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Membrane bioreactor treating kraft evaporative condensate at a high temperature under different operational… Alsuliman, Abdullah 2003

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Membrane Bioreactor Treating Kraft Evaporator Condensate At A High Temperature Under Different Operational Conditions And Turpentine Shockloads  By  Abdullah Alsuliman B.Sc. University of Technology, 1986 M.Sc. University of Baghdad, 1992  A thesis submitted in partial fulfilment 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 February 2003 © Abdullah Alsuliman  In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department  or  by  his  or  her  representatives.  It  is  understood  that  copying  or  publication of this thesis for financial gain shall not be allowed without my written permission.  Department The University of British Columbia Vancouver, Canada Date  DE-6 (2/88)  Abstract This study was initiated to assess the feasibility of biological treatment and reuse of kraft pulp mill evaporator condensate, using a high temperature MBR operated at a short solids retention time (SRT) and low hydraulic retention time (HRT). In addition, the mechanisms responsible for the fouling of the membrane were examined. The decline in the biomass concentration associated with short SRT operation affected membrane fouling. Furthermore, the impact of short-term turpentine shock loads on the overall removal kinetics of the contaminants of concern present in the evaporator condensate was investigated.  To obtain as much data as possible within a short time frame, a lab scale system consisting of two bench scale high temperature MBRs was operated at different operational SRTs and FIRTs. The SRT conditions selected were 15 and 10 days. The associated HRTs set at either 12, 10, or 8 hours. Other operating parameters were selected according to recommendations from a membrane manufacturing company and from a previous study (Berube, 2000).  Methanol, monoterpenes, and organic compounds represented by total organic carbon (TOC) were identified as the primary contaminants of concern contained in the evaporator condensate. Methanol and monoterpenes are of concern primarily because they are hazardous air pollutants (HAP) and/ or foul odorous compounds. They contribute 60 to 75 % of the biochemical oxidation demand (BOD) in the evaporator condensate (Hough et al, 1977).  The results of the study indicated that the biological removal of the contaminants of concern using a high temperature MBR operated at a short SRT (as short as 10 days) and a low HRT (as low as 10 hours) was feasible. However, when the HRT was decreased from 10 to 8 hours (organic load increased), the mixed microbial culture responsible for the removal of methanol was inhibited. The potential toxic contaminants present in the evaporator condensate exhibited an immediate influence on the biotic removal kinetics  and removal efficiencies of methanol. For monoterpenes and T O C , the significant decline in the values of overall removal kinetics and efficiencies, when HRT was lowered to 8 hours, was due to the short contact time imposed.  Investigation of the membrane performance indicated that the reduction in the permeate flux with time and the resulting cleaning intervals were a function of the operational SRTs and HRTs. Membrane fouling was found to be a function of the mixed liquor volatile suspended solids (MLVSS) concentration in the M B R and the operational transmembrane pressure (TMP). Membrane fouling was mainly controlled by pore plugging resistance (R ) rather than concentration polarization (R ) and membrane resistances pp  cp  (R ). Rpp composed from 60 to 80 % of the total foulant resistance. m  Turpentine shock loads exerted a significant impact on the overall removal kinetics of the main contaminants of concern in evaporator condensate. Overall removal rates decreased significantly as the spiked monoterpenes accumulated in the MBRs. The overall removal rates decreased more significantly when the spiking concentrations of monoterpenes were increased from 300 to 1500 mg/L.  Table of Contents ABSTRACT  I  T A B L E O F CONTENTS LIST OF FIGURES  Ill VII  LIST OF ABBREVIATIONS AND ACRONYM ACKNOWLEDGEMENTS  X XIII  CHAPTER 1 INTRODUCTION  1  1.1 MOTIVATION OF RESEARCH  1  1.2 THESIS ORGANIZATION  3  CHAPTER 2 BACKGROUND AND LITERATURE REVIEW  4  2.1 SOURCES AND QUANTITY OF EVAPORATOR CONDENSATE  4  2.2 CHARACTERISTICS OF EVAPORATOR CONDENSATES  7  2.3 TREATMENT OF EVAPORATOR CONDENSATE  8  2.3.1 Stripping method  9  2.3.2 Biological Treatment  11  2.3.2.1 Anaerobic Biological Treatment  11  2.3.2.2  Aerobic Biological Treatment  11  2.3.2.3  Aerobic Membrane Bioreactor Treatment  15  CHAPTER 3 OBJECTIVES OF T H E RESEARCH  22  CHAPTER 4 EXPERIMENTAL APPARATUS AND METHODS OF ANALYSIS 24 4.1 EXPERIMENTAL APPARATUS 4.1.1 Membrane Biological Reactor System  24 24  4.1.1.1 Aerobic Bioreactor  24  4.1.1.2 Ultrafiltration Unit  24  iii  4.1.1.3  Pump Used for the MBR  2  4.1.1.4  Instrumentation  27  4.1.1.5  Feeding Tank  2  g  2  g  VlATERIALS 4.2.1 Wastewater Feed  6  28  4.2.2 Nutrient Solution  29  4.2.3 Biomass  30  4.3 EXPERIMENTAL METHODS  30  4.3.1 Start-up the MBR and Biomass Acclimatization  31  4.3.2 Experimental Investigation  31  4.3.3 Operation and Monitoring the MBR  32  4.3.4 Membrane Cleaning  34  4.3.5 Sampling Protocol and Preparation  35  4.3.6 Analytical Methods and Equipment  37  4.3.6.1  Solids Concentration  37  4.3.6.2  Conductivity  37  4.3.6.3  Total Organic Carbon (TOC) Concentration  37  4.3.6.4  Methanol Concentration  38  4.3.6.5  Turpentine Concentration  38  4.3.6.6 pH  40  4.3.6.7  Permeate Flow Rate  40  4.3.6.8  Statistical Analyses  41  CHAPTER 5 RESULTS AND DISCUSSION 5.1 PHASES 1 AND 4 5.1.1 Methanol Removal. 5.1.2 Monoterpenes Removal  42 42 42 52  5.1.3 TOC Removal  61  5.1.4 Sludge Production  70  5.2 PHASE 2 5.2.1 Permeate Flux 5.2.2 Fouling Mechanisms 5.3 PHASE 3  71 71 76 79  IV  CHAPTER 6 CONCLUSIONS AND RECOMMENDATIONS 6.1 C O N C L U S I O N S  85 85  6.1.1 Feasibility of the Biological Removal of Methanol, Monoterpenes and TOCfrom the Real Evaporator Condensate  85  6.1.2 Identification of the Removal Kinetics and Efficiencies of Methanol, Monoterpenes, and TOC  85  6.1.3 Identification of the Mechanism Responsible for the Membrane Fouling  87  6.1.4 Identification of the Impacts of Turpentine Shock Loads on the MBRs' performance. 88 6.2 R E C O M M E N D A T I O N  89  REFERENCES  91  APPENDIX 1 DATA C O L L E C T E D DURING PHASE 1  98  A l . 1 R E M O V A L KINETICS FOR M E T H A N O L A N D TURPENTINE A 1.2 R E M O V A L K I N E T I C S F O R T O C  98 104  A1.3 S O L I D C O N C E N T R A T I O N S A N D R E M O V A L E F F I C I E N C I E S O F M E T H A N O L , TURPENTINE, A N D T O C  114  A l .4 O B S E R V E D G R O W T H Y I E L D D A T A  122  APPENDIX 2 D A T A C O L L E C T E D DURING PHASE 3  125  A2.1 R E M O V A L K I N E T I C S F O R M E T H A N O L A N D T U R P E N T I N E  125  A2.2 R E M O V A L K I N E T I C S F O R T O C  130  APPENDIX 3 D A T A C O L L E C T E D DURING PHASE 4  139  A3.1 S T R I P P I N G K I N E T I C S F O R M E T H A N O L A N D T U R P E N T I N E  139  A3.2 S T R I P P I N G K I N E T I C S F O R T O C  141  v  List of Tables Table 2.1 Terpenes identified in kraft m i l l aerated lagoons  9  Table 2.2 T y p i c a l concentrations oi the main contaminants o f concern  10  Table 4.1 Specifications and operating limits o f the Membralox T l - 7 0 ultrafiltration  27  Table 4.2 Characteristics o f the evaporator condensate in the study  29  Table 4.4 Summary of the experimental work during the study  33  Table 4.5 Summary of operating parameters  34  Table 4.6 Temperature programme for G C analysis o f methanol samples  38  Table 4.7 Temperature programme for G C analysis of monoterpenes  39  Table 5.1 Methanol removal coefficients during Phase 1  52  Table 5.2 First order overall and biological removal coefficients for T O C during Phase 1  65  Table 5.3 Biomass growth yields for R I and R 2 during Phase 1  71  Table 6.1 Summary o f the results obtained in the present study and the previous studies  86  vi  List of Figures Figure 1.1 Typical kraft pulping process  5  Figure 1.2 Typical turpentine recovery systems  6  Figure 4.1 Schematic of bench scale high temperature MBR used in the study  25  Figure 4.2 Membrane unit used for the M B R (Membralox 1T-70)  26  Figure 4.3 Schematic of the cleaning system  36  Figure 5.1 Concentration of methanol in M B R during a typical batch feed cycle  43  Figure 5.2 Estimated contributions of methanol striping  45  Figure 5.3 Average M L V S S concentrations during Phase 1  47  Figure 5.4 Methanol specific biological utilization coefficients ( K  u m  ) during Phase 1  Figure 5.5 Influents and effluents methanol concentrations for RI and R2 Figure 5.6 Methanol removal efficiencies for RI and R2  47 48 48  Figure 5.7 Influent and effluent methanol concentrations and methanol overall removal efficiency for RI (Phase 1, Run 5: SRT=15 days, HRT=10 hours)  49  Figure 5.8 Influent and effluent methanol concentrations and methanol overall removal  49  efficiency for RI, (Phase 1, Run 4: SRT=15 days, HRT= 8 hours)  49  Figure 5.9 Influent and effluent methanol concentrations and methanol overall removal efficiency for RI (Phase 1, Run 3: SRT= 10 days, HRT= 12 hours) Figure 5.10 Influent and effluent methanol concentrations and methanol overall efficiency for R2 (Phase 1, Run 3: SRT= 10 days, HRT= 10 hours) Figure 5.11  50 removal 50  Influent and effluent methanol concentrations and methanol overall removal  efficiency for R2 (Phase 1, Run 4: SRT= 10 days, HRT= 8 hours)  51  Figure 5.12 Concentration of monoterpenes in M B R during a typical batch feed cycle  53  Figure 5.13 Estimated contributions of monoterpenes stripping to the overall observed  56  Figure 5.14 Monoterpene specific biological utilization coefficients  57  Figure 5.15 Influents and effluents monoterpenes concentrations for RI and R2  57  (Phase 1, Run 1: SRT=15 days, HRT=12 hours)  57  Figure 5.16 Monoterpenes removal efficiencies for RI and R2  58  (Phase 1, Run 1: SRT= 15 days, HRT=12hours)  58  Figure 5.17 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for RI (Phase 1, Run 5: SRT=15 days, HRT=10 hours)  58  Figure 5.18 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for RI (Phase 1, Run 4: SRT=15 days, HRT= 8 hours)  59 vii  Figure 5.20 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for R2 (Phase 1, Run 3: SRT=10 days, HRT= 10 hours)  60  Figure 5.21 Influent and effluent monoterpenes concentrations and monoterpenes  60  overall removal efficiency for R2 (Phase 1, Run 4: SRT=10 days, HRT= 8 hours)  60  Figure 5.22 Concentration of TOC in M B R during a typical batch feed cycle  63  Figure 5.23 Estimated contributions of TOC stripping  64  Figure 5.24 TOC specific biological utilization coefficients ( K  u T O C  ) during Phase 1  66  Figure 5.25 Influents and effluents TOC concentrations of for RI and R2  66  (Phase 1, Run 1: SRT=15 days, HRT=12 hours)  66  Figure 5.26 TOC removal efficiencies for RI and R2 (Phase 1, Run 1: SRT= 15 days HRT=12 hours)  67  Figure 5.27 Influent and effluent TOC concentrations and TOC overall removal  67  efficiency for RI (Phase 1, Run 5: SRT=15 days, HRT=10 hours)  67  Figure 5.28 Influent and effluent TOC concentrations and TOC overall removal  68  efficiency for R I (Phase 1, Run 4: SRT=15 days, HRT=8 hours)  68  Figure 5.29 Influent and effluent TOC concentrations and TOC overall removal  68  efficiency for RI (Phase 1, Run 3: SRT=10 days, HRT=12 hours)  68  Figure 5.30 Influent and effluent TOC concentrations and TOC overall removal  69  efficiency for R2 (Phase 1, Run 3: SRT=10 days, HRT=10 hours)  69  Figure 5.31 Influent and effluent TOC concentrations and TOC overall removal  69  efficiency for R2 (Phase 1, Run 4: SRT=10 days, HRT=8 hours)  69  Figure 5.32 Permeate flux with time for R2 (Phase 2, Run 1: SRT =15 d, HRT= 12 hrs, M L V S S =1820 mg/L) Figure 5.33 Permeate flux with time for R2 (Phase 2, Run 2: SRT =15 d, HRT= 10 hrs, =2670 mg/L) Figure 5.34 Permeate flux with time for R2 (Phase 2, Run 3: SRT =10 d, HRT= 10 hrs, =2060 mg/L) Figure 5.35 Permeate flux with time for R2 (Phase 2, Run 4: SRT =10 d, HRT= 8 hrs, =380 mg/L)  72 MLVSS 72 MLVSS 73 MLVSS 73  Figure 5.36 Permeate flux with time for RI (Phase 2, Run 5: SRT =15 d, HRT= 10 hrs, M L V S S =2500 mg/L)  74  Figure 5.37 Permeate flux with time for R I (Phase 2, Run 4: SRT =15 d, HRT= 8 hrs, M L V S S =450 mg/L)  74  Figure 5.38 Permeate flux with time for R I (Phase 2, Run 3: S R T =10 d, H R T = 12 hrs, M L V S S =1340 mg/L)  75  Figure 5.39 Variation o f serial resistances with time for R I  77  Figure 5.40 Variation o f serial resistances with time for R2  77  Figure 5.41 Percentages of R , R , and R o f the total resistance with time for R I  78  Figure 5.42 Percentages of R , R , and  78  m  m  p p  p p  c p  Rc of P  the total resistance with time for R 2  Figure 5.43 Variation of overall methanol removal rates with the sequence o f spiked batch feed cycles for R I during Phase 3 ( S R T =15 days, HRT=10 hours)  82  Figure 5.44 Variation o f overall methanol removal rates with the sequence o f spiked batch feed cycles for R 2 during Phase 3 ( S R T =15 days, HRT=12 hours)  82  Figure 5.45 Variation o f monoterpenes overall removal rates with the sequence o f spiked  83  batch feed cycles for R I during Phase 3 ( S R T =15 days, H R T = 1 0 hours)  83  Figure 5.46 Variation o f monoterpenes overall removal rates with the sequence o f spiked batch feed cycles for R 2 during Phase 3 ( S R T =15 days, HRT=12 hours)  83  Figure 5.47 Variation o f overall T O C removal rates with the sequence o f spiked batch  84  feed cycles for R I during Phase 3 ( S R T =15 days, H R T = 1 0 hours)  84  Figure 5.48 Variation o f overall T O C removal rates with the sequence o f spiked batch  84  feed cycles for R 2 during Phase 3 ( S R T =15 days, H R T = 1 2 hours)  84  ix  List of Abbreviations and Acronym u  Dynamic Viscosity (N.sec/m )  AP  Trans-membrane pressure (N/m )  ASB  Aerated stabilization basin  AST  Activated sludge treatment  ATP  Adenosine triphosphate  BCTMP  Bleached chemi-thermomechanical pulp  BOD  Biochemical oxygen demand (mg/L)  CFV  Crossflowvelocity  ClvieOH  Concentration of methanol in the MBR (mg/L)  COD  Chemical oxygen demand (mg/L)  COFI  Council of Forest Industries  CTMP  Chemi-thermomechanical pulp  Cturp  Concentration of monoterpenes in the MBR (mg/L)  EPA  Environmental Protection Agency (United States)  FID  Flame ionization detector  GC/MS  Gas chromatography/mass spectrometric  HAP  Hazardous air pollutant  HRT  Hydraulic retention time (hours)  Jf  Pure water flux for membrane fouled by real evaporator condensate  2  2  (m /m -sec) 3  2  Ji  Pure water flux for the cleaned membrane (m /m -sec)  Jv  Flux with real evaporator condensate (m /m -sec)  Kbio.t  First order coefficient for biological removal of monoterpenes (/minute)  Kbio.TOC  First order coefficient for biological removal of TOC (/minute)  3  3  2  2  Zero order coefficient for methanol removal (mg/L minute) K i  First order coefficient for methanol removal (/minute)  K-s.turp  Half saturation concentration for monoterpenes (mg/L)  K MeOH  Half saturation concentration for methanol (mg/L)  Kstrip.Me  First order coefficient for stripping of methanol (/minute)  m  s  K-strip.TOC  First order coefficient for stripping of TOC (/minute)  K-strip.turp  First order coefficient for stripping of monoterpenes (/minute)  K-tot.t  First order coefficient for total removal of monoterpenes (/minute)  Ktot.TOCt  First order coefficient for total removal of TOC (/minute) Specific methanol utilization coefficient (/day)  K-uTOC  Specific TOC utilization coefficient (/mg/L.day)  Kuturp  Specific monoterpenes utilization coefficient (/(/mg/L.day)  MBR  Membrane bioreactor  MeOH  Methanol  MLSS  Mixed liquor suspended solids (mg/L)  MLVSS  Mixed liquor volatile suspended solids (mg/L)  MWCO  Molecular weight cut-off  NCASI  National Council for Air and Stream Improvement  NSERC  Natural Science and Engineering Research Council of Canada  OUR  Oxygen uptake rate (mg/L.minute)  PAPRICAN  Pulp and Paper Research Institute of Canada  RI  Reactor number 1  R2  Reactor number 2  Rep  Concentration polarization resistance (/m)  Rm  Membrane resistance (/m)  Rpp  Pore plugging resistance (/m)  RSC  Reduced sulphur compound (mg/L)  Rt  Total resistance (/m)  S  Concentration of multi-component substrate (mg/L as TOC)  SFM  Sustainable Forest Management Network of Centres of Excellence  SN  Non-biodegradable component of the multi-component substrate (mg/L as TOC)  Snv  Non-volatile component of the multi-component substrate (mg/L as TOC)  SN'  Non-volatile, non-biodegradable, component of the TOC (mg/L)  SPF  Screw press filtrates  SRT  Solids retention time (days) xi  TMP  Trans-membrane pressure (kPa)  TOC  Total organic carbon (mg/L)  UBC  University of British Columbia  X  Concentration of MLVSS in the MBR (mg/L)  Y  o b 5  Observed growth yield (mg VSS/mg MeOH)  xii  Acknowledgements I would like to thank Dr. Eric Hall for giving me the opportunity to work on this project. His endless patience and understanding have encouraged me and made this thesis possible. My thanks also to Dr. Pierre Berube for his consultancy during the research, careful review of thesis, and insightful suggestions. Special thanks go to Paula Parkinson and Susan Harper for their help during the chemical analysis portion of the research project. I would also like to thank the industrial support of Western Pulp's Squamish mill and Ms. Jeanne Taylor. I am also grateful to Rachel Jen for her help during the start up period. My thanks also go to Alessandro Monti for his consultancy during the research. My thanks also to Tim Patterson and Peter Taylor for their technical help. Finally, I wish to thank Ali Adnan and my family especially my parents and my w ife Z ahraa f or t he moral support during the study.  This research was achieved through the technical and financial contributions provided by the Pulp and Paper Research Institute of Canada (PAFRICAN), the Natural Science and Engineering Research Council of Canada/ Council of Forest Industries (NSERC/COFI), Industrial Research Chair (IRC), the Sustainable Forest Management Network of Centres of Excellence (SFM), and the University of British Columbia (UBC). The UBC Pulp and Paper Centre provided laboratory space for this project.  xiii  Chapter 1 Introduction 1.1 M o t i v a t i o n o f Research  The kraft sector of the pulp and paper industry is working to reduce the amount of the fresh water used and the volume of effluent discharged to the environment, by recycling process wastewater more extensively within the pulping process. However, reusing a large portion of wastewater could result in ambient air quality problems because of the subsequent release of hazardous air pollutants (HAP) and foul odorous compounds contained in the wastewater. Moreover, maximizing the degree of wastewater reuse by recycling a large amount of wastewater within the pulp mill may result in an increase in the concentration of dissolved and colloidal contaminants in both the pulp and wastewater streams, as well as an increase in operating temperatures. The increased contaminant concentrations in recycled wastewater may negatively affect mill operation and paper quality. Therefore, tighter regulatory requirements and higher public concerns about environmental issues have encouraged the pulp and paper industry to undertake research to refine the quality of effluents. One strategy to minimize some of the problems associated with a high degree of closure and wastewater reuse in a pulp and paper mill, is the insertion of a treatment step into the wastewater recirculation system, for purging the recycled wastewater stream of significant contaminants. The reduction of contaminants in the recycled wastewater stream will result i n decreased contamination of the pulp and higher paper quality.  There is an increasing interest in the treatment and reuse of evaporator condensate. Sebbas (1987), and Pekkanen and Kiiskila (1996), in their study, indicated the possibility of using treated evaporator condensate as process water in brown stock washing, recausticizing and bleaching instead of using clean water. A number of conventional technologies exist that could be used to treat the condensate for reuse. Steam or air stripping is the technology most commonly used to treat the foul condensate. However, the relatively poor treatment efficiencies and the high costs associated with this treatment technology provide incentives to investigate and develop better technologies for evaporator condensate treatment for reuse. Among the potential treatment technologies  1  for evaporator condensate, which offer effluents o f a high quality, is a high temperature aerobic membrane bioreactor (MBR). A high temperature MBR is identified as one of the most promising novel technologies. Studies that have investigated the treatment o f evaporator condensates using an MBR to date include: Berube (2000), at the University of British Columbia (UBC) Pulp and Paper Centre (PPC), who demonstrated the feasibility of removing the main contaminants which were methanol and reduced sulphur compounds (RSC) from synthetic and real evaporator condensates using bench scale high temperature MBRs; and Jen (2002), using the same conditions and apparatus of the first study, showed the feasibility of using a high temperature MBR to treat real condensates that were subjected to methanol and black liquor shock loads.  Terpenes are initially present in pulp wood and some react during the pulping process to form other terpenes. The concentration o f terpenes in evaporator condensates is reduced significantly when turpentine recovery is practiced, however, if losses occur, terpenes would be found in various process streams throughout the kraft mill. Therefore, there is interest in studying the biological treatment o f these compounds and how it will be affected in the event of turpentine shock loads, which could happen accidentally.  The development of membrane technology, including microfiltration and ultrafiltration processes, has expanded its application field into the treatment of pulp and paper wastewaters. However, wide spread adoption of these processes by pulp and paper mills has been limited, to a large extent due to the rapid fouling of the membranes. This generates a significant motivation for investigating and understanding the mechanisms responsible for membrane fouling.  The present thesis project was initiated as an extension of the previous studies on MBR at UBC PPC to examine the performance of MBRs for treating real foul condensate at a high temperature under different operational conditions. The impact of turpentine shock loads on the biological treatment of foul condensate using the MBR, and the mechanisms responsible for a rapid reduction in the permeatefluxwere studied in detail.  2  1.2 Thesis Organization Chapter 2 presents background information about the sources, the chemical composition of the foul condensate, and the possible alternative technology systems (treatment system options) that could be used to treat foul condensate with the emphasis on MBR. Chapter 3 outlines the objectives of the research. Chapter 4 describes the experimental techniques and materials used. In Chapter 5, the results obtained from the experiments perfonned are presented and discussed. Finally, Chapter 6 gives conclusions and recommendations for further study.  The experimental data are presented in the Appendices. Appendix 1 contains the data collected for the overall removal kinetics and removal efficiencies of the main contaminants of concern. Appendix 1 also contains the data collected for the biomass growth kinetics. Appendix 2 contains the data collected for the overall removal kinetics of the main contaminants of concern under turpentine shock load tests. Appendix 3 contains the data collected during the abiotic tests of the main contaminants of concern.  