOC Utilization Coefficient (mg/Lmin) 2 CM C D d C O cq 00 d d d o T— CM d h-d C O d C O oo d . "c— CM p T— p Final TOC Conc. In MBR (mg/L) 2 C O c-in o C D o i n r-CO C M C D -<r x— O ) 00 C D cn C D C O r~ T f T f T -C O C O T— o co CM C O . X— C D CM C D r-. CM o CM C D 00 CM T f Final TOC Conc. In MBR (mg/L) 2 O) r-03 C O r-. (0 C M C O C O CM 00 in C O in CM r-CM o C O CM C D T f C O C D C O C O 00 C O C M C D i n CO O T f CM C D m 00 OO m Initial TOC Conc. In MBR (mg/L) 2 o 00 C D C O 00 OO r--h-T -T f C M oo C M C M C M o CM r -CM C M s C M s C M o oo C M CM o C O C O s T f T f 00 00 C D C M C D C M C O oo C M o C M Initial TOC Conc. In MBR (mg/L) 2 C M C O T— OO co T— f--C O T— o o> h- C O C M • * C M cn T— C M cn o CM CM CM o T f C M C O T f C M 00 co C M m C M T f CM C O a 00 T f T f T -C O C M T -C O o Methanol Utilization Coefficient (mg/L-min) 2 C N CM C O CM C M <0 CM C M C M CM CM CM CM O ) T -C O C O C M O CM r-C M T f CM T— C O C O C M C M C M CM —^ CM T f CM Methanol Utilization Coefficient (mg/L-min) 2 o> C M o> T— oq T— T~ C M C M C O C M m CM T f CM o> C O T f C M C M T f C M CM C M C D T f T f T— i n Final Methanol Conc. In MBR (mg/L) 2 O O O o O O o O m T— o O O O O o o C O C D C O C M C M o Final Methanol Conc. In MBR (mg/L) r—< O CM in C O C M o C O C O o O o O TT x— o O C D O O in C O 00 C O C D h- O o C O 5> C O o c _^ 2 O C O C M C O i n C M C D C O C M r>-CM CM o> C O C M T f C M T f m C M o T f CM f-CM C O CM m C M O i n C M c n •tf C M C O C M C O C O CM C D co C M o o C O C O O 00 T f C M C N C O C N Inil Meth Com ME (mc 2 CM m m C M CM C O T f CM m w CM T f T f CM CM r-C M CM O m CM C M T f CM CM C M C O C O CM x— co C M r -T f CM C D m C M C O C O C M o C O r -T f C O CM C O T f m Black Liquor Carryover Test C Q C M C O T f <n T - C M C O Tf in X— C M C O T f m - C M C O T f m Black Liquor Carryover Test tn 0) H C M C O T f o o 600 L-MeOH-l L-MeOH-E S-MeOH-l S-MeOH-E 5 10 15 Time (day) (a) Methanol Concentration Profile Time (day) (b) TOC Concentration Profile Figure 5.14 (a) and (b) Methanol and TOC Concentration Profiles during the Black Liquor Carryover Tests (L: Long-term; S: Short-term; MeOH: Methanol; I: Initial Contaminant Concentration in the M B R during a Batch Cycle; E: Final Effluent Contaminant Concentration in the M B R during a Batch Cycle; Time - 1 s t day: August 3, 2001) 69 Time from the Start of the Test (hr) Figure 5.15 Methanol, TOC, and COD Utilization Coefficients Profiles during the First Black Liquor Carryover Test (Black Liquor Concentration: 4 ml BL/ L condensate; L: Long-term; S: Short-term) r-s l-L Time from the Start of the Test (hr) Figure 5.16 Methanol, TOC, and COD Utilization Coefficients Profiles during the Second Black Liquor Carryover Test (Black Liquor Concentration: 8 ml BL/ L condensate; S: Short-term; L: Long-term) 70 As shown in Figure 5.17 and Table 5.5, an inhibitory effect was observed from the M B R exposed to the third long-term black liquor carryover test. The methanol removal coefficient continuously and gradually decreased throughout the third long-term black liquor carryover test. However, methanol removal efficiency still remained above 95 %. TOC, and COD removal efficiency decreased slightly and were 35 and 53 %, for the long-term black liquor carryover test. i r~— T I 0 2 4 6 8 10 Time from the Start of the Teat (hr) Figure 5.17 Methanol, TOC, and COD Utilization Coefficients Profiles during the Third Black Liquor Carryover Test (Black Liquor Concentration: 12 ml BL/ L condensate; S: Short-term; L: Long-term) As illustrated in Figure 5.18 and Table 5.5, there were deleterious effects on both MBRs from the fourth black liquor carryover test, both long-term and short-term. The methanol utilization coefficient of R l that was subjected to a long-term test decreased by 50 % and 71 there was residual methanol observed in both MBRs. Since methanol removal accounted for most of the TOC and COD removal, TOC, and COD removal efficiencies dropped dramatically with methanol removal efficiency. As observed from Figure 5.14 and data from Appendix 4, for the short-term test, the M B R recovered relatively fast and the methanol concentration returned to normal levels after two feed cycles (4 hours). Comparatively, the long-term test upset the M B R and the system recovered only after two days of normal operation. Excess TOC and COD concentrations were observed in the MBRs. 4 6 Time from the Start of the Teat (hr) —9—Methanol-L -+-TOC-L —+-COD-L • Methanol-S -&-TOC-S -+-COD-S Figure 5.18 Methanol, TOC, and COD Utilization Coefficients Profiles during the Fourth Black Liquor Carryover Test (Black Liquor Concentration: 24 ml BL/ L condensate; L: Long-term; S: Short-term) 72 5.5.3 Colour Removal The colour of condensate used during this study was usually light brown and approximately 700 A.P.H.A of apparent colour and 400 A.P.H.A of true colour. With black liquor carryover, the colour of condensate turned darker and increased dramatically even with a small amount of black liquor addition. The addition of 4 mL black liquor in one litre of condensate increased the colour from 700 to 1000 A.P.H.A as apparent colour and from 400 to 700 A.P.H.A as true colour. 3000 T -Time (day) Figure 5.19 Colour of the MBRs Permeate and Condensate (Influent) over the Period of Methanol Shock Loading Tests (BL: Black Liquor Carryover Test; A: Apparent Colour; T: True Colour; L: Permeate of M B R Exposed to Long-term Shock Loading; S: Permeate of M B R Exposed to Short-term Shock Loading; Time - 1 s t day: Aug. 2,2001) The colour of the permeate remained relatively constant throughout the period of the black liquor carryover tests, as illustrated in Figure 5.19. The apparent colour and the true 73 colour of condensate with black liquor carryover increased from 700 to 2800 A.P.H.A and from 400 to 1300 A.P.H.A, but the true colour of permeate only increased from 250 to 400 A.P.H.A. The permeate colour returned to normal shortly after the tests were completed. However, black liquor carryover didn't significantly increase the colour of permeate. The MBRs showed great ability to cope with significant colour increase by black liquor carryover. 5.5.4 Solids Removal and Permeate Flux The MBRs removed 100 % of suspended solids and suspended solids removal efficiency was not affected by black liquor carryover because the pore size of the membrane (500 Angstroms) was smaller than the filter size (1450 Angstroms) used in determination of suspended solids by Standard Methods (APHA/AWWA/WEF, 1995). 3500 3000 3> 2500 g 2000 | 1500 3> 1000 500 0 BL2 BL3 10 Time (day) SL4_ 15 -R1-VDS -R1-TDS -R2-VDS •R2-TDS 20 Figure 5.20 Volatile and Total Solids Concentrations of the M B R Permeates over the Black Liquor Carryover Testing Period (BL: Black Liquor Carryover Test; VDS: Volatile Dissolved Solids; TDS: Total Dissolved Solids; R l : Permeate of M B R 1; R2: Permeate of M B R 2; Time - 1 s t day: August 2,2001) 74 The dissolved solids concentrations of the permeates were not greatly affected by the simulated black liquor carryover (Figure 5.20). A slight increase of dissolved solids concentrations was observed during the black liquor carryover tests, as indicated for B L 3 and B L 4. Thereafter, the solids concentrations returned to normal levels. Since the ability of a membrane bioreactor to remove non-biodegradable dissolved solids is poor (Ragona, 1998), the low impact on permeate dissolved solids concentrations is probably because black liquor carryover mostly increased the suspended solids concentrations of the condensate, not the dissolved solids concentration. The flux of the membranes decreased more rapidly with the higher solid concentrations of condensate with black liquor carryover and the membrane would need more frequent cleaning i f the black liquor carryover continued (See Appendix 6 and Section 5.7). 5.5.5 MLVSS Concentrations Black liquor is a complex mixture of materials and contains many contaminants that may exert toxic effects on a mixed microbial culture. The M L V S S concentrations, as shown in Figure 5.21, slightly declined for both MBRs during the period of the black liquor carryover tests. Similarly, the observed growth yields of the MBRs also decreased during the period of black liquor carryover tests (for R l decreased from 0.0254 to 0.0241, and for R2 decreased from 0.026 to 0.024). However, the effect of black liquor on the growth yield of biomass was not clearly observed and needs further study to be clarified. 75 Condensate used during black liquor carryover tests was collected from Howe Sound Pulp and Paper Ltd. (Port Mellon, BC, Canada). Therefore, two MBRs were acclimatized to the new condensate for two weeks. Steady state operation was assumed to have been reached because stable M L V S S concentrations and 95% methanol removal efficiencies were observed. The M L V S S concentration profiles during the steady state (day 0 to 15) are shown in Figure 5. 21. 1500 -I , , r - , , , 1 0 5 10 15 20 25 30 35 Day Figure 5.21 M L V S S Concentrations Profiles during Black Liquor Carryover Tests (Time - 1 s t day: July 16,2001; Dashed Line: Start of the Black Liquor Carryover Test) 5.5.6 Summary The performances of the MBRs weren't significantly affected and were able to degrade the excess COD and TOC during the first and second black liquor carryover tests. The third long-term black liquor carryover test started to show an inhibitory effect on the M B R performance, while the third short-term black liquor carryover test didn't seriously 76 influence the contaminant removal efficiencies of the MBR. The fourth black liquor carryover test had deleterious effects on the MBRs, both short-term and long-term. Methanol removal efficiency was greatly decreased by the simulated black liquor carryover and influenced TOC and COD removal efficiencies. For the short-term test, the MBR recovered relatively fast and the methanol concentration returned to normal levels after two batches (4 hours). Comparatively, the long-term test upset the MBR and the system recovered after two days. The colour of the MBR permeates remained relatively constant throughout the period of the black liquor carryover tests. The excess colour resulted from black liquor carryover was mostly removed from the membrane filters and only increased the true colour of permeate from 250 to 400 A.P.H.A. The MBRs removed all of the suspended solids, but their ability to remove non-biodegradable dissolved solids was poor. During the black liquor carryover tests, a slight increase of the dissolved solids concentrations of the permeate was observed. However, the flux of the membrane decreased more rapidly (discussed in more detail in section 5.7) and the membrane would need more frequent cleaning if the black liquor carryover continued. The observed growth yield and MLVSS concentrations slightly declined for both MBRs during the period of the black liquor carryover tests. However, the effect of black liquor on the growth yield of biomass was not clearly observed and needs further study to be clarified. 