Open Collections

UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

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

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

Item Metadata

Download

Media
831-ubc_2003-0133.pdf [ 6.29MB ]
Metadata
JSON: 831-1.0063616.json
JSON-LD: 831-1.0063616-ld.json
RDF/XML (Pretty): 831-1.0063616-rdf.xml
RDF/JSON: 831-1.0063616-rdf.json
Turtle: 831-1.0063616-turtle.txt
N-Triples: 831-1.0063616-rdf-ntriples.txt
Original Record: 831-1.0063616-source.json
Full Text
831-1.0063616-fulltext.txt
Citation
831-1.0063616.ris

Full Text

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 TOC, 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 MBR and the operational trans-membrane pressure (TMP). Membrane fouling was mainly controlled by pore plugging resistance (Rp p) rather than concentration polarization (R c p) and membrane resistances (Rm). Rpp composed from 60 to