3  Chapter 2 Background and Literature Review 2.1 Sources and Quantity of Evaporator Condensate In general, there are two methods to carry out pulping. These two methods are chemical and mechanical pulping. In chemical pulping the lignin in the woodfibreis degraded and dissolved away with chemicals, leaving behind most of the cellulose and hemicelluloses. Mechanical pulping separates the fibres by application of mechanical stress and energy. The dominant process in the world is a form of chemical pulping, the kraft process. Kraft is the German word for strength and pulp produced from the kraft process is known for its s uperior s trength p roperties ( Smook, 1 992). I n t he k raft p ulping p rocess, chemicals (sodium sulphide and sodium hydroxide) are added to the wood to convert the lignin to soluble products. Consequently, these products, which are discharged in the spent cooking liquor, (which is also referred to as weak black liquor) are recovered and reused. The recovery process begins with the concentration of the weak black liquor by evaporation. The material that is commonly referred to as evaporator condensate is evaporated during the thickening process and then condensed. The evaporator condensate is typically segregated into a foul and a cleaner fraction. The foul fraction is formed from the initial evaporation of weak black liquor. This foul fraction typically accounts for less than 40% of the total evaporator condensate flow (Blackwell et al., 1979). The clean fraction of the evaporator condensate is formed from the subsequent evaporation of the partially thickened black liquor. This cleaner fraction contains  fewer volatile  contaminants and typically is clean enough to be reused without treatment (Blackwell et al., 1979).  The foul fraction of condensate usually originatesfromthe condensation of digester relief and blow vapours, and the vapours from multiple-effect evaporators. Batch and continuous digesters are commonly used. Figure 1.1 shows a typical kraft pulping process (using batch digester). For batch digesters, normally there are two sources of contaminated condensate, which are the accumulator overflow and the after-condenser condensate. The latter may flow to a turpentine decanter for recovery. The decanter  Figure 1.1 Typical kraft pulping process (AdaptedfromTai, 1998)  underflow becomes the foul condensate, which is rich in turpentine. Figure 1.2 shows a typical turpentine recovery system in which turpentine is recovered and collected for its commercial value, however, losses and spillages could occur leading to various concentrations of terpenes throughout the pulping process. The quantity of evaporator condensate can range from 800 to 1300 kg/admt (air dried metric tonne) for digesters combined with blow steam to 15,000 kg/admt without blow steam, which is diluted with cooling water (Blackwell et al, 1979). For continuous digesters, the liquor extracted is normally flashed in two stages, with the first stage providing steam for the steaming  vessel and the second stage going to a condenser. Vapours vented from the steaming vessel are normally combined with the second-stage liquor flash tank vapour and condensed. The condensate flows to a turpentine decanter for turpentine removal, and the underflow from the decanter is the continuous digester foul condensate. Typical flows are 300 to 400 kg/admt (Blackwell et ai, 1979). The evaporator condensates coming from multiple-effect evaporators usually originate from the shell side of the evaporator effects, the evaporator condenser, and the steam-jet ejector system. The quantities of the foul condensate that originate from these evaporators range from 5300 to 8000 kg/admt (Blackwell etal., 1979).  VAPOR  RELIEF  g  TUHREtLTJtl!  Figure 1.2 Typical turpentine recovery systems (AdaptedfromSmook, 1992)  2.2 Characteristics of Evaporator Condensates The foul fraction of evaporator condensates contains toxic and odorous materials and contributes 60 to 75 % of the biological oxygen demand (BOD) of an unbleached kraft mill wastewater and 50 to 60 % of the BOD of bleached kraft mill wastewater (Hough and Sallee, 1977). Of the combined mill wastewater, the principal BOD and odourcontributing substances in the foul condensates a re m ethanol, t erpene c ompounds, and reduced sulphur compounds (RSC), and terpene and reduced sulphur compounds, respectively. Foul condensates contain several impurities at concentrations between trace levels and about 1 % by weight (Blackwell et al, 1979). These impurities are either present in the wood initially, are formed by process reactions in digesters and elsewhere, or are added at some points in the process. Therefore, the exact composition and concentration of the compounds in the evaporator condensates are functions of a number of parameters, including the wood species pulped, the pulping process used, the evaporator and condensate configuration, and the use of a turpentine r ecovery s ystem. Most of these impurities are volatiles, which evaporate from black liquor along with water. However, non-volatile compounds such as resin and fatty acids are present in the condensates as a result of the physical entrainment of black liquor from the evaporators to the condensates (Blackwell et al, 1979). Over 60 compounds have been identified to be present in evaporator condensate. Among them are alcohols, ketones, terpenes, reduced sulphur compounds (RSC), phenolics, acids and aldehydes (Blackwell et al, 1979).  Of the chemical compounds present in the evaporator condensate, methanol and terpenes were identified as the main contaminants of concern in the present study. Methanol, the main organic compound in the foul condensates, is believed to originate from the alkaline hydrolysis of 4-o-methyl glucuronic acid residues in the hemicelluloses during the pulping process. These residues are typically present in greater amount in hardwoods than in softwoods (Blackwell et al, 1979). Terpene compounds, which are the other main components of BOD and odour substances, are present in the wood initially and some react in the process to form other terpene species. Crude sulfate turpentine represents a class of organic compounds that consists mainly of mono- and sesquiterpene. All terpene  compounds have a basic carbon skeleton made up of ten carbon atoms (Cio) despite the fact that they may have acyclic, cyclic or bicyclic structures. They belong to a family of terpenes in which each member is composed of multiple of five carbon atoms (C5) (Pinder, 1960; Templeton, 1969). In the pulping process, the crude sulfate turpentine is composed mainly of monoterpenes but it may also contain a few percent of sesquiterpenes (Wilson, 1974). Both monoterpenes and sesquiterpenes are further classified into hydrocarbons, ketones, and alcohols. Table 2.1 lists the common terpene compounds, which have been identified in kraft mill secondary treatment systems.  Terpene c oncentrations d epend also on the wood species pulped. For instance, terpene concentrations can varyfromalmost nothing for hardwood pulping (Cook et al., 1973) to levels as high as 2.5 % by weight in digester condensate from softwood pulping (Ronnholm, 1974). Provided that turpentine recovery is practiced within a pulp mill, as explained in Section 2.1, the concentrations of terpenes in the decanter underflow, which depend mainly on decanter separation efficiency, are typically 400 to 4000 mg/L (Wilson etal, 1975).  Typical concentrations of the main contaminants of concern in the foulfractionof the evaporator condensate are presented in Table 2.2.  Typically, the temperature of evaporator condensate ranges from 55 to 70 °C and the pH typically varies from 7.5 to 8.5. However the pH can be much higher when weak black liquor is physically entrained into the condensers during evaporation. (Zuncich et al., 1993).  2.3 Treatment of Evaporator Condensate As discussed previously, in order for the evaporator condensates to be reused as process water inside the pulp mills without any problems regarding HAP or foul odours, the removal of the main contaminants from the foulfractionof the evaporator is required. The treatment of foul condensates can be achieved either by stripping or by chemical and  Table 2.1 Terpenes identified in kraft mill aerated lagoons (Adapted from Wilson and Hurtfiord, 1975) alpha-pinene santene camphene sabinene beta-pinene myrcene alpha-phellandrene 1,4-cineole limonene 1,8-cineole beta-phellandrene 3-carene p-cymene terpinolene fenchone camphor linalool fenchyl alcohol terpinene-4-ol borneol alpha-terpineol anethole  biological reductions of organics. The first option can be pursued using air or steam stripping while the second option can involve anaerobic or aerobic biological reactions.  2.3.1 Stripping method A number of kraft pulp mills currently air or steam strip foul evaporator condensate before discharging to the environment. The performance of strippers in removing the contaminants exist in the e vaporator condensate has b een investigated by a number of studies. Hough et al. (1977) reported that an air stripper can remove 90 % or more of the RSC and make a significant reduction in condensate toxicity, but will reduce BOD by only 10 to 20 %. The same study reported that steam stripping reduces RSC by more than 95 %, and methanol by 70 to 75 % depending on the number of stages in the column and  9  Table 2.2 Typical concentrations of the main contaminants of concern present in the foul condensate (Adapted from Blackwell et al., 1979) Parameter  Batch  Batch  Continuous  Evaporator  Evaporator Stripper  digester  digester  digester  multiple  condenser  vent  blow  condensate  condensate  condensate  condensate  condensate  Methanol  1300-  250-9100  670-8900  180-700  180-1200  mg/L  12000  Terpenes  0.1-5500  0.1-1100  100-25000  0.1-150  0.1-620  1-9600  800-11500  720-9200  1950-8800.  60-1100  450-2500  800-  feed  14010000  mg/L TOC (mg/L as  13000  BOD) Suspended  30-70  solids mg/L  the ratio of steam to feed wastewater (Hough, 1977). Zuncich et al. (1993) indicated that for a methanol removal efficiency of 85 %, the steam rate required was approximately 15 to 18 % by weight of the feed rate. The same study mentioned that for methanol removal efficiencies of greater than 90 %, the amount of steam required for stripping increased significantly. The solubility of turpentine in the water rises when other solvents such as methanol are present in the mixture. Therefore, for condensates with methanol contents higher than the proportion of turpentine, almost 100 % turpentine recovery could be achieved when the methanol content was decreased as low as possible (Ronnholm, 1974). Steam stripping of pulp mill condensates offered 75 to 95 % and 65 % turpentine removal efficiencies for batch and continuous digesters, respectively. Most of the terpenes measured were monoterpenes (Wilson, 1974).  10  2.3.2 Biological Treatment 2.3.2.1 Anaerobic Biological Treatment Anaerobic biological treatment may consist of primary clarification followed by an anaerobic biological step and often, secondary clarification. Anaerobic treatment systems have a n umber o f advantages over steam and air stripping including lower operational costs, an ability to treat h igh strength wastes, and methane production to offset power costs (Jurgensen et al., 1985). Yamaguchi et al. (1990) reported that an anaerobic fixed film system with a relatively high organic load (up to 34.5 kg BOD/m *day) could 3  achieve 90 % BOD removal from evaporator condensate. However, the same study showed that the residual concentration of COD in the treated effluents was more than 800 mg/L. In another study, an anaerobic up-flow sludge blanket system at a loading rate of 25 kg COD/ m *day achieved COD and methanol removal efficiencies of 85 and 99 % 3  respectively (Wiseman et al., 1998). The treated effluents, for the latter study, contained COD and BOD at concentrations of 695 and 185 mg/L respectively. A literature search did not reveal any published data regarding terpenes removals using anaerobic treatment.  The existence of toxic chemicals in the condensate matrix when treating combined condensates, accompanied with pH and temperature variations, could upset biological treatment processes. One study reported that the removal efficiency of BOD from an anaerobic sludge blanket process for treating combined mill condensates, was only 40 % at a loading rate of 16 kg BOD / m *day (Carpenter and Berger, 1984). Another study 3  showed that only 60 % COD removal efficiency was achieved when treating a mixture of three different mill condensates. Increasing the operating temperature to above 50 °C reduced this removal efficiency down to 20 % (Welander et al, 1999). They suggested that pre-stripping, to remove RSC from the condensate, is required to ensure stable operation in an anaerobic biological system. 2.3.2.2 Aerobic Biological Treatment Conventional aerobic biological treatment systems for pulp and paper wastewaters usually consist of aerated lagoons, activated sludge treatment systems (AST), or a sequencing batch reactor (SBR). The treatment process may include a primary treatment  step, where the wastewater is settled in a primary clarification tank, followed by an aerobic biological treatment step and a secondary clarifier where the biomass is settled from the treated effluent. There are many parameters that affect the rate of contaminant removal in aerobic bioreactors, among them are: aeration tank configuration, sludge recirculation ratio, biomass concentration, rate of aeration and oxygen transfer rate, operating temperature, and pH. Aerobic treatment, however, has been considered as an alternative to anaerobic treatment due to the high BOD and COD removal efficiencies achieved. Barton et al. (1998), in their study of foul condensate treatment options, compared the performance of an activated sludge system to that of an anaerobic up-flow sludge blanket. They found that the activated sludge system offered 99 and 92 % methanol and COD removal efficiencies respectively, as compared with the 81 and 68 % removals achieved for methanol and COD respectively with anaerobic treatment. In the same study, the organic loading rates for the aerobic and anaerobic systems were 0.88 g BOD/g MLVSS (mixed liquor volatile suspended solids) and 10 to 20 kg COD/ m -day 3  respectively. The same study showed that the methanol and COD concentrations in the AST effluents, which were 97 and 420 mg/L, respectively, were less than those in the anaerobic treatment effluents (645 and 1859 mg/L for methanol and COD respectively).  Aerobic treatment systems, by and large, are typically more resistant to toxic substances or shock loads than anaerobic systems (Alvarez and Shaul 1999). Lu et al. (2000) investigated the performance of an MBR treating industrial wastewater from high strength fermentation plants by applying an organic shock load during a long run. The lab scale experiment lasted 252 days, during which the organic load was increased from 0.28 to 0.95 kg TOC/m *day by increasing the influent TOC concentrations from 800 to 2500 3  mg/L. The increase in the measured biomass concentrations from 3000 to 14,000 mg/L absorbed the increase in the organic load and maintained TOC removal efficiencies of about 94 %. The performance of aerated fixed film (APF) biological systems subjected to organic shock loads applied was investigated in a long term experiment (Hamoda and AlSharekh, 1999). In this study, the applied organic load was increased from 5 to 120 g BOD/m «day with a slight decrease in the organic removal efficiency from 97 to 88.5 %  12  for BOD andfrom73.6 to 67.8 % for COD. The increase in the organic loading rate was accompanied by an increase in the biofilm specific oxygen uptake rate (OUR).  Aerobic activities could be inhibited due to the presence of toxic substances. Sarlin et al. (1999) observed that the OUR in the aeration tanks of a conventional activated sludge system t reating p ulp a nd p aper e ffluents w as r educed w hen t here w ere c hemical spills into the system. Turpentine, which was recovered and stored in the mill in a large quantity, was among the chemicals included in the spills. It was found that chemical spills with total turpentine concentrations of 12,000 mg/L could reduce the OUR by 50%. Another study focused on the impact of chemical spills on aerobic treatment of newsprint mill effluents using an AST plant (Orr et al, 1997). In this study, the toxicity effect of the chemicals used by a newsprint mill on the activity of microorganisms was evaluated by measuring the OUR in the system and the total adenosine triphosphate (ATP) released by microbial cell wall lysis. The OUR and ATP results indicated that 4 out of 23 of the chemicals spilled to the treatment plant produced an adverse effect on the treatment system biomass. These four chemicals were hydrogen peroxide, metal pacifier, sodium hypochlorite, and a reducing compound. Although spills of these chemicals at the concentrations studied did not kill the biomass completely, they were likely to cause a reduction in the treatment efficiency.  Aerobic biodegradation of terpene compounds has been the main interest of many studies. Wilson and Hrutfiord (1975) investigated the fate and removals of monoterpenes in aerated lagoon treatment unbleached and bleached kraft mill effluents. This study showed that aerated lagoon can remove 90 % and 65 % of total terpenes from both unbleached and bleached mill wastewaters, respectively. For the unbleached mill, the average concentrations of total terpenes in the influents and effluents were 7.2 and 0.76 mg/L respectively, while for the bleached mill, they were 1.85 and 0.65 mg/L for the influents and effluents respectively. Schwartz et al. (1990) studied the fate of two terpenes, anethole and dipentene, in a bench scale activated sludge system treating synthetic sewage. In this study, complete removal of the terpenes was achieved (both terpenes were removed to below the detection limit). Overall removal efficiencies were  13  93 and 99 % for dipentene and anethole respectively and 90 % for total organic carbon (TOC). The fate of two species of terpenes, which were d-limonene and terpinolene, was studied in detail with an activated sludge system treating domestic wastewater spiked with these terpenes (Alvarez and Shaul, 1999). In this study, effluent concentrations averaged 10 ug/L for influent concentrations of 10 mg/L for both terpenes investigated. In this process, more than 90 % of the terpenes entering the aeration basin were biodegraded to other compounds. Misra et al. (1996) studied the potential of aerobic biotransformation of selected monoterpene species (hydrocarbons and alcohols) using batch experiments inoculated with enriched cultures of forest soils. T he m onoterpenes investigated were d-limonene, alpha-pinene, gama-terpinene, and terpinolene as hydrocarbons and arbanol, linalool, plinol, and alpha-terpineol as alcohols. All of the hydrocarbon monoterpenes and two of the alcohol monoterpenes (plinol and alphaterpineol), were readily degraded at 23 °C. Biodegradation rates ranged between 0.029 to 0.053 mg/L*hour for the hydrocarbons and varied from as low as 0.038 mg/L* hour for the arbanol to as high as 0.1 mg/L-hour for alpha-terpineol. The high degree of mineralization of alpha-terpineol was due to the initial significant conversion of the original terpenes to intermediates and side products that either degraded slowly or were recalcitrant to biodegradation. Biotransformation of the alpha-terpineol was accompanied by the formation of trace levels of other species of monoterpenes due to rearrangements of carbon skeletons.  Cook et al. (1973), using an activated sludge system with inactivated biomass, observed that the removal efficiencies of methanol and COD were only 5.7 and 8.3 % respectively. Using the same system with inoculated biomass, the observed COD and methanol removal efficiencies were 98 and 80 % respectively. This confirms that stripping due to the aeration system could not account for the methanol and COD removals observed. On the other hand, for the two terpenes (dipentene and anethole) spiked into a synthetic wastewater, Schwartz et al. (1990), while using a standard bench scale activated sludge system, observed that 90 % of the total mass was air stripped due to the aeration system. The high removal rate achieved in the stripping process was due to the highly volatile nature of both of the terpenes investigated and because of their low solubility in the 14  wastewater. Using the same aeration treatment system, both biodegradation and sorption processes accounted for only 8.7 and 1 % removal for dipentene and anethole respectively. In the same study, the TOC removal efficiencies due to air stripping were 89 and 91 % for dipentene and anethole respectively. Another study found that stripping of d-limonene and terpinolene accounted for only 10 % of the total mass removed in the aeration unit of an activated sludge system treating municipal wastewater spiked with these terpenes (Alvarez and Shaul, 1999). 2.3.2.3 Aerobic Membrane Bioreactor Treatment A membrane bioreactor (MBR) is similar to an activated sludge process with the exception that a membrane filter replaces the final clarifier. Therefore, an MBR is a biological treatment process to remove organic matter combined with a membrane separation technique to remove suspended solids. Complete solids-liquid separation can be accomplished regardless of the ability of the solids to settle and this prevents failure of the system due to the loss of biomassfromthe process. The membrane separation process is a compact and easy operation, therefore, the development of membrane technology, including micro filtration and ultrafiltration treatments, has expanded into the treatment of wastewaters from the pulp and paper industries. Many recent papers have been published on the use of MBRs for treating various streams in pulp and paper mills, including foul condensates. Berube (2000) investigated the kinetics of removing the main contaminants from synthetic and real foul condensates using a high temperature MBR. This study showed that over 99 and 93 % of the methanol and organic contaminants measured as TOC, respectively, could be removed. The concentrations of methanol and TOC in the influent evaporator condensate, which were 964 and 504 mg/L respectively, were reduced to below detection limits (approximately 0.5 mg/L) for methanol and to less than 52 mg/L for the TOC. The solids retention time (SRT) was 20 days and the hydraulic retention time (HRT) was 12 hours, the specific methanol and TOC utilization coefficients were 0.72 and 0.66 /day. Tardif (1996) investigated using tubular ultrafiltration membranes to treat mechanical newsprint Whitewater at a high temperature (55 °C). In that study, the removal efficiency for total COD was 77.9 %. Ragona and Hall (1998), while investigating the treatment of 15  mechanical newsprint Whitewater at 55 °C using two systems, which were an MBR and a stand-alone ultrafiltration membrane, reported that total COD removal efficiency was in the range of 48 to 54 % and 23 to 36 % for the MBR and ultrafiltration membrane, respectively. In the latter study, COD removal efficiency was lower than that observed in the former study because both systems were operated with a low HRT (8 hours). Bohman et al. (1991) observed that COD and BOD removals were in the range of 69 to 74 % using membranefiltrationcombined with biological treatment for the purification of bleach plant effluents.  On the other hand, wide adoption of membrane processes by pulp and paper mills has been limited, to a large extent, because of membrane fouling. Fouling is a phenomenon that causes the filtration capacity (membrane flux) to decrease with prolonged use (Dorica, 1986). Membrane flux is defined as the volume of liquid passing through an area of the filter per unit time and is controlled by a variety of parameters. In the case of filtering biosolids, flux is controlled by trans-membrane pressure (TMP), liquid viscosity, and the resistances across the membrane surface (Magara and Itoh, 1991).  