77 5.6 Mil l Shutdown Test This test was designed to simulate a shutdown of the mill operation, which usually lasts 7 to 10 days. For ten days, the feeding, heating systems, and pH controller of the MBR were turned off. The aeration and circulation rates through membrane were turned down to just maintain aerobic conditions in the reactor. Subsequently, the MBR was restarted gradually by controlling temperature and feed rate, as described thoroughly in section 4.2.4. Data are presented in Appendix 5 and summarized in section 5.6. Results are discussed in section 5.6. 5.6.1 pH and Temperature of M B R Temperature and pH in the reactor were recorded on a daily basis and are shown in Table 5.6. About six hours after shutdown, the temperature in the reactor gradually decreased from 60 °C to 32 °C, slightly higher than room temperature. Temperature fluctuated with room temperature, but was never under 30 °C (ambient temperature was 20 to 28 °C during the test). This is probably because the membrane reactor was situated in an insulated box and heat generated from circulation through the membrane unit increased the heat content of the system. The pH increased from 6.5 to 8.4 slowly, and remained at approximately 8.4 after the sixth day of the shutdown test. The increase of pH throughout the shutdown period was possibly due to the stripping of dissolved carbon dioxide. 78 Table 5.6 Temperature and pH Conditions in M B R during M i l l Shutdown Test Time Temperature (°C) PH August 24, 2001 9:00 60 6.57 11:00 47 6.87 13:00 49 6.96 15:00 32 7.08 August 25, 2001 9:00 31 7.60 August 26, 2001 9:00 32 7.92 August 27, 2001 9:00 34 8.16 August 28, 2001 9:00 31 8 18 August 29, 2001 9:00 34 8.37 August 30, 2001 9:00 34 8.34 August 31, 2001 9:00 33 8.39 September 1, 2001 9:00 35 8.31 September 2, 2001 9:00 32 8.40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Day Figure 5.22 Temperature Profile during the M i l l Shutdown Test (Dashed Lined Indicates the End of the M i l l Shutdown Period. At the Same Time, the MBRs were Returned to Normal Operating Conditions) 79 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Day Figure 5.23 pH Profile during the M i l l Shutdown Test (Dashed Lined Indicates the End of the M i l l Shutdown Period. At the Same Time, the MBRs were Returned to Normal Operating Conditions) 5.6.2 Methanol , T O C , and C O D Removal During the 10 days of the shutdown test, a batch test was performed every two days to monitor the activity of the system. A volume of 400 ml of kraft condensate was fed to the reactor and methanol, TOC, and COD concentrations were measured every 15 minutes for two hours. The methanol, TOC and COD utilization coefficient profiles are shown in Figure 5.24. It is obvious that the methanol, TOC and COD utilization coefficients decreased during the shutdown period. The methanol utilization coefficient decreased from 3 to 0.3; the TOC removal coefficient dropped from 1.34 to 0.1; and the COD removal coefficient declined from 4.3 to 1.3. However, the system recovered along with the increase of organic loading fairly well. It was shown that the M B R was capable of handling the long shutdown period and could recover in a short time to full capacity. No deleterious effects from the shutdown were observed. The methanol removal coefficient 80 recovered from 0.3 to 2.1; the TOC removal coefficient climbed back to 0.9; COD removal coefficient also increased to 3.9. •Methanol —•—TOC * COD Figure 5.24 Methanol, TOC, and COD Utilization Coefficients Profiles over the M i l l Shutdown Test Period (Dashed Lined Indicates the End of the M i l l Shutdown Period.) 5.6.3 MLVSS concentrations During the mill shutdown test, food was not available and microorganisms were forced to metabolize their own protoplasm without replacement. As a result, the M L V S S concentration in the membrane bioreactor decreased, as expected, from 3000 mg/L to 1200 mg/L over ten days (refer to Figure 5.25). After re-starting the feed, biomass M L V S S concentration increased back to 2400 mg/L, at a faster rate than the rate of decrease during the mill shutdown. No deleterious effects on the biomass from shutdown were observed. Poor settling ability commonly observed after shutdown in conventional 81 activated sludge system is not a concern with an M B R system because of the complete retention of biomass by the membrane unit. 3000 , Day Figure 5.25 M L V S S Concentration in the M B R during the M i l l Shutdown Test Period (Dashed Lined Indicates That the M i l l Shutdown Period, 10 days, finished. At the Same Time, the MBRs are Back to Normal Operating Conditions) 5.6.4 Summary Methanol, TOC and COD utilization coefficients decreased during the shutdown period. However, the M B R system recovered along with an increase of organic loading fairly well, and it was obvious that M B R was capable of tolerating the long shutdown period and could recover in a short time to full capacity. No deleterious effects from shutdown were observed. 82 5.7 Membrane Performance 5.7.1 Initial Membrane Flux Two 500-Angstrom Membralox Tl-70 filters used in Berube's (2000) study were used during the period of steady state experimentation. The initial permeate flux of the membrane was measured by filtering tap water through the membrane at the same operating conditions as those during steady state experiment (refer to Table 4.2). The initial membrane flux was determined to be 160 L/(m -hr). Permeate flux gradually decreased and membrane cleaning was performed when flux dropped to 40 L/(m2-hr). Due to irreversible loss of permeate flux of one membrane, two new 500-Angstrom Membralox Tl-70 filters with new casings were purchased and used for R2 during the periods of methanol shock loading tests, black liquor carryover tests, and mill shutdown test. Rl continuously used the previous membrane filter until the end of the experiment. The initial flux of the new membrane was determined to be 122 L/(m2-hr). Permeate flux gradually decreased and membrane cleaning was performed when flux dropped to 40 L/(m2-hr). 5.7.2 Permeate Flux Membrane permeate flux was affected by a variety of factors. Since fouling was not the main interest of this study, this section simply presents permeates flux data and observations. The performances of the ultrafiltration membranes used in Rl and R2 during this study are illustrated in Figure 5.26 and 5.27 respectively. 83 Maximum flux always occurred immediately following a membrane cleaning, and decreased rapidly in the first few days to approximately 55 % of the maximum flux. Then, it declined slowly until another membrane cleaning was performed. The time required for a membrane cleaning varied between the different filters and throughout this study. 300 Figure 5.26 Permeate Flux of R l (S: Steady-state; M : Methanol Shock Loading Tests; N : New New Combined Condensate from Howe Sound Pulp and Paper Ltd (Port Mellon, B C , Canada); B: Black Liquor Carryover Tests) The membrane bioreactor R l was capable of operating for up to 65 days without cleaning. During the black liquor carryover test, R l didn't require the membrane cleaning even though the solids content of feed was 2 to 4 times higher than usual. The decrease rate of permeate flux during the period of black liquor carryover tests is slightly higher than that under normal operating conditions, but became stable after the tests were completed. 84 160 , , . ^ , 1 0 50 100 150 200 250 Day Figure 5.27 Permeate Flux of R2 (S: Steady-state; M : Methanol Shock Loading Tests; N : New Combined Condensate from Howe Sound Pulp and Paper Ltd (Port Mellon, B C , Canada); B: Black Liquor Carryover Tests) In the beginning of the steady state, the membrane bioreactor R2 was capable of operating for up to 45 days without cleaning. Irreversible loss of permeate flux was observed on May 2001. Therefore, R2 was replaced with the new membrane filter and casing. The filter is the same configuration as the old one, except there is no stainless steel fitting on both ends. The new casing is only different on the part of membrane seal system. The minor difference should not cause any significant difference on membrane performance (Personal communication, Rishi Sondhi, 2001, U.S. Filter, Deland, Florida). After R2 was replaced with the new membrane unit, the M B R 2 system required much more frequent cleaning than before. As shown in Figure 5.27, the membrane flux dropped more rapidly and it required cleaning every 4 to 6 days. To clarify whether the high 85 cleaning frequency was caused by the different mixed liquors of the two MBRs, the membrane unit of R2 was connected with reactor 1 for three days after cleaning. However, similar rapid flux decrease and low membrane flux were observed. Therefore, it was concluded that the lower membrane flux resulted from the nature of the new membrane unit, not from the different mixed liquors in the M B R reactors. More investigation is required to identify the causes of the membrane fouling. 86 Chapter 6 Conclusions and Recommendations 6.1 Conclusions Steady State Experiment The results of the present study during the steady state experiments are summarized and compared with Berube's (2000) results, as shown in Table 6.1. Table 6.1 Summary of the results of the steady state experiment of the present study and Berube's (2000) research Methanol Removal Efficiency (%) Specific Methanol Utilization Coefficient (day1) TOC Removal Efficiency (%) Specific TOC Utilization Coefficient (day"') MLVSS Concentration (mg/L) Operating Conditions SRT (days) HRT (hrs) Methanol Concentration (mg/L) Present Study 95 Rl: 1.03 R2: 1.47 64 Rl:0.51 R2:0.74 Rl:3000 R2:2500 38 9 1200 Berube (2000) 99 0.59 93 0.66 2500 20 18 900 The major conclusions from the experiment were as follows. 1. The MBRs exhibited stable removal of the main contaminants, methanol and organic components expressed as TOC. The difference between TOC removal efficiencies of 87 the present study and Berube's research (2000) was due to the different calculation methods used for removal efficiency, as explained in section 5.3.1. 2. With a long SRT (38 days), the MBRs exhibited a low observed growth yield, 0.0347 for R l and 0.0254 for R2. Low growth yield is considered an advantage of the process because of the associated low biosolids management cost. 3. The M B R was operated as long as 65 days without membrane cleaning. However, unknown causes resulted in the irreversible fouling of the membrane unit for R2 and may be a potential problem for M B R operation. Methanol Shock Loading Tests The MBRs were subjected to three methanol shock loading tests. By adding methanol into the feed condensate, the methanol concentrations of the feed condensate were increased by 1.5, 2, and 2.5 times. R l was subjected to four shock loadings to investigate long-term effects, and R2 was subjected to one shock loading to identify short-term effects. Major findings of the methanol shock loading tests are as follows. 1. The MBRs were reasonably stable and able to achieve the same removal efficiency when the load was increased by 1.5 and 2 times instantaneously. When the feed strength was increased by a factor of 2.5, the MBRs showed distinct signs of 88 overload. However, R l recovered about four hours after the short-term shock loadings, and R2 recovered two days after the long-term shock loadings. 2. An overload of methanol seemed to disturb the biomass and the colour of the permeate increased slightly after the methanol shock loading test in which methanol concentration was increased by 2.5 times. 3. Excess methanol from the methanol shock loading tests increased slightly the growth yields and the M L V S S concentrations in the MBRs. Black Liquor Carryover Tests The effects of simulated black liquor spills on a high temperature M B R treating kraft condensate was investigated by four black liquor carryover tests. Concentrations of 4 mL, 6 mL, 8 mL and 16 mL black liquor per litre kraft condensate were chosen as the intensities of the black liquor carryover tests of the present study. The reactor was subjected to four shock loadings to investigate long-term effects, and one shock loading to identify short-term effects. Major conclusions are as follows. 1. The performances of MBRs weren't significantly affected, as the systems were able to degrade the excess COD and TOC during black liquor carryover tests with 4 mL and 6 mL black liquor per litre evaporator condensate. The long-term black liquor carryover test with 8 mL black liquor per litre evaporator condensate started to show 89 an inhibitory effect on the M B R performance. The short-term black liquor carryover test at the same black liquor concentration didn't seriously influence the contaminant removal efficiencies of the M B R . 2. The black liquor carryover test with 16 mL black liquor per litre evaporator condensate resulted in deleterious effects on the MBRs, both short-term and long-term. Methanol removal efficiency was greatly decreased by the black liquor carryover and influenced TOC and COD removal efficiencies. For the short-term test, the M B R recovered relatively fast and the methanol concentration returned to normal levels after two batch cycles (4 hours). Comparatively, the long-term test upset the M B R and the system recovered after two days. 3. The colour of the M B R s ' permeates remained relatively constant throughout the period of the black liquor carryover tests. The excess colour resulted from black liquor carryover was mostly removed by the membrane filters and only increased true colour of permeate from 250 to 400 A.P.H.A. 4. A slight increase in the dissolved solids concentrations of the permeate during the black liquor carryover tests was observed. The MBRs removed all of the suspended solids, but their ability to remove non-biodegradable dissolved solids was poor. 5. The permeate flux of the membrane decreased more rapidly and the membrane would need more frequent cleaning i f the black liquor carryover continued. 90 6. The observed growth yield and M L V S S concentrations declined slightly for both MBRs during the period of the black liquor carryover tests. However, the effect of black liquor on the growth yield of biomass was not clearly observed and needs further study to be clarified. Mill Shutdown Tests Methanol, TOC, and COD utilization coefficients decreased during the shutdown period. However, the M B R system recovered along with an increase of feed loading fairly well, and it was obvious that M B R was capable of handling the 10-day shutdown period and was able to recover in a short time to full capacity. No deleterious effects from a 10-day shutdown were observed. 6.2 Recommendations With limited time, the present research project could only discover the tip of the iceberg regarding the effects of transient loads on the M B R performance. There were new questions generated and waiting to be answered. The following are possible areas of further research to complete our understanding of high temperature M B R treating kraft mill condensate. 91 1. The effects of temperature variations on the high temperature M B R were not investigated and are important to improve our understanding of the stability of the high temperature M B R system treating kraft condensate. 2. The performance of the membrane was not the focus of the present study. However, irreversible fouling was observed for one of the membrane unit and may be a potential problem for the membrane bioreactor. Further research is required to optimize the M B R operation with respect to the membrane performance. 3. The purpose of the present study was to examine the treatment of kraft evaporator condensate by high temperature M B R . To be more economically attractive, further research is required to investigate the feasibility of a high temperature M B R treating kraft combined condensate, both the evaporator and digester areas. Especially, Dr. Barton suggested that turpentine shock loading would be the one of main interests of the study on the treatment system of kraft combined condensate treatment (personal communication, Doug Barton, 2001, NCASI). 4. M L V S S concentration of M B R commonly ranges from 10,000 to 30,000 mg/L at various SRT. During the present study, low M L V S S concentrations were observed and could be a potential factor causing unstable M B R operation. Further research is needed to identify the causes and the effects of the low M L V S S concentrations on the M B R performance. 92 Shock loads are often divided into two ways: either short-term shock loads which only last a few hours, or long-term changes of days or weeks duration before returning to the original operating conditions (Nachaiyasit and Stuckey, 1997a). During the present study, the long-term shock loads only lasted approximately one HRT. To further investigate the effects of long-term shock loadings on the M B R performance, longer shock loadings should be applied to system. r 93 References: Allen D.G. and Tripathi C.S., 1998, Feasibility study of thermophilic aerobic biological treatment of bleached kraft mill effluent, Proceedings 1998 TAPPI International Environmental Conference, Part 3, TAPPIPRESS, Atlanta, 1189-1201. 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M . and Venkataraman B., 1993, Design considerations for stream stripping of kraft condensates, Proceedings TAPPI Environmental Conference, 201-207. 104 Appendix 1 Characteristics of Kraft Condensate During the period of steady state testing and the methanol shock loading tests, the evaporator condensate was shipped from the Western Pulp Limited Partnership bleached kraft mill (Squamish, BC, Canada) to U B C . The characteristics of the evaporator condensate used for the present study are presented in Table A l - 1. Combined condensate was collected from Howe Sound Pulp and Paper Limited Partnership (Port Mellon, B C , Canada) during the black liquor spill tests and mill shutdown test. The characteristics of the combined condensate are presented in table A l -2. Notably, received condensate that had conductivity greater than 800 u.S was discarded and not considered as representative samples. 105 Table A 1 - 1 Characteristics of Evaporator Condensate from Western Pulp Ltd. Conductivity PH Methanol TOC TOC filtered TOC solid(%) Methanol as TOC(%) (MS) (mg/L) (mg C/L) (mg C/L) 13-Jul-00 175 6.5 487 273 252 7.7 66.9 19-Jul-00 195 6.5 324 290 261 10.0 41.9 2-Aug-00 150 7 393 273 256 6.2 54.0 9-Aug-00 500 9 455 373 352 5.6 45.7 30-Aug-00 385 6 458 468 417 10.9 36.7 14-Sep-00 270 6 529 434 413 4.8 45.7 5-Oct-200 260 6 456 418 380 9.1 40.9 12-Oct-00 290 8.5 433 444 438 1.4 36.6 18-Oct-00 320 8.5 457 513 464 9.6 33.4 25-Oct-00 260 8 936 464 458 1.3 75.6 2-Nov-00 540 8.47 319 297 278 6.4 40.3 9-Nov-00 135 7.5 399 350 348 0.6 42.8 15-Nov-OO 170 7.88 363 302 281 7.0 45.1 23-Nov-OO 145 7.39 427 360 342 5.0 44.5 6-Dec-00 130 7.47 374 359 338 5.8 39.1 13-Dec-00 385 7.16 441 400 378 5.5 41.3 20-Dec-00 360 7.14 508 294 273 7.1 64.8 10-Jan-01 580 7.86 359 440 392 10.9 30.6 17-Jan-01 580 7.80 373 416 400 3.8 33.6 24-Jan-01 600 7.43 319 371 301 18.9 32.2 31-Jan-01 590 7.42 341 364 259 28.8 35.1 7-Feb-01 490 7.89 319 348 240 31.0 34.4 14-Feb-01 480 7.99 317 276 222 19.6 43.1 28-Feb-01 590 8.1 399 342 310 9.4 43.8 8-Mar-01 680 8.7 359 414 402 2.9 32.5 14-Mar-01 720 8.4 378 432 408 5.6 32.8 4-Apr-01 500 8.5 324 336 330 1.8 36.2 11-Apr-01 630 8.94 325 348 332 4.6 35.0 18-Apr-01 210 7.42 225 199 182 8.5 42.4 25-Apr-01 210 7.49 213 207 183 11.6 38.6 2-May-01 380 7.91 317 212 196 7.5 56.1 9-May-01 395 7.91 277 180 152 15.6 57.7 16-May-01 430 7.94 321 240 208 13.3 50.2 23-May-01 255 8.17 309 164 148 9.8 70.7 30-May-01 395 8.17 347 248 208 16.1 52.5 6-Jun-01 255 8.14 243 160 148 7.5 57.0 13-Jun-01 370 8.34 304 204 188 7.8 55.9 20-Jun-01 470 7.93 335 244 224 8.2 51.5 27-Jun-01 370 8.01 359 248 212 14.5 54.3 Average 381 7.7 380 326 297 9.3 45.4 +/-(10%) 44 0.2 31 25 24 2 3.0 Table A 1 - 2 Characteristics of Combined Condensate from Howe Sound Pulp and Paper Ltd. Conductivity PH Methanol TOC TOC filtered TOC solid(%) Methanol as TOC(%) COD (mg/L) (mg C/L) (mg C/L) (mg 02/L) 1 500 8.6 4920 2085 1980 5 88 9310 2 500 8.4 5080 1985 1880 5 96 9180 3 450 8.2 4860 2185 1910 13 83 9420 Average 483 8.4 4953 2085 1923 8 89 9303 +/-(10%) 27 0.2 108 95 49 4.1 6 114 106 Appendix 2 Data Collected During Steady State Experiment Appendix 2 contains the data collected during steady state experiment. Results from batch tests monitoring removal kinetics of methanol and total organic carbon (TOC) are presented in Table A2 - 1 to A2 - 12 for Reactor 1, and Table A2 - 13 to Table A2- 24 for reactor 2. For these tables, the parameter K is the zero order coefficient for the biological removal of contaminant (mg/L-min). The parameter Co is the initial concentration in the M B R and the parameter Ce is the final TOC concentration in the M B R , derived from the second zero order removal coefficient. The R 2 value is the coefficient of determination for linear regression. The calculations for observed growth yields of R l and R2 are presented in Table A2 - 25 and Table A2 - 26. Results from methanol removal efficiency tests are summarized in Table A2 - 27. The incidents happened during the steady state experiment are summarized in Table A2 -28. 107 C o n t a m i n a n t R e m o v a l - S t e a d y S ta te - R e a c t o r T a b l e A 2 - 1 M a r c h 28 , 2001 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 227.6 166 30 186 152 45 172.1 122 60 123 103 75 32.4 94 90 0 87 Co (Ce) 284.2 190.7 ( 7 1 . 1 ) K 3 1.47 0.53 R 2 0.92 0.958 0.995 T a b l e A 2 - 2 A p r i l 13, 2001 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 213.3 158 30 186.5 138 45 132.7 126 60 68.9 105 75 26.5 93 90 0 86 C o (Ce) 272.9 174.5 ( 6 6 . 2 ) K 3.3 1.14 0.63 R 2 0.985 0.99 0.977 T a b l e A 2 - 3 A p r i l 18, 2001 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 233.9 144 30 133.1 124 45 115.2 98 60 61.2 79 75 39.3 73 90 12.5 68 Co (Ce) 243.4 166.5 ( 56.4 ) K 2.7 1.47 0.37 R 2 0.926 0.997 0.997 T a b l e A 2 - 4 M a y 1 , 2 0 0 1 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 237.6 152 30 163.2 118 45 148.7 92 60 114.3 81 75 94.5 78 90 33.2 73 Co (Ce) 258.2 170.5 ( 6 4 . 9 ) K 2.4 7.59 0.27 R 2 0.953 0.955 0.98 T a b l e A 2 - 5 M a y 8, 2001 T i m e Methano l T O C (min) (mg/L) (mg/L) 15 272.2 188 30 225.9 154 45 209 .5 150 60 174.4 123 75 152.9 109 90 111.5 103 Co (Ce) 296.8 203.5 ( 8 1 . 3 ) K 2 1.33 0.67 R 2 0.986 0.929 0.95 T a b l e A 2 - 6 M a y 12, 2001 T i m e Methano l T O C (min) (mg/L) (mg/L) 15 213.3 144 30 188.9 130 45 167.7 102 60 132.2 83 75 105.3 75 90 68.8 70 Co (Ce) 246 .9 167.5 ( 56.9 ) K 1.9 1.41 0.43 R 2 0.993 0.986 0.983 108 C o n t a m i n a n t R e m o v a l - S t e a d y S ta te T a b l e A 2 - 7 M a y 22 , 2001 - R e a c t o r 1 - C o n ' t T a b l e A 2 - 1 0 J u n e 10, 2001 Time Methanol TOC (min) (mg/L) (mg/L) 15 219.8 152 30 190.7 136 45 128.9 112 60 52.9 95 75 22.1 88 90 3.2 79 Co (Ce) 269.4 172.5 ( 6 3 . 