Membrane flux decline during permeation is the cumulative effect of several mechanisms. These include the following resistances: associated with the membrane material (R ), pore plugging (R ), and concentration polarization ( R c ) . Each one could m  P  pp  be c orrelated w ith flux d ecline. F lux d ecline c aused b y R is usually governed by the m  membrane material and solute interactions. R p is determined by the relative sizes of the P  solutes and pores as well as the operating conditions. R c is the formation of a P  concentration gradient of solutes established at the membrane surface due to the preferential transport of solvent through the membrane. The higher solute concentration at the surface results in a higher osmotic pressure (especially for nanofiltration and reverse osmotic membranes), thereby reducing the effective driving force. In addition, as a material accumulates at a membrane surface, the concentration polarization may become a dominant resistance (Wijmans et al, 1984). The concentration gradients can be established within minutes (Towers et al, 1994). The rejected matter near the membrane surface can be transported back to the bulk liquid by diffusion as a result of Brownian  16  motion, shear-induced lift, or electrostatic repulsion. For Brownian motion, the diffusivity increases with decreasing particle size (below 0.01 [Jm), while for shearinduced lift, the diffusivity increases with increasing particle size (above 10 pm) (Wiesner and Chellam, particles of  Therefore, membranes are most susceptible to fouling by  pm in size since the influence of both diffusive forces is small  0.01-10  (Ramamurthy et al,  1992).  1995).  Membrane resistances (R  and Rc ) are affected by operating conditions, namely the P  pp  trans-membrane pressure (TMP), the applied cross flow velocity (CFV) and the system temperature (Dal-Cin et al,  1996).  Membrane resistances can be incorporated in the flux model equation as shown below (Wijmans et al, 1985).  j  =  AP p(R +R +R ) m  where: AP  p p  2  c p  is the trans-membrane pressure (N/m ) , u is the 2  (Nsec/m ), R , R , a n d R 2  m  1  pp  cp  dynamic viscosity  are membrane resistances (/m), and J is the membrane v  flux (m /m - sec). 3  2  Serial resistances due to multiple fouling mechanisms are correlated with flux loss under specified operating parameters (TMP, C F V and temperature). Thus, membrane fluxes can be determined as follows:  (Ji) is the pure water flux for the cleaned membrane, which is a function of the membrane material.  (Jf) is the pure water flux for the membrane, which has been fouled by permeation of the real evaporator condensate.  17  (J ) is the flux with the real evaporator condensate. v  From Equation 2.1, the equations used to estimate each individual resistance are as follows:  R from Equation 2.1 (pure water permeability for R only) m  m  Ji R p=( —i)R P  T  2.3  m  f  J  Rep =(j—  l ) R - Rpp  ;  m  ;  2.4  Then each resistance is often expressed as a function of the total resistance (R ) as t  follows:  %R  m  =^ K  xlOO, %R =^LxlOO, %R =--3Lxl00 R R pp  t  cp  t  2.5  t  A literature search preceding the present study did not reveal any published information regarding the fouling mechanisms of membranes treating evaporator condensate. However, fouling mechanisms of membranes treating various types of industrial and domestic wastewaters under different operational conditions has been investigated by a number of authors.  Magara and Itoh (1991) found that the development of the cake layer which affected the fouling of the membrane was predominantly a function of the bulk liquid suspended solids concentration, and that the thickness of this layer was determined by fluid shear stress and operating pressure. They observed a decrease in the flux with high concentrations of suspended solids.  Dufresne et al. (1996) examined the fouling of a membrane treating various pulping  18  streams. They found that the major decrease in the flux across the membrane was attributed to those substances with a molecular weight of more than 500 kDalton (kDa). This result contradicts the published result of Shimizu et al. (1993) who worked on filtering microbial cells from pulp mill effluents. In the latter research, the formation of the cake layer was controlled mainly by the shear induced back transport of particles (controlled by the lift velocity), which was governed by the smallest size of particles existing in the water being filterd.  Dal-Cin et al. (1996) studied the mechanisms of fouling of an ultrafiltration membrane treating pulp mill effluents using different membrane materials and pore sizes. For an operating TMP of 345 kPa (50 psi), they observed that the dominant membrane fouling mechanism was related to the membrane pore size or its molecular weight cut-off (MWCO), rather than to membrane material. The higher the MWCO (more than 500 kDa), the lower J f / Jj and J  v  / Ji ratios observed. That means pore plugging and  concentration polarization resistances increased with membrane pore size.  Ramamurthy et al. (1995) studied the performance of ultrafiltration membranes treating screw press filtrates (SPF) from a chemi-thermomechanical pulp (CTMP) mill with different operating parameter values (TMP, and CFV). They found that foulant layers were induced mainly by concentration polarization and gel layer formation. Both of these layers increased with the operating pressure and decreased with linear velocity. The resistance of these layers amounted to about 48 % of the total filtration resistance at an operating pressure of 345 kPa, while membrane resistance ( R m ) was dominant for operating pressures of less than 200 kPa.  Ahn et al. (1998) investigated using a nanofiltration membrane for the recycling of paper mill effluents. They observed that concentration polarization was the dominant resistance in the membrane fouling due to the accumulation of pollutants in the feed solution. They concluded that maintaining appropriate pollutant concentrations in the feed solution is an important design parameter for nanofiltration membranes.  19  Ben Aim (1999) and Nagaoka et al. (1996) showed that membrane fouling was a function of biomass concentration. They concluded that the reduction in the permeate flux at higher MLVSS concentrations could be attributed mainly to an increase in the MLVSS concentrations. Their results suggest that the high biomass concentration, which increased the bulk liquid viscosity, could reduce the shear over the membrane surface.  Fan et al. (2000) examined fouling mechanisms in an external ceramic ultrafiltration membrane coupled to an aerobic bioreactor. They found that the fouling was directly related to the permeate flux and the operational SRT, rather than to the biomass concentration.  During their test, the biomass concentration in the aerobic reactor  decreased significantly from 7500 to 3000 mg/L as the operational SRT was changed from 20 to 5 days. Within that range of SRTs, the average cleaning interval of the membrane tended to increase as SRT increased. However, the cleaning intervals fluctuated for even the same SRT condition due to variations in the quality of the influent wastewater.  Lubbecke et al. (1995) studied the effect of an increase in biomass concentration on the reduction of permeate flux using laminar and turbulent flow conditions over a membrane surface. They observed that for turbulent flow conditions, there was no effect of the MLVSS concentration on the permeate flux. However, when laminar conditions were maintained over the membrane surface, they observed that the permeate flux declined at higher MLVSS concentrations (more than 7000 mg/L).  Tardieu et al. (1996) analysed the chemical composition of the foulant layer accumulated on the surface of a tubular ceramic membrane of an MBR used to treat urban wastewater. During the normal filtration conditions of that study, no filtration cake (gel layer) was formed on the membrane surface, instead a thin foulant layer was formed, which was responsible for permeate flux decline. The mineral composition of the influent wastewater played the major role in controlling the thickness of this layer. Iron and also, to a lower extent zinc and copper, appeared to be much more concentrated in the foulant  20  layer than in the suspension supernatant. An increase in the sludge concentration did not influence cleaning frequency of the membrane.  Manttari et al. (1997) examined the effects of nanofiltration operating conditions including temperature, TMP, CFV, and pH and the concentration of influent wastewater on the reduction of permeate flux. During their test, an increase in the operating temperature from 35 to 50 °C improved permeate flux by 25 %. However, the same membrane fouled more rapidly at the highest temperature (50 °C). Their result also indicated that the higher the flow velocity used, the higher the TMP required to maintain a constant permeate flux. The pH of the solution had a considerable effect on the ability of the membrane to retain various substances. Increasing the pH from 3 to 6.5 improved the retention ability of the membrane by 20 %. As the pH increased, the substances became more soluble (most substances in pulp mill effluents are negatively charged). Moreover, the repulsive forces on the membrane surface increased with increasing pH as the membrane became more negatively charged. The membrane permeate flux decreased consequently. An increase in the salt concentration of the influent decreased the flux and led to a decrease in the rejection of the COD and chloride in the system.  21  < i V  «  1  Chapter 3 Objectives of the Research  H •[  The hypothesis stated at the outset of this research was as follows: "The biological  r  treatment of real foul condensate using a high temperature MBR operated under short  11  SRT and low HRT is feasible ".  :|  As discussed in Section 1.1, this research work was a continuation of the effort initiated by Berube (2000) and f ollowed b y Je n (2002) at the University of British Columbia's  1  Pulp and Paper Centre. Under Berube's (2000) study, the ability of a high temperature  j  MBR to treat kraft mill evaporator condensate was proven. For the same study,  i  operational conditions were chosen to control the MLVSS concentration at 2500 mg/L  1  and to achieve over 95 % methanol removal efficiency. The operating conditions were as  1  follows: optimal operating temperature and pH were 60 °C and neutral respectively, SRT  1  and HRT were 20 days and 12 hours respectively, and other operational parameters were selected according to the membrane manufacturing company. In the Jen (2002) study, the SRT and HRT were chosen to achieve a MLVSS concentration in the range of 10,000 to 30,000 mg/L and sludge production rate as minimal as possible. Therefore SRT and HRT were chosen to be 38 days and 9 hours respectively.  Following the Berube (2000) and Jen (2002) studies, the main objective was to maximize the economic feasibility of the process by developing design and operational strategies that would minimize the surface area required of the membrane and reducing bioreactor volume. In fact, very little is known about the treatment kinetics and efficiency of an MBR treating real foul condensate with different operational conditions (HRT and SRT). To achieve the aim of the study, the MBRs were run with short SRTs, which could potentially o ffer 1 ess membrane fouling, and low HRTs, which means high volumetric organic load applied. Therefore, multiple operational combinations of SRT and HRT were chosen. Operational SRTs were 12 and 10 days with the associated HRTs of 12, 10, and 8 hours. Other operational parameters were chosen according to Berube (2000) study.  22  H iI  Considering the main aim of the study, which was to develop design and operational  ^  conditions that would minimize membrane surface area required and the problem of  i  'i  J-J  membrane fouling encountered in the previous studies that dealt with evaporator condensate (Berube, 2000; Jen, 2002), studying the membrane performance and fouling mechanisms was initiated within the main aim of the study.  H  '  £  As indicated in Section 1.1, terpene compounds released during the pulping processes  f}  might flow directly to a treatment plant. Moreover, terpene spills may occur accidentally  ^'  in pulp mills. The volume and the strength of such incidents may have deleterious effects  r?  on a biological treatment process. The ability of a treatment system to achieve satisfactory removal efficiency following a terpenes shock load is an important criterion for evaluating its suitability for a full-scale implementation. Therefore, investigating the effects of turpentine shock loads on the performance of a high temperature MBR was the other main interest of the present study.  The specific objectives were established and are as listed below.  1. Determine the feasibility of the biological removal of the main contaminants of concern present in the real evaporator condensate using a high temperature MBR operated with short a SRT and a low HRT.  2. Identify the removal kinetics and efficiencies of the main contaminants of concern present in the evaporator condensate during each experimental condition of SRT and HRT.  3. Study membrane performance and identify the mechanism responsible for the fouling of a membrane treating real foul condensate at high temperature.  4. Determine the impacts of turpentine shock loads on the performance of a high temperature MBR treating kraft pulp mill evaporator condensate.  23  Chapter 4 Experimental Apparatus and Methods of Analysis This chapter describes all materials and experimental methods used for this study. 4.1 Experimental Apparatus  4.1.1 Membrane Biological Reactor System Two bench scale high temperature membrane bioreactors (MBRs) were used during the study with different operational conditions. The MBRs were identical, except that their liquid levels were different. Each MBR was composed of an aerobic bioreactor, an ultrafdtration unit and a feed pre-heating tank. Figure 4.1 shows a schematic of the MBRs used. 4.1.1.1 Aerobic Bioreactor The aerobic reactor tank component was a stainless steel cylinder with a diameter of 13.5 cm and height of 42.6 cm. Ports were located in the lid of the reactor for feeding of wastewater and nutrients, recycling mixed liquor and permeate, and for wasting of sludge. Liquid volumes for the first and second runs were 1475 mL and 1100 mL for the first reactor (RI) and second reactor (R2) respectively (due to foaming problems that occurred in R2, the liquid volume for R2 was less that that for RI). To minimize the amount of wastewater feed required for Runs 3, 4, and 5, reactor volumes were reduced to 950 mL and 750 mL for RI and R2 respectively. Air was supplied through a fine stone diffuser at a rate of 0.5 L/minute. 4.1.1.2 Ultrafiltration Unit The cross-flow ceramic tubular ultrafiltration unit used for the system was a Membralox, Tl-70 distributed by the U.S. Filter Corporation of Warrendale, PA, USA. The nominal pore size of the ceramic membranes was 500 Angstroms. The filter unit was 250 mm in length with a channel inside diameter (ID) of 7 mm. The membrane surface area was 0.0055 m . Other specifications and operating limits of the membrane module as 2  provided by the manufacturer are given in Table 4.1. Figure 4.2 illustrates this unit and its accessories.  Heating coil Condensate feed pump  Feeding tank  Solenoid valve  Nutrient feed pump Time controller  Ultrafiltration Membrane  pH controller  |Solenoid valve  I  T  Float switcRTZT"  t  0  I  NaOH feed  pH Probe  Treated effluent Diffuser Recycling pump  Air  Reactor  Temperature controller  Heating plate  Recycle line Filtrate line Electrical line ._.  Feed, nutrient, and NaOH line  Figure 4.1 Schematic of bench scale high temperature MBR used in the study  25  5'!  ?  Figure 4.2 Membrane unit used for the MBR (Membralox IT-70)  i I  A glycerine-filled pressure gauge with an operating range of 0 to 400 kPa (0 to 60 psi)  *  was installed at the membrane outlet to enable measurement of TMP through the unit.  '  This gauge was fitted with chemical seal to prevent clogging by particulate matter. 4.1.1.3 Pump Used for the MBR The pump used for recirculating the MBR mixed liquor was a Moyno Model SP 33304  i progressive cavity pump, distributed by Robbins-Myers of Springfield, Ohio, USA.  26  Table 4.1 Specifications and operating limits of the Membralox Tl-70 ultrafiltration membrane used in this study Model  Membrane ceramicfilterTl-70  Material of construction  99.9 % alpha alumina  Housing material  316 1 stainless steel  Nominal pore size  500 Angstrom  Configuration  Single 7 mm internal diameter  Nominal membrane surface area  0.0055 m  Pressure limit  790 kPa(115psi)  Recommended operating pressure  140-200 kPa (20-30 psig)  Temperature limit  225 °C  pH operating range  0-14  Recommended velocity  2-4 m/sec  Suggested flux (tap water)  5-250 mL/min  2  4.1.1.4 Instrumentation Liquid temperature was maintained during the study using a hot plate under each reactor. This plate was controlled via a temperature sensor in the recycling line as shown in Figure 4.1. A mixing tank also contained a portable heater for heating the influent wastewater and the nutrient solution. The liquid level in the reactor was maintained during each run using a float switch connected to a two way solenoid valve for permeate flow wasting via a control box. As the permeate flow rate exceeded the average influent wastewater rate in each cycle, the two-way solenoid valve for wasting permeate flow was opened for only part of the feed cycle time, which was 2 hours. When the liquid level of the mixed liquor in the reactor reached the high level, the float switch triggered to the two-way valve via a time delay switch in order to start wasting permeate flow (time delay selected for each batch feed cycle was 30 minutes). Similarly, when the liquid level of the mixed liquor returned to the designed working level of the reactor, the float switch turned off the two-way valve to circulate the permeate flow back to the reactor.  4.1.1.5 Feeding Tank The feeding tank, which is shown in Figure 4.1, was constructed from stainless steel with a volume of 1 liter. For each batch feed cycle, influent wastewater to the reactor was pumped (Masterflex pump) to the feeding tank, m ixed w ith t he n utrient s olution, p reheated with a stainless steel heating coil for 30 minutes, after which the temperature of the feed was approximately equal to that of the operating temperature of the MBR, and a solenoid valve, located at the bottom of the feeding tank, opened automatically via time control switch allowing the feed to be added to the MBR. 4.2 Materials 4.2.1 Wastewater Feed The influent to the bioreactor consisted of a real evaporator condensate (foul condensate) that was shipped from the Western Pulp Limited Partnership bleached kraft pulp mill (Squamish, B.C, Canada).  Shipments of the evaporator condensates were sent to the research laboratory where the bench scale MBR was located (once per week). The evaporator condensate was collected from the "Contaminated Condensate Seal Tank" and consisted of condensate that was a mixturefromfive condensers (personal communication, Taylor, J., Western Pulp Limited Partnership, Squamish, B.C, Canada). At the Western Pulp Limited Partnership mill, the evaporator condensatefromthe batch digester flows directly to the mill treatment plant, which is a pure oxygen activated sludge system. There is no turpentine recovery system at the Western Pulp mill.  During the study, the kraft condensate shipments were immediately sampled and characterized. Then the condensates were acidified to a pH of approximately 4 with HCL, stored at temperature of 4 °C, and typically used within one week. Prior to use as a feed, the kraft condensate was transferred to a smaller 4 L sealed feed container, which was stored at 4 °C.  The evaporator condensate shipments were sampled and analyzed for methanol, monoterpenes, TOC, pH, and conductivity. Table 4.2 presents characteristics of evaporator condensate measured during the study (raw data are presented in Tables A1.41 to A1.48). During the study, evaporator condensate shipments with conductivity greater than 800 uS were discarded. A high conductivity indicated the presence of a significant amount of black liquor entrainment into the evaporator condensate (Jen, 2002).  Table 4.2 Characteristics of the evaporator condensate in the study Parameter  Average value measured*  Number of samples  Methanol (mg/L)  721 ± 19.75  33  Monoterpenes (mg/L)  21.4±3.57  30  TOC (mg/L)  316 ±14.9  31  pH  6.5-7.5  34  Conductivity (pS)  300-500  34  * 90 % confidence limit was used for the average intervals  4.2.2 Nutrient Solution Nitrogen, phosphorus and a number of other trace nutrients (iron, calcium, potassium, magnesium) were added to the influent feed for the optimal growth of microorganisms in the biological system.  The estimated nitrogen and phosphorus requirements were based on the influent methanol concentration of 721 mg/L as indicated in Table 4.2. It was assumed that 1.5 mg of BOD was equivalent to 1 mg of methanol (i.e. complete oxidation of methanol to CO2 and H2O). These requirements were increased by approximately 30 % to ensure nonlimiting conditions. For the trace nutrients, non-limiting concentrations were targeted as recommended in a previous study (Berube, 2000). Table 4.3 shows the concentrations of the different nutrients, per litre of evaporator condensate.  29  M ii  Table 4.3 Characteristics of nutrient solution Nutrients  Approximate nutrient concentration per litre of  i »  evaporator condensate (mg/L) NH4NO3  200  ii  KH P0  150*(300)  Tl  MgS0 .7H 0 2  25  1k  CaCl .7H 0  70  n ii  FeCl .6H 0  20  2  4  4  2  3  2  2  * Due to precipitation of K H P 0 , the dosage was doubled. 2  4  H 1 5  During the preparation of the nutrient solution, phosphate solids were formed. These  !y  solids were removed from the nutrient solution by allowing the solids to settle overnight  l i  and then decanting the supernatant. To account for the amount of phosphorus removed  * •. ti  with the precipitate, the amount of K H P 0 4 added to the nutrient solution was doubled.  7  4.2.3 Biomass  2  t  Biomass inoculum sources were selected in an attempt to provide a mixed microbial t  i  inoculum that was able to degrade and metabolize typical constituents in the foul  1  condensate. Biomass (aerobic sludge) sources were: waste activated sludge (WAS) from  I  a full scale pure oxygen activated sludge system treating kraft pulp mill effluent (Western  •f  Pulp Limited Partnership bleached kraft pulp mill, Squamish, Canada), and settled sludge  i r  from  a pilot scale activated sludge system treating municipal wastewater (UBC Civil Engineering Pilot Plant, Vancouver, Canada).  i 4.3 Experimental Methods i  In this section, the start-up of the MBRs and biomass acclimatization, experimental J  investigation, operation and monitoring of the MBRs, membrane cleaning, the sampling protocol and the analytical methods are described.  4.3.1 Start-up the MBR and Biomass Acclimatization During the start-up, the MBRs were inoculated with two sources of sludges as mentioned in Section 4.2.3. Approximately 500 mL of inoculum from each source were added directly to the MBRs at the same time and the reactor tanks were topped-off with tap water. This was repeated approximately one week following the initial inoculation. After inoculating, both reactors were operated at 25 % of their designed load (25 % of designed flow rates with a full waste strength) for two days, then the organic loadings were increased to 50 % of their design values for another 2 days. Finally, both reactors were operated at their full designed load. Operating conditions during this period were maintained as presented later in Table 4.5.  Initial steady state conditions were assumed to have been reached when the concentration of mixed liquor volatile suspended solids (MLVSS) and the rate of methanol removal in the MBRs were constant. For the first run of the study, steady state conditions for both reactors were reached after approximately 4 weeks following the initial inoculation. For other runs, steady state conditions were assumed after a period equal to one solids retention time (SRT). 4.3.2 Experimental Investigation This research work was divided into four phases. Phase 1 investigated the overall removal kinetics and removal efficiencies (biological + stripping) of the main contaminants of concern present in the evaporator condensate. Phase 2 investigated the mechanisms for membrane fouling. Phases 3 and 4 investigated the overall removal kinetics under turpentine shock loads and the abiotic removal kinetics respectively.  