7 ) K 3.2 1.3 0.53 R 2 0.965 0.994 0.995 T a b l e A 2 - 8 M a y 29 , 2001 Time Methanol TOC (min) (mg/L) (mg/L) 15 207.6 144 30 151.5 111 45 101.1 96 60 50.3 76 75 0 72 90 0 65 Co (Ce) 258.2 161.5 ( 54.1 ) K 3.5 1.46 0.37 R 2 0.999 0.972 0.976 T a b l e A 2 - 9 J u n e 4 , 2001 Time Methanol TOC (min) (mg/L) (mg/L) 15 207.6 143 30 178.5 123 45 133.5 107 60 84.3 89 75 37.6 80 90 0 73 Co (Ce) 257.9 160 ( 57.1 ) K 2.9 1.19 0.53 R 2 0.996 0.998 0.995 Time Methanol TOC (min) (mg/L) (mg/L) 15 213 .8 148 30 182.7 128 45 139.8 106 60 107.6 77 75 37 71 90 0 66 Co (Ce) 267.3 173.5 ( 54.4 ) K 2.9 1.57 0.37 R 2 0.985 0.992 0.997 T a b l e A 2 - 1 1 J u n e 14, 2001 Time Methanol TOC (min) (mg/L) (mg/L) 15 214.4 145 30 162.8 125 45 122.4 110 60 93 .5 97 75 46 .8 89 90 3.3 77 Co (Ce) 250 .4 159 ( 57.3 ) K 2.7 1.06 0.67 R 2 0.995 0.99 0.987 T a b l e A 2 - 1 2 J u n e 24 , 2001 Time Methanol TOC (min) (mg/L) (mg/L) 15 215.3 145 30 173.8 134 45 124.9 113 60 73.4 93 75 42 .5 87 90 0 77 Co (Ce) 257.2 165.5 ( 59.4 ) K 2.9 1.18 0.53 R 2 0.996 0.984 0.98 109 C o n t a m i n a n t R e m o v a l - S t e a d y S t a t e - R e a c t o r 2 T a b l e A 2 - 1 3 M a r c h 28 , 2001 T a b l e A 2 - 1 6 M a y 1 , 2 0 0 1 T i m e Methanol T O C T i m e Methano l T O C (min) (mg/L) (mg/L) (min) (mg/L) (mg/L) 15 190.8 138 15 226 144 30 161.9 108 30 190.5 118 45 142.1 100 45 148.7 98 60 113.5 73 60 112.7 85 75 75.4 69 75 93.2 78 90 40.2 63 90 31.5 69 Co (Ce) 224.8 155.5 ( 53.3 ) Co (Ce) 263.8 160.5 ( 53.7 ) K 2 1.35 0.33 K 2.5 1.3 0.53 R 2 0.989 0.96 0.987 R2 0.986 0.979 0.995 T a b l e A 2 - 1 4 A p r i l 14, 2001 T a b l e A 2 - 1 7 M a y 8, 2001 T i m e Methanol T O C T i m e Methano l T O C (min) (mg/L) (mg/L) (min) (mg/L) (mg/L) 15 207.2 148 15 238 .9 163 30 163.8 138 30 204.6 146 45 148.2 106 45 168.8 129 60 114 95 60 120.3 107 75 94.6 88 75 85.6 94 90 22.7 79 90 54.3 87 Co (Ce) 241.5 169.5 ( 63.7 ) Co (Ce) 278.3 182.5 ( 6 5 . 6 ) K 2.2 1.27 0.53 K 2.5 1.23 0.67 R 2 0.9535 0.952 0.995 R2 0.997 0.996 0.971 T a b l e A 2 - 1 5 A p r i l 23 , 2001 T a b l e A 2 - 1 8 M a y 12, 2001 T i m e Methanol T O C T i m e Methano l T O C (min) (mg/L) (mg/L) (min) (mg/L ) (mg/L) 15 179.5 134 15 213.4 134 30 158.4 104 30 174.3 120 45 121.6 86 45 132.5 92 60 92.8 76 60 88.4 76 75 54.3 70 75 41.1 68 90 4.5 63 90 0 63 Co (Ce) 223.5 140 ( 50.6 ) Co (Ce) 259.4 156 ( 4 9 . 9 ) K 2.3 1.2 0.43 K 2.9 1.35 0.43 R 2 0.986 0.9481 0.998 R2 0.999 0.983 0.983 110 C o n t a m i n a n t R e m o v a l - S t e a d y S ta te - R e a c t o r 2 - C o n ' t T a b l e A 2 - 1 9 M a y 22 , 2001 T a b l e A 2 - 2 2 J u n e 10, 2001 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 197.1 150 30 178.2 129 45 127.4 114 60 82.3 95 75 36.9 87 90 0 80 C o (Ce) 249.1 167 ( 64.8 ) K 2.8 1.2 0.5 R 2 0.991 0.999 0.999 T a b l e A 2 - 20 M a y 29 , 2001 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 199.5 130 30 164.5 116 45 125.6 102 60 96.3 81 75 58.8 74 90 24.6 64 Co (Ce) 233.6 147.5 ( 4 7 . 1 ) K 2.3 1.07 0.57 R 2 0.999 0.989 0.99 T a b l e A 2 - 21 J u n e 4 , 2001 T i m e Methanol T O C (min) (mg/L) (mg/L) 15 219.5 140 30 187.4 123 45 127.8 109 60 105.7 82 75 74.2 76 90 38.1 68 Co (Ce) 252.3 160.5 ( 53.9 ) K 2.4 1.25 0.47 R 2 0.985 0.979 0.993 T i m e Methano l T O C (min) (mg/L ) (mg/L) 15 233.6 157 30 199.4 139 45 144.8 119 60 120.4 103 75 79 93 90 37.6 84 C o (Ce) 272.4 175 ( 6 5 . 3 ) K 2.6 1.21 0.63 R 2 0.994 0.998 0.999 T a b l e A 2 - 2 3 J u n e 14, 2001 T ime Methanol T O C (min) (mg/L) (mg/L) 15 214.4 143 30 188.3 127 45 143.5 111 60 122.2 89 75 94 .5 84 90 52.3 74 C o (Ce) 247.2 162 ( 59.8 ) K 2.1 1.19 0.5 R 2 0.991 0.9932 0.964 T a b l e A 2 - 2 4 J u n e 24 , 2001 T i m e Methano l T O C (min) (mg/L) (mg/L) 15 229.3 149 30 190.4 131 45 154.3 118 60 111.2 95 75 82.4 88 90 41 .7 77 C o (Ce) 265 .4 167 ( 59.7 ) K 2.5 1.17 0.6 R 2 0.998 0.989 131.7 111 Table A2 - 25 Growth Yield of Reactor 1 During Period of Steady State Tests Date Cumulative Methanol MLVSS Sludge Cumulative Cumulative Time Consumed Wasted Methanol Solids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 28-Mar-01 0 457 5320 261 0 0 29-Mar-01 1 418 5320 261 5016 261 30-Mar-01 2 438 3593 176 10272 437 31-Mar-01 3 471 3593 176 15924 613 2-Apr-01 5 518 3593 176 28356 965 12-Apr-01 15 486 4120 202 86676 2984 13-Apr-01 16 451 5398 265 92088 3248 14-Apr-01 17 492 5398 265 97992 3513 16-Apr-01 18 468 5661 277 103608 3790 17-Apr-01 19 468 4622 226 109224 4017 18-Apr-01 20 386 4622 226 113856 4243 19-Apr-01 21 372 4622 226 118320 4470 20-Apr-01 22 394 4622 226 123048 4696 23-Apr-01 23 414 4083 200 128016 4896 24-Apr-01 24 448 4083 200 133392 5096 25-Apr-01 25 442 5267 258 138696 5354 26-Apr-01 26 503 5267 258 144732 5612 27-Apr-01 27 451 5267 258 150144 5870 30-Apr-01 30 395 5267 258 164364 6645 1-May-01 31 350 5267 258 168564 6903 2-May-01 32 488 5267 258 174420 7161 3-May-01 33 476 4967 243 180132 7404 4-May-01 34 498 4967 243 186108 7648 7-May-01 37 462 4700 230 202740 8338 8-May-01 38 470 2472 121 208380 8460 9-May-01 39 478 2472 121 214116 8581 12-May-01 42 486 3333 163 231612 9071 14-May-01 44 447 3333 163 242340 9397 16-May-01 46 429 3489 171 252636 9739 17-May-01 47 473 3489 171 258312 9910 18-May-01 48 439 3455 169 263580 10079 20-May-01 50 488 3455 169 275292 10418 21-May-01 51 477 3455 169 281016 10587 22-May-01 52 467 4044 198 286620 10786 23-May-01 53 491 4044 198 292512 10984 24-May-01 54 479 4044 198 298260 11182 26-May-01 56 470 3517 172 309540 11527 27-May-01 57 483 3517 172 315336 11699 29-May-01 59 490 3517 172 327096 12044 30-May-01 60 428 3517 172 332232 12216 31-May-01 61 458 3617 177 337728 12393 1-Jun-01 62 465 3617 177 343308 12570 4-Jun-01 65 492 3300 162 361020 13055 5-Jun-01 66 450 3300 162 366420 13217 6-Jun-01 67 494 3300 162 372348 13379 7-Jun-01 68 429 3167 155 377496 13534 8-Jun-01 69 493 3167 155 383412 13689 10-Jun-01 71 459 2983 146 394428 13982 11-Jun-01 72 443 2983 146 399744 14128 12-Jun-01 73 430 2983 146 404904 14274 14-Jun-01 74 446 3306 162 410256 14436 16-Jun-01 76 434 3306 162 420672 14760 17-Jun-01 77 435 3283 161 425892 14921 20-Jun-01 80 447 2800 137 441984 15332 Growth Yield 0.0347 'Measured MLVSS Value in Bold. 112 Table A2 - 26 Growth Yield of Reactor 2 During Period of Steady State Tests Date Cumulative Methanol MLVSS Sludge Cumulative Cumulative Time Consumed Wasted Methanol Solids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 28-Mar-01 0 476 2567 133 0 0 1-Apr-01 4 415 2305 120 19920 479 2-Apr-01 5 457 2305 120 25404 599 3-Apr-01 6 425 2420 126 30504 725 4-Apr-01 7 465 2420 126 36084 851 7-Apr-01 10 412 2420 126 50916 1229 8-Apr-01 11 473 2420 126 56592 1354 12-Apr-01 15 483 2420 126 79776 1858 14-Apr-01 17 447 1842 96 90504 2049 16-Apr-01 19 483 2611 136 102096 2321 18-Apr-01 21 465 2611 136 113256 2592 19-Apr-01 22 484 2611 136 119064 2728 23-Apr-01 26 458 2733 142 141048 3297 24-Apr-01 27 448 3067 159 146424 3456 25-Apr-01 28 423 3067 159 151500 3616 26-Apr-01 29 484 3067 159 157308 3775 27-Apr-01 30 473 3067 159 162984 3935 30-Apr-01 33 472 3067 159 179976 4413 1-May-01 34 455 3067 159 185436 4572 2-May-01 35 487 3067 159 191280 4732 3-May-01 36 496 2264 118 197232 4850 4-May-01 37 483 2264 118 203028 4967 7-May-01 40 460 2555 133 219588 5366 8-May-01 41 462 2555 133 225132 5499 12-May-01 45 437 2555 133 246108 6030 16-May-01 49 464 3206 167 268380 6697 17-May-01 50 426 3206 167 273492 6864 18-May-01 51 461 3206 167 279024 7031 20-May-01 53 433 3206 167 289416 7364 21-May-01 54 432 3206 167 294600 7531 22-May-01 55 455 2833 147 300060 7678 23-May-01 56 479 2833 147 305808 7825 24-May-01 57 480 2833 147 311568 7973 26-May-01 59 418 2633 137 321600 8246 27-May-01 60 482 2633 137 327384 8383 29-May-01 62 454 2754 143 338280 8670 30-May-01 63 439 2754 143 343548 8813 31-May-01 64 519 2900 151 349776 8964 1-Jun-01 65 486 2900 151 355608 9115 4-Jun-01 68 451 2767 144 371844 9546 5-Jun-01 69 497 2767 144 377808 9690 6-Jun-01 70 489 2767 144 383676 9834 7-Jun-01 71 487 3000 156 389520 9990 8-Jun-01 72 283 3000 156 392916 10146 10-Jun-01 74 468 2617 136 404148 10418 11-Jun-01 75 499 2617 136 410136 10554 12-Jun-01 76 448 2617 136 415512 10690 14-Jun-01 78 470 2472 129 426792 10947 16-Jun-01 80 478 2472 129 438264 11205 17-Jun-01 81 439 2472 129 443532 11333 20-Jun-01 84 477 2283 119 460704 11689 Growth Yield 0.0254 'Measured MLVSS Value in Bold. 113 Table A2 - 27 Methanol Removal During the Period of Steady State Tests Reactor 1 Reactor 2 Date Day# Methanol Removal Efficiency (%) Influent Methanol Concentration (mg/L Condensate) Initial Methanol Concentration (mg/L mixed liquor) Average Effluent Concentration (mg/L mixed liquor) Date Day# Methanol Removal Efficiency (%) Influent Methanol Concentration (mg/L Condensate) Initial Methanol Concentration (mg/L mixed liquor) Average Effluent Concentration i mg/L mixed liquor) 26-Oct-OO 29-Oct-00 31-Oct-00 04-Nov-OO 07-Nov-OO 1 4 6 10 13 95 99 99 92 96 1186 1156 1288 1255 1175 263.6 256.9 286.2 278.9 261.1 13.2 2.6 2.9 22.3 10.4 26-Oct-OO 28-Oct-00 31-Oct-OO 05-Nov-OO 07-Nov-OO 1 3 6 11 13 96 98 97 97 78 1186 1147 1288 1238 1175 263.6 254.9 286.2 275.1 261.1 10.5 5.1 8.6 8.3 57.4 10-Nov-OO 12-Nov-OO 17-Nov-OO 21-Nov-OO 28-Nov-OO 16 18 23 27 34 96 97 99 98 97 1097 1154 1247 1124 1146 243.8 256.4 277.1 249.8 254.7 9.8 7.7 2.8 5.0 7.6 09-Nov-OO 13-Nov-OO 17-Nov-OO 20-Nov-OO 28-Nov-OO 15 19 23 26 34 93 96 95 98 99 1101 1161 1247 1138 1146 244.7 258.0 277.1 252.9 254.7 17.1 10.3 13.9 5.1 2.5 02-Dec-OO 05-Dec-00 10-Dec-00 12-Dec-00 17-Dec-OO 38 41 46 48 53 96 93 80 94 93 1268 1254 1168 1174 1169 281.8 278.7 259.6 260.9 259.8 11.3 19.5 51.9 15.7 18.2 04-Dec-00 06-Dec-00 09-Dec-00 13-Dec-00 15-Dec-00 40 42 45 49 51 96 96 95 97 96 1278 1244 1214 1177 1194 284.0 276.4 269.8 261.6 265.3 11.4 11.1 13.5 7.8 10.6 21-Dec-OO 23-Dec-OO 26-Dec-OO 29-Dec-OO 31-Dec-00 57 59 62 65 67 94 95 95 98 99 1236 1185 1265 1099 1084 274.7 263.3 281.1 244.2 240.9 16.5 13.2 14.1 4.9 2.4 20-Dec-00 22-Dec-00 25-Dec-00 29- Dec-OO 30- Dec-00 56 58 61 65 68 98 95 96 61 80 1210 1180 1243 1099 1433 268.9 262.2 276.2 244.2 318.4 5.4 13.1 11.0 95.2 63.7 03-Jan-01 05-Jan-01 10-Jan-01 13-Jan-01 15-Jan-01 70 72 77 80 82 89 96 84 99 98 1568 1244 1183 1172 1212 348.4 276.4 262.9 260.4 269.3 38.3 11.1 42.1 2.6 5.4 05-Jan-01 07-Jan-01 12-Jan-01 14-Jan-01 17-Jan-01 72 74 79 81 84 95 96 94 97 98 1244 1227 1166 1165 1216 276.4 272.7 259.1 258.9 270.2 13.8 10.9 15.5 7.8 5.4 19-Jan-01 23-Jan-01 26-Jan-01 28-Jan-01 30-Jan-01 86 90 93 95 97 98 99 97 95 97 1208 1163 1175 1224 1263 268.4 258.4 261.1 272.0 280.7 5.4 2.6 7.8 13.6 8.4 19-Jan-01 23-Jan-01 25-Jan-01 28-Jan-01 31-Jan-01 86 90 92 95 98 96 68 92 95 97 1208 1163 1187 1224 1270 268.4 258.4 263.8 272.0 282.2 10.7 8 2 7 21.1 13.6 8.5 03-Feb-01 07-Feb-01 10-Feb-01 12-Feb-01 15-Feb-01 101 105 108 110 113 86 99 99 96 91 1255 1236 1218 1186 1202 278.9 274.7 270.7 263.6 267.1 39.0 2.7 2.7 10.5 24.0 03-Feb-01 08-Feb-01 10-Feb-01 13-Feb-01 16-Feb-01 101 106 108 111 114 98 99 99 98 95 1255 1243 1218 1186 1197 278.9 276.2 270.7 263.6 266.0 5.6 2.8 2.7 5.3 13.3 19-Feb-01 23-Feb-01 26-Feb-01 02-Mar-01 04-Mar-01 117 121 124 128 130 82 94 95 98 92 1254 1232 1174 1154 1136 278.7 273.8 260.9 256.4 252.4 50.2 16.4 13.0 5.1 20.2 19-Feb-01 21-Feb-01 23-Feb-01 27-Feb-01 03-Mar-01 117 119 122 126 129 96 97 98 93 78 1254 1233 1213 1158 1136 278.7 274.0 269.6 257.3 252.4 11.1 8.2 5.4 18.0 55.5 07-Mar-01 11-Mar-01 14-Mar-01 16-Mar-01 19-Mar-01 133 137 140 142 145 96 96 98 97 96 1216 1200 1233 1254 1155 270.2 266.7 274.0 278.7 256.7 10.8 10.7 5.5 8.4 10.3 08-Mar-01 11-Mar-01 13-Mar-01 17-Mar-01 19-Mar-01 134 137 139 143 145 95 93 95 90 96 1220 1200 1241 1237 1155 271.1 266.7 275.8 274.9 256.7 13.6 18.7 13.8 27.5 10.3 21-Mar-01 23-Mar-01 25- Mar-01 26- Mar-01 27- Mar-01 147 149 151 152 153 93 94 95 99 99 1123 1012 1279 1158 1074 249.6 224.9 284.2 257.3 238.7 17.5 13.5 14.2 2.6 2.4 22- Mar-01 23- Mar-01 25-Mar-01 29- Mar-01 30- Mar-01 148 149 151 155 156 98 97 90 95 97 1123 1012 1279 1143 1254 249.6 224.9 284.2 254.0 278.7 5.0 6.7 28.4 12.7 8.4 28-Mar-01 30-Mar-01 09- Apr-01 10- Apr-01 11- Apr-01 154 156 166 167 168 92 96 96 97 99 1132 1254 1086 1228 1198 251.6 278.7 241.3 272.9 266.2 20.1 11.1 9.7 8.2 2.7 31-Mar-01 01-Apr-01 04- Apr-01 05- Apr-01 09-Apr-01 157 158 161 162 166 97 94 89 92 99 1222 1184 1085 1085 1123 271.6 263.1 241.1 241.1 249.6 8.1 15.8 26.5 19.3 2.5 13- Apr-01 14- Apr-01 15- Apr-01 16- Apr-01 1S-Apr-Q1 170 171 172 173 175 98 97 96 93 80 1165 1124 1095 1152 1124 258.9 249.8 243.3 256.0 249.8 5.2 7.5 9.7 . 