During the study, the two bench scale MBRs were operated and the samples taken from each MBR were analysed s eparately. E ach e xperimental p hase i nvolved m ultiple r uns. During Phases 1, 2, and 3 in order to collect data as much as possible over a short period, SRT and HRT combinations were chosen to be different between the MBRs as indicated in Table 4.4. Phase 1 involved five runs in which four of them (last ones) were used in 31  Phase 2, as presented in Table 4.4. In Phases 1 and 2, operational disruptions occurred for RI during the second run. During Phase 2, Run 5, as indicated in Table 4.5, the influence of TMP on membrane fouling mechanisms was investigated by varying this operational parameter between the MBRs investigated. In Phase 3, a series of short-term turpentine shock load tests were applied to the MBRs. This testing, as noted in Table 4.4, involved three experiments (Runs). Each experiment, which continued for 10 hours, contained five consecutive spiked batch feed cycles. Total monoterpene concentrations spiked into the influent feed (evaporator condensate), for each batch feed cycle, were 300, 750 and 1500 mg/L for the first, second, and third experiment respectively. Monoterpene species that were spiked into the influent feed were: alpha-pinene, a hydrocarbon; myrtenol, an alcohol; and camphor, a ketone. During Phase 3 both reactor liquid levels changed as a result of foaming that occurred during the three Runs. Therefore, MLVSS measurements were not taken during that phase. Stripping of methanol, monoterpenes, and T O C were investigated in Phase 4, which involved three runs. An abiotic test was conducted during Phase 4, Run 1, in which reactor biomass was inactivated by adding sodium azide to a concentration of 10,000 mg/L in the MBR. Sodium azide at this concentration in the MBR has been shown to be enough to inactivate the biomass used in the previous study (Berube, 2000). Phase 4, Runs 2 and 3 included two tap water tests for each reactor.  4.3.3 Operation and Monitoring the MBR The MBRs were fed semi-continuously by adding a mixture of real evaporator condensate and nutrients, once every 2 hours. To prevent excessive temperature fluctuations in the MBR, the liquid temperature of both reactors was controlled as indicated in Sections 4.1.1.4 and 4.1.1.5.  The pH of the mixed liquor in the MBR was controlled using a pH meter /controller that added sodium hydroxide as required to maintain the pH at neutral point.  The SRT in the process was controlled manually during each run by daily wastage of a preset volume of mixed liquor from the recycling line at the start of a selected batch  Table 4.4 Summary of the experimental work during the study Phase  Run  number  1  2  1  2  3  4  Acclimatization  Sampling  Dates  Dates  25-Nov-Ol  27-Dec-01  To  To  27-Dec-01  8-Jan-02  9-Jan-02  20-Jan-02  To  To  20-Jan-02  l-Feb-02  2-Feb-02  ll-Feb-02  To  To  ll-Feb-02  2l-Feb-02  22-Feb-02  6-Mar-02  To  To  06-Mar-02  18-Mar-  Reactor 1 (RI)  Reactor 2 (R2)  SRT  HRT  SRT  HRT  (days)  (hours)  (days)  (hours)  15  12  15  12  '15  '10  15  10  10  12  10  10  15  8  10  8  15  10  15  12  Other  02 19-Mar-02  6-Apr-02  To  To  presented  06-Apr-02  20-Apr-02  in Table 4.5  1  -  25-Apr-02  15  10  15  12  2  -  30-Apr-02  15  10  15  12  'S=750 mg/L  3  -  2-May-02  15  10  15  12  'S=1500mg/L  5-May-02  15  10  10  12  inactivated  5  2  3  4  1 2 &  J  S= 300 mg/L  biomass test  5-May-02  3 IT,,  TMP was as  clean water test  ,  RI failed during Phasel, Run 2 as indicated in Section 4.3.2  Foaming problems occurred during Phase 3  2  3  S is monoterpenes spiking concentrations  33  cycle. HRT was controlled by maintaining a constant mixed liquor volume in the reactor tank as explained in Section 4.1.1.4. The operational HRTs and SRTs during the study are shown in Table 4.4. Operating conditions applied to both reactors during the study are summarized in Table 4.5. These conditions were set based on the recommendations from the membrane manufacturing company and the results obtained by Berube, (2000). Table 4.5 Summary of operating parameters Design parameters  Value  Operating temperature °C  60  pH  6.5-7  Cross flow velocity (CFV) m/sec  3  Trans-membrane pressure (TMP) kPa (psi)  200/*66 (30/* 10)  * TMP for R2 during Phase 2, Run 5 was 66.6 kPa (10 psi), see Section 4.3.2  Applying high a cross flow velocity of 3 m/sec over the membrane surface was expected to increase the rate of back diffusion of the solid particles, which in turn, would increase the permeate flux during each run. This velocity corresponded to a recycling flow of 38 mL/sec through the recycling line from the reactor. The trans-membrane pressure was maintained for all runs using a flow restriction valve on the downstream end of the recycling line, except as noted in Table 4.5.  4.3.4 Membrane Cleaning During each run, the permeate flux through the membrane component of the MBR decreased with time. Therefore, membrane cleaning as recommended by the membrane supplier was required to recover a portion of the initial permeate flux. Prior to removal of the membranefromthe system for cleaning, the pressure on the membrane was relieved and biomass or concentrate was removed by opening the plug valve on the outlet of the filtration unit. The recycling pump was shut off, the filter apparatus was drained out and the valves were closed. The membrane module, gauges, and valves were then 34  disconnected from the system. The membrane module, valves and gauges were then connected to the cleaning system as shown in Figure 4.3.  The cleaning procedure used during the study was as r ecommended b y t he m embrane supplier company (U.S. Filter, 1996) and as revised by Berube, (2000). This procedure was as follows:  1. Close permeate port to set cross-membrane pressure to 0 atmospheres. 2. Pump clean tap water through membrane for approximately 10 minutes. 3. Pump a NaOCL solution (200 to 300 mg/L) through membrane for approximately 10 minutes 4. Pump clean tap water through membrane for 1 minutes. 5. Pump a 2 % NaOH caustic solution through the membrane for 30 minutes. 6. Open permeate port and pump the caustic solution through the membrane for another 30 mites 7. Pump clean tap water through membrane until pH of the permeate is neutral (approximately 15 minutes) 8. Close permeate port 9. Pump a 2 % HN03 acid solution through the membrane for 30 minutes. 10. Open permeate port and pump the acid solution through the membrane for another 20 minutes. 11. Pump clean tap water through the membrane until pH of the permeate is neutral (approximately 15 minutes.)  4.3.5 Sampling Protocol and Preparation Samples for the estimation of removal kinetics for contaminants of concern during high temperature biological treatment were collected and analysed at regular intervals following the start of selected batch feed cycles. The regular intervals of collecting samples were as follows: 0, 10, 20, 30, 40, 60, 70 and 80 minutes, 0, 10, 20, 30, and 40 minutes, and 0, 10,20, 30,40, and 60 minutes for Phases 1, 3, and 4 respectively.  Samples collected for analyses were withdrawn from the ultrafiltration cartridge permeate line. The membrane casing was drained before sampling to minimize the dilution effect that can occur in the membrane casing. The samples collected from the ultrafiltration cartridge permeate line did not requirefiltrationbefore analysis. For each batch cycle selected, 15 mL samples were collected infiredglass vials with Teflon-lined caps.  Permeate  Concentrate  Cleaning solution Ultrafiltration unit  Recycling ^  ^+  pump Permeate flow Recycle flow  Figure 4.3 Schematic of the cleaning system  Samples for the estimation of removal efficiencies were collected and analysed for the influent wastewater and permeate flow for selected batch cycles. Influent wastewater was sampled from the feeding tanks after mixing with the nutrient solution and pre-heating for 30 minutes. Permeate, which was collected for the whole cycle, was sampledfromthe  ultrafiltration cartridge permeate line as shown in Figure 4.1. Removal efficiency samples were collected in 400 mL Naglene containers.  Samples for the mixed liquor suspended solids (MLSS) were taken directly from the reactor for selected batch cycles right after feeding the reactor with influent wastewater. Reactor contents were mixed thoroughly by hand and then 50 mL were taken in Naglene containers for analysis.  The acclimatization period for each run was monitored by measuring the gradual changes in the removal of the contaminants of main concern. Therefore, for every run during the acclimatization period prior to steady state, samples for removal kinetics, overall removal efficiency, and MLSSS were collected randomly twice a week.  4.3.6 Analytical Methods and Equipment The analytical methods used in this study are presented below. All influent samples were filtered through a 0.45-pm cellulose nitrate syringe membrane filter cartridge before analysis. Details regarding Quality Assurance /Quality Control (QA/QC) procedures are given in the sections below.  4.3.6.1 Solids Concentration Samples were analysed for total suspended solids (TSS), and volatile suspended solids (VSS) according to Standard Methods (APHA et al., 1995). Samples of mixed liquor were collected and analyzed in duplicate. 4.3.6.2 Conductivity Only influent samples were analyzed for conductivity. The conductivity was measured using a Radiometer Copenhagen CDM3 conductivity meter. The samples were acclimatized to a standard temperature of 20 °C before measurement. 4.3.6.3 Total Organic Carbon (TOC) Concentration Total organic carbon (TOC) samples were measured by a combustion-infrared method according to Standard Methods (APFIA et ai, 1995) using a TOC analyzer (Shimadzu  TO-500, Columbia, USA). The TOC analyzer was calibrated with each set of samples as described in the instruction manual provided by the manufacturing company. For each set of samples, duplicates and one distilled water as a blank were run.  4.3.6.4 Methanol Concentration Permeate and influent samples were measured by direct injection into a gas chromatograph (GC) (HP5890, Hewlett Packard Co. Avondale, PA, USA) with a 30 m long wide bore capillary column (DBWAX 0.53 MMID, J & W Scientific, Folsom, CA, USA) and a flame ionization detector (FED detector). Butanol with concentration of 550 mg/L was used as the internal standard for all methanol analysis. Each GC vial was filled with 1 mL of aqueous sample and 100 uL of internal standard The FID carrier gas was composed of helium at a linear velocity of 20 cm/sec at 135 °C. The temperature programme used is detailed in Table 4.6. The method detection limit was approximately 0.1 mg/L. All samples were analysed in duplicate, and occasionally in triplicate. A blank was also analysed for every set of samples. Table 4.6 Temperature programme for GC analysis of methanol samples Time (min)  Temperature °C  Rate of change (°C/min)  1.00 to 3.00  40  Stable  3.00 to 7.00  40 to 100  15°C/min  7.00 to 9.50  100 to 200  40 °C/min  4.3.6.5 Turpentine Concentration An analytical method using external standards was developed to measure the concentration of monoterpenes in aqueous samples after consultation with the National Council for Air and Stream Improvement (NCASI), (Personal communication, Larry LaFleur, NCASI, Corvallis, OR, USA). The pH of the samples, after collection, was adjusted to 10-11 using a stock solution of 1 N sodium hydroxide. Liquid-liquid extraction was used to recover monoterpenesfromthe aqueous solution. Methylene chloride with purity 98 % was used as an external extraction  solvent. A 10 mL volume of each sample was extracted twice for 10 minutes with equal volumes of solvent. After the extraction, the solvent emulsion was broken by centrifuging the extract solutions at 2800 rpm for 10 minutes. The extracts were then transferred to 100 pL glass inserts in standard GC vials (3 mL Teflon-lined glass vials) prior to analysis. For the permeate samples, before being transferred to the GC vials, the solvent extracts were concentrated by allowing the methylene chloride to evaporate under nitrogen gas and the concentrate was diluted to 1 mL with methylene chloride.  Extracted samples were analyzed using a Hewlett-Packard 6890 gas chromatograph with a 30 m HP-5 phenyl methyl siloxane column of internal diameter of 0.32 mm and fdm thickness of 0.25 pm (J & W Scientific, Folson, CA) and detected using a flame ionization detector (FID). The carrier gas was helium at a linear velocity of 36 m/sec at 280 °C. The temperature programme used is detailed in Table 4.7.  Table 4.7 Temperature programme for GC analysis of monoterpenes Time (min)  Temperature °C  Rate of change (°C/min)  1.00 to 3.00  40  Stable  3.00 to 24.00  40 to 250  10°C/min  24.00 to 26.00  250  Stable  Identification  of monoterpenes  was performed using gas chromatography/mass  spectrometric (GC/MS) analysis. The mass spectrometer used was a Hewlett Packard 5973 coupled to the GC described above. Mass spectrometer operating conditions were as below.  Transfer temperature: 280 °C Ion source temperature: 230 °C Ion source pressure: 1 - 3 x 10 mm Hg 6  Mass range 45 to 450 Sensitivity: 1-10 39  Mass library: Wiley  Three standards representing three classes of monoterpenes were used as reference standards. Monoterpene classes were hydrocarbon, ketone, and alcohol. Among these three classes, the most abundant species found in kraft mill wastewaters were used. These species were: alpha-pinene, a hydrocarbon; myrtenol, an alcohol; and camphor, a ketone. Gas chromatogram peak areas of the monoterpenes presented in the samples were summed up to estimate total monoterpene concentrations. These concentrations were reported in mg/L as alpha-pinene, myrtenol, and camphor.  Extraction efficiencies for the monoterpenes analysed, and for the solvent to water ratio used, were determined by spiking known amounts of pure terpene standards into the influent wastewater (foul condensate) and measuring their recovery efficiencies. Terpenes spiked were: alpha-pinene, myrtenol, and camphor and their recovery efficiencies were 98, 92, and 94 % respectively. Results of monoterpene concentrations during the study were adjusted using the recovery efficiencies according to the proportions of terpene species of the total terpene concentrations.  Samples of influent wastewater and permeate were preserved for up to 24 hours at 4 °C in amber glass vials with Teflon-lined caps. Influent and permeate samples were analysed in duplicate.  4.3.6.6 pH The pH of the influent, and mixed liquor was measured using a Beckman Model PHI 44 pH meter with automatic temperature compensation. The pH meter was calibrated using standard buffers of pH 4.0, and 7. 4.3.6.7 Permeate Flow Rate The rate of permeate flow from both MBRs was monitored daily by collecting permeate in a graduated cylinder and determining the volume filtered as a function of time.  4.3.6,8 Statistical Analyses Removal kinetics and efficiencies were analysed for standard deviation and confidence intervals. The 90 % confidence intervals were constructed from the means to indicate the variability of the data presented (Johnson, 1994).  Chapter 5 Results and Discussion As indicated in Section 4.3.2, the performance of the MBRs was investigated in 4 experimental phases. The following sections discuss the results obtained for these phases. The raw data, upon which the discussion of results is based, are presented in Appendices A l to A3.  5.1 Phases 1 and 4 This section discusses the results for the overall and stripping removal kinetics and the removal efficiencies of methanol, monoterpenes, and the trace organic compounds represented by the total organic carbon (TOC). The rate of biomass growth, which was investigated in Phase 1, is also discussed in detail in this section. 5.1.1 Methanol Removal One of the common approaches to modeling the uptake rate of methanol as a single substrate by a mixed culture of microorganisms is the application of the Monod equation (Metcalf and Eddy, 1991). This equation is presented as follows: dC d  M e O H  =  K  u  m  CJ^OH  (  t  C  + M  where —  [ dt  e  s  O  H  K  S  )  X  5  1  M e O H  the rate of biological removal of methanol (mg/L' minute), C  is the concentration of methanol in the MBR (mg/L), K s  M e O H  M e O H  is the half saturation  concentration for methanol uptake (mg/L), K i s the specific methanol utilization u m  coefficient  (/day),  Xis the concentration of MLVSS in the MBR (mg/L).  In addition to biological removal, methanol can be stripped to the atmosphere by the aeration system during biological treatment. The rate of methanol stripping can be estimated using afirstorder relationship as presented in Equation 5.2 (Berube, 2000):  dC MeOH dt where K  ~ K strip Me  s t r i p M e  .5.2  C MeOH  is the rate of methanol removal due to stripping (/minute)  A combination of Equations 5.1 and 5.2 yields Equation 5.3, which represents the overall methanol removal rate. dC MeOH dt  - K  u m  ?  C MeOH  ( C  MeOH  +  K  S  •)X  +  .5.3  ^ s t r i p M e • ^"MeOH  MeOH  According to Equation 5.3, the rate of methanol removal is a function of the concentration of methanol remaining in an aerobic treatment system. However, for Phase 1, Runs 1, 2, 3 and 5, methanol removal rates during individual batch feed cycles followed zero order kinetics as illustrated in Figure 5.1. For Phase 1, Run 4, the rate of methanol removal appeared to be first order due to the high organic load applied to the MBRs.  •  overall test  A abiotic test  80 cn  E  70  -•  c o  —. TO —'  C CD O c o O  o c  CD J=  "5 80  Figure 5.1 Concentration of methanol in MBR during a typical batch feed cycle (Solid line: Equation 5.4 fitted to concentration of methanol in MBR during biotic test; dashed line: Equation 5.2 fitted to concentration of methanol in MBR during inactivated biomass test) 43  For Phase 1 and all runs apartfromRun 4, the zero order removal rate observed over the range of methanol concentrations investigated, indicated that the change in the concentration of methanol in the MBRs over time was not influenced by the concentration of methanol remaining in the MBRs. In addition, the zero order removal rate confirmed that the concentration o f methanol i n the MBRs was not inhibiting the uptake of methanol by the mixed microbial culture. This agrees with results reported from previous studies, which also dealt with the treatment of evaporator condensate using mixed cultures of methanol-utilizing microorganisms, which were cultivated at high temperature. Berube (2000) reported that, for methanol concentrations of less than 100 mg/L, the rate of uptake of methanol was neither limited nor inhibited by the concentration of methanol remaining in the MBR. Jen (2002) reported that for a higher range of methanol concentrations in the MBRs examined (up to approximately 260 mg/L), the rate of biological removal of methanol followed zero order kinetics.  Furthermore, the zero order overall removal rates observed for Phase 1, Runs 1, 2, 3, and 5, indicated that the stripping of methanol due to the aeration system, did not account for a significantfractionof the methanol removed from the MBRs. This is consistent with the relatively low first order coefficient for the stripping of methanol estimated using inactivated biomass test as illustrated in Figure 5.1. Thefirstorder coefficient for the stripping of the methanol was estimated by fitting Equation 5.2 to the concentrations of the methanol over time in the MBRs measured during the abiotic tests (inactivated biomass and clean water). Results from the non-linear regression analysis are presented in Tables A3.1 to A3.3. The average value of the first order coefficient for the stripping of methanol based on the abiotic tests was estimated to be 0.000817 ± 0.00027 /minute. At this rate, the estimated contributions of methanol stripping due to the aeration system to the overall observed methanol removals, for the combinations of operational SRTs and FIRTs studied, are shown in Figure 5.2. At the rate of methanol stripping observed by Berube (2000) using a real condensate, which was 0.00024 ± 0.000046 /minute, stripping of methanol due to aeration accounted for less than 1 % of the total mass of methanol removed from the MBR. The difference in the contribution of methanol stripping between the present and Berube (2000) study could be due to the differences in the 44  Run 1  Run 2&5  SRT=15d  SRT=15d  Run 4  Run 3  Run 3  Run 4  nol  100  XI  -w CO 60  ima  90 ca .c c: 80 o5 CL Q . 70 o •o  50 40 -  H—»  LU  o x>  30 -  0 TO CO  20 -  <  val  c  10 -  0)  o o E  0) 0_  a> or  0 SRT=15d  SRT=10d  SRT=10d  SRT=10d  HRT=12 hr HRT=10 hr HRT=8 hr HRT=12 hr HRT=10 hr HRT=8 hr  Figure 5.2 Estimated contributions of methanol striping to the overall observed methanol removals during Phase 1  reactor configurations (liquid depths) and aeration rates per unit volume. Although not investigated during the present study, different liquid depths and aeration rates can affect the mass-transfer rate of methanol from the liquid phase (methanol volatilization rate), which in turn can result in different stripping rates.  For Phase 1, Runs 1, 2, 3, and 5, when limiting and inhibiting conditions were not observed, and when the stripping due to the aeration system was assumed to be insignificant, Equation 5.3 can be rewritten as a zero order relationship as follows:  dCMeOH dt  -  where K  K  u m  m 0  X  ~  K  m 0 '  .5.4  is the zero order coefficient for the biological removal of methanol (mg/L-  minute)  Equation 5.4 was fitted to the methanol concentrations measured during Phase 1, Runs 1, 2, 3 and 5. The estimated values of the zero order coefficients for the overall removal of  45  methanol are presented in Tables A l . l to A1.12 and Tables A. 1.17 to A1.21. These results were estimated using linear regression analysis by fitting Equation 5.4 to the measured concentrations of methanol during selected batch feed cycles. The specific methanol biological utilization coefficients (K ), for the combinations of the operational um  SRTs and HRTs applied, are shown in Figure 5.4. These coefficients were estimated by dividing the zero order coefficients for biological removal of methanol by MLVSS concentrations measured during the corresponding batch feed cycles and shown in Figure 5.3. The zero order methanol removal coefficients (K ) observed during Phase 1, Runs m0  1, 2, 3 and 5, are presented in Table 5.1.  As illustrated in Figure 5.4, a decrease in the HRT from 1 2 to 10 hours resulted in a significant reduction in the specific methanol biological utilization coefficients. The specific methanol biological utilization coefficients decreasedfromapproximately 0.70 ± 0.172 /day to 0.49 ± 0.052 /day and 0.83 ±0.17 /day to 0.43 ± 0.047 /day when the HRT was decreased from 12 to 10 hours, for SRTs of 15 and 10 days, respectively. This result indicates that the increase in the organic load did exert an effect on the observed specific methanol biological utilization coefficient in the high temperature MBR. For both SRT conditions ( 15 and 1 0 days), the increase in the organic load applied as the HRT was decreased from 1 0 to 8 hours, inhibited the mixed microbial culture. At an HRT of 8 hours, as shown in Figure 5.2, stripping accounted for essentially all of the observed removal of methanol.  The steady state MLVSS and the associated methanol removal efficiencies for selected batch feed cycles for Phase 1, are presented in Tables A1.41 to A1.48. Figures 5.5 to 5.11 show influent and effluent methanol concentrations and methanol overall removal efficiencies during Phase 1. Overall removal efficiency was estimated by dividing total concentration of contaminant that was reduced during the whole b atch feed cycle (the difference between influent and effluent contaminant concentrations) by influent contaminant concentration in the condensate. The average methanol concentration in the effluent was determined for the total volume of effluent collected from a batch feed cycle.  3 5 0 0 -i  JEuinJL  BunJ2&5_  -RunA.  JRiinJL  JRunJL  JBuoA.  