17.9 50.0 11-Apr-01 13-Apr-01 15- Apr-01 16- Apr-01 20-Ap_r-01 168 170 172 173 177 97 98 94 93 87 1198 1165 1095 * 1152 1206 266.2 258.9 243.3 256.0 268.0 8.0 5.2 14.6 17.9 34.8 21- Apr-01 22- Apr-01 23- Apr-01 24- Apr-01 25- Apr-01 178 179 180 181 182 94 93 94 95 95 1006 1266 1241 1186 1162 223.6 281.3 275.8 263.6 258.2 13.4 19.7 16.5 13.2 12.9 21- Apr-01 22- Apr-01 23- Apr-01 24- Apr-01 27-Apr-01 178 179 180 181 184 93 88 94 97 92 1006 1266 1241 1186 1162 223.6 281.3 275.8 263.6 258.2 15.6 33.8 . 16.5 7.9. 20.7 28- Apr-01 29- Apr-01 30- Apr-01 01-May-01 n?-Mav-01 185 186 187 188 189 98 99 89 96 84 1088 1278 1156 1100 1233 241.8 284.0 256.9 244.4 274.0 4.8 2.8 28.3 9.8 43.8 28- Apr-01 29- Apr-01 30- Apr-01 01-May-01 04-May-01 185 186 187 188 191 91 97 97 99 99 1088 1278 1156 1100 1243 241.8 284.0 ' 256.9 244.4 276.2 21.8 8.5 7.7 2.4 2.8 ivioy w i 05- May-01 06- May-01 07- May-01 10-May-01 1° -Ma \ / -n i 192 193 194 197 199 99 98 98 99 97 1167 1336 1248 1111 1322 259.3 296.9 277.3 246.9 293.8 2.6 5.9 5.5 2.5 8.8 05-May-01 09-May-01 13- May-01 14- May-01 15- May-01 192 196 200 201 202 96 95 99 97 93 1168 1125 1314 1256 1252 259.5 250.0 292.0 279.1 278.3 10.4 12.5 2.9 8.4 19.5 14- May-01 15- May-01 16- May-01 18-May-01 201 202 203 205 206 95 97 86 99 99 1256 1256 1188 1142 1208 279.1 279.1 264.0 253.8 268.4 14.0 8.4 37.0 2.5 2.7 17- May-01 18- May-01 19- May-01 20- May-01 21- May-01 204 205 206 207 208 91 86 92 94 89 1233 1142 1208 1212 1121 274.0 253.8 268.4 269.3 249.1 24.7 35.5 21.5 16.2 27.4 i y-ividy^j i 20- May-01 21- May-01 22- May-01 24-May-01 207 208 209 211 213 96 91 82 94 95 1212 1121 1304 1281 1052 269.3 249.1 289.8 284.7 233.8 10.8 22.4 52.2 17.1 11.7 23- May-01 24- May-01 26- May-01 27- May-01 28- May-01 210 211 213 214 215 95 99 98 94 93 1288 1281 1052 1077 1052 286.2 284.7 233.8 239.3 233.8 14.3 2.8 4.7 14.4 16.4 ^o-rviay-'J i 28-May-01 30- May-01 31- May-01 01-Jun-01 no Ii m n-1 215 217 218 219 220 98 92 96 96 98 1162 1231 1054 1155 1161 258.2 273.6 234.2 256.7 258.0 5.2 21.9 9.4 10.3 5.2 29-May-01 01- Jun-01 02- Jun-01 03- Jun-01 04- Jun-01 216 219 220 221 222 97 98 99 99 94 1217 1205 1161 1135 1168 270.4 267.8 258.0 252.2 259.6 8.1 5.4 2.6 2.5 15.6 UV-JUn-UI 05- Jun-01 06- Jun-01 07- Jun-01 08- Jun-01 i n Ii i n m 223 224 225 226 228 97 96 93 94 92 1135 1296 1204 1125 1210 252.2 288.0 267.6 250.0 268.9 7.6 11.5 18.7 15.0 21.5 05-Jun-01 07- Jun-01 08- Jun-01 09- Jun-01 11-Jun-01 223 225 226 227 229 99 92 93 95 99 1135 1204 1125 1225 1225 252.2 267.6 250.0 272.2 272.2 z.o 21.4 17.5 13.6 2.7 i u-jun-ui 11- Jun-01 12- Jun-01 14-Jun-01 16- Jun-01 17- Jun-01 20-Jun-01 229 230 232 234 235 238 98 99 95 96 93 92 1225 1127 1112 1200 1167 1157 272.2 250.4 247.1 266.7 259.3 257.1 5.4 2.5 12.4 10.7 18.2 20.6 13- Jun-01 14- Jun-01 17-Jun-01 231 232 235 94 96 99 1194 • 1112 I 1167 265.3 247.1 259.3 15 9 9.9 2.6 Avera I 94.2 I 1188 264.0 1S.2 Averaae I 94.9 I 1189 264.2 I 13.6 1 1 4 Table A2 - 28 M B R Operating Incidents Date Day Reactor Problem Nov. 1,2001 7 R l Excess foam was observed and caused loss of mixed liquor. Nov. 6, 2001 12 R2 Excess foam was observed and caused loss of mixed liquor. Dec. 8, 2001 44 R l The bearing of the recirculation pump wore out and failed to pump the mixed liquor through membrane unit. Therefore, the mixed liquor overflew. A volume of 1 litre of mixed liquor was lost. Dec. 29, 2001 65 R2 The pH probe was damaged by leakage. It resulted in pumping remained sodium hydroxide solution into the reactor. The pH increased to 9.2. Therefore, the mixed liquor was partly replaced by the mixed liquor from the backup reactor. The containers of sodium hydroxide were replaced by smaller bottle to minimize the damage i f it happened again. Jan. 23, 2001 90 R2 The permeate solenoid valve was malfunctioned by overheat. The mixed liquor level in the reactor increases to the lid of the reactor, causing splashing and the loss of some mixed liquor. Feb. 16, 2001 114 R l A programming error in the control timer caused the overload of evaporator condensate. It resulted in decreased removal efficiencies. Mar. 1, 2001 127 R2 The connection between the temperature probe and temperature controller was not tight enough and resulted in wrong temperature signal. The system was cooled to 53 °C and gradually heated back to 60 °C after the problem was fixed. Mar. 14, 2001 140 R2 The pH probe was damaged by leakage. It resulted in pumping remained sodium hydroxide solution into the reactor. The pH increased to 8.3. Therefore, the mixed liquor was partly replaced by the mixed liquor from the backup reactor. The pH probe for R l was replaced by another model, but the port for pH probe of R2 was too small for the replacement. Apr. 17, 2001 174 R l Excess foam was observed and caused loss of mixed liquor. May 2, 2001 189 R l Feed valve was clogged by solids and resulted in no feed into R l for 12 hrs. 115 Appendix 3 Data Collected During Methanol Shock Loading Experiment Appendix 3 contains the data collected during methanol shock loading experiment. Results from first, second, and third shock loading tests monitoring removal kinetics of methanol and total organic carbon (TOC) are presented in Table A3 - 1 to A3 - 5, Table A3 - 6 to A3 - 10, and Table A3 - 11 to A3 - 15. Some batch tests were performed during the methanol shock loading tests and are summarized in Table A3 - 16 to A3 - 21. For these tables, the parameter K is the zero order coefficient for the biological removal of contaminant (mg/L-min). The parameter Co is the initial concentration in the M B R and the parameter Ce is the final TOC concentration in the M B R , derived from the second zero order removal coefficient. The R 2 value is the coefficient of determination for linear regression. The calculations for observed growth yields of R l and R2 are presented in Table A3 - 22 and Table A3 - 23. Results of colour tests during methanol shock loading tests are summarized in Table A3 -24. 116 Methanol Shock Loading Test 1 - June 25, 2001 ( 1800 mg / L) Table A3 -1 Batch Cycle 1 Table A3 - 5 Batch Cycle 5 Reactor 1 Reactor 2 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 320.7 188 349.8 186 15 200.6 131 214.5 123 30 276.6 167 307.7 157 30 135.9 107 158.8 97 45 197.1 131 249.9 129 45 71.5 96 106.5 80 60 133.9 112 199.5 110 60 8.2 73 51.7 62 75 56.8 95 157.4 93 75 0 66 0.0 53 90 0 87 101.7 84 90 0 58 0 49 Co (Ce) 398.2 215.5 (60.9) 401.9 209.5 (56.3) Co (Ce) 264.8 148 (43.2) 268.2 140.5 (35.6) K 4.5 1.76 0.83 3.3 1.71 0.87 K 4.3 1.23 0.5 3.6 1.33 0.43 R2 0.993 0.985 0.959 0.998 0.992 0.969 R2 0.979 0.982 0.999 0.989 0.99 0.953 Table A3 - 2 Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 30 281.4 144.2 174.3 109 60 201.4 93.6 80.3 77 90 56.4 77.9 0 49 Co (Ce) 404.8 171.5(64.2) 259.2 138.3(33.1) K 3.8 1.1 2.9 1.0 R2 0.973 0.915 0.998 0.999 Table A3 - 3 Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 30 290.6 133 190.7 93 60 173.9 97 52.9 65 90 66.5 63 3.3 39 Co (Ce) 401.1 165.7 (60.4) 269.7 119.3(32.3) K 3.7 1.1 3.1 0.9 R2 0.999 0.989 0.931 0.991 '. Table A3 - 4 Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 30 281.4 123 201.6 99 60 180.9 89 51.1 64 90 71.4 60 7.4 38 Co (Ce) 387.9 153.7 (59.8) 280.9 128 (30.9) K 3.5 1.1 3.2 1.0 R2 0.999 0.998 0.908 0.993 117 Methanol Shock Loading Test 2 - June 28, 2001 ( 2400 mg / L ) Table A3-6 Batch Cycle 1 Table A3-10 Batch Cycle 5 Reactor 1 Reactor 2 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 451.7 216 468.2 224 15 214.3 136 215.6 140 30 366.1 175 410.2 187 30 157.8 114 164.8 114 45 282.4 146 349.4 145 45 103.1 96 111.7 102 60 196.9 104 285.9 110 60 45.9 72 61.8 78 75 114.3 86 226.3 86 75 0 64 11 71 90 31.1 77 164.3 81 90 0 59 0 66 Co (Ce) 533.8 251.5 (48.5) 532.8 262.5 (48.4) Co (Ce) 268.7 157 (45.9) 266.4 158 (53.7) K 5.6 2.43 0.9 4.1 2.56 0.97 K 3.7 1.4 0.43 3.4 1.32 0.4 R 2 0.978 0.995 0.964 0.984 0.999 0.875 R2 0.942 0.997 0.983 0.966 0.983 0.991 Table A3 - 7 Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 446.4 183 199.6 85 45 265.2 132 61.2 53 75 88.7 77 0 31 Co (Ce) 536.4 207.5 (55.6) 268.2 95.2 (33.8) K 6.0 1.7 4.6 0.9 R 2 0.9821 0.864 0.995 0.995 Table A3 - 8 Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 470.7 240 181.7 95 45 316.8 189 74.6 66 75 200.9 131 0 37 Co (Ce) 531.8 268.8(62.1) 264.8 106 (29.4) K 4.5 1.8 3.6 0.9 R 2 0.993 0.999 0.999 0.946 Table A3 - 9 Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 465.9 224 186.5 91 45 334.8 188 82.9 60 75 254.3 157 0 33 Co (Ce) 510.4 239.9(107.9) 238.3 106 (31.7) K 3.5 1.1 3.5 1 R 2 0.981 0.998 0.999 0.946 118 Methanol Shock Loading Test 2 - July 2, 2001 (3000 mg / L) TableA3-11 Batch Cycle 1 Table A3-15 Batch Cycle 5 Reactor 1 Reactor 2 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 643.1 265 647.2 238 15 1512.6 612 615.2 184 30 624.3 262 625.8 234 30 1466.5 604 546.3 174 45 601.9 254 604.3 231 45 1418.7 596 536.7 170 60 574.3 248 579.6 224 60 1363.2 572 502.6 164 75 554.6 243 558.1 220 75 1330.5 556 428.9 152 90 533.1 238 536.6 214 90 1274.8 528 427 146 Co (Ce) 668.4 273.2 670.6 243.3 Co (Ce) 1559.6 636.8 642.2 191.2 K 1.5 0.4 1.5 0.3 K 3.1 1.1 2.5 0.5 R 2 0.966 0.954 0.882 0.984 R 2 0.997 0.954 0.946 0.983 Table A3-12 Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 1090.4 400 725.9 264 45 1005.9 384 651.3 256 75 927.5 371 598.8 250 Co (Ce) 1129.9 408 754 267.2 K 2.7 0.5 2.1 0.2 R 2 0.98 0.999 0.99 0.993 Table A3 -13 Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 1314.4 537 676.6 252 45 1230.6 529 624.5 238 75 1149.9 523 561.1 220 Co (Ce) 1352.9 540.2 707.4 259 K 2.7 0.2 1.9 0.5 R 2 0.999 0.993 0.997 0.999 Table A3 -14 Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 1634.5 687 649.8 252 45 1534.7 665 588.6 238 75 1465.3 651 516.7 220 Co (Ce) 1671.7 694.7 684.9 259 K 2.9 0.6 2.2 0.5 R 2 0.989 0.984 0.998 0.999 119 < 0) O =d O a f- E O =d 1-' co E ^ ^ to s s S S «) N CD O CO IT) CM CO CD CO O P T f CD CD Cn T - CO i - . m co CM CM T -CN CN CN CN CN CN T-; CO CO CO cn oo T f T— cn T f o n n i o o n m T f co co co CN « ) 0 « ) 0 « ) 0 t- co TT co r- 0 1 CD co oi "* O "O CD CN CO to CO CD Si* o O Tf >> < o 2 15 E CO c II S S2 co cn oi Tf 52 ^  O f- CD CO cn r- co ui o cn cn r-£> ?! £ ?! cn co f- CO CN d <° S° <o co cn co i2 I! 