3000 • 2500 -  D) E 2000 CO CO 1 5 0 0 -  >  1000 500 -  r  0 -  SRT=15d SRT=15d SRT=15d SRT=10d SRT=10d SRT=10d HRT=12 hr HRT=10 hr HRT=8 hr HRT=12 hr HRT=10 hr HRT=8 hr  Figure 5.3 Average MLVSS concentrations during Phase 1 (error bars represent 90 % confidence interval for measurement)  CO N  -RunJ_  1.2  c o  Run  Run 3  -RunJL  5^  CO XI 0.8  0.6  +  0.4  o 0) Q. CO  0.2  SRT=15 d  SRT=15d  SRT=10 d  SRT=10d  H R T = 1 2 hr  HRT=10 hr  HRT=12 hr  H R T = 1 0 hr  For HRT=8 hrs, biotic removal was insignificant  Figure 5.4 Methanol specific biological utilization coefficients ( K  u m  ) during Phase 1  (error bars represent 90 % confidence interval for measurement)  •R1 influent  •R2 influent  •R1 effluent  • R2 effluent  1000 E 900 c 800 o 700 _ ' *-i— 600 <v o 500 c o 400 O 300 1 o ro 200 ^—• 100 0 27-Dec-01  30-Dec-01  2-Jan-02  5-Jan-02  8-Jan-02  Dates  Figure 5.5 Influents and effluents methanol concentrations for RI and R2 (Phase 1, Run 1: SRT=15 days, HRT=12 hours)  -±-R1  27-Dec-01  30-Dec-01  -«-R2  2-Jan-02  6-Jan-02  8-Jan-02  Dates  Figure 5.6 Methanol removal efficiencies for RI and R2 (Phase 1, Run 1: SRT= 15 days, HRT=12 hours)  •Influent 1000 j 13) 900 E c 800 o ro 700 c 600 a 0) o 500 c o 400 O o 300 c TO 200 -C 100 0> 2 0 ¥ 6-Apr-02  •Effluent  • Efficiency  _l  j (  10-Apr-02  15-Apr-02  20-Apr-02  Dates  Figure 5.7 Influent and effluent methanol concentrations and methanol overall removal efficiency for RI (Phase 1, Run 5: SRT=15 days, HRT=10 hours)  -A—Influent  CD  0 6-Mar-02  •Effluent  10-Mar-02  • Efficiency  15-Mar-02  0 18-Mar-02  Dates  Figure 5.8 Influent and effluent methanol concentrations and methanol overall removal efficiency for RI, (Phase 1, Run 4: SRT=15 days, HRT= 8 hours)  49  T*—Influent  • Effluent  —•— Efficiency  1000  100  E  >> o c  99.8 0) 99.6 iot 99.4 Ul 99.2 ro > o• 99 E ' 98.8 0 98.6 tr ~o tz ro + 98.4 sz 98.2 a)  c o  4-  CO  c  Q) O  c o O o c ro J:  11-Feb-02  14-Feb-02  18-Feb-02  21-Feb-02  Dates  Figure 5.9 Influent and effluent methanol concentrations and methanol overall removal efficiency for RI (Phase 1, Run 3: SRT= 10 days, HRT= 12 hours)  •Influent  •Effluent  •Efficiency  =d 1000 i  900  11-Feb-02  14-Feb-02  18-Feb-02  21-Feb-02  Dates  Figure 5.10 Influent and effluent methanol concentrations and methanol overall removal efficiency for R2 (Phase 1, Run 3: SRT= 10 days, HRT= 10 hours)  50  •Influent  •Effluent  1000  •Efficiency 100 ^  E c o o c o O o c CO  6-Mar-02  10-Mar-02  15-Mar-02  Dates  Figure 5.11 Influent and effluent methanol concentrations and methanol overall removal efficiency for R2 (Phase 1, Run 4: SRT= 10 days, HRT= 8 hours)  For Phase 1, Run 4, as shown in Figure 5.2, during which the HRT was 8 hours, the estimated contributions of methanol stripping due to the aeration system to the overall observed methanol removals were 92 and 95 % for SRTs 15 and 10 days, respectively. This indicates that stripping due to the aeration system accounted for essentially all of the reduction in the methanol concentrations during Phase 1, Run 4. Therefore, for this run, when the biotic removal of methanol was assumed to be insignificant, Equation 5.3 can be rewritten as afirstorder relationship as follows:  dC MeOH dt  where: K  ~K  m l  m l  ' C  M e 0 H  .5.5  is thefirstorder coefficient for the overall removal of methanol (/minute)  Equation 5.5 was fitted to concentrations of methanol over time in the MBRs. The estimated results of the first order coefficients for the overall removal of methanol are presented in Tables A1.13 to A1.16. These results were estimated using non-linear regression analysis byfittingEquation 5.5 to the concentrations of methanol over time in the MBRs during the selected batch feed cycles within Phase 1, Run 4. The first order  51  overall methanol removal coefficients ( K ) for Phase 1, Run 4 are presented in Table m l  5.1.  Table 5.1 Methanol removal coefficients during Phase 1 SRT  (day)  I  WTTT HRT  I  r  KmO  (hours)  (mg/L- minute)  15  12  0.88 ±0.175  15  10  0.86 ± 0.0945  15  2  K  m 0  m l  (/minute)  0.0009 ±0.00013  10  12  0.783 ±0.169  10  10  0.627 ± 0.068  10 1K  Kml  0.00082 ±0.00022  is the zero order coefficient for the biological removal of methanol (mg/L' minute) is thefirstorder coefficient for the overall removal (mostly by stripping) of methanol (/minute)  5.1.2 Monoterpenes Removal Monoterpenes removal rates were not constant with time. The concentration of monoterpenes measured during selected batch feed cycles followed a first order relationship as presented in Equation 5.7 and illustrated in Figure 5.12.  A relationship describing the removal of monoterpenes from a biological treatment  ^  system, as presented in Equation 5.6 below, was developed using the same principles as for Equation 5.3.  dC tur  Ht U l  c ^turp ^ " t V " —— Murp ^turp  P —V  f  +JS  w  , -i-J^strip.turp • ^turp v  n  5.6  52  30  40  50  Time min  Figure 5.12 Concentration of monoterpenes in MBR during a typical batch feed cycle (Solid line: Equation 5.7 fitted to concentrations of monoterpenes In the MBR; dashed line: Equation 5.6 (stripping part only) fitted to concentration of monoterpenes in MBR during inactivated biomass test)  dC turp . where: — i s dt  the rate of removal of monoterpenes (mg/L* minute), K . is the specific  monoterpenes biological utilization coefficient (/minute), Ks^^ is the half saturation concentration for monoterpenes uptake (mg/L), K  stri  ^  is thefirstorder coefficient for  the stripping of monoterpenes (/minute), and C , ^ is the concentration of monoterpenes remaining in the MBR (mg/L).  The first older removal rate for monoterpenes indicated that the concentrations of monoterpenes in the MBRs were not inhibiting the uptake of monoterpenes by the mixed microbial culture. However, the first order removal rate for monoterpenes indicated that the concentrations of monoterpenes in the MBRs were limiting the uptake of monoterpenes by the mixed microbial culture (i.e. K s ^ »  C  tuip  ).  53  For limiting and non-inhibiting conditions, Equation 5.6 can be simplified to a first order relationship as presented in Equation 5.7:  dCturp ~~  where: K  ( bio.t K  b i o t  (/minute), K  +  K tri .t)-C, s  P  u r p  =K  t o t  ,  .C  t u r p  5.7  is thefirstorder coefficient for the biological removal of monoterpenes t o t  t  is the first order coefficient for the total removal of monoterpenes  (/minute).  Equation 5.7 wasfittedto the concentrations of monoterpenes measured with time in the MBRs during Phase 1. The estimates of thefirstorder coefficients for the overall removal of monoterpenes are presented in Tables A l . l to A1.21. These results were estimated using non-linear regression analysis by fitting Equation 5.7 to the measured concentrations of monoterpenes during the selected batch feed cycles.  The first order coefficient for the stripping of monoterpenes was estimated byfittingthe second part of Equation 5.6 to the concentrations of the monoterpenes in the MBRs over time measured during the abiotic tests (inactivated biomass and clean water). Results from the non-linear regression are presented in Tables A3.1 to A3.3. The average value of the first order coefficient for the stripping of monoterpenes, based on the abiotic tests, was estimated to be 0.00157 ± 0.00032 /minute. At this rate, the estimated contributions of monoterpenes stripping due to the aeration system to the overall observed monoterpenes removals, for the combinations of operational SRTs and HRTs studied, are shown in Figure 5.13.  Figure 5.13 shows that the SRT exerted the major influence on the contributions of monoterpenes stripping to the overall observed monoterpenes removal. As shown in Figure 5.13, the estimated contributions of monoterpenes stripping due to the aeration system to the overall observed monoterpenes removal during Phase 1 rangedfrom16 to 55 %. As indicated in the literature review, for the biological wastewater treatment plants, 54  stripping of terpenes due to aeration systems of the total mass of terpenes removal could account from low to high percentages depending on the nature of wastewater treated, terpene species, and operational parameters of the plants. Schwartz et al. (1990) reported that 90 % of the total mass of terpenes (dipentene and anethole) was air stripped due to the aeration system, while Alvarez and Shaul (1999) reported that the mass of terpenes (d-limonene and terpinolene) stripped accounted only 10 % of total mass of terpenes removed in the aeration unit of an activated sludge system.  The first order coefficients for the biological removal of monoterpenes were estimated based on the difference between the first order coefficients for the total removal of monoterpenes measured for different combinations of operational SRTs and HRTs and the first order coefficient for the stripping of monoterpenes. The specific monoterpenes utilization coefficients were estimated by dividing the first order coefficient for the biological removal of monoterpenes by the MLVSS concentrations measured during the selected batch feed cycles.  The specific monoterpenes biological utilization coefficients (Km), for the combinations of the operational SRTs and HRTs applied, are shown in Figure 5.14. The result indicates that the SRT exerted a major influence on the monoterpenes specific biological utilization coefficients. As the operational SRT was decreased from 15 to 10 days, the specific monoterpenes utilization coefficients decreased from approximately 0.0083 ±0.0015 to 0.00258 ± 0.0013 /mg/L-day andfrom0.006 ± 0.0016 to 0.00193 ± 0.00076 /mg/L-day for operational HRTs of 12 and 10 hours, respectively. This indicated that the biological activity of mixed microbial culture for monoterpene biodegradation decreased significantly as the operational SRT was decreasedfrom15 to 10 days. This suggests that the microbial culture degrading monoterpenes were washed out at a shorter SRT (10 days). Over the range of data investigated, HRT did not significantly affect the specific utilization coefficient for monoterpenes.  Monoterpenes removal efficiencies, for the selected batch feed cycles within Phase 1, are presented in Tables A1.41 to A1.48. Figures 5.15 to 5.21 show influent and effluent 55  V) <D  |s? 2 o c o T> <U  c? a. c  '5.  W O ~  LU  £  <1)  CO  D)  >  o c E d) CD CO  (j or <D  0_  100 90 80 70 60 50 40 30 20 10 0  Run 1  Run 2&5  Run 4  Run 3  Run 3  •  ISSlV H R hr h r  h r  ^  S  Sl  I  = 5 d S R T = 1  H  R  T  =  8  Run 4  h  h  r  H  R  T  =  ° 1  hr  d S R T 2  H  =1°« 0 hr  R  T  =  1  SRT=10d HRT=8 hr  Figure 5.13 Estimated contributions of monoterpenes stripping to the overall observed monoterpenes removal during Phase 1  monoterpene concentrations and monoterpene overall removal efficiencies for Phase 1. As shown in these figures, monoterpenes concentrations in the influent (condensate) during Phase 1fluctuatedbetween 10 and 30 mg/L. Although the evaporator condensate was always collectedfromthe same location, and was shipped via sealed containers, this fluctuation was expected since monoterpenes could be volatilized in the condensers and the condensate seal tank (boiling point for monoterpenes ranges between 100 to 150 °C, at 760 mm Hg, Paul et al, 1968). However, monoterpenes overall removal efficiencies during Phase 1, for both reactors, remained relatively constant at a level of about 80 to 85 %. This level was comparable to those reported by others for biological systems dealing with terpene compounds. Wilson and Hrutfiord (1975) reported that monoterpenes removal efficiencies in aerated lagoons treating unbleached and bleached kraft mill effluents were 90 and 65 % for the unbleached and bleached effluents respectively. Alvarez and Shaul (1999) reported that about 90 % of two terpenes investigated (dlimonene and terpinolene) was removed from domestic wastewater spiked with these terpenes using an activated sludge system. Therefore, it appears that the overall removal of monoterpenes at a high temperature is feasible. However, as for the overall methanol removal efficiencies, when the HRT was decreasedfrom10 to 8 hours for both SRTs  56  Run 1  0.012  Run 2&5  Run 4  Run 3  Run 3  Run 4  c  o  0.01  ro  +  M >> CO  w  0.008  d 0.006  -  -*-> <D C 0 . 0 0 4 O .«>  -  CL  c  o  s i  0.002  o  0)  QL  SRT=15d  CO  SRT=15d  SRT=15d  SRT=10 d  SRT=10d  SRT=10d  H R T = 1 2 h r H R T = 1 0 hr H R T = 8 hr H R T = 1 2 hr H R T = 1 0 h r H R T = 8 hr  Figure 5.14 Monoterpene specific biological utilization coefficients (K ) during Phase 1 ut  (error bars represent 90 % confidence interval for measurement)  —A—R1 i n f l u e n t  e o  30-,  2  25  c:  27-Dec-01  -m-  R 2 influent  30-Dec-01  - + - R 1  2-Jan-02  effluent  6-Jan-02  R 2 effluent  8-Jan-02  Dates  Figure 5.15 Influents and effluents monoterpenes concentrations for RI and R2 (Phase 1, Run 1: SRT=15 days, HRT=12 hours)  57  27-Dec-01  30-Dec-Gi  2-Jan-02  6-Jan-02  8-Jan-02  Dates  Figure 5.16 Monoterpenes removal efficiencies for RI and R2 (Phase 1, Run 1: SRT= 15 days, HRT=12hours)  -Influent  •Effluent  • Efficiency  30  | a> E  2  100 90 80 + 70 60 50 40 30 + 20 10 0  5  M  | . i c o  8  c o O  2  0  10  0 6-Apr-02  9-Apr-02  ro >  O vP  E ^  or g  o .3> c o ro i E •B UJ  12-Apr-02 15-Apr-02 18-Apr-02 Dates  Figure 5.17 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for RI (Phase 1, Run 5: SRT=15 days, HRT=10 hours)  58  -A— Influent  -*-Effluent  - • - Efficiency  Figure 5.18 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for RI (Phase 1, Run 4: SRT=15 days, HRT= 8 hours)  Influent  - « - Effluent  - • - Efficiency 100  11-Feb-02  14-Feb-02  17-Feb-02  20-Feb-02  Dates  Figure 5.19 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for RI (Phase 1, Run 3: SRT=10 days, HRT= 12 hours)  59  -A—Influent e  o ro c a) o tz o O w cu c <D CL i—  a> o  • Effluent  •Efficiency  30 25 20 |> 15 10 -j 5 0 11-Feb-02  14-Feb-02  17-Feb-02  20-Feb-02  Dates  Figure 5.20 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for R2 (Phase 1, Run 3: SRT=10 days, HRT= 10 hours)  • Influent  6-Mar-02  9-Mar-02  •Effluent  12-Mar-02  •Efficiency  15-Mar-02  18-Mar-02  Dates  Figure 5.21 Influent and effluent monoterpenes concentrations and monoterpenes overall removal efficiency for R2 (Phase 1, Run 4: SRT=10 days, HRT= 8 hours)  60  investigated (15 and 10 days), the overall monoterpenes removal efficiencies declined significantly as shown in Figures 5.18 and 5.21. This decline in the monoterpenes overall removal efficiency could be due to a relatively short contact time (between the microbial culture and the contaminant in the MBRs) as compared with others for the other operational HRTs (12 and 10 hours).  5.1.3 TOC Removal As discussed in Section 2.2, methanol and monoterpenes were identified as the primary contaminants of concern contained in evaporator condensate. The removals of these contaminants from the evaporator condensate were outlined in the previous sections. However, as indicated in Section 2.2, evaporator condensate also contains a number of secondary contaminants of concern that must also be removed before the evaporator condensate can be reused as a process water. It is difficult to monitor the removal of each contaminant individually due to the large number of organic compounds contained in real evaporator condensate and because most of these compounds exist at trace levels. Therefore, TOC, as a multi-component parameter, was selected to measure the concentrations of all organic compounds present in the evaporator condensate.  For selected batch feed cycles within Phases 1 and 4, the changes in the concentrations of TOC and methanol in the MBR were measured over time. The concentrations of methanol expressed as a TOC equivalent (methanol-TOC), were calculated by multiplying the measured methanol concentrations by the ratio of the molecular weight of the carbon in the methanol to the molecular weight of the methanol (12/32).  As illustrated in Figure 5.22, the overall and stripping removal rates of TOC were not constant with time, while the overall methanol-TOC removal rate was constant with time. This result is similar to that reported by Berube (2000) who indicated that TOC removal from the foul condensate by mixed microbial culture followed a pseudo-first order rate.  61  For the overall TOC removal, to account for the potential non-linear relationship for the biodegradation of the organic compounds in the evaporator condensate and to consider the presence of a non-biodegradable TOC fraction, a first pseudo order relationship was adaptedfromBerube (2000) as follows:  dS - tot.TOc(S-S ') - K d t  K  N  u  T  0  C  X(S-S )+ K N  s t r i p T 0 C  5.8  (S-Snv)  dS where: — is the rate of removal of TOC (mg/L-minute), K dt  u T O C  is the first order  biological TOC specific utilization coefficient (/mg/L.day), X is M L V S S concentration (mg/L), S is the concentration of the multi-component substrate (mg/L as TOC), S  N  the non-biodegradable component of the multi-component substrate (mg/L as TOC), S is non-volatile, non-biodegradable component of the TOC (mg/L), K  s t r i p T  Q  C  is 1 N  is the first  order coefficient for stripping of TOC (/minute), Snv is the non-volatile component of the multi-component substrate, and K  t o t T O C  is the first order coefficient for the overall  removal of TOC (/minute).  For Phase 1, as illustrated in Figure 5.22, Equation 5.8 was fitted to the TOC concentrations in the MBRs, which were measured during selected batch feed cycles. Non-linear regression was used to estimate the non-biodegradable component of the influent TOC for each set of TOC measurements. Results from the non-linear regression analysis are presented in Tables A1.22 To A1.40. The concentrations of the nonbiodegradable TOC component are presented in Tables A1.22 To A1.40. First and zero order overall removal coefficients for TOC and methanol-TOC, respectively (K t.Toc and to  K o) are presented in Table 5.2. m  As illustrated in Figure 5.22, the abiotic TOC removal rate followed a first order relationship. Therefore, the stripping part (second term) of Equation 5.8 was fitted to the concentrations of the TOC in the MBRs measured during the abiotic tests (inactivated  62  • abiotic test A overall test • MeOH as TOC 80 E c o  T  70 60  ro 50 c <u o c o O O O  A--  40  A  30 4 20 10 A 20  40 Time min  60  80  Figure 5.22 Concentration of TOC in MBR during a typical batch feed cycle (Small dashed line: Equation 5.4 fitted to the concentration of methanol as TOC; long dashed line: Equation 5.8 fitted to concentration of TOC; solid line: s tripping t erm i n Equation 5.8 fitted to TOC concentrations measured during clean water test)  biomass and clean water). Results from the non-linear regression analysis are presented in Tables A3.4 to A3.6. The average value of the first order coefficient for the stripping of TOC, based on the abiotic tests, was estimated to be 0.03155 ± 0.0035 /minute. At this rate, the estimated contributions of TOC stripping due to the aeration system to the overall observed TOC removals, for the combinations of operational SRTs and HRTs studied, are shown in Figure 5.23. At the rate of TOC stripping observed by Berube (2000), which was 0.014 /minute, stripping of TOC due to aeration accounted for less than 5 % of the total mass of TOC removedfromthe MBR. The higher TOC stripping rates observed during the present study are likely due to different reactor configurations and aeration rates.  For the combinations of operational SRTs and HRTs applied, the specific TOC biological utilization coefficients are shown in Figure 5.24. These coefficients were estimated by dividing the average first order coefficients for biological TOC removal by the MLVSS concentrations measured during the selected batch feed cycles. Thefirstorder coefficient for the biological TOC removal was estimated by subtracting thefirstorder stripping  100 90  ro > o  E  Run 1  Run 2&5  Run 3  Run 3  Run 4  80  O O  cn c  t-  CL  70 60  .9- 50 <D tt ro w 40  TJ  •I ^  30  o  20  "(?J TJ J  cn tt 10  ro <  -*-» c Q) CD Q.  Run 4  0  1  111  1  SRT=15d SRT=15d SRT=15d SRT=10d SRT=10d SRT=10d HRT=12 hr HRT=10 hr HRT=8 hr HRT=12 hr HRT=10 hr HRT=8 hr  Figure 5.23 Estimated contributions of TOC stripping to the overall TOC removal during Phase 1  coefficient from the first order coefficient for the overall removal of TOC (Equation 5.8). For the combinations of operational SRTs and FfRTs applied, the first order coefficients for the biological removal of TOC (Kbio.TOc) are presented in Table 5.2.  As illustrated in Figure 5.24, the combined effect of a reduction in the zero order coefficients for the biological removal of TOC and the increase in the concentration of MLVSS in the MBRs when the HRT was decreased from 12 to 10 hours resulted in a significant reduction in the specific TOC biological utilization coefficients. The specific TOC biological utilization coefficients decreased from approximately 0.0276 ± 0.0035 to 0.0078 ± 0.0022 /mg/L-day and 0.018 ± 0.005 to 0.007 ± 0.0012 /mg/L-day when the HRT was decreased from 12 to 10 hours, for SRTs of 15 and 10 days, respectively. This result indicates that the increase in the organic load exerted an effect on the observed specific TOC biological utilization coefficient in the high temperature MBR. However, as shown in Figure 5.24, the mixed microbial culture utilizing TOC was not significantly inhibited due to reducing the HRTfrom10 to 8 hours. For operational SRTs of 15 and 10 days, TOC specific biological utilization coefficients remained relatively constant at  64  Table 5.2 First order overall and biological removal coefficients for TOC (K . oc and tot T  io-TOc) and zero order for methanol-TOC (Kmo ) during Phase 1 SRT  HRT  (day)  Ktot.TOC  KbioTOC  KmO  (hours)  (/minute)  (/minute)  (mg/L minute)  15  12  0.066 ± 0.0045  0.0349 ± 0.0044  0.33 ±0.066  15  10  0.045 ± 0.0039  0.0137±0.0039  0.31 ±0.043  15  8  0.043 ± 0.0055  0.00580 ± 0.001  0.177 ±0.067  10  12  0.042 ±0.0013  0.0100 ±0.0048  0.315 ±0.097  10  10  0.0355 ±0.0056  0.0083 ± 0.00087  0.23 ± 0.024  10  8  0.032 ± 0.0040  0.0021 ±0.00021  0.07 ± 0.053  0.0078 ± 0.0022 to 0.009 ± 0.0021 /mg/L-day and 0.007 ± 0.0012 to 0.0076 ± 0.0015 /mg/L-day, respectively, when HRT was loweredfrom10 to 8 hours.  The TOC removal efficiencies and MLVSS concentrations for the selected batch feed cycles are presented in Tables A1.41 to A1.48. Figures 5.25 to 5.31 show influent and effluent TOC concentrations and overall TOC removal efficiencies during Phasel. TOC concentrations of the influent (condensate) during Phase 1 fluctuated between 230 to 400 mg/L due to the variation in the concentrations of the organic compounds in the condensate as indicated in Section 5.1.2. For the operational SRTs and HRTs applied during Phase 1, overall TOC removal efficiencies ranged between 72 to 83 %. This range, as compared with the previous studies, was higher than that observed by Jen (2002) which was 64 % (SRT = 39 days, HRT = 9 hours) and lower than that observed by Berube (2000) which was 91 % (SRT = 20 days, HRT = 12 hours). The variation in the results was due to the different methods for estimating removal efficiencies that were used and because the MBRs were operated with different SRTs and HRTs. For the present study, removal efficiencies were calculated as indicated in Section 5.1.1, while for the previous studies (Berube, 2000), removal efficiencies were based on the difference between the contaminant concentrations in the influent and contaminant concentrations in the MBRs at the end of the batch feed cycle.  65  0)  o !E 0) o O c g  Run 1  0.035  Run 2&5  Run 4  Run 3  Run 3  Run 4  0.03 0.025  ro a 0.02 N  5 ^ 0 . 0 1 5 4o.oi  4-  0.005 0  o D.  