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CO CO CN CO S i * o o i t Table A3 - 22 Growth Yield of Reactor 1 Dur ing Period of Methanol Shock loading Tests Date Cumula t ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methano l Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 23-Jun-01 0 458 2867 140 0 0 24-Jun-01 1 447 3033 149 5364 149 25-Jun-01-Cyc le1 2 716 3033 149 11444 297 25-Jun-01-Cyc le2 702 3033 149 12146 25-Jun-01-Cyc le3 708 3033 149 12854 25-Jun-01-Cyc le4 696 3033 149 13550 25-Jun-01-Cyc le5 478 3033 149 14028 26-Jun-01 3 482 3333 163 17402 787 27-Jun-01 4 458 3333 163 2 2 8 9 8 951 28-Jun-01-Cyc le 1 5 948 3333 163 29342 1114 28-Jun-01-Cyc le 2 954 3333 163 30296 28-Jun-01-Cyc le 3 942 3333 163 31238 2 8 - J u n - 0 1 - C y c l e 4 938 3333 163 32176 28-Jun-01-Cyc le 5 488 3333 163 32664 29-Jun-01 6 496 3500 172 36136 2143 30-Jun-01 7 433 3500 172 4 1 3 3 2 2314 l -Ju l -01 8 487 3567 175 4 7 1 7 6 2489 2-Jul-01 -Cycle 1 9 336 2833 139 53356 2628 2 -Ju l -01 -Cyc le2 602 2833 139 53958 2 -Ju l -01 -Cyc le3 616 2833 139 54574 2 -Ju l -01 -Cyc le4 647 2833 139 55221 2-Jul-01-Cycle 5 702 2833 139 55923 3-Jul-01 10 318 2833 139 58149 2767 4-Jul-01 11 386 2967 145 62781 2912 5-Jul-01 12 405 2967 145 67641 3058 6-Jul-01 13 4 5 4 3267 160 73089 3218 7-Jul-01 14 4 4 8 3267 160 78465 3378 8-Jul-01 15 439 3267 160 8 3 7 3 3 3538 9-Jul-01 16 452 3267 160 8 9 1 5 7 3698 Growth Yield 0.0415 *Measured M L V S S Va lue in Bold. 121 Table A3 - 23 Growth Yield of Reactor 2 Dur ing Period of Methanol Shock loading Tests Date Cumulat ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methano l Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 23-Jun-01 0 468 3067 159 0 0 24-Jun-01 1 436 3267 170 5616 170 25-Jun-01-Cyc le1 2 732 3267 170 11580 340 25-Jun-01-Cyc le2 478 3267 170 12058 25-Jun-01-Cyc le3 505 3267 170 12563 25-Jun-01-Cyc le4 492 3267 170 13055 25-Jun-01-Cyc le5 498 3267 170 13553 26-Jun-01 3 487 3403 177 16962 517 27-Jun-01 4 479 3403 177 2 2 7 1 0 694 28-Jun-01-Cyc le 1 5 937 3403 177 2 9 3 9 5 871 28-Jun-01-Cyc le 2 505 3403 177 2 9 9 0 0 28-Jun-01-Cyc le 3 496 3403 177 30396 2 8 - J u n - 0 1 - C y c l e 4 492 3403 177 30888 28-Jun-01-Cyc le 5 498 3403 177 31386 29-Jun-01 6 4 8 3 3533 184 34767 1054 30-Jun-01 7 477 3650 190 40491 1244 l -Ju l -01 8 4 6 9 3650 190 4 6 1 1 9 1434 2-Jul -01-Cycle 1 9 332 3700 192 52079 1626 2 -Ju l -01 -Cyc le2 468 3700 192 52547 2 -Ju l -01 -Cyc le3 362 3700 192 52909 2 -Ju l -01 -Cyc le4 377 3700 192 53286 2 -Ju l -01 -Cyc le5 560 3700 192 53846 3-Jul-01 10 442 3700 192 56940 1819 4-Jul-01 11 453 3833 199 6 2 3 7 6 2018 5-Jul-01 12 467 3833 199 67980 2217 9-Jul-01 16 472 3900 203 90636 3029 Growth Yield 0.0334 *Measured M L V S S Va lue in Bold. 122 Table A3 - 24 Colour Data of Reactor 2 Dur ing Period of Methanol Shock loading Tests Reactor 1 Reactor 2 Condensa te Permeate Condensa te Permeate Apparen t T rue True , PH Apparent T rue T rue PH 17-Jun-01 700 400 200 7.44 700 4 0 0 2 0 0 7.12 18-Jun-01 700 400 160 6.54 700 4 0 0 210 7.4 19-Jun-01 700 420 210 6.66 700 4 2 0 160 6.93 21-Jun-01 720 420 240 6.93 720 4 2 0 2 0 0 7.17 22-Jun-01 750 450 200 7.66 750 4 5 0 160 7.31 25-Jun-01 750 450 200 7.02 750 4 5 0 160 7.25 26-Jun-01 700 400 160 6.78 700 4 0 0 160 6.78 27-Jun-01 800 500 160 7.5 800 500 200 7.5 28-Jun-01 700 400 160 7.72 700 4 0 0 160 7.07 29-Jun-01 700 420 210 8.07 700 4 2 0 200 7.45 30-Jun-01 680 400 210 7.3 680 4 0 0 210 7.66 1-Jul-01 750 420 210 7.23 750 4 2 0 200 7.6 2-Jul-02 700 400 280 7.37 700 4 0 0 240 7.35 3-Jul-01 700 400 280 7.17 700 4 0 0 2 6 0 7.12 4-Jul-01 700 420 210 7.04 700 420 2 4 0 6.86 5-Jul-01 720 4 2 0 240 7.17 720 420 220 7.17 6-Jul-01 750 4 5 0 240 7.13 750 4 5 0 260 7.11 7-Jul-01 750 4 5 0 220 7.15 750 4 5 0 240 6.52 123 Appendix 4 Data Collected During Black liquor Carryover Experiment Appendix 4 contains the data collected during black liquor carryover experiment. Results from first, second, third, and fourth shock loading tests monitoring removal kinetics of methanol, total organic carbon (TOC) and chemical oxygen demand (COD) are presented in Table A4 - 1 to A4 - 5, Table A4 - 6 to A4 - 10, Table A4 - 11 to A4 - 15, and Table A4 - 16 to A4 - 20. Some batch tests were performed during the black liquor carryover tests and are summarized in Table A4 - 21 to A4 - 29. For these tables, the parameter K is the zero order coefficient for the biological removal of contaminant (mg/L-min). The parameter Co is the initial concentration in the M B R and the parameter Ce is the final TOC concentration in the M B R , derived from the second zero order removal coefficient. The R 2 value is the coefficient of determination for linear regression. The calculations for observed growth yields of R l and R2 are presented in Table A4 - 30 to table A4 - 33. Results of colour tests during black liquor carryover tests are summarized in Table A4 -34. Results of solid tests during black liquor carryover tests are summarized in Table A4 - 35. 124 Black Liquor Carryover (BL) Test 1 - August 4, 2001 (4 mL BL/ L Condensate ) Table A4 -1 Contaminant Removal of BL Test 1 - Batch Cycle 1 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 216.2 165 664 220.8 160 679 30 187.8 142 654 193.5 141 613 45 169 133 597 165.8 124 524 60 128.5 109 568 132.1 101 486 75 103.4 101 549 82.6 95 430 90 72.4 94 473 59.2 87 357 Co (Ce) 247.5 181.5 78.8 714.7 259.8 180 72.9 734.5 K 1.9 1.18 0.5 2.5 2.2 f.29 0.47 4.2 R2 0.994 0.974 0.999 0.954 0.99 0.996 0.993 0.991 Table A4 - 2 Contaminant Removal of BL Test 1 - Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 30 192.7 160 670 178.6 170 587 60 149.7 128 633 125.4 146 450 90 77.1 102 554 40.2 129 333 Co (Ce) 255.4 188 735 253.1 189.3 710.7 K 2 1 1.9 2.3 0.7 4.2 R 2 0.979 . 0.996 0.958 0.983 0.99 0.998 Table A4 - 3 Contaminant Removal of BL Test 1 - Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 30 196.8 155 716 183.2 165 566 60 132.5 126 643 107.4 140 473 90 83.6 93 582 65.5 129 388 Co (Ce) 250.8 186.7 781 236.4 180.7 653.7 K 1.9 1 2.2 2 0.6 3 R 2 0.994 0.999 0.997 0.973 0.952 0.999 125 Black Liquor Carryover (BL) Test - August 4, 2001 (4 mL BU L Condensate ) • Con't Table A4 - 4 Contaminant Removal of BL Test 1 - Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 30 185.7 166 720 158.3 158 528 60 155.6 129 606 52.2 132 400 90 79.8 112 501 2.5 115 332 Co (Ce) 246.3 189.7 828 226.8 178 616 K 1.8 0.9 3.7 2.6 0.7 3.3 R 2 0.942 0.956 0.999 0.958 0.986 0.97 Table A4 - 5 Contaminant Removal of BL Test 1 - Batch Cycle 5 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 212.6 158 851 210.2 158 592 30 198.2 139 803 188.4 146 544 45 168.8 110 779 143.2 131 528 60 134.5 102 739 116.5 109 498 75 86.3 92 713 98.8 101 480 90 64.1 87 679 65.4 92 444 Co (Ce) 255.4 176.5 71.2 877.7 239 176.5 74.8 609.4 K 2.1 1.31 0.5 2.2 1.9 1.08 0.57 1.8 R 2 0.971 0.961 0.964 0.993 0.987 0.981 0.999 0.965 126 Black Liquor Carryover (BL) Test 2 - August 7, 2001 ( 8 mL BL/ L Condensate ) Table A4 - 6 Contaminant Removal of BL Test 2 • Batch Cycle 1 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 208.4 219 722 218.9 221 772 30 170.7 193 633 181.3 203 732 45 160.2 178 613 158.8 179 673 60 123.6 159 563 126.8 156 653 75 86.2 146 424 96.5 148 633 90 42.7 142 64.8 141 Co (Ce) 243.8 236 123.1 790 246.9 244.5 125.83 799.7 K 2.1 1.3 0.57 4.4 2 1.46 0.5 2.4 R 2 0.978 0.988 0.915 0.923 0.998 0.996 0.999 0.954 Table A4 - 7 Contaminant Removal of BL Test 2 - Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 208.7 204 737 218.6 210 1001 45 131.4 173 680 158.7 189 927 75 68.8 155 535 85.1 174 837 Co (Ce) 241.2 214.1 802.2 254.3 218 1044.7 K 2.3 0.8 3.4 2.2 0.6 2.7 R2 0.996 0.977 0.941 0.997 0.991 0.997 Table A4 • 8 Contaminant Removal of BL Test 2 - Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 182.1 210 753 211.5 202 1011 45 128.1 185 659 139.7 175 910 75 31.3 168 536 86.4 135 799 Co (Ce) 226.9 219.2 812.1 239.7 220.9 1065.7 K 2.5 0.7 3.6 2.1 1.1 3.5 R 2 0.974 0.988 0.994 0.993 0.988 0.999 127 Black Liquor Carryover (BL) Test - August 7, 2001 ( 8 mL BL/ L Condensate ) - Con't Table A4 - 9 Contaminant Removal of BL Test 2 - Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 206.9 200 733 196.8 195 923 45 154.3 177 653 115.8 166 836 75 61.9 160 534 82.5 143 712 Co (Ce) 249.8 209 789.3 217.4 207 981.9 K 2.4 0.7 3.3 1.9 0.9 3.5 R 2 0.976 0.993 0.987 0.945 0.996 0.99 Table A4 -10 Contaminant Removal of BL Test 2 - Batch Cycle 5 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 205.4 202 713 202.3 210 824 30 188.6 195 683 174.3 195 755 45 170.3 181 629 155.5 182 695 60 121.8 158 594 123.1 161 631 75 96.3 148 534 89.5 157 573 90 72.4 143 68.4 148 Co (Ce) 241.5 220.5 127.2 764.7 231.2 227 136.2 883.4 K 1.9 0.97 0.5 3 1.8 1.07 0.43 4.2 R 2 0.978 0.943 0.964 0.989 0.994 0.989 0.953 0.999 128 Black Liquor Carryover (BL) Test -3 August 10,2001 (12 mL BL/ L Condensate) Table A4 -11 Contaminant Removal of BL Test 3 - Batch Cycle 1 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 232.3 223 673 215.9 237 683 30 190.2 200 624 167.8 209 653 45 140.4 185 554 138.7 195 614 60 57.6 166 524 91 176 495 75 43.1 160 465 63.8 166 475 90 20.2 147 17.6 160 376 Co (Ce) 272.4 240 129.6 722.8 250.9 253.5 143.7 768.1 K 3 1.24 0.63 3.4 2.6 1.31 0.53 4.2 R 2 0.956 0.994 0.957 0.99 0.995 0.981 0.98 0.959 Table A4 -12 Contaminant Removal of BL Test 3 - Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 230.2 236 663 207 240 771 45 164.2 210 586 115.8 215 654 75 87.5 192 478 32.1 181 512 Co (Ce) 267.7 245.7 714.4 249.5 256.3 839.9 K 2.4 0.7 3.1 2.9 1 4.3 R 2 0.998 0.989 0.991 0.991 0.992 0.997 Table A4 -13 Contaminant Removal of BL Test 3 - Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 230.9 259 788 214.3 265 798 45 162.9 232 723 118.3 231 668 75 104.9 216 620 54.8 203 589 Co (Ce) 260.7 267.9 836.3 248.8 279.5 841.8 K 2.1 0.7 2.8 2.7 1 3.5 R2 0.998 0.979 0.983 0.987 0.997 0.981 129 Black Liquor Carryover (BL) Test - August 10, 2001 (12 mL BL/ L Condensate ) - Con't Table A4 -14 Contaminant Removal of BL Test 3 - Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 215.4 266 816 229.2 289 771 45 133.8 235 721 143.2 254 676 75 74.3 219 578 83.1 231 513 Co (Ce) 247.0 275.3 883.5 261.4 301.5 846.8 K 2.4 0.8 4 2.4 1 4.3 R 2 0.992 0.967 0.987 0.99 0.986 0.978 Table A4 -15 Contaminant Removal of BL Test 3 - Batch Cycle 5 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 223.3 297 890 220.1 322 938 30 199.7 280 827 168.8 294 854 45 149.8 245 782 123.4 276 788 60 120.4 227 713 75.4 259 716 75 98.7 210 637 36.8 244 638 90 54.6 206 0 240 Co (Ce) 258.7 323.5 182.8 955.8 262.9 343.3 219.2 1008.2 K 2.2 1.63 0.7 4.1 3.1 1.53 0.63 4.9 R 2 0.989 0.98 0.887 0.993 0.998 0.985 0.89 0.999 130 Black Liquor Carryover (BL) Test 4 - August 16, 2001 (24 mL BU L Condensate) Table A4 -16 Contaminant Removal of BL Test 4 - Batch Cycle 1 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 231.8 324 870 238.5 326 904 30 212.6 308 798 196.9 302 858 45 177.3 . 