SRT=15d SRT=15d SRT=15d SRT=10d SRT=10d SRT=10d HRT=12 HRT=10 HRT=8 h r HRT=12 HRT=10 HRT=8 h r hr hr hr hr  co  Figure 5.24 T O C specific biological utilization coefficients (KUTOC) during Phase 1 (error bars represent 90 % confidence interval for measurement)  •R1 influent  •R2 influent-  •R1 effluent  •R2 effluent  500  27-Dec-01  30-Dec-01  2-Jan-02  5-Jan-02  8-Jan-02  Dates  Figure 5.25 Influents and effluents TOC concentrations of for RI and R2 (Phase 1, Run 1: SRT=15 days, HRT=12 hours)  66  •A-R1  27-Dec-01  30-Dec-01  -»-R2  2-Jan-02  5-Jan-02  8-Jan-02  Dates ;  I  Figure 5.26 TOC removal efficiencies for RI and R2 (Phase 1, Run 1: SRT= 15 days, HRT=12 hours)  -A—Influent  •Effluent  • Efficiency  |>500  100  §400  80  03  £300  60  §200  40  100  20  o O  o Q  0 6-Apr-02 9-Apr-02 12-Apr-02 15-Apr-02 18-Apr-02 Dates  >, o c <u 'o  se UJ  "CO  vP  > tfo  E  0) 01  o O  Figure 5.27 Influent and effluent TOC concentrations and TOC overall removal efficiency for RI (Phase 1, Run 5: SRT=15 days, HRT=10 hours)  67  - ± — Influent  •Effluent  • Efficiency  500  6-Mar-02  10-Mar-02  15-Mar-02  18-Mar-02  Dates  Figure 5.28 Influent and effluent TOC concentrations and TOC overall removal efficiency for RI (Phase 1, Run 4: SRT=15 days, HRT=8 hours)  O £  100 50  11-Feb-02  14-Feb-02  17-Feb-02  20-Feb-02  Dates  Figure 5.29 Influent and effluent TOC concentrations and TOC overall removal efficiency for RI (Phase 1, Run 3: SRT=10 days, HRT=12 hours)  68  •Effluent  -A— I n f l u e n t  •Efficiency  ch 450 400 * c o 350 -  --  E  2  300 -  £ £  250 200 150 100  < -  c n  ,  O O O  w A  E  —  (1  --  J k  • -  0 -  1  11-Feb-02  ,  II 20  •  •  100 90 o 80 ca) 70 o it 60 UJ 50 ro > o E 10  1  14-Feb-02  17-Feb-02  20-Feb-02  0)  a: o  O r-  Dates  Figure 5.30 Influent and effluent TOC concentrations and TOC overall removal efficiency for R2 (Phase 1, Run 3: SRT=10 days, HRT=10 hours)  Influent  6-Mar-02  —•—Effluent  9-Mar-02  —•—Efficiency  12-Mar-02  15-Mar-02  18-Mar-02  Dates  Figure 5.31 Influent and effluent TOC concentrations and TOC overall removal efficiency for R2 (Phase 1, Run 4: SRT=10 days, HRT=8 hours)  The significant decline of T O C overall removal efficiencies when HRT was lowered from 10 to 8 hours for both SRT runs of 15 and 10 days, as shown in Figures 5.28 and 5.31 respectively, could be due to relatively short contact time as discussed in Section 5.1.2. 5.1.4 Sludge Production The observed net growth yield is a valuable coefficient, which enables the operator of a biological treatment process to assess the net cumulative mass of sludge produced per net cumulative mass of substrate consumed over a reasonably long period of time. The observed net growth yield (Y b ) is particularly useful to determine the ratio of the mass 0  S  of sludge produced per mass of substrate actually destroyed (mineralized).  Yobs of a mixed culture of methanol-consuming microorganisms can be related to the amount of methanol consumed as presented in Equation 5.9:  Yobs =  Mass of VSS formed during a run Mass of methanol consumed during a run  5.9  Detailed calculations for the observed growth yield during Phase 1, for RI and R2, are presented in Tables A1.49 to A1.55. Table 5.3 presents observed growth yields during Phase 1.  Not surprisingly for both RI and R2, the observed growth yields presented in Table 5.3 increased as the organic load applied (food availability) increased and SRT decreased. In biological treatment processes, the rate of metabolism and bacterial growth is a function of the ability of the microorganisms to process the substrate. This ability depends on the availability of food and nutrients and on operational and environmental factors. For high rate treatment plants (conventional biological treatment systems treating municipal wastewaters), in which the source of food and nutrients is not limited, sludge yields range from 0.4 to 0.8 mg VSS/mg BOD (Metcalf and Eddy, 1991). The differences in the 5  observed growth yield values obtained in the present studyfromthose obtained in the 70  Table 5.3 Biomass growth yields for RI and R2 during Phase 1 Reactor  Run  SRT (days)  'HRT (hours)  Yobs  (mg VSS /mg MeOH) RI  1  15  12  0.219  RI  5  15  10  0.250  RI  3  10  12  0.243  R2  1  15  12  0.233  R2  2  15  10  0.269  3  10  10  0.304  R2 —  —  .  . — '  For HRT=8 hours, stripping accounted for essentially all methanol removal in the MBRs  previous studies, which investigated the biological removal of evaporator condensate using the MBR operated under different operational SRT and HRT conditions, confirmed the influence of the operating conditions on the results. Observed growth yields were 0.2 mg VSS/mg MeOH in Berube's (2000) research (SRT=20 days, HRT=12 hours) and in the range of 0.034 to 0.025 mg VSS/mg MeOH in Jen's (2002) research (SRT=39 days, HRT=9 hours). 5.2 Phase 2 This section presents and discusses the results of the permeate flux observations for the MBRs and the mechanisms responsible for membrane fouling. 5.2.1 Permeate Flux The results of the permeate flux reduction with time obtained during Phase 2, for R2 and RI, are shown in Figures 5.32 to 5.35 and 5.36 to 5.38 respectively.  Figures 5.32 to 5.38 illustrate that for both membranes, permeate flux was affected by the operational SRT and HRT. For R2, as shown in Figure 5.32, the membrane was capable of operating for up to 336 hours without chemical cleaning when MLVSS concentration was 1820 mg/L. When the MLVSS concentration increased after changing the  71  1.2  0  48  144  96  192  240  288  336  Time hours  Figure 5.32 Permeate flux with time for R2 (Phase 2, Run 1: SRT =15 d, HRT= 12 hrs, MLVSS =1820 mg/L)  1.2  °- 0.2 A  0  20  40  60  80  100  120  140  160  Time hours  Figure 5.33 Permeate flux with time for R2 (Phase 2, Run 2: SRT =15 d, HRT= 10 hrs, MLVSS =2670 mg/L)  72  0  48  96  144  192  240  288  Time hours  Figure 5.34 Permeate flux with time for R2 (Phase 2, Run 3: SRT =10 d, HRT= 10 hrs, MLVSS =2060 mg/L)  73  1.20  o- 0.20 0.00 48  96  144  192  240  288  336  Time hours  Figure 5.36 Permeatefluxwith time for RI (Phase 2, Run 5: SRT =15 d, HRT= 10 hrs, MLVSS =2500 mg/L)  48  96  144  192  Time hours  Figure 5.37 Permeatefluxwith time for RI (Phase 2, Run 4: SRT =15 d, HRT= 8 hrs, MLVSS =450 mg/L)  74  1.2 tz  a.  0.2 A 0  -I  ,  ,  0  48  96  _,_ 144  192  , 240  288  Time hours  Figure 5.38 Permeate flux with time for RI (Phase 2, Run 3: SRT =10 d, HRT= 12 hrs, MLVSS =1340 mg/L) operational SRT and HRT conditions, the same membrane had to be cleaned frequently (Figures 5.33 and 5.34). In addition, the slope of the permeate flux curve with time in Figure 5.33 was steeper than that in Figure 5.34 (in Figure 5.33, the membrane had to be cleaned chemically every 45 to 48 hours as compared to every 90 to 95 hours in Figure 5.34). Figure 5.35 shows that although the flow rate increased (as the HRT was lowered to 8 hours), there was no significant additional membrane fouling as the slope of the permeate curve with time was not steep and the membrane was capable of operating for up to 110 hours without chemical cleaning. Like R 2, the membrane for RI had to be cleaned lessfrequentlywhen the MLVSS concentration decreased after changing the operating SRT and HRT conditions. The membrane was capable of operating without chemical cleaning for up to approximately 192 hours and more than 170 hours when MLVSS concentration was 1340 and 450 mg/L respectively, compared to approximately 60 hours when MLVSS concentration was 2500 mg/L. This can be shown by comparing Figures 5.38 and 5.37 with Figure 5.36. This implies that, for both membranes, it was the mass flux (product of solids concentration in the MBR and the permeate flux), which decreased to a minimum value during the 8 hours HRT runs (193 to 270 mg/m 'minute 2  75  and 270 to 315 mg/m -minute for R2 and RI, respectively) that affected the fouling of the 2  membrane during the study.  5.2.2 Fouling Mechanisms Membrane fouling mechanisms were investigated during Phase 2, Run 5. For this run, serial membrane resistances attributed to the membrane material, pore plugging, and concentration polarization were correlated with the flux loss using the flux decline model indicated in Section 2.3.3.3. Operating parameter settings used during Run 5 were as indicated in Table 4.5. The influence of the TMP on the membrane fouling mechanism was investigated by varying this operational parameter between the MBRs (operational TMPs for RI and R2 were 200 (30) and 66 (10) kPa (psi), respectively). Figures 5.39 and 5.40 show the variation of membrane  (Rm),  pore plugging  (Rp ), P  and concentration  polarization (Rc ) resistances with time during Phase 2, Run 5 for RI and R2 P  respectively.  During Phase 2, Run 5, Figures 5.39 and 5.40 show that the filtration resistance was mainly attributed to R contributions of R  pp  pp  rather than to R c or R for both membranes investigated. The P  m  resistance to the total resistances were .80 % and 60 to 80 % as  shown in Figures 5.41 and 5.42 for RI and R2 respectively. In addition, Figures 5.39 and 5.40 show that the foulant layer resistances were significantly influenced by the operational TMP and MLVSS concentration. For RI, in which TMP and MLVSS concentration were 200 kPa(30 psi) and 2500 mg/L, respectively, Rp and R<;p ranged P  from 39 x 10 to 52 x 10 /m and 4.8 x 10 to 8.11 x 10 /m respectively. While, for 12  12  12  12  R2 in which the TMP and MLVSS concentration were 66 kPa (10 psi) and 1820 mg/L, respectively, Rp and R^ rangedfrom9 x 10 to 22.7 x 10 An and 1.45 x 10 to 2.86 x 12  12  12  P  12  10  /m respectively. Further research is required to achieve higher permeate fluxes by  optimizing the operating conditions and selecting appropriate membrane pore sizes.  76  o X  <1) o c ro to '</>  TMP = 30 psi 150 200 250 Time hours  300  350 400  Figure 5.39 Variation of serial resistances with time for RI (Phasel, Run 5: SRT= 15 days, HRT=10 hours, MLVSS concentration = 2500 mg/L)  -•-Rm  -4—Rpp  -»-Rcp  25.00  TMP =10 psi Time hours  Figure 5.40 Variation of serial resistances with time for R2 (Phase 2, Run 5: SRT= 15 days, HRT=12 hours, MLVSS concentration = 1820 mg/L)  77  O  c  ro OT  -*—' 'OT  0)  oc  ro o  a) cn ro  a  <D  0_  50  100  150 200 250 Time hours  300  350 400 TMP= 30 psi  Figure 5.41 Percentages of R , R , and Rc of the total resistance with time for R I m  pp  P  (Phase 1, Run 5: SRT= 15 days, HRT=10 hours, MLVSS concentration = 2500 mg/L)  •Rm 0)  o c ro  S2  'OT <D  CC  "ro o OJ O)  •JS c 0)  £ Q.  •Rpp  •Rep  100 90 80 70 60 -{ 50 40 -I 30 20 10 0 0  100  150  200  Time hours  250  300 350 TMP = 10 psi  Figure 5.42 Percentages of Rm, Rp , and R^of the total resistance with time for R2 P  (Phasel, Run 5: SRT= 15 days, HRT=12 hours, MLVSS concentration = 1820 mg/L)  78  5.3 Phase 3 In order to investigate the effects of turpentine shock loads on the performance of a high temperature MBR, as discussed in Chapter 3, a series of short-term turpentine shock load tests were applied to the MBRs as described in Section 4.3.2.  This section discusses the results for the overall (biological + stripping) removal kinetics of the methanol, monoterpenes, and the trace organic compounds represented by TOC for each turpentine shock load test. As indicated in Section 4.3.2, it was not possible to accurately control the liquid level in the MBRs due to the excessive foaming that occurred during the turpentine shock load tests (Phase 3). Therefore, stripping rates of the contaminants that were measured during Phase 4 were not applicable to the data observed in this section. In addition, MLVSS samples were not taken during Phase 3.  During Phase 3 in which monoterpenes were spiked at concentrations of 300, 750, and 1500 mg/L for the first, second, and third Run, respectively, the observed methanol removal rates were constant with time and with the concentration of methanol remaining in the MBRs. The zero order removal rates indicated that the concentrations of methanol over time in the MBRs neither limited nor inhibited the uptake of methanol by the mixed microbial culture. Thus, Equation 5.4, which is a linear regression relationship, was fitted to the concentrations of methanol in the MBRs. Estimates of the zero order coefficients for the overall removal of methanol are presented in Tables A2.1 to A2.15.  As shown in Figures 5.43 and 5.44, for RI and R2 respectively, the zero order coefficients for the overall removal of methanol declined during each test (run). The zero order methanol removal rates for RI decreased more than those for R2. This was expected since the organic load applied to RI was higher (smaller HRT) than that for R2. For both the MBRs investigated, Figures 5.43 and 5.44 show that the overall methanol removal coefficients recovered completely following the end of the first and second shockload experiments.  79  During Phase 3, overall monoterpenes removal rates followed a first order relationship as presented in Equation 5.7. Consequently, Equation 5.7 was fitted to the concentrations of monoterpenes over time measured during thefive-spikedbatch feed cycles of each Run within Phase 3. Resultsfromnon-linear regression analysis for thefirstorder coefficients of the overall removal of monoterpenes are presented in Tables A2.1 to A2.15. As shown in Figures 5.45 and 5.46, for RI and R2 respectively, the first order coefficients for the monoterpenes overall removal declined during each test. As with methanol, the monoterpenes removal rates for RI decreased more than those for R2. Figures 5.45 and 5.46  show that the overall monoterpenes  removal coefficients  recovered by  approximately 63 and 81 % for RI and R2, respectively following the end of the first shockload experiment and recovered completely for both MBRs following the end of the second shockload experiment.  For the non-methanolic organic compounds removal, the changes in the concentrations of TOC and methanol in the MBRs were measured over time during thefive-spikedbatch feed cycles of each run within Phase 3. Methanol expressed as TOC was calculated as indicated in Section 5.1.3. The overall TOC removal rates were not constant with time, while the overall methanol-TOC removal rates were constant with time. To account for the potential non-linear relationship for the biodegradation of the organic compounds in the evaporator condensate and to consider the presence of a non-biodegradable fraction within these compounds, the overall TOC removal rates were estimated as afirstorder relationship as explained in Section 5.1.3. Equation 5.8 was fitted to the TOC concentrations in the MBR measured over time during the five spiked batch feed cycles of each Run within Phase 3. Non-linear regression analysis was used to estimate the nonbiodegradable component of the influent TOC for each run of TOC measurements.  Results from the non-linear regression analysis are presented in Tables A2.16 To A2.30, which show the concentrations of the non-biodegradable TOC. Like the methanol and monoterpenes, the overall TOC removal coefficients declined during each test as shown in Figures 5.47 and 5.48 for RI and R2, respectively. For both the MBRs investigated,  80  Figures 5.47 and 5.48 show that the overall TOC removal coefficients recovered completely following the end of the first and second shockload tests.  In conclusion, within the range of data investigated, the performance of the MBRs was significantly affected due to applying turpentine shock loads. At the start of each batch feed cycle within Phase 3, initial terpene concentrations in the MBRs as compared with those during Phase 1, Run 5 in which the MBRs were operated under the same conditions without turpentine shockloads, increased approximately 4, 7, and 16 times for the first, second, and third run respectively. As a result, terpene shockloads exhibited an inhibitory effect on the mixed microbial culture that degraded methanol in which overall removal rates followed a zero order relationship. For monoterpenes and TOC, overall removal rates that followed a first order relationship, declined significantly as the terpenes accumulated over a short time period (10 hours) in the reactors. For the main contaminants of concern, the rate of decline in the values of the overall removal coefficients increased as the concentrations of terpenes spiked into the influent feed increased from 300 to 1500 mg/L.  81  0) c E E  •1st Run  -2nd Run  —•—3rd Run  1.05 -,  0.9  1  0.75 -  '  c  (D o  0.6 -  SE  <D 0 . 4 5 -  O  o  t_  <D  "D i_  O  0.3 0.15 -  o  a> N  0 2  3  4  Order of batch feed cycle  Figure 5.43 Variation of overall methanol removal rates with the sequence of spiked batch feed cycles for RI during Phase 3 (SRT =15 days, HRT=10 hours)  2  3  4  Order of batch feed cycle  Figure 5.44 Variation of overall methanol removal rates with the sequence of spiked batch feed cycles for R2 during Phase 3 (SRT =15 days, HRT=12 hours)  82  0)  1 st Run -4— 2 nd Run - • - 3rd Run  0.009 0.008 -: 0.007  c 0.006 o 0.005  it  0  0.004  |  0.003  6  0.002 -I  1  0.001  LL  0 0  1  2  3  4  5  6  Order of batch feed cycle Figure 5.45 Variation of monoterpenes overall removal rates with the sequence of spiked batch feed cycles for RI during Phase 3 (SRT =15 days, HRT=10 hours)  •1st Run —4—2 nd Run • 3rd Run cu 0.009  .1 |j § H c3 1 3  o -4->  0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0 1  2 3 4 Order of batch feed cycle  5  6  Figure 5.46 Variation of monoterpenes overall removal rates with the sequence of spiked batch feed cycles for R2 during Phase 3 (SRT =15 days, HRT=12 hours)  83  •1st Run a> c E  a D  it o O  •2 nd Run  • 3rd Run  0.075 0.06 A 0.045 0.03  •p  O  0.015 ]  2  3  4  Order of batch feed cycle  Figure 5.47 Variation of overall TOC removal rates with the sequence of spiked batch feed cycles for RI during Phase 3 (SRT =15 days, HRT=10 hours)  •1st Run cu  | c 0) 'o  •2 nd Run  0.075  -3rd Run  0.06 0.045  it o O ^CD 0.03 -i •E O r 0.015 i ii. —r—  1  2  3  4  5  Order of batch feed cycle  Figure 5.48 Variation of overall TOC removal rates with the sequence of spiked batch feed cycles for R2 during Phase 3 (SRT =15 days, HRT=12 hours)  84  Chapter 6 Conclusions and Recommendations 6.1 Conclusions 6.1.1 Feasibility of the Biological Removal of Methanol, Monoterpenes and TOC from the Real Evaporator Condensate Phase 1 investigated using MBRs to treat real evaporator condensate at a high temperature with a particular interest in maximizing the economic feasibility of the process. Thus, the target was to operate the MBRs at a short SRT and a low HRT and determine the feasibility of the biological removal of the main contaminants of concern present in the evaporator condensate. From this investigation, the following conclusion can be drawn.  1. It was feasible to achieve the biological removal of methanol, monoterpenes, and TOC using a high temperature MBR operated with an SRT as short as 10 days and an HRT as low as 10 hours.  6.1.2 Identification of the Removal Kinetics and Efficiencies of Methanol, Monoterpenes, and TOC The results of the biotic removal kinetics and overall removal efficiencies for the main contaminants of concern are summarized and compared with previous studies as shown in Table 6.1.  The conclusions below can be drawnfromthe results of the present study, which were applicable for both the operational SRTs of 15 and 10 days.  1. An increase in the organic load in the high temperature MBR (when HRT was lowered from 12 to 10 hours) caused a reduction in the values of the specific methanol, monoterpenes, and TOC biological utilization coefficients. For monoterpenes, specific biological utilization coefficients declined mainly because of decreasing operational SRT rather thanfromlowering the operational HRT.  85  Table 6.1 Summary of the results obtained in the present study and the previous studies  Study  Overall removal  Specific biological utilization coefficient (/day  efficiency (%)  for methanol and TOC for Berube (2000) study, and /mg/L.day for monoterpenes and TOC for present study  Methanol HRT=12 Present  hrs  study  HRT=10  'Turp TOC  Methanol  'Turp  TOC  98  86.2  83  0.70±0.17  0.0083±0.0015  0.027±0.0035  98  85.3  78  0.006±0.0011  0.0078±0.002  38  47.3  35.85  0.0048±0.0022  0.009±0.0021  97.5  81.5  79.4  0,83±0.17  0.0025±0.0013  0.0186±0.014  97  80  76.75  0.43±0.04  0.00193±0.0007  0.007±0.002  34  34.9  28.3  2  0.00384±0.0025  0.0076±0.001  0.49±0.05  hrs SRT=15  HRT=8  days  hrs HRT=12  2  hrs Present  HRT=10  study  hrs HRT=8  SRT=10  hrs  days Berube (2000)  99  93  0.59±01  0.66±0.05  95  64  1.03±0.13  0.51±0.072  SRT=38 days  to  to  HRT=9hrs  1.47±0.15  0.74±0.06  SRT=20days HRT=12 hrs Jen (2002)  Turp is monoterpenes 2  For the operational SRTs of 15 and 10 day, when HRT was lowered to 8 hours, stripping  accounted for essentially a 11 of the reduction in the concentration of methanol in RI and R2, respectively.  86  2. As the organic load applied to the MBRs was increased further (when HRT was lowered from 10 to 8 hours), the mixed microbial culture, which degraded methanol was inhibited. The potential toxic contaminants present in the evaporator condensate had an immediate influence  on the methanol removal kinetics  and efficiencies.  For  monoterpenes and TOC, the significant decline in the values of overall removal kinetic coefficients and removal efficiencies, when HRT was lowered to 8 hours, could be due to a short contact time offered.  3. With operational conditions of a short SRT (15 to 10 days) and a low HRT (12 to 10 hours), the observed growth yields ranged from 0.21 to 0.30 mg VSS / mg methanol.  6.1.3 Identification of the Mechanism Responsible for the Membrane Fouling Phase 2 investigated the performance of the membrane during the steady state conditions. This investigation included measuring the permeate flux reduction with time and identifying membrane resistances. From this investigation, the conclusions applicable for both membrane units can be drawn as below.  1. The operational SRT and HRT conditions affected the reduction of the permeate flux with time and the resulting cleaning intervals.  2. For both membranes, the mass flux, which decreased to a minimum value during the operation at an 8-hour HRT, affected the fouling of the membrane during the study.  3. Membrane fouling was controlled mainly by pore plugging resistance, rather than by concentration polarization or membrane resistances. Pore plugging resistance contributed about 60 to 80 % of the total filtration resistance.  4. The pore plugging and concentration polarization resistances were functions of the operational TMP and MLVSS concentration in the MBRs. When the TMP and MLVSS concentration were changed from 200 kPa (30 psi) to 66 kPa (10 psi) and from 2500 to  87  1820 mg/L, respectively, the pore plugging and concentration polarization resistances reduced 57-77 % and 41-83 %, respectively.  6.1.4 Identification of the Impacts of Turpentine Shock Loads on the MBRs'perfc ormance Phase 3 investigated the overall removal kinetics under short-term turpentine shock load conditions. Three shock load experiments, each with different concentrations of monoterpenes, were applied to the MBRs. Thus, the impact of different monoterpene spiking concentrations on the overall removals of the contaminants of concern was investigated. From this investigation, conclusions can be drawn as below.  1. Within the range of the data investigated, the turpentine shock loads exerted an impact on the overall removal of the contaminants of concern present in the evaporator condensate. Within each shock load experiment, overall removal coefficients for methanol, TOC, and monoterpenes decreased gradually as the monoterpenes accumulated in the MBRs. Ln addition, it was observed that as the concentrations o f monoterpenes introduced to the MBRs increased, the overall removal rates decreased more significantly.  2. The rate of decrease in the values of the removal coefficients of the contaminants of concern present in the evaporator condensate was a function of organic load applied to the MBR. The higher the organic load applied (the lower HRT), the higher was the observed reduction in the values of the overall removal coefficient.  3. Overall removal coefficients, following the end of thefirstshockload experiment (after 120 hours), for methanol and TOC recovered completely, while they recovered partly for monoterpenes (63 and 81 % for RI and R2, respectively). Following the end of the second shockload experiment (after 72 hours), overall removal coefficients for methanol, TOC, and monoterpenes recovered completely.  88  6.2 Recommendation Based on the findings of the study and a survey of current literature, investigations are suggested to be carried out in the following areas.  1. Biotic oxidation of monoterpenes was a partfromthe total removal of monoterpenes from evaporator condensate in a high temperature MBR. A better understanding of the kinetics and the fate of monoterpenes during the biotic removal is required to properly operate a high temperature MBR for the removal of monoterpenes.  2. For both the operational SRTs of 15 and 10 days, the overall removal coefficients and removal efficiencies of the main contaminants of concern decreased as the operational HRT was lowered from 10 to 8 hours. Further research is required to investigate the transitional changes in the values of these kinetics and efficiencies at the operational HRT of 9 hours. In addition, investigation of the biological removal of the contaminants of concern under wide range of the operational SRTs and HRTs is required.  