296 756 158.7 280 744 60 142.2 287 723 133.9 259 715 75 118.7 273 648 104.5 238 673 90 95.6 261 588 58.7 223 610 Co (Ce) 262.8 334.4 919.8 268.6 344.1 956.1 K 1.9 0.8 3.6 2.3 1.4 3.9 R 2 0.992 0.995 0.988 0.993 0.996 0.97 Table A4 -17 Contaminant Removal of BL Test 4 - Batch Cycle 2 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 276.5 478 997 265.9 287 876 45 247.6 432 887 216.7 258 772 75 194.5 411 805 144.3 238 649 Co (Ce) 301.0 490.6 1040.3 300.2 297.8 935.9 K 1.4 1.1 3.2 2 0.8 3.8 R 2 0.972 0.956 0.993 0.988 0.989 0.998 Table A4 -18 Contaminant Removal of BL Test 4 - Batch Cycle 3 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 332.3 594 1131 267.6 281 866 45 271.2 567 1029 208.8 260 745 75 247.1 525 958 135.5 226 635 Co (Ce) 347.4 613.8 1169.1 303 296.9 921.9 K 1.4 1.2 2.9 2.2 0.9 3.9 R 2 0.941 0.985 0.99 0.996 0.982 0.999 131 Black Liquor Carryover (BL) Test - August 16,2001 (24 mL BL/ L Condensate) - Con't Table A4 -19 Contaminant Removal of BL Test 4 • Batch Cycle 4 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 417.8 696 1285 235.6 275 824 45 376.5 668 1189 195.7 257 720 75 351.8 636 1138 112.6 242 596 Co (Ce) 431.5 711.7 1314.3 273.6 282.8 884.3 K 1.1 1 2.5 2.1 0.6 3.8 R 2 0.979 0.999 0.97 0.961 0.997 0.997 Table A4 - 20 Contaminant Removal of BL Test 4 - Batch Cycle 5 Reactor 1 Reactor 2 Time Methanol TOC COD Methanol TOC COD (min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 15 529.8 687 1547 232.7 262 745 30 527.5 675 1487 187.6 244 697 45 525.1 660 1487 143.9 239 645 60 494.4 642 1428 125.8 219 578 75 475 629 1378 80.2 211 488 90 413.7 614 1368 50.3 205 433 Co (Ce) 571.1 703.3 1577.3 262 270.4 823.1 K 1.5 1 2.4 2.4 0.8 4.3 R 2 0.83 0.998 0.956 0.99 0.968 0.99 132 Contaminant Removal Data During the Test Period of Black Liquor Carryover Tests Table A4 - 21 Batch Test on August 3, 2001 Table A4 - 24 Batch Test on August 11, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 187.5 139 214.9 149 30 141.8 118 163.4 128 45 87.8 93 96.2 103 60 28.6 82 60.7 88 75 0 75 18.2 79 90 0 69 0 74 Co (Ce) 244.1 157 56.2 259.5 169 58.9 K 3.5 1.3 0.43 3.3 1.39 0.47 R 2 0.997 0.98 1 0.988 0.99 0.97 Table A4 - 22 Batch Test on August 5, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 234.4 152 231.5 170 30 173.6 138 196.6 152 45 105.5 109 138.7 139 60 54.6 84 90.2 113 75 0 79 54.4 103 90 0 71 11.3 95 Co (Ce) 293.9 179 58.9 278.1 190 78.7 K 4.1 1.55 0.43 3.0 1.23 0.6 R 2 0.997 0.98 0.98 0.995 0.98 1 Table A4 - 23 Batch Test on August 8, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 237.4 147 227.6 143 30 174.3 124 193.5 115 45 114.7 101 144.8 92 60 46.8 81 102.5 79 75 15.8 75 74.5 71 90 0 68 15.8 65 Co (Ce) 289 169 55.6 272.3 161 107 K 3.8 1.47 0.43 2.8 1.43 0.47 R 2 0.988 1 1 0.994 0.98 0.99 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 254.6 157 234.5 156 30 198.7 129 198.6 136 45 143.2 97 164.5 114 60 98.8 88 123.4 87 75 53.2 80 66.7 79 90 0 73 24.5 75 Co (Ce) 300.5 178 57.8 284.1 181 62.3 K 3.4 1.6 0.5 2.8 1.53 0.4 R 2 0.997 0.96 1 0.992 1 0.964 Table A4 - 25 Batch Test on August 13, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 213.8 136 205 136 30 176.9 116 165.2 117 45 100.5 93 92.4 93 60 64.3 74 63.7 74 75 19.8 69 18.4 69 90 0 62 0 65 Co (Ce) 265.2 157 98.3 251.4 158 55.8 K 3.3 1.39 0.4 3.2 1.4 0.3 R 2 0.985 1 0.99 0.984 1 0.996 Table A4 - 26 Batch Test on August 15, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 209.9 144 207.8 134 30 169.8 124 165.6 119 45 121.5 96 121.1 98 60 71.7 80 86.7 75 75 26.4 74 44.8 70 90 0 69 0 64 Co (Ce) 259.4 166 102 246.7 156 52.8 K 3.1 1.47 0.37 2.7 1.32 0.37 R 2 0.999 0.99 1 0.999 0.99 0.998 Contaminant Removal Data During the Test Period of Black Liquor Carryover Tests - Con't Table A4-27 Batch Test on August 17, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 476.6 243 223.3 136 30 438.3 228 185.2 121 45 401.9 213 150 104 60 372.2 198 105.5 86 75 355.4 184 77.4 76 90 336.8 166 26.8 70 Co (Ce) 494.6 258.2 263.1 154 53.7 K 1.9 1.01 2.6 1.11 0.53 R* 0.972 0.999 0.996 1 0.98 Table A4 - 28 Batch Test on August 18, 2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 222.2 126 213.2 126 30 175.4 107 154.1 107 45 123.8 84 97.8 83 60 96.5 67 64.5 68 75 64.3 60 46.5 62 90 19.7 54 0 57 Co (Ce) 254.3 146 41.2 242.1 146 45.4 K 2.6 1.33 0.43 2.8 1.32 0.37 R2 0.991 1 1 0.956 0.99 1 Table A4 - 29 Batch Test on August 19,2001 Reactor 1 Reactor 2 Time Methanol TOC Methanol TOC (min) (mg/L) (mg/L) (mg/L) (mg/L) 15 213.3 131 203.2 129 30 168.8 111 168.8 108 45 94.5 85 110.5 87 60 67.1 69 71.8 69 75 33.8 63 23.5 61 90 0 55 0 58 Co (Ce) 253.7 152 40.9 252.5 149 45.8 K 3.1 1.41 0.47 3 1.34 0.37 0.971 0.99 0.99 0.995 1 0.94 134 T a b l e A 4 - 30 G r o w t h Y i e l d o f R e a c t o r 1 D u r i n g A c c l i m a t i z a t i o n b e f o r e B l a c k L i q u o r C a r r y o v e r T e s t s Date Cumula t ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methano l Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 16-Jul-01 0 432 2150 105 0 0 19-Jul-01 3 477 2683 131 17172 394 25-Jul-01 9 458 2900 142 50148 1247 27-Jul-01 11 462 2683 131 61236 1510 30-Jul-01 14 449 2667 131 77400 1902 1-Aug-01 16 473 2767 136 88752 2173 Growth Yield 0.0245 T a b l e A 4 - 31 G r o w t h Y i e l d o f R e a c t o r 1 D u r i n g P e r i o d o f B l a c k L i q u o r C a r r y o v e r T e s t s Date Cumula t ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methanol Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 3-Aug-01 0 441 2533 133 0 0 4-Aug-01-Cyc le 1 1 392 2533 124 392 0 4-Aug-01-Cyc le 2 432 2533 124 824 4-Aug-01-Cyc le 3 414 2533 124 1238 4 - A u g - 0 1 - C y c l e 4 393 2533 124 1631 4-Aug-01-Cyc le 5 302 2533 124 1933 5-Aug-01 2 421 2533 124 4 8 8 0 133 7-Aug-01 -Cycle 1 4 449 2307 113 15656 359 7-Aug-01-Cycle 2 432 2307 113 16088 7-Aug-01-Cycle 3 403 2307 113 16491 7 - A u g - 0 1 - C y c l e 4 440 2307 113 16931 7-Aug-01-Cycle 5 426 2307 113 17357 8-Aug-01 5 448 2307 113 20493 472 10-Aug-01-Cycle 1 7 468 2307 113 32193 585 10 -Aug -01 -Cyc le2 482 2307 113 32675 10-Aug-01-Cycle 3 453 2307 113 33128 1 0 - A u g - 0 1 - C y c l e 4 448 2307 113 33576 10-Aug-01-Cycle 5 468 2307 113 34044 11-Aug-01 8 435 2307 113 37089 698 13-Aug-01 10 462 1833 90 4 8 1 7 7 878 15-Aug-01 12 439 1833 90 58713 1057 16-Aug-01-Cycle 1 13 408 1833 90 4 1 9 8 5 1147 16-Aug-01-Cycle 2 307 1833 90 4 2 2 9 2 16-Aug-01-Cycle 3 300 1833 90 4 2 5 9 2 16-Aug -01 -Cyc le4 243 1833 90 4 2 8 3 5 16-Aug-01-Cycle 5 324 1833 90 4 3 1 5 9 17-Aug-01 14 338 1833 90 4 5 5 2 5 1237 18-Aug-01 15 357 1900 93 4 9 8 0 9 1330 20-Aug-01 17 410 1900 93 59649 1516 23-Aug-01 20 429 2017 99 75093 1813 *Measured M L V S S Va lue in Bold. Growth Yield 0.0241 135 T a b l e A 4 - 32 G r o w t h Y i e l d o f R e a c t o r 2 D u r i n g A c c l i m a t i z a t i o n b e f o r e B l a c k L i q u o r C a r r y o v e r T e s t s Date Cumulat ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methano l Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 16-Jul-01 0 448 2133 111 0 0 19-Jul-01 3 483 3000 156 17388 4 6 8 25-Jul-OI 9 469 3217 167 51156 1472 27-Jul -01 11 475 2300 120 6 2 5 5 6 1711 30-Jul -01 14 466 2433 127 79332 2090 1-Aug-01 16 482 2600 135 9 0 9 0 0 2361 Growth Yield 0.026 T a b l e A 4 - 33 G r o w t h Y i e l d o f R e a c t o r 2 D u r i n g P e r i o d o f B l a c k L i q u o r C a r r y o v e r T e s t s Date Cumulat ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methano l Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 3-Aug-01 0 463 2617 136 0 0 4 -Aug-01-Cyc le 1 1 485 2617 136 4 8 5 136 4-Aug-01 -Cycle 2 476 2617 961 4-Aug-01-Cyc le 3 442 2617 1403 4 - A u g - 0 1 - C y c l e 4 430 2617 1833 4-Aug-01-Cyc le 5 445 2617 2278 5-Aug-01 2 463 2 6 1 7 136 5519 272 7-Aug-01-Cycle 1 4 462 2367 123 17093 518 7-Aug-01-Cycle 2 4 8 0 2367 17573 7-Aug-01 -Cycle 3 452 2367 18025 7 - A u g - 0 1 - C y c l e 4 406 2367 18431 7-Aug-01 -Cycle 5 424 2367 18855 8-Aug-01 5 4 4 8 2367 123 21991 641 10-Aug-01-Cycle 1 7 479 2367 123 33222 888 10 -Aug-01 -Cyc le2 477 2367 33699 10-Aug-01-Cycle 3 4 7 3 2367 34172 1 0 - A u g - 0 1 - C y c l e 4 515 2367 34687 10-Aug-01-Cycle 5 4 6 0 2367 35147 11-Aug-01 8 472 2367 123 38451 1011 13-Aug-01 10 4 6 0 2200 114 49491 1239 15-Aug-01 12 4 3 9 2200 114 60027 1468 16-Aug-01 -Cycle 1 13 508 2200 114 66199 1583 1 6 - A u g - 0 1 - C y c l e 2 558 2200 66757 16-Aug-01 -Cycle 3 567 2200 67324 1 6 - A u g - 0 1 - C y c l e 4 511 2200 67835 16-Aug-01-Cycle 5 4 9 3 2200 68328 17-Aug-01 14 475 2200 114 71653 1697 20-Aug-01 17 481 2 8 1 7 146 88969 2137 *Measured M L V S S Va lue in Bold Growth Yield 0.024 136 T a b l e A4 - 34 C o l o u r Data During P e r i o d o f B l a c k L i q u o r C a r r y o v e r T e s t s Reactor 1 Reactor 2 Condensa te Permeate Condensa te Permeate Apparent T rue True PH Apparen t T rue T rue pH Augus t 2 700 400 240 7.19 700 4 0 0 240 7.06 Augus t 3 680 400 220 7.15 680 4 0 0 240 7.12 4-Aug-01 9:00 1000 800 240 7.23 1000 800 240 7.07 4-Aug-01 11:00 1000 800 240 7.15 700 4 0 0 240 7.07 4-Aug-01 13:00 1040 820 240 6.72 700 4 0 0 240 7.02 4-Aug-01 15:00 1040 820 220 6.96 700 4 0 0 220 7.1 4-Aug-01 17:00 700 400 240 7.01 700 4 0 0 240 6.97 Augus t 5 700 420 240 7.41 700 4 2 0 240 6.96 Augus t 6 720 420 310 6.71 720 4 2 0 310 6.84 7-Aug-01 9:00 1400 1000 240 7.01 1400 1000 240 6.97 7-Aug-01 11:00 700 400 210 6.8 1400 1000 240 6.75 7-Aug-01 13:00 700 400 240 7.22 1340 960 300 7.46 7-Aug-01 15:00 700 400 240 7.52 1400 100 4 2 0 6.09 7-Aug-01 17:00 700 4 0 0 240 7.13 700 4 0 0 420 7.27 Augus t 9 700 380 360 7.04 700 380 240 6.54 10-Aug-01 9:00 1800 1200 280 6.6 1800 1200 240 6.46 10-Aug-01 11:00 660 350 240 6.38 1840 1200 240 6.33 10-Aug-01 13:00 660 350 240 7.39 1800 1180 350 6.81 10-Aug-01 15:00 660 350 240 6.48 1800 1200 310 6.63 10-Aug-01 17:00 660 350 240 6.37 660 3 5 0 310 6.61 Augus t 11 750 450 350 6.73 750 4 5 0 310 6.75 Augus t 12 750 450 240 6.99 750 4 5 0 300 6.69 Augus t 13 700 4 0 0 240 6.96 700 4 0 0 300 6.72 Augus t 14 800 500 350 6.57 800 500 490 6.45 Augus t 15 700 400 280 6.57 700 4 0 0 310 6.36 16-Aug-01 9:00 2800 1400 280 6.87 2800 1400 240 6.4 16-Aug-01 11:00 2800 1400 350 7.05 700 4 2 0 280 6.62 16-Aug-01 13:00 2800 1400 420 7.14 700 4 2 0 310 6.77 16-Aug-01 15:00 2800 1400 560 6.77 700 4 2 0 310 6.7 16-Aug-0117:00 700 420 600 7.28 700 4 2 0 350 6.46 Augus t 17 680 4 0 0 680 5.98 680 4 0 0 510 6.69 Augus t 18 750 4 2 0 490 6.89 750 4 2 0 490 6.53 Augus t 20 660 360 350 7.79 660 360 300 6.59 Augus t 21 700 400 280 6.5 700 4 0 0 250 6.74 Augus t 22 700 400 350 7.63 700 4 0 0 280 6.64 137 Table A4 - 35 Sol ids Concentrat ion Data Dur ing Period of Black L iquor Carryover Tests P e r m e a t e f r o m R e a c t o r 1 P e r m e a t e f r o m R e a c t o r 2 T D S (mg/L) V D S (mg/L) T D S (mg/L) V D S (mg/L) Augus t 2 1180 650 1520 970 Augus t 3 1020 580 1500 760 4-Aug-01 9:00 1261 630 1550 517 4-Aug-01 11:00 1160 630 1260 580 4-Aug-01 13:00 1230 660 1420 700 4-Aug-01 15:00 1240 710 1480 780 4-Aug-01 17:00 1260 730 1450 760 Augus t 5 800 350 1700 760 Augus t 6 1440 930 1590 640 7-Aug-01 9:00 1440 710 1560 900 7-Aug-01 11:00 1610 890 1810 1040 7-Aug-01 13:00 1540 780 1940 1230 7-Aug-01 15:00 1190 440 1640 740 7-Aug-01 17:00 1340 520 1670 720 Augus t 9 1605 590 1690 735 10-Aug-01 9:00 1420 630 2200 1260 10-Aug-01 11:00 1450 610 2190 1270 10-Aug-01 13:00 1430 620 2280 1280 10-Aug-01 15:00 1400 660 2340 1250 10-Aug-01 17:00 1560 770 2 3 5 0 4 8 0 Augus t 11 2360 640 1890 520 Augus t 12 1680 520 1680 1240 Augus t 13 2530 1400 1950 1570 Augus t 14 2120 1400 1240 895 Augus t 15 1420 585 1450 1020 16-Aug-01 9:00 1595 740 1660 980 16-Aug-01 11:00 1880 960 1620 1070 16-Aug-01 13:00 2000 990 1690 1300 16-Aug-01 15:00 2030 1060 1690 1350 16-Aug-01 17:00 3030 1610 2040 1480 Augus t 17 2460 1530 1720 1250 Augus t 18 1900 1340 1690 1100 138 Appendix 5 Data Collected During Mill Shutdown Experiment Appendix 5 contains the data collected during mill shutdown experiment. Results from batch tests monitoring removal kinetics of methanol, total organic carbon (TOC), and chemical oxygen demand (COD) are presented in Table A5 - 1 to A5 - 9. For these tables, the parameter K is the zero order coefficient for the biological removal of contaminant (mg/L-min). The parameter Co is the initial concentration in the M B R and the parameter Ce is the final TOC concentration in the M B R , derived from the second zero order removal coefficient. The R value is the coefficient of determination for linear regression. The calculations for observed growth yields of R2 are presented in Table A5 -10. 