3. Further research work is required to investigate the effects of operational conditions, which include temperature, CFV, and pH of the mixed liquor on the fouling mechanisms of the membrane. These operational conditions, including TMP, could be optimized to maximize permeate flux.  4. In pulp and paper mills, there may be periods of accidental terpene spills, which could direct terpenes to the treatment plants for days or weeks. Therefore, it is required to investigate the impacts of turpentine shock loads on the MBR for a long-term study. Further research is also required to investigate the recovery of the biological activity following turpentine shockloads.  5. Due to foaming problems that occurred during turpentine shockload experiments, MLVSS samples were not taken. In addition, due to foaming, it was not possible to accurately control the liquid level in the MBRs. As a result, removal kinetics estimated  89  during Phase 3 (turpentine shockloads) for the main contaminants of concern did not include a stripping analysis. Therefore, for the future related research, it is highly recommended to use defoaming device in order to keep foaming under control.  6. D ue to time constraints during the present study, the periods for collecting samples during steady state conditions within each run were short (average two weeks). In order to get more representative data, more samples are required within each run. This point can be useful in the future related research.  90  References Ahn K., Cha H., Yeom I., and Song K. 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Yamaguchi M., Tanimoto Y., Minami k., Okamura K., Naritomi T., and Hake J. (1990) Thermophilic methane fermentation of evaporator condensate from kraft pulp mill, Proceedings TAPPI Environmental Conference, 631-639.  Zuncich J.L., Vora V.M. and Venkataraman B. (1973) Design considerations for seam stripping of kraft mill foul condensates, Proceedings TAPPI Environmental Conference, 201-207.  97  Appendix 1 Data Collected During Phase 1 Appendix 1 contains the data collected for the overall removal kinetics and efficiencies of methanol (MeOH), turpentine (turp), and TOC and solid concentrations for runs 1 to 5. This appendix also contains the data colleted for the biomass growth rate.  A l . l Removal Kinetics for Methanol and Turpentine The results from the investigation of the removal kinetics for selected batch feed cycles are presented in Tables A l . l to A1.21. For these tables, for runs 1, 2, 3, and 5, the parameter K corresponds to the zero order coefficient for the overall (biological + stripping) removal of methanol (mg/L- minute), as represented in Equation 5.4, and to the first order coefficient for the removal of methanol for run 4 and turpentine (/minute), as represented in Equations 5.5 and 5.7 respectively. The R values presented in these tables 2  are the coefficient of determination for 1 inear r egression (zero order equation) and the correlation index square for non-linear regression (first order equation).  Runl [RI SRT =15 days, HRT= 12 hrs, R2 the same as RI] Table A l . l MeOH and turp removal 1 st set 1 set  RI  st  R2  Table Al.2 MeOH and turp removal 2 set nd  2  set  nd  RI  R2  Time  MeOH  Turp  MeOH  Turp  Time  MeOH  Turp  MeOH  Turp  min  mg/L  mg/L  mg/L  mg/L  min  mg/L  mg/L  mg/L  mg/L  0  80  7.94112  32  5.12864  0  47  10.92  38.14  10  82  7.61024  26  4.46688  10  45  3.971  28.34  20  62  6.94848  22  3.97056  20  41.5  12  30  45  6.28672  22  3.80512  30  31.8  8  40  19  5.7904  0.1  3.80512  40  26.44  0  60  0  4.9632  0  2.97792  60  11.34  3.259  0  70  0  3.47424  0  2.4816  70  5.46  2.961  0  80  0  K  1.59  0.0107  0.67  0.00953  K  0.63  R  0.91  0.92  0.78  0.95  R  0.98  0  80  2  4.715  0  2.118  0.014  1.06  /  0.64  0.95  /  98  Table A l .3 MeOH and turp removal 3 3 set  RI  rd  Time  rd  set  R2  Table A l .4 MeOH and turp removal 4 set th  4 set  RI  th  R2  Turp  MeOH  Turp  Time  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  min  mg/L  mg/L  mg/L  mg/L  0  47.43 7.114  29.44  3.971  0  39  5.46  30.17  3.971'  10  35.11 4.798  21.22  10  34.5  3.805  15.46  3.193  20  26.76  11.4  20  24.5  3.292  12.7  2.151  30  21.26 2.978  3.143  30  14.7  3.226  5.88  2.498  5.3  MeO H  min  mg/L  3.64  40  13  2.564  40  60  0.13  1.985  60  70  2.482  70  80  80  1.936  K  0.76  0.014  0.902  0.012  K  0.87  0.017  0.75  0.008  R2  0.98  0.77  0.99  0.97  R2  0.986  0.83  0.90  0.65  Table A1.5 MeOH and turp removal 5 set 5 th set  RI  RI  Time  MeOH  Turp  MeOH  Turp  min  mg/L  mg/L  - mg/L  mg/L  0  93  9.596  10  92  20  86  6.948  30  85.2  6.75  40  72.8  60  62  K  0.54  0.012  1.052  R2  0.93  0.93  0.97  32.7 17 9.9  99  Run 2 R2only( SRT =15 days, HRT= 10 hrs) Table A1.6 MeOH and turp removal l set s l  1 set  Table A1.7 MeOH and turp removal 2  nd  R2  st  2 set  set  R2  nd  Time  MeOH  Turp  Time  MeOH  Turp  min  mg/L  mg/L  min  mg/L  mg/L  0  90.55  15.22  0  51  10  77.9  10  44.4  20  76.4  14.062  20  38  30  34.9  8.7683  30  29.2  10.092  40  19.84  8.3547  40  10.754  60  29.2  60  0  70  25.3  70  0  6.783  K  0.95  0.0163  K  0.85  0.0081  R  0.84  0.699  R  0.99  0.94  z  2  Table A1.8 MeOH and turp removal 3 set  3 set  R2  rt  Time  MeOH  Turp  min  mg/L  mg/L  0  52  10.42272  10  39.4  8.76832  20  24.1  6.28672  30  14.3  5.7904  40  12.2  60  0  70  0  K  1.04  0.014  R  0.94  0.906  2  4.46688  100  Run3 [SRT (Rl=10d,R2=10d), HRT (Rl=12hrs,R2=10hrs)] Table A 1.9 MeOH and turp removal 1 set st  1 set  RI  st  Time  R2  Table ALIO MeOH and turp removal 2 set nd  2 set  RI  nd  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  min  R2  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  45.8  5.625  59.1  Time min  0  55  10  44  20  28.7  30  21.8  40  14.4  7.61  82.4 80  2.7794  10  45  5.96  72.35  2.7463  20  40.5  5.4595  30.7  5.64  61.3  2.6636  30  36.74  5.1286  24  3.59  57.4  40  30.05  4.6323  22  3.4742  60  44.9  60  11.8  18  2.9614  70  40  2.3493  70  5.8  4.5331  48.23  3.6  2.8456  K  0.911  0.64  0.0029  K  0.61  0.0034  0.69  0.0044  R  0.974  0.98  0.98  R  0.95  0.85  0.82  0.86  2  1  Table A l . l 1 MeOH and turp removal 3rd set Table A 1.12 MeOH and turp removal 4th set 3 set  RI  ra  R2  4 set  RI  th  R2  Time  MeOH  Turp  MeOH  Turp  Time  MeOH  Turp  MeOH  Turp  min  mg/L  mg/L  mg/L  mg/L  min  mg/L  mg/L  mg/L  mg/L  0  50.96  6.6672  53.2  4.8  0  40.9  5.7904  56.53  4.3014  10  41.9  0  39.4  10  41.3  5.2941  45.9  4.2187  20  33.6  0  31.6  20  30  24  6.3198  22  40  8.34  5.8069  21.2  60  0  5.1286  19  ' 70  0  4.9797  0  K  0.89  0.0045  0.55  R  0.97  0.81  2  0.89  3.8051  4.7812  3.9209  30  20.8  40  17  22.2  60  0  20  70  0  4.682  0  3.6231  0.0047  K  0.72  0.0026  0.63  0.0025  0.86  R  0.97  0.57  0.84  0.81  3.6231  5  4.7316  23.5  3.7389  101  Run 4 [SRT (Rl=15d,R2=10d), HRT (Rl=8hrs,R2=8hrs)] Table A1.13 MeOH and turp removal first set 1 set  RI  st  R2  2  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  664  17.43  121  10  664  11.952  120  20  643  10.906  120  30  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  449  16.766  402  9  6.308  10  427  16  409  5.312  20  60  640  70  623.9  K  0.0008 0.0019 0.001 0.0033  119  5.5776  113  0.058  394.6  7.304  418.7  7.2542  14.442  404  6.142  13.446  397  8.4162  30 40  0.79  R2 MeOH  640.8 11.786  13.612  RI Turp  •  2  set  nd  MeOH  40  R  Table A1.14 MeOH and turp removal 2nd set  60 70  0.6  0.6  430  K R  2  447  0.0008 0.0028 0.0003 0.0022 0.35  0.96  0.12  0.18  Table Al.l5 MeOH and turp removal 3rd set Table A 1.16 MeOH and turp removal 4th set 3 set  RI  ra  R2  4 set  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  384  13.197  250  13.048  257  10  RI  th  R2  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  693  9.628  7.802  10  690  9.1134  20  381  244.8  6.806  20  689  30  •  239  7.47  30  674  40  385  246  7  40  666  8.3  60  353  10  230  60  656  6.972  70  366  9.5  228  70  649  8.798  K  0.001 0.0049 0.002 0.0023  K  0.001 0.0027  R  0.56  R  0.96  2  0.99  0.81  0.23  2  0.435  102  Run 5 [SRT (15d for both reactors) HRT (Rl=10hrs,R2=12hrs), repeat runs 2 and 1] Table A 1.17 MeOH and turp removal 1 set st  1 set  RI  st  R2  Table A 1.18 MeOH and turp removal 2nd set 2 set  MeOH Turp MeOH Turp Time min mg/L mg/L mg/L  mg/L  0  51.4  10  28.28  20  21.04  30  13.9  40  5.6  60 70  RI  nd  R2  MeOH Turp MeOH Turp Time min mg/L  mg/L  mg/L  mg/L  0  66.5  10.7  10  63.5  9.3  20  54.4  12.9  4.5  30  46.37  10.7  3.2  9.9  40  34.5  10.7  3.7  0  8.3  60  16.5  7.4  0  7.8  70  3.2  11.1  4.4  3.3  K  0.797 0.0045  K  0.92 0.0055  0.0045  R  0.873 0.806  R  0.98  0.532  2  Table A 1.19 MeOH and turp removal 3rd set . 5 set  RI  m  R2  2  Table A 1.20 MeOH and turp removal 4th 4 set  mg/L  mg/L  0  55.4  12.8  56.17  10  58  8.6  48.37  20  50.77  9.1  43.95  30  9.9  RI  th  MeOH Turp MeOH Turp Time min mg/L  mg/L  0.307  R2  MeOH Turp MeOH Turp Time min mg/L  mg/L  mg/L  mg/L  8.6  71.4  8.7  63.9  7.7 7.6  0  63.7  11.8  10  58  11.2  20  56.1  7.5  58.25  11  30  43.3  7.6  55.15  40  34.28 8.049  26.6  10.2  40  32  8.5  52.2  60  16.27  4.8  17.19  10.08  60  13.64  5  40  7.1  70  7  7.2  11.56  7.8  70  3.8  4.9  36  6.3  0.75 0.0094 0.64 0.0057  K  0.89 0.0085  0.96  R*  0.98  K R  2  0.63  0.99  0.802  0.733  0.48 0.0035 0.98  0.857  Table A1.21 MeOH and turp removal 5th set 3  set  rd  RI  R2  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  50.23  10.4  50.37  10  41.37  8.4  38.94  20  37.44  6.4  27.68  30  33  5.9  24.36  40  29.03  8.6  19  60  9.7  5.8  12.5  70  2.63  4.7  14.31  K  0.66  0.0086  R  0.97  0.631  2  0.49 0.86  A1.2 Removal Kinetics for T O C The results from the investigation of the removal kinetics for selected batch feed cycles are presented in Tables A1.22 to A1.40. For these tables, the parameter K corresponds to the first order coefficient for the overall (biological + stripping) removal of TOC ('minute), as represented in Equation 5.8, and to the zero order coefficient for the removal of methanol expressed as TOC (mg/L minute), as represented in Equations 5.4. The parameter Sp corresponds to the residual TOC concentration in the MBR at the end of the selected batch feed cycles (mg/L).  The R values presented in the following tables are the correlation index square for non2  linear regression (first order equation), and the coefficient of determination for linear regression (zero order equation).  The MeOH ** and TOC* presented in the following tables, are the concentrations of methanol expressed as TOC (mg/L) and TOC values accounting for the nonbiodegradation components respectively. 104  Runl [(RI SRT =15 days, HRT= 12 hrs, R2 the same as RI)] Table A1.22 TOC removal for thefirstset 1 set  Reactor RI  st  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=57  mg/L  mg/L  Sp=47  0  30  99  41.1  12  59  11.6  10  30.75  93  35.1  9.75  59  11.6  20  23.25  88  30.1  8.25  58.7  11.3  30  16.9  76.6  18.7  8.25  57  9.6  40  7.13  68.5  10.6  0.038  55  7.6  60  -  66.3  8.4  0  48  0.6  70  -  59.3  1.4  0  48  0.6  80  -  58  0.1  0  47.5  0.1  K  0.59  -  0.063  0.25  -  0.059  R  0.91  -  0.94  0.78  -  0.85  2  Table A1.23 TOC removal for the second set 2 set  Reactor RI  nd  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=75  mg/L  mg/L  Sp=50  0  17.63  97.1  21.3  14.30  83  77.1  10  16.88  91.4  15.6  10.63  83  77.1  20  15.56  90.7  14.9  4.50  71.4  65.5  30  11.93  88.4  12.6  3  69.9  64  40  9.92  83.4  7.6  0  60  4.25  76.53  0.73  0  60.5  54.6  70  2.05  76  0.2  0  80  -  K  0.237  -  0.98  -  R  2  0  51.5  0.065  0.4  -  0.065  0.86  0.95  -  0.96  Table A1.24 TOC removal for the third set 3 set  Reactor RI  rd  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=42  mg/L  mg/L  Sp=42  0  14.63  68.23  25.83  11.31  47  4.55  10  12.94  63  20.6  5.80  44.32  1.87  20  9.19  50.53  8.13  4.76  43.39  0.94  30  5.51  48.14  5.74  2.21  44.7  2.25  40  1.99  44  1.6  -  44.11  0.05  60  -  42.5  0.1  -  -  -  70  -  43.6  1.2  -  -  -  80  -  -  -  -  28.9  K  0.327  -  0.066  0.28  -  0.088  R  0.98  -  0.76  0.9  -  0.63  2  Table A 1.25 TOC removal for the fourth set 4 set  Reactor RI  th  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=30  mg/L  mg/L  Sp=23  0  17.8  73.9  42  11.04  33.6  9.8  10  13.2  60.1  28.2  7.9575  27.15  3.35  20  10.0  40.6  8.7  4.275  25  1.2  30  8.0  40  8.1  0  24.85  1.05  40  4.9  38  6.1  0  24.6  0.8  60  0.0  37  5.1  0  23.95  0.15  70  0  32  0.1  0  80  0  K  0.286  R  0.985  2  -  0  8.8  0.066  0.33  -  0.063  0.74  0.99  -  0.94  Table A1.26 TOC removal for the fifth set 5 set  Reactor RI  m  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=85  mg/L  mg/L  Sp=65  0  34.875  118  33  12.2625  78  13  10  34.5  118  33  6.375  71.25  6.25  20  32.25  112  27  3.7125  68.75  3.75  30  31.95  -  -  -  40  27.3  87.5  2.5  -  -  -  60  23.25  -  -  -  -  -  70  -  -  -  -  -  -  80  -  -  -  -  -  -  K  0.2  -  0.066  0.42  -  0.062  R  0.93  -  0.83  0.95  -  0.98  2  Run 2 [R2 only SRT =15 days, HRT= 10 hrs] Table A l .27 TOC removal for second set 2 set nd  Time min  Table A l .28 TOC removal for the third set  Reactor R2 MeOH** TOC mg/L  mg/L  3 set  Reactor R2  rd  TOC*  MeOH** TOC  Sp=58  TOC*  Time min  mg/L  mg/L  Sp=32  0  19.5  59.5  22.5  0  19.125  10  16.65  85  26.2  10  14.775  20  14.25  74  15.2  20  9.0375  57  20  30  10.95  66  7.2  30  5.3625  42  5  40  7.44  59  0.2  40  4.575  40  3  60  0  64.9  6.1  60  -  70  0  60  1.2  70  38  1  K  0.29  -  0.043  K  0.39  -  0.048  R  0.99  -  0.5755  R  0.94  -  0.91  2  2  Run 3 [ SRT(Rl=10d,R2=10d),HRT(Rl=12hrs,R2=10hrs] Table A 1.29 TOC removal for the first set  1 set  Reactor RI  st  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=58  mg/L  mg/L  Sp=49  0  20.625  -  30.9  69.1  19.6  10  16.5  79  20  10.7625  30  8.175  22.9875  54.2  4-7  40  5.4  21.525  51.4  1.9  60  0  60  2  16.8375  50.7  1.2  70  0  59.8  1.8  15  50.5  1  K  0.38  -  0.044  0.24  -  0.043  R  0.97  -  0.98  0.98  -  0.97  2  21  30 27.1313  69.9  11.9  108  Table A1.30 TOC removal for the second set 2 set  Reactor RI  nd  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=54  mg/L  mg/L  Sp=34  0  17.175  75  21  22.1625  10  16.875  18.0863  70.7  36.7  20  15.1875  69.9  15.9  11.5125  49.6  15.6  30  13.7775  63.6  9.6  9  45.4  11.4  40  11.2688  56.6  2.6  8.25  44  10  60  4.425  6.75  36.9  2.9  70  2.175  0  36.9  2.9  K  0.229  -  0.047  0.25  -  0.041  R'  0.954  -  0.73  0.82  -  0.95  Table A1.31 TOC removal for the third set 3 set  Reactor RI  rd  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=42  mg/L  mg/L  Sp=52  0  19.11  61  18.5  19.95  60  7.5  10  15.7125  14.775  58.5  6  20  12.6  11.85  54  1.5  30  9  8.25  40  3.1275  7.95  53  0.5  60  0  45  2.5  7.125  53  0.5  70  0  43  0.5  0  53  0.5  K  0.38  -  0.045  0.2  -  0.041  R  0.98  -  0.89  0.814  -  0.83  z  109  Table A1.32 TOC removal for the forth set 4 set  Reactor RI  th  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=41  mg/L  mg/L  Sp=31  0  15.3375  65  23.5  21.1988  53  21  10  15.4875  17.2125  49  17  45.5  13.5  20 30  7.8  8.8125  40  6.375  8.325  40  8  60  0  45  3.5  7.5  37  5  70  0  43  1.5  0  32.5  0.5  K  0.25  -  0.036  0.23  -  0.043  R  0.935  -  0.98  0.84  -  0.78  2  Run 4 [SRT (Rl=15d,R2=10d), HRT (Rl=8hrs,R2=8hr] Table A1.33 TOC removal for the first set 1 set  Reactor RI  st  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=262  mg/L  mg/L  Sp=90  0  249  283  21  45.375  100  10.5  10  249  20  241.125  281.22  19.22  30  240.3  279.93  17.93 92  2.5  45 45  40 60  240  264  2  44.625  91  1.5  70  233.963  266.2  4  41.25  91  1.5  K  0.186  -  0.033  0.0425  -  0.029  0.79  -  0.78  0.6  -  0.96  R  2  110  Table Al.34 TOC removal for the second set 2  set  nd  Reactor RI  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=217  mg/L  mg/L  Sp=168  0  168.375  254  37  150.75  183  14.2  10  160.125  247  30  153.375  175  6.2  20  233  16  147.975  175  6.2  30  221  4  223  6  157.013  172  3.2  149.25  169  0.2  146.25  172  3.2  40  161.25  60  227  70  167.625  K  0.128  -  0.041  0.0477  -  0.037  R  0.35  -  0.92  0.117  -  0.51  2  Table Al.35 TOC removal for the third set 3 set  Reactor RI  rd  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Time min  mg/L  mg/L  Sp=201  mg/L  mg/L  123  0  144  211  10  93.75  138  15  211  10  96.375  136  13  91.8113  138  15  89.625  130  7  92.25  132  9  86.25  128  5  10 20  142.875  30 40  144.375  202  60  132.375  178  70  137.25  202  1  85.5  124  1  K  0.13  -  0.038  0.138  -  0.032  R  0.56  -  0.83  0.806  -  0.76  2  1  Table A 1.36 TOC removal for the fourth set 4 set th  Reactor RI  Reactor R2  MeOH**  TOC  TOC*  MeOH**  TOC  Time min  mg/L  mg/L  Sp=265  mg/L  mg/L  0  259.875  287.1  21.9  10  258.75  285.65  20.45  20  258.375  282.75  17.55  30  252.75  40  249.75  278.4  13.2  60  246  274.05  8.85  70  243.375  266.8  1.6  K  0.257  -  0.030  R  0.96  -  0.72  2  TOC*  Run 5 [RI only SRT 15 days, HRT =10hrs, repeat run 2 ] nd  Table A l .37 TOC removal for the 2 set nd  2 set  Reactor RI  nd  MeOH** TOC  Table Al.38 TOC removal for the 3 set rd  3 set  Reactor RI  rd  TOC*  MeOH** TOC  TOC*  Time min  mg/L  mg/L  Sp=45  Time min  mg/L  mg/L  Sp=45  0  24.9375  61  15.5  0  18.8363  66  20.7  10  23.8125  58  12.5  10  15.5138  61  15.7  20  20.4  61  15.5  20  14.04  57  11.7  30  17.3888  59  13.5  30  12.375  53.5  8.2  40  12.9375  57  11.5  40  10.8863  51  5.7  60  6.1875  50  4.5  60  3.6375  49  3.7  70  1.2  46  0.5  70  0.98625  45.5  0.2  K  0.34  -  0.04  K  0.247  -  0.053  0.98  -  0.67  R  0.97  -  0.83  R  T  2  112  Table A l .39 TOC removal for fourth set 4 set  Reactor RI  th  MeOH** TOC  Table A1.40 TOC removal the fifth set 5 set th  TOC*  Reactor RI MeOH** TOC  TOC*  Time min  mg/L  mg/L  Sp=53  Time min  mg/L  mg/L  Sp=46  0  23.8875  80  27  0  20.775  65  18.8  10  21.75  75.5  22.5  10  21.75  57  10.8  20  21.0375  71  18  20  19.0388  63  16.8  30  16.2375  67  14  30  40  12  65  12  40  12.855  58.5  12.3  60  5.115  53.5  0.5  60  6.10125  53  6.8  70  1.425  56  3  70  2.625  46.5  0.3  K  0.33  -  0.046  K  0.282  -  0.042  R  0.98  -  0.98  R  0.964  -  0.58  2  z  A1.3 Solid Concentrations and Removal Efficiencies of Methanol, Turpentine, and TOC The concentrations of MLVSS, and methanol, turpentine, and TOC removal efficiencies measured during Phase 1 are presented in Tables A1.41 to A1.48 Run 1 [SRT =15 days, HRT = 12 hrs for both reactors] Table A 1.41 MeOH, turpentine, and TOC and solids measurements for sets 1,2, and 3 Efficiency first set  Efficiency second set  Efficiency third set  Reactor one (RI)  Reactor one (RI)  Reactor one (RI)  TOC inf mg/L  402 TOC inf mg/L  408  TOC inf mg/L  —  TOC eff mg/L  64  65  TOC eff mg/L  —  —  TOC eff mg/L  TOC efficiency %  84.08 TOC efficiency %  84.1  TOC efficiency %  MeOH ifl mg/L  728.5 MeOH ifl mg/L  708  MeOH ifl mg/L  810  0  MeOH eff mg/L  16  MeOH eff mg/L  0  MeOH eff mg/L  MeOH efficiency%  100 MeOH efficiency%  100  MeOH efficiency%  98  Turp.inf mg/L  14.2 Turp.inf mg/L  15.4  Turp.inf mg/L  18.4  Turp.eff mg/L  1.95 Turp.eff mg/L  2  Turp.eff mg/L  2.82  Turp.eff%  86.2 Turp.eff %  87.52  Turp.eff %  84.67  MLVSS mg/L  1610 MLVSS mg/L  2000  MLVSS mg/L  1650  Reactor two (R2)  Reactor two (R2)  Reactor two (R2)  TOC inf mg/L  380 TOC inf mg/L  365  TOC inf mg/L  TOC eff mg/L  80  51.5  TOC eff mg/L  85.89  TOC efficiency %  720  MeOH ifl mg/L  790  0  MeOH eff mg/L  0  100  MeOH efficiency%  100  TOC efficiency %  TOC eff mg/L  78.95 TOC efficiency %  MeOH ifl mg/L  668 MeOH ifl mg/L  MeOH eff mg/L  75  MeOH efficiency%  MeOH eff mg/L  88.77 MeOH efficiency%  Turp.inf mg/L  10.2 Turp.inf mg/L  15.66  Turp.inf mg/L  9.18  Turp.eff mg/L  1.5  2.65  Turp.eff mg/L  0.72  Turp.eff mg/L  Turp.eff %  85.2 Turp.eff %  83.08  Turp.eff %  92.16  MLVSS mg/L  2200 MLVSS mg/L  1600  MLVSS mg/L  1930  114  Tabel A1.42 MeOH, turpentine, and TOC and solids measurements for sets 4, and 5 Efficiency fourth set  E fficiencyfifthset  Reactor one (RI)  Reactor one (RI)  TOC inf mg/L  312  TOC inf mg/L  336  TOC eff mg/L  86.5  TOC eff mg/L  44  TOC efficiency %  72.28  TOC efficiency %  86.90  MeOH ifl mg/L  930  MeOH ifl mg/L  764  MeOH eff mg/L  10.1  MeOH eff mg/L  0  MeOH efficiencyVo  98.91  M eOH efficiency /" 0  100  Turp. inf mg/L  18.8  f urp.inf mg/L  18.32  Turp.eff mg/L  4.3  Turp.eff mg/L  2.92  Turp.eff%  77.13  Turp.eff %  84.53  MLVSS mg/L  1850  MLVSS mg/L  1900  Reactor two (R2)  Reactor two (R2)  TOC inf mg/L  312  TOC inf mg/L  356  TOC eff mg/L  51.2  TOC eff mg/L  36.6  TOC efficiency %  83.59  TOC efficiency %  89.72  MeOH ifl mg/L  650  MeOH ifl mg/L  745  MeOH eff mg/L  0  MeOH eff mg/L  0  MeOH efficiency%  100  MeOHefficiency%  Turp .inf mg/L  10.3  T urp.inf mg/L  12.83  Turp.eff mg/L  1.39  Turp. eff mg/L  0.61  Turp.eff %  86.5  rurp.eff%  95.25  MLVSS mg/L  1890  MLVSS mg/L  1550  100  115  Run 3, [SRT (Rl=10d,R2=10d), HRT (Rl=12hrs,R2=10hrs)] Tabel A l .43 MeOH, turpentine, and TOC and solids measurements for sets 2 and 3 Efficiency 1 set Run 3  Efficiency 2  Reactor one (RI)  Reactor one (RI)  st  nd  set Run 3  TOC inf mg/L  258  TOC inf mg/L  279  TOC eff mg/L  55  TOC eff mg/L  62  TOC efficiency %  78.68  TOC efficiency %  77.78  MeOH ifl mg/L  648  MeOH ifl mg/L  710  MeOH eff mg/L  0  MeOH eff mg/L  8.5  MeOH efficiency%  100  MeOH efficiency%  98.80  Turp.inf mg/L  22  Turp.inf mg/L  21.9  Turp.eff mg/L  4.2  Turp.eff mg/L  4.5  Turp. eff %  80.9  Turp.eff %  79.4  MLVSS mg/L  1450  MLVSS mg/L  1600  Reactor two (R2)  Reactor two (R2)  TOC inf mg/L  266  TOC inf mg/L  280  TOC eff mg/L  45  TOC eff mg/L  65  TOC efficiency %  82  TOC efficiency %  76  MeOH ifl mg/L  668  MeOH ifl mg/L  712  MeOH eff mg/L  1  MeOH eff mg/L  0  MeOH efficiency%  99.85  MeOH efficiency%  Turp.inf mg/L  20.25  Turp.inf mg/L  19.32  Turp.eff mg/L  3.5  Turp.eff mg/L  3.3  Turp.eff %  82  Turp.eff %  82.9  MLVSS mg/L  2089  MLVSS mg/L  2380  100  116  Tabel A1.44 MeOH, turpentine, and TOC and solids measurements for sets 3 and 4 Efficiency 3 set Run 3  Efficiency 4 set Run 3  Reactor one (RI)  Reactor one (RI)  rd  th  TOC inf mg/L  284  TOC inf mg/L  281  TOC eff mg/L  60  TOC eff mg/L  47  TOC efficiency %  78.87  TOC efficiency %  83.27  MeOH ifl mg/L  741  MeOH ifl mg/L  740  MeOH eff mg/L  0  MeOH eff mg/L  0  MeOH efficiency%  100  MeOH efficiency%  100  Turp.inf mg/L  17.1  Turp.inf mg/L  15.1  Turp.eff mg/L  3.2  Turp.eff mg/L  3.22  Turp.eff %  81.2  Turp.eff %  78.68  MLVSS mg/L  1220  MLVSS mg/L  1100  Reactor two (R2)  Reactor two (R2)  TOC inf mg/L  284  TOC inf mg/L  281  TOC eff mg/L  70  TOC eff mg/L  72  TOC efficiency %  75  TOC efficiency %  74  MeOH ifl mg/L  746  MeOH ifl mg/L  742  MeOH eff mg/L  0  MeOH eff mg/L  0  MeOH efficiency%  100  MeOH efficiency%  100  Turp.inf mg/L  18.48  Turp.inf mg/L  18.84  Turp.eff mg/L  8.2  Turp.eff mg/L  3  Turp.eff %  77.2  Turp.eff %  84.2  MLVSS mg/L  1815  MLVSS mg/L  1960  117  Run 4 [SRT (Rl=15d,R2=10d), HRT (Rl=8hrs,R2=8hrs)]  Table A1.45 MeOH, turpentine, and TOC and solids measurements for sets 1 and 2 Efficiency I ' set Run 4  Efficiency 2  Reactor one (RI)  Reactor one (RI)  s  nd  set Run 4  TOC inf mg/L  399  TOC inf mg/L  410  TOC eff mg/L  299  TOC eff mg/L  280  TOC efficiency %  25  TOC efficiency %  31.7  MeOH ifl mg/L  760  MeOH ifl mg/L  795  MeOH eff mg/L  500  MeOH eff mg/L  380  MeOH efficiency%  34  MeOH efficiency%  52  Turp.inf mg/L  34.4  Turp.inf mg/L  26.24  Turp.eff mg/L  Turp.eff mg/L  16.4  Turp.eff %  Turp.eff %  MLVSS mg/L  630  Reactor two (R2)  MLVSS mg/L  37 510  Reactor two (R2)  TOC inf mg/L  359  TOC inf mg/L  333  TOC eff mg/L  270  TOC eff mg/L  213  TOC efficiency %  27.7  TOC efficiency %  MeOH ifl mg/L  670  MeOH ifl mg/L  630  MeOH eff mg/L  229  MeOH eff mg/L  466  MeOH efficiency%  38  MeOH efficiency%  36  26  Turp.inf mg/L  20.2  Turp.inf mg/L  19.8  Turp.eff mg/L  14  Turp.eff mg/L  12  Turp.eff %  30  Turp.eff %  39  MLVSS mg/L  310  MLVSS mg/L  480  118  Tabel A1.46 MeOH, turpentine, and TOC and solids measurements for sets 3 and 4 Efficiency 3  rd  set Run 4  Efficiency 4 set Run 4 th  Reactor one (RI)  Reactor