139 B a t c h T e s t Da ta D u r i n g Mi l l S h u t d o w n T e s t T a b l e A 5 - 1 A u g u s t 25 , 2001 ( D a y 2 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 259.7 202 838 30 243.9 199 809 45 237.7 197 760 60 225.5 196 730 75 203.1 191 662 90 198.3 183 642 Co (Ce) 272.2 206.7 885.3 K 0.8 0.2 2.8 R 2 0.974 0.897 0.984 T a b l e A 5 - 2 A u g u s t 27 , 2001 ( D a y 4 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 314.3 219 850 30 300.6 209 762 45 289.9 208 713 60 281.7 204 703 75 272.6 202 683 90 261.4 199 595 C o (Ce) 322.4 219.3 869.9 K 0.7 0.2 2.9 R 2 0.994 0.904 0.92 T a b l e A 5 - 3 A u g u s t 29 , 2001 ( D a y 6 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 286.1 210 846 30 282.4 204 846 45 280.4 203 806 60 270.3 202 738 75 264.9 200 689 90 260.2 199 679 Co (Ce) 293 .5 209.8 904.7 K 0.4 0.1 2.6 R 2 0.968 0.869 0.941 T a b l e A 5 - 7 S e p t e m b e r 4 , 2001 ( D a y 12 ) T a b l e A 5 - 4 A u g u s t 3 1 , 2001 ( D a y 8 ) Reactor 1 T i m e Methano l T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 247.8 203 930 30 241.7 201 871 45 238.6 199 871 60 237.9 197 862 75 234.2 194 803 90 223.5 192 793 Co (Ce) 251.8 205.5 944.8 K 0.3 0.1 1.7 R 2 0.902 0.995 0.905 T a b l e A 5 - 5 S e p t e m b e r 2, 2001 ( D a y 10 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 278.4 207 950 30 274.3 2 0 6 940 45 271.3 204 920 60 266.6 202 920 75 267.6 201 881 90 254.4 195 852 Co (Ce) 283.3 210.2 977.2 K 0.3 0.1 1.3 R 2 0.875 0.906 0.921 T a b l e A 5 - 6 S e p t e m b e r 3, 2001 ( D a y 11 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 62.8 78 324 30 55.9 72 287 45 49.9 64 253 60 45.4 60 191 75 38.8 58 163 90 33.2 4 9 115 Co (Ce) 68.1 82.6 370.1 K 0.4 0.4 2.8 R 2 0.998 0.973 0.993 140 Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 111.1 137 4 9 6 30 96.7 133 443 45 81.3 124 404 60 60.2 113 337 75 49 .5 108 315 90 28.3 99 274 Co (Ce) 128.9 146.6 534.3 K 1.1 0.5 3 R 2 0.995 0.988 0.986 T a b l e A 5 - 8 S e p t e m b e r 5, 2001 ( D a y 13 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 162 189 718 30 140.3 173 677 45 104.9 169 617 60 91.5 159 567 75 62.3 144 533 90 41.8 137 475 Co (Ce) 185.3 197.5 767.5 K 1.6 0.7 3.2 R 2 0.991 0.981 0.996 T a b l e A 5 - 9 S e p t e m b e r 6, 2001 ( D a y 1 4 ) Reactor 1 T i m e Methanol T O C C O D (min) (mg/L) (mg/L) (mg/L) 15 210.8 223 813 30 185.5 215 727 45 151.4 188 678 60 117.6 184 613 75 83.5 164 587 90 56.9 158 499 Co (Ce) 245.2 236.9 858.3 K 2.1 0.9 3.9 R 2 0.998 0.964 0.983 T a b l e A 5 - 1 0 G r o w t h Y i e l d o f R e a c t o r 2 D u r i n g P e r i o d o f Mi l l S h u t d o w n T e s t Date Cumula t ive Methanol M L V S S Sludge Cumula t ive Cumulat ive T i m e C o n s u m e d W a s t e d Methano l Sol ids (day) (mg/cycle) (mg/L) (mg/day) (mg) (mg) 23-Aug-01 0 0 2383 124 0 0 24-Aug-01 1 0 2350 122 0 122 25-Aug-01 2 531 2350 122 531 244 26-Aug-01 3 0 2350 122 531 367 27-Aug-01 4 598 1617 84 1129 451 28-Aug-01 5 0 1617 84 1129 535 29-Aug-01 6 517 1350 70 1646 605 30-Aug-01 7 0 1350 70 1646 675 31-Aug-01 8 469 1250 65 2115 740 1-Sep-01 9 0 1250 65 2115 805 2-Sep-01 10 475 1300 68 2 5 9 0 873 3-Sep-01 11 123 1300 68 2590 940 4-Sep-01 12 235 1383 72 4 0 6 6 1012 5-Sep-01 13 346 1400 73 6886 1085 6-Sep-01 14 450 1683 88 11038 1173 Growth Yield 0.106 *Measured M L V S S Value in Bold. 142 Appendix 6 Data of Permeate Flux and Membrane Cleaning Procedure Appendix 6 contains the data of permeate flux collected throughout entire experimental period. Results are presented in Table A6 - 1. Based on discussions with Berube (2000) and supplier (US Filter), the membrane cleaning procedure was used during the present study and is presented as below. Membrane Cleaning Procedure: 1. Disconnect the membrane unit with the flow restriction valve from the system 2. Drain the membrane unit and connect them to another progressive cavity pump 3. Close permeate ports (Figure 3.2) and open the valve so that the trans-membrane pressure is negligible. 4. Flush the system with water for 10 minutes 5. Rinse with a solution containing 200 to 300 ppm of NaOCl for 10 minutes 6. Pump clean water through membrane for 1 minute 7. Circulate a 20% NaOH solution through the membrane for 30 minutes 8. Pump a 20% NaOH solution through the membrane at trans-membrane pressure of 5-10 psi for 30 minutes. 9. Drain the membrane by opening both sides of permeate ports 10. Flush with distill water until pH of permeate is close to neutral (approximately 15 minutes) 143 11. Check permeate flow rate, which should be close to the rate that measure at the first clean water permeability test under the same condition, to confirm that the cleaning is complete 144 Table A6-1 Permeate Flux o f Membrane Dur ing the Present S t u d y Reactor 1 Reactor 2 Reactor 1 Reactor 2 Date D a y # Flux (L /m 2 h) Date D a y # Flux (L /m 2 h) Date D a y # Flux (L /m 2 h) Date Day # 26-Oct-OO 29-Oct-00 31-Oct-OO 04-Nov-OO 07-Nov-OO 1 4 6 10 13 160 130 100 90 80 26-Oct-OO 28-Oct-00 31-Oct-OO 05-Nov-00 07-Nov-OO 1 3 6 11 13 150 130 110 90 80 22-May-01 24-May-01 26-May-01 28-May-01 30-May-01 209 211 213 215 217 100 90 90 80 90 28- May-01 29- May-01 0 1 - Jun-01 02- Jun-01 03- Jun-01 215 216 219 220 221 10-Nov-OO 12-Nov-OO 17-Nov-OO 21-Nov-OO 28-Nov-OO 02-Dec-OO 05-Dec-00 10-Dec-00 12-Dec-00 17-Dec-00 21-Dec-OO 23-Dec-OO 26-Dec-OO 29-Dec-OO 31-Dec-00 03-Jan-01 05-Jan-01 10-Jan-01 13-Jan-01 15-Jan-01 19-Jan-01 23-Jan-01 26-Jan-01 28-Jan-01 30-Jan-01 03-Feb-01 07-Feb-01 10-Feb-01 12-Feb-01 15-Feb-01 19- Feb-OT 20- Feb-01 22- Feb-01 23- Feb-01 26-Feb-01 02-Mar-01 04-Mar-01 07-Mar-01 11-Mar-01 14-Mar-01 16-Mar-01 19-Mar-01 21-Mar-01 23-Mar-01 25-Mar-01 26- Mar-01 27- Mar-01 28- Mar-01 30-Mar-01 09-Apr-01 10- Apr-01 1 1 - Apr-01 13- Apr-01 14- Apr-01 15- Apr-01 16-Apr-01 18-Apr-01 2 1 - Apr-01 22- Apr-01 23- Apr-01 24- Apr-01 25- Apr-01 28- Apr-01 29- Apr-01 30- Apr-01 0 1 - May-01 02- May-01 05- May-01 06- May-01 07- May-01 16 18 23 27 34 70 80 80 90 80 09-Nov-OO 13-Nov-OO 17-Nov-OO 20-Nov-00 28-Nov-OO 38 41 46 48 53 70 70 60 60 150 04-Dec-OO 06-Dec-00 09-Dec-00 13-Dec-00 15-Dec-00 10-May-01 12-May-01 14- May-01 15- May-01 16- May-OI 57 59 62 65 67 130 110 100 90 90 20-Dec-00 22-Dec-00 25-Dec-00 29- Dec-OO 30- Dec-00 70 72 77 80 82 80 70 70 80 90 05-Jan-01 07-Jan-01 12-Jan-01 14-Jan-01 17-Jan-01 86 90 93 95 97 80 80 70 70 60 19-Jan-01 23-Jan-01 25-Jan-01 28-Jan-01 31-Jan-01 101 105 108 110 113 60 60 60 50 60 03-Feb-01 08-Feb-01 10-Feb-01 13-Feb-01 16-Feb-01 18- May-01 19- May-01 20- May-01 2 1 - May-01 117 118 120 121 124 60 160 140 130 100 19-Feb-01 21-Feb-01 23-Feb-01 27-Feb-01 03-Mar-01 128 130 133 137 140 90 80 70 80 60 08-Mar-01 11-Mar-01 13-Mar-01 17-Mar-01 19-Mar-01 142 145 147 149 151 80 80 90 70 60 22- Mar-01 23- Mar-01 25-Mar-01 29- Mar-01 30- Mar-01 152 153 154 156 166 60 150 140 120 90 31-Mar-01 01-Apr-01 04- Apr-01 05- Apr-01 09-Apr-01 167 168 170 171 172 80 90 90 90 80 11-Apr-01 13-Apr-01 15- Apr-01 16- Apr-01 20-Apr-01 173 175 178 179 180 80 80 80 70 70 2 1 - Apr-01 22- Apr-01 23- Apr-01 24- Apr-01 27-Apr-01 181 182 185 186 187 80 80 70 80 70 28- Apr-01 29- Apr-01 30- Apr-01 01-May-01 04-May-01 15 19 23 26 34 40 42 45 49 51 56 58 61 65 68 188 189 192 193 194 80 70 70 60 60 05-May-01 09-May-01 13- May-01 14- May-01 15- May-01 197 199 201 202 203 60 70 50 60 60 17- May-01 18- May-01 19- May-01 20- May-01 2 1 - May-01 205 206 207 208 140 130 120 110 23- May-01 24- May-01 26- May-01 27- May-01 72 74 79 81 84 86 90 92 95 98 101 106 108 111 114 117 119 122 126 129 134 137 139 143 145 148 149 151 155 156 157 158 161 162 166 168 170 172 173 177 178 179 180 181 184 185 186 187 188 191 192 196 200 201 202 204 205 206 207 208 210 211 213 214 80 70 60 70 80 31-May-01 0 1 - Jun-01 02- Jun-01 05- Jun-01 06- Jun-01 218 219 220 223 224 80 80 90 70 70 04- Jun-01 05- Jun-01 07- Jun-01 08- Jun-01 09- Jun-01 222 223 225 226 227 60 60 140 110 90 80 80 70 60 60 70 60 60 50 50 50 140 120 100 90 80 70 60 60 50 50 60 50 50 130 100 90 80 70 60 50 40 140 110 100 90 80 80 70 60 60 50 50 40 120 100 90 80 80 70 60 70 50 40 120 100 70 40 110 90 80 70 60 60 50 40 100 80 70 07- Jun-01 08- Jun-01 10- Jun-01 1 1 - Jun-01 12- Jun-01 225 226 228 229 230 80 70 60 70 80 11-Jun-01 13- Jun-01 14- Jun-01 17- Jun-01 18- Jun-01 229 231 232 235 236 14-Jun-01 16- Jun-01 17- Jun-01 20- Jun-01 2 1 - Jun-01 232 234 235 238 239 22- Jun-01 23- Jun-01 24- Jun-01 25- Jun-01 26- Jun-01 240 241 242 243 244 27- Jun-01 28- Jun-01 29- Jun-01 30- Jun-01 01-Jul-01 02- Jul-01 03- Jul-01 04- Jul-01 05- Jul-01 06- Jul-01 07- Jul-01 08- Jul-01 09- Jul-01 10- Jul-01 1 1 - Jul-01 12- Jul-01 13- Jul-01 14- Jul-01 15- Jul-01 16- Jul-01 17- Jul-01 18- Jul-01 19- Jul-01 20- Jul-01 2 1 - Jul-01 22- Jul-01 23- Jul-01 24- Jul-01 25- Jul-01 26- Jul-01 27- Jul-01 28- Jul-01 29- Jul-01 30- Jul-01 3 1 - Jul-01 0 1 - Aug-01 02- Aug-01 03- Aug-01 04- Aug-01 05- Aug-01 06- Aug-01 07- Aug-01 08- Aug-01 09- Aug-01 10- Aug-01 1 1 - Aug-01 12- Aug-01 13- Aug-01 14- Aug-01 15- Aug-01 16- Aug-01 17- Aug-01 18- Aug-01 19- Aug-01 20- Aug-01 2 1 - Aug-01 22- Aug-01 23- Aug-01 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301 302 80 80 150 130 120 110 100 90 95 90 90 100 95 90 90 90 85 80 75 80 75 80 85 70 70 60 70 60 70 150 140 130 120 110 100 90 100 100 90 90 80 80 90 80 80 90 150 140 130 120 100 90 85 90 90 85 85 80 80 75 70 75 70 60 65 60 60 60 19- Jun-01 20- Jun-01 2 1 - Jun-01 22- Jun-01 23- Jun-01 237 238 239 240 241 24- Jun-01 25- Jun-01 26- Jun-01 27- Jun-01 28- Jun-01 242 243 244 245 246 29- Jun-01 30- Jun-01 0 1 - Jul-01 02- Jul-01 03- Jul-OI 247 248 249 250 251 04- Jul-01 05- Jul-01 06- Jul-01 07- Jul-01 08- Jul-01 252 253 254 255 256 09- Jul-01 10- Jul-OI 1 1 - Jul-01 12- Jul-01 13- Jul-01 257 258 259 260 261 14- Jui-01 15- Jul-01 16- Jul-01 17- Jul-01 18- Jul-01 ^04 263 264 265 266 19- Jul-01 20- Jul-01 2 1 - Jul-01 22- Jul-OI 23- Jul-01 267 268 269 270 271 24- Jul-01 25- Jul-01 26- Jul-01 27- Jul-01 28- Jul-01 272 273 274 275 276 29- Jul-01 30- Jul-01 3 1 - Jul-01 0 1 - Aug-01 02- Aug-01 277 278 279 280 281 03- Aug-01 04- Aug-01 05- Aug-01 06- Aug-01 07- Aug-01 282 283 284 285 286 08- Aug-01 09- Aug-01 10- Aug-01 1 1 - Aug-01 12- Aug-01 287 288 289 290 291 13- Aug-01 14- Aug-01 15- Aug-01 16- Aug-01 17- Aug-01 292 293 294 295 296 18- Aug-01 19- Aug-01 20- Aug-01 297 298 299 145 

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