one (RI)  TOC inf mg/L  351  TOC inf mg/L  353  TOC eff mg/L  209  TOC eff mg/L  188  TOC efficiency %  40.4  TOC efficiency %  46.7  MeOH ifl mg/L  741  MeOH ifl mg/L  660  MeOH eff mg/L  555  MeOH eff mg/L  400  MeOH efficiency%  25  MeOH efficiency%  Turp.inf mg/L  31  Turp.inf mg/L  22.32  Turp.eff mg/L  15.1  Turp.eff mg/L  9.96  Turp.eff % MLVSS mg/L  50 310  Reactor two (R2)  Turp.eff % MLVSS mg/L  39  55 350  Reactor two (R2)  TOC inf mg/L  330  TOC inf mg/L  TOC eff mg/L  250  TOC eff mg/L  TOC efficiency %  24.2  TOC efficiency %  MeOH ifl mg/L  600  MeOH ifl mg/L  MeOH eff mg/L  360  MeOH eff mg/L  MeOH efficiencyVo  40  MeOH efficiency%  Turp.inf mg/L  16  Turp.inf mg/L  Turp.eff mg/L  9.29  Turp.eff mg/L  Turp.eff %  40.2  Turp.eff %  MLVSS mg/L  370  MLVSS mg/L  119  Run 5 [SRT (15d for both reactors), HRT (Rl=10hrs,R2=12hrs), repeat runs 1 and 2] Tabel A 1.47 MeOH, turpentine, and TOC and solids measurements for sets land 2 Efficiency 1 set Run 5 = repeat l &2 run st  st  nd  Reactor one (RI)  Efficiency 2 set Run5 =repeat l &2 run nd  nd  Reactor one (RI)  TOC inf mg/L  230 TOC inf mg/L  TOC eff mg/L  60  TOC efficiency %  st  73.9  290  TOC eff mg/L  58  TOC efficiency %  80  MeOH ifl mg/L  595 MeOH ifl mg/L  760  MeOH eff mg/L  25  40  MeOH efficiency%  MeOH eff mg/L  95.7 MeOH efficiency%  94.7  Turp.inf mg/L  27  Turp.inf mg/L  21.4  Turp.eff mg/L  4.5  Turp.eff mg/L  3  Turp.eff %  83.3 Turp.eff %  85.9  MLVSS mg/L  2850 MLVSS mg/L  2910  Reactor two (R2)  Reactor two (R2)  TOC inf mg/L  270 TOC inf mg/L  268  TOC eff mg/L  67  44  TOC efficiency % MeOH ifl mg/L MeOH eff mg/L  TOC eff mg/L TOC efficiency %  710 MeOH ifl mg/L 0  MeOH eff mg/L  708 0  MeOH efficiency%  100 MeOH efficiency%  100  Turp.inf mg/L  24  Turp.inf mg/L  21  Turp.eff mg/L  2.7  Turp.eff mg/L  2.6  Turp.eff %  88.7 Turp.eff %  MLVSS mg/L  2310 MLVSS mg/L  1750  120  Table A 1.48 MeOH, turpentine, and TOC and solids measurements for sets 3 and 4 Efficiency 3 set, Run 5 ra  &2  nd  th  =repeat 1  st  Efficiency 4 set, Run 5 m  run  m  ^repeat 1  st  & 2 run nd  Reactor one (RI)  Reactor one (RI)  TOC inf mg/L  310 TOC inf mg/L  311  TOC eff mg/L  60  TOC eff mg/L  62  TOC efficiency %  80  TOC efficiency % MeOH ifl mg/L MeOH eff mg/L  80.6  798 MeOH ifl mg/L 17  MeOH eff mg/L  MeOH efficiency%  97.8 MeOH efficiency%  Turp.inf mg/L  25.2 Turp.inf mg/L  Turp.eff mg/L  3.2  Turp.eff %  86.6 Turp.eff %  MLVSS mg/L  2200 MLVSS mg/L  Reactor two (R2) TOC inf mg/L TOC eff mg/L  0 100  Turp.eff mg/L  2093  Reactor two (R2) 265 TOC inf mg/L 70  TOC efficiency %  TOC eff mg/L  254 58  TOC efficiency %  MeOH ifl mg/L  675 MeOH ifl mg/L  MeOH eff mg/L  1.4  MeOH efficiency%  827  MeOH eff mg/L  99.2 MeOH efficiency%  Turp.inf mg/L  44  Turp.inf mg/L  Turp.eff mg/L  9.9  Turp.eff mg/L  Turp.eff %  77.5 Turp.eff %  MLVSS mg/L  1925 MLVSS mg/L  670 0 100  1670  121  A1.4 Observed Growth Yield Data Summary of the observed growth yield calculations for the combinations of SRTs and HRTs used are presented in Tables A1.49 to A1.55  Table A l .49 Observed growth yield calculations for RI (SRT 15 days, H R T = 12 hrs) Reactor volume =(1475+295)= 1770 ml  Dates  Set Cumulative CO Influent Time  mg/L  flow  Flux (ml/min)  day  filter  MeOH  MLVSS  Sludge  (mg/L.min) consumed (mg/L)  wasted  MeOH  solids  ml/d  (mg)  (mg)  m  effluent ml/hr  27-Dec-  Time of Total K  mg/cycle  Cumulative Cumulative  (min)  1  0  80  147.5  6  49.2  1.59  141.60  1610  118  0  0  2  3  47  147.5  6  49.2  0.63  82.84  2000  118  2982.229  708  2-Jan-02 3  6  39  147.5  5  59.0  0.76  69.03  1650  118  5467.309  1292.1  6-Jan-02 4  10  47.4  147.5  5  59.0  0.87  83.90  1850  118  9494.413  2165.3  8-Jan-02 5  12  93  147.5  3.9  75.6  0.54  100.35  1900  118  11902.87  2613.7  Yield  0.219586  01 30-Dec01  Table A l . 50 Observed growth yield calculations for R2 (SRT 15 days, HRT = 12 hrs) Reactor volume =(1100+220)= 1320 ml Dates  Set Cumulative CO Influent Time  mg/L  day  flow  Flux (ml/min)  Time of Total K filter  (ml  effluent  /hr)  (min)  MeOH  MLVSS  Sludge  (mg/L.min) consumed (mg/L)  wasted  MeOH  solids  (ml/d)  (mg)  (mg)  m  mg/cycle  Cumulative Cumulative  1  0  32  110  6.25  35.2  0.67  42.24  2200  88  0  0  2  3  38.1  110  6  36.7  0.63  50.34  1600  88  1805.76  422.4  2-Jan-02 3  6  29  110  4.6  47.8  0.9  38.28  1930  88  3706.56  931.92  6-Jan-02 4  10  30.2  110  2.9  75.9  0.75  39.82  1890  88  6901.506  1597.2  8-Jan-02 5  12  32.7  110  1.85  118.9  1.05  39.69  1550  88  8008.023  1870  27-Dec01 30-Dec01  Yield  0.233516  122  Table A l . 51 Observed growth yield calculations for R2 (SRT 15 days, HRT = 10 hrs) Reactor volume =(1100+275)= 1375 ml Dates  Set Cumulative CO Influent Time  mg/L  flow  Flux  Time of  (ml/min)  filter  day  Total K  m  MLVSS Sludge Cumulative Cumulative  (mg/L. min) consumed (mg/L) wasted  effluent ml/hr  MeOH  mg/cycle  MeOH  solids  (ml/d)  (mg)  (mg)  (min)  20-Jan-02  1  0  90.6  137.5  6.25  44.0  0.95  121.98  2610  91.6  0  0  26-Jan-02  2  6  51  137.5  6  45.8  0.85  70.13  2525.  91.6  5049  1387.74  l-Feb-02  3  12  52  137.5  4.6  59.8  1.04  71.50  2479  91.6  10197  2750.198  Yield  0.2697O7  Table A l . 52 Observed growth yield calculations for RI (SRT 10 days, HRT = 12 hrs) Reactor volume =(1475+295)= 1770 ml Dates  Set Cumulative CO Influent Time  mg/L  day  ll-Feb-02  flow  Flux  Time of  (ml/min)  filter  (ml  effluent  /hr)  (min)  Total K  m  MeOH  MLVSS Sludge Cumulative Cumulative  (mg/L. min) consumed (mg/L) wasted mg/cycle  MeOH  solids  (ml/d)  (mg)  (mg)  1  0  55  147.5  3.9  75.6  0.91  95.19  1450  177  0  0  14-Feb-02 2  3  45.8  147.5  3.75  78.7  0.61  78.03  1600  177  2809.061  849.6  18-Feb-02 3  7  51  147.5  2.85  103.5  0.89  84.85  1220  177  6881.74  1713.36  21-Feb-02 4  10  40.9  147.5  4  73.8  0.72  71.27  1100  177  9447.532  2297.46  Yield  0.243181  Table A l . 53 Observed growth yield calculations for R2 (SRT 10 days, HRT = 10 hrs) Reactor volume =(1100+275)= 1375 ml Dates  Set Cumulative CO Influent Time  mg/L  day  flow  Flux (ml/min)  Time of Total K,,, filter  (ml  effluent  /hr)  (min)  MeOH  MLVSS Sludge Cumulative Cumulative  (mg/L.min) consumed (mg/L) wasted mg/cycle  MeOH  solids  (ml/d)  (mg)  (mg)  ll-Feb-02  1  0  82.4  137.5  2.88  95.5  0.64  95.66  2380  137.5  0  0  14-Feb-02  2  3  59.1  137.5  2.85  96.5  0.69  75.37  2089  137.5  2713.199  861.7125  18-Feb-02  3  7  53.2  137.5  4.85  56.7  0.55  70.62  1815  137.5  6103.054  1859.963  21-Feb-02  4  10  56.5  137.5  3.5  78.6  0.63  73.54  1960  137.5  8750.661  2668.463  Yield  0.304944  123  Table A l . 54 Observed growth yield calculations for RI (SRT 15 days, HRT = 10 hrs) Reactor volume =(950+237)= 1187 ml Dates  Set Cumulative CO Influent Time  mg/L  day  flow  Flux (ml/min)  Time of Total K fdter  (ml  effluent  /hr)  (min)  6-Apr-02  1  0  10-Apr-02  2  4  66.5  118.5  2.9  81.7  15-Apr-02  3  9  55.4  118.5  5.5  18-Apr-02  4  12  63.7  118.5  20-Apr-02  5  14  50.2  118.5  ra  MeOH  MLVSS Sludge Cumulative Cumulative  (mg/L.min) consumed (mg/L) wasted mg/cycle  (ml/d)  MeOH  solids  (mg)  (mg)  0  0  0.00  2850  0.92  75.23  2850  79  3610.948  900.6  43.1  0.75  65.76  2910  79  7556.536  2050.05  3.15  75.2  0.89  72.78  2200  79  10176.77  2571.45  2.3  103.0  0.66  55.00  2093  79  11496.7  2902.144  Yield  0.252433  124  Appendix 2 Data Collected During Phase 3 Appendix 2 contains the data collected for the overall removal kinetics of methanol (MeOH), turpentine (turp), and total organic carbon (TOC) for the turpentine shock load test. Three runs of shock loads were applied to the MBR in which monoterpens concentrations spiked to the influent evaporator condensate were 300, 750 and 1500 mg/L for thefirst,second and third tests respectively. A2.1 Removal Kinetics for Methanol and Turpentine The results from the investigation of the removal kinetics for five batch feed cycles within each set are presented in Tables A2.1 to A2.15. For these tables, the parameter K corresponds to the zero order coefficient for the overall (biological + stripping) removal of methanol (mg/L minute), as represented in Equation 5.4, and to the first order coefficient for the removal of turpentine (/minute), as represented in Equations 5.7. The R  values presented in these tables are the coefficient of determination for linear  regression (zero order equation) and the correlation index square for non-linear regression (first order equation).  Table A2.1 MeOH and turp removal for  Table A2.2 MeOH and turp removal for 1  1 run, 1 batch cycle  run, 2 batch cycle  st  st  Time  Reactor RI  minute MeOH  nd  Reactor R2  Turp MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  77  35  68  41  10  69.74  29.7  59.98  20  62.5  28.74  30  51.65  40  Time minute  Reactor RI  Reactor R2  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  58.81  46.94  66.79  -  40.07  10  53.8  43.97  61.75  34.28  55.17  38.2  20  44.19  43.28  51.38  32.4  26.79  50.72  25.5  30  37.43  40.19  45.3  30.45  43.6  24.27  45.4  35  40  30.08  35.84  46.6  28.28  K  0.84  0.0084  0.54  0.0077  K  0.73  0.0063  0.56  0.0064  R  0.99  0.95  0.98  0.93  R  0.97  0.934  0.89  0.99  2  1  125  Table A2.3 MeOH and turp removal for  Table A2.4 MeOH and turp removal for 1  1 run, 3 batch cycle  run, 4 batch cycle  st  rd  Time min  Reactor RI MeOH  th  Reactor R2  Turp MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  60.73  41.9  65.53  43.513  10  56.51  41.1  58.81  35.49  20  51.45  36.29  56.78  30  42.65  33.66  47.99  40  34.51  33.55  K  0.66 0.97  R  2  Time min  Reactor RI  Reactor R2  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  44.38  42.2  68.63  10  51.84  44.88  63.22  27.3  20  43.25  39.61  60.09  26.31  34.58  30  37.12  41.79  52  25.67  43.41  31.8  40  27.8  36.98  48.54  24.61  0.0064  0.55  0.0065  K  0.47  0.0034  0.51  0.0039  0.91  0.97  0.8  R  0.709  0.53  0.98  0.99  2  Table A2.5 MeOH and turp removal for 1 run, 5 batch cycle st  th  Time min  Reactor RI MeOH  Reactor R2  Turp MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  62.41  36.3  69.178  38.85  10  40.49  36  63.16  36.07  20  57.29  35.15  55.91  37.7  30  48  35.2  51.32  40  42.2  34.2  48.73  K  0.32  0.0014 0.52  R  0.29  0.921  2  0.972  34.12 0.0028. 0.71  126  Table A2.6 MeOH and turp removal for  Table A2.7 MeOH and turp removal for 2'  2 run, 1 batch cycle  run, 2 batch cycle  na  st  Time min  Reactor RI MeOH  nd  Reactor RI  Turp MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  97.8  70.19  46.7  57.7  10  87.16  72.44  37.72  20  88.6  66.87  40  62.3  K  Time min  Reactor RI  Reactor RI  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  106  100.53  38.9  71.21  56.6  10  104.72  95.41  57.93  64.26  34.9  50.66  20  90.8  93.78  31.44  63.45  58.05  19.8  45.57  40  81.3  85.42  23.33  54.96  0.847 0.0053  0.64  0.0063  K  0.66  0.0039  0.98  0.96  R  0.93  0.98  R  0.9  2  0.85  2  0.584 0.0061 0.46  0.95  Table A2.8 MeOH and turp removal for  Table A2.9 MeOH and turp removal for 2'  2" run, 3 batch cycle  run, 4  r  Reactor RI  batch cycle  Reactor RI  Reactor  Reactor RI  RI MeOH Time  mg/L  Turp MeOH  Turp  mg/L  mg/L  mg/L  min  Time  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  min  0  104.83 101.79  39.9  79.46  0  113.7  108.09  48.79  76.72  10  123.75 96.47  44.7  46.6  10  124.6  110.27  37.8  73.42  69.7  20  104.91  103.51  41.26  69.84  21.4  60  40  101  97.1  27.73  65.64  20  97.9  95.614 33.48  40  87.8  89.88  K  0.619 0.0029  0.53  0.0038  K  0.44  0.0029  0.46  0.0039  R  0.48  0.82  0.05  R  0.52  0.85  0.83  0.98  2  0.955  2  127  Table A2.10 MeOH and turp removal for 2 run, 5 batch cycle nd  th  Reactor RI MeOH  Reactor R2  Turp MeOH  Turp  mg/L  mg/L  mg/L  0  98.98 112.67 36.17  85.3  10  86.47 109.81  36  82.44  20  92.41  111.07  33.2  80.8  40  88  108.2  20.13  78.2  K  0.19  0.0009  0.41  0.0021  R  0.34  0.73  0.88  0.96  Time  mg/L  min  2  Table A2.11 MeOH and turp removal for  Table A2.12 MeOH and turp removal for 3  3 run, 1 batch cycle  run, 2 batch cycle  rd  st  Reactor RI MeOH Time  mg/L  1  nd  Reactor R2  Turp MeOH  Turp  mg/L  mg/L  mg/L  min  Reactor RI  Time  Reactor R2  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  35.5  136.72  min  0  218  119  42  96.6  0  197.18  138  10  202  115  39.2  96.17  10  184  139  27.557 122.92  20  184.38  110  28.3  90.57  20  183.99  140  20.02 119.77  30  174.48  114  21.67  77.98  30  153.9  130  15  123.42  40  182.67  40  168  131  10.74  108.6  K  0.98  0.0058  0.76  0.007  K  0.88  0.005  0.62  0.0046  R  0.78  0.958  0.977  0.82  R  0.69  0.936  0.98  0.77  2  12.3  2  128  Table A2.13 MeOH and turp removal for  Table A2.14 MeOH and turp removal for 4'  3 run, 3 batch cycle  run, 4  rd  rd  Reactor RI MeOH Time  mg/L  th  Reactor R2  Turp MeOH  Turp  mg/L  mg/L  mg/L  min  batch cycle Reactor RI  Time  Reactor R2  MeOH  Turp  MeOH  Turp  mg/L  mg/L  mg/L  mg/L  191  53  154.1  min  0  204  154  41.13  139  0  10  185.86  153  31.23  136.26  10  190  186  49.75  157.67  20  203.69  136  39.21  135.92  20  188.75  180  38.7  143.47  30  180  135  30.05  136.15  30  183  167  45  40  182.4  141  23.35 121.149  40  182  170  39.3  K  0.49  0.0028  K  0.29  0.0019  R  0.43  0.64  R  0.91  0.97  2  0.0036 0.367 0.74  0.64  Table A2.15 MeOH and turp removal for 3 run, 5 batch cycle rd  th  Time  Reactor RI  Reactor R2  min MeOH  Turp MeOH  Turp  mg/L  mg/L  mg/L  mg/L  0  183  157  72  166.5  10  182.4  164  75.1  167.29  20  182.2  155  67.8  162.8  164  67.26  161.3  163  69.32  159.2  30 40  182.3  K  0.015 0.0007 0.132  R  0.51  2  0.77  0.41  0.0013 0.91  2  142.43  0.321 0.0024 0.65  0.661  A2.2 Removal Kinetics for T O C The results from the investigation of the removal kinetics for the five batch feed cycles within each set are presented in Tables A2.16 to A2.30. For these tables, the parameter K corresponds to the first order coefficient for the overall (biological + stripping) removal of TOC (/minute), as represented in Equation 5.8, and to the zero order coefficient for the removal of methanol-TOC (mg/L minute), as represented in Equations 5.4. The parameter Sp corresponds to the residual TOC concentration in the MBR at the end of the selected batch feed cycles (mg/L).  The R values presented in the following tables are the correlation index square for non2  linear regression (first order equation), and the coefficient of determination for linear regression (zero order equation).  The MeOH ** and TOC* presented in the following tables, are the concentrations of methanol expressed as TOC (mg/L) and TOC values accounting for the nonbiodegradation components respectively.  130  Table A2.16 TOC removal for 1 run, 1 batch cycle st  Time min  st  Reactor one RI  Reactor two R2  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=70  mg/L  mg/L  Sp=84  0  28.875  82  12  25.5  101  17  10  26.1525  73  3  22.4925  97  13  20  23.4375  72  2  20.68875  94  10  30  19.36875  71  1  19.02  90  6  40  16.35  71  1  17.025  85  1  K  0.31  -  0.063  0.21  -  0.064  R2  0.99  -  0.87  0.98  -  0.81  Table A2.17 TOC removal for 1 run, 2 batch cycle st  nd  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=72  mg/L  mg/L  Sp=83  0  22.05375  85  13  25.04625  96  13  10  20.175  82  10  23.15625  96  13  20  16.57125  81  9  19.2675  92  9  30  14.03625  75  3  16.9875  85  2  40  11.28  74  2  17.475  85  2  K  0.27  -  0.045  0.213  -  0.056  R2  0.99  -  0.80  0.89  -  0.83  Table A2.18 TOC removal for 1 run, 3 batch cycle st  rd  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=77  mg/L  mg/L  Sp=80  0  22.77375  87  10  24.57375  97  14  10  21.19125  83  6  22.05375  88  5  20  19.29375  81  4  21.2925  91  8  30  15.99375  80  3  17.99625  85  2  40  12.94125  79  2  16.27875  85  2  K  0.24  -  0.039  0.2  -  0.048  R2  0.97  -  0.99  0.97  -  0.78  Table A2.19 TOC removal for 1 run, 4 batch cycle st  Time min  th  Reactor one RI  Reactor two R2  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=71  mg/L  mg/L  Sp=82  0  16.6425  82  10.5  25.94175  93  11  10  19.44  77  5.5  23.685  92  10  20  16.21875  75  3.5  20.96625  90  8  30  13.92  75  3.5  19.245  40  10.425  74  2.5  18.27375  84  2  K  0.17  -  0.032  0.19  -  0.043  R2  0.7  -  0.89  0.97  -  0.89  132  Table A2.20 TOC removal for 1 run, 5 batch cycle st  th  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=72  mg/L  mg/L  Sp=82  0  23.40375  79  7  25.73625  89  8  10  15.18375  79  7  23.7075  89  8  20  21.48375  78  6  22.53375  87  6  30  18  76  4  19.5  85  4  40  15.825  74  2  18.2025  83  2  K  0.12  -  0.0307  0.19  -  0.034  R2  0.29  -  0.82  0.98  -  0.88  Table A2.21 TOC removal for 2 run, 1 batch cycle nd  st  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=95  mg/L  mg/L  Sp=92  0  46.365  115  20  17.5125  110  18  10  39.27  107  12  14.145  99  7  20  34.05  102  7  13.0875  95  3  40  27.19875  96  1  7.425  94  2  K  0.46  -  0.058  0.24  -  0.062  R2  0.90  -  0.97  0.98  -  0.83  133  Table A2.22 TOC removal for 2  nd  run, 2 batch cycle nd  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=101  mg/L  mg/L  Sp=86  0  36.675  115  14  14.9625  99  13  10  32.685  115  14  16.7625  95  9  20  33.225  110  9  12.555  93  7  40  23.3625  104  3  8.025  88  2  K  0.31  -  0.04  0.21  -  0.0467  R2  0.9  -  0.93  0.82  -  0.96  Table A2.23 TOC removal for 2 Time  min  nd  run, 3  rd  batch cycle  Reactor one RI  Reactor two R2  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=99  mg/L  mg/L  Sp=93  0  39.31125  121  16  14.5875  103  10  10  46.40625  112  7  21.72375  109  16  20  36.7125  116  11  11.79  101  8  40  32.925  108  3  8.74875  95  2  K  0.23  -  0.037  0.21  -  0.046  R2  0.48  -  0.73  0.456  -  0.77  134  Table A2.24 TOC removal for 2  nd  run, 4  th  batch cycle  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=115  mg/L  mg/L  Sp=96  0  42.6375  126  11  18.29625  107  11  10  46.725  128  13  14.175  105  9  20  39.34125  125  10  15.4725  102  6  40  35.83125  118  3  10.39875  98  2  K  0.21  -  0.035  0.175  -  0.043  R2  0.64  -  0.98  0.83  -  0.96  Table A2.25 TOC removal for 2 run, 5 batch cycle nd  th  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=120  mg/L  mg/L  Sp=98  0  37.1175  124  4.2  13.56375  111  12.5  10  32.42625  123  3.2  13.5  105  6.5  20  34.65375  123  3.2  12.45  105  6.5  40  29.625  121  1.2  7.54875  106  K  0.12  -  0.03  0.15  -  0.032  R2  0.72  -  0.92  0.88  -  0.75  135  Table A2.26 TOC removal for 3 run, 1 batch cycle rd  st  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=100  mg/L  mg/L  Sp=108  0  81.75  154  9.5  13.3125  132  24  10  75.75  153  5.5  10.33388  122  14  20  69.1425  136  0.5  7.5075  118  10  30  65.43  135  4.5  5.625  120  12  40  68.50125  141  9.5  4.0275  109  1  K  0.36  -  0.061  0.23  -  0.065  R2  0.78  -  0.44  0.98  -  0.7  Table A2.27 TOC removal for 3 run, 2 batch cycle rd  nd  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=125  mg/L  mg/L  Sp=93  0  73.9425  138  13  15.75  111  18  10  69  138  13  14.7  107  14  20  68.99625  140  15  10.6125  98  5  30  57.7125  130  5  8.12625  96  3  40  63  128  3  4.6125  96  3  K  0.33  -  0.042  0.28  -  0.051  R2  0.69  -  0.74  0.97  -  0.89  136  Table A2.28 TOC removal for 3 run, 3 rd  batch cycle  rd  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=130  mg/L  mg/L  Sp=94  0  76.5  119  24  15.42375  105  11  10  69.6975  115  23  11.71125  103  9  20  76.38375  110  6  14.70375  100  6  30  67.5  114  5  11.26875  97  3  40  68.4  11  8.75625  97  3  K  0.184  -  0.0309  0.137  -  0.037  R2  0.43  -  0.41  0.64  -  0.94  Table A2.29 TOC removal for 3 run, 4 rd  th  batch cycle  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=180  mg/L  mg/L  Sp=109  185  4.6  19.875  116  7  0 10  71.25  183  2.6  18.65625  116  7  20  70.78125  182  1.6  14.5125  114  5  30  68.625  182  1.6  16.875  113  4  40  68.25  182  1.6  14.7375  111  2  K  0.11  -  0.026  0.12  -  0.0307  R2  0.91  -  0.76  0.65  -  0.87  137  Table A2.30 TOC removal for 3  rd  run, 5 batch cycle th  Reactor one RI  Reactor two R2  Time min  MeOH**  TOC  TOC*  MeOH  TOC  TOC*  mg/L  mg/L  Sp=154  mg/L  mg/L  Sp=118  0  68.625  157  3  27  123  5  10  68.4  164  10  28.1625  122  4  20  68.325  155  1  25.425  121  3  164  10  25.2225  120  2  30 40  68.3625  163  9  25.995  120  2  K  0.0057  -  0.022  0.049  -  0.025  R2  0.51  -  0  0.411  -  0.94  138  Appendix 3 Data collected during Phase 4 Appendix 4 contains the data collected during the abiotic tests of methanol, monoterpenes and TOC.  A3.1 stripping kinetics for methanol and turpentine The resultsfromthe investigation of the abiotic removal of methanol and monoterpenes, using inactivated biomass and clean water tests, are presented in Tables A3.1 to A3.3. For these tables, the parameter K corresponds to the first order coefficient for the stripping of methanol and monoterpenes (/minute), as presented in Equations 5.2 and 5.5 (stripping part).  The R values, presented in the following tables, are the correlation index square for non2  linear regression.  Table A3.1 Methanol and turpentine removal in MBR (inactivated biomass test) Inactivated  RI  R2  Biomass  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  74.1  10.7  72.56  9.95  10  71.95  8.48 9.57  10 20  80.98  11.5  72.98  30  75.7  12.6  70.47  40  78.12  11.5  70.12  60  73.12  10.04  68.9  K  0.0008  0.0018  0.0009  0.00141  0.49  0.5  0.81  0.3126  R  z  9.58  139  Table A3.2 Methanol and turpentine removal in MBR (clean water test 1) Clean  RI  R2  Water  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  73.84  4.81  10  3.3.9  4.39  72.46  20  89  4.3  71.8  4.63  30  81.63  3.47  63.29  4.61  40  94.6  5.6  63.84  2.94  60  87.41  4.01  60.57  K  0.0004  0.0018  0.0008  0.0021  R  0.0273  0.41  0.33  0.79  z  Table A3.3 Methanol and turpentine removal in MBR (clean water test 2) Clean Water  RI  R2  MeOH  Turp  MeOH  Turp  Time min  mg/L  mg/L  mg/L  mg/L  0  54.98  4.54  39.42  2.57  10  61.69  3.66  33.13  2.81  20  56  4.6  34.93  2.84  30  51.55  5.29  32  3.32  40  57.5  60  56  K  0.0006  R  0.438  z  2.84 33.11  3.66  0.0012  0.0014  0.0011  0.0265  0.578  0.0069  140  A3.2 Stripping Kinetics for T O C The results from the investigation of the abiotic removal of TOC using inactivated biomass and clean water tests are presented in Tables A3.4 to A3.6. For these tables, the parameter K corresponds to the first order coefficient for the stripping of methanol expressed as TOC (/ minute), and TOC (/ minute) as presented in Equations 5.2 and 5.7 (stripping part), respectively.  The R values, presented in these tables, are the correlation index square for non-linear regression.  The MeOH ** and TOC* presented in the following tables, are the concentrations of methanol expressed as TOC (mg/L) and TOC values accounting for the nonbiodegradation components respectively.  Table A3.4 TOC removal in MBR (inactivated biomass test) Reactor one RI  Reactor two R2  Time  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  Minute  mg/L  mg/L  Sp=100  mg/L  mg/L  Sp=100  0  28.3875  168  68  27.21  106  6  147  47  26.98125  103  3  161  61  27.3675  103  3  119  19  26.42625  102  2  10 20  29.295  30 40  27.7875  113  13  26.295  60  27.42  112  12  25.8375  101  1  K  0.0008  -  0.033  0.0009  -  0.0277  R  0.49  -  0.821  0.81  -  0.942  2  141  Table A3.5 TOC removal in MBR (clean water test 1) Time Minute  Reactor one RI  Reactor two R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  mg/L  mg/L  Sp=30  mg/L  mg/L  Sp=17.5  0  20.6175  36.25  6.25  13.2  21  3.5  10  23.13375  34  4  12.42375  21  3.5  20  21  33  3  13.09875  20  2.5  30  19.33125  32  2  12.375  20  2.5  40  21.5625  32  2  19  1.5  60  21  30  0  12.41625  18  0.5  K  0.0004  -  0.0297  0.0008  -  0.032  R  0.0273  -  0.93  0.33  -  0.884  2  Table A3.6 TOC removal in MBR (clean water test 2) Time Minute  Reactor one RI  Reactor two R2  MeOH**  TOC  TOC*  MeOH**  TOC  TOC*  mg/L  mg/L  Sp=29  mg/L  mg/L  P=22.5  0  33.375  34  5  29  6.5  10  32.77875  32  3  25.6125  26  3.5  31  2  25.21875  25  2.5  30  1  . 23.73375  25  2.5  30  1  23.94  24  1.5  20 30  31.575  40 60  32.2125  30  1  24  23  0.5  K  0.0006  -  0.0282  0.0014  -  0.0392  R  0.43  -  0.79  0.578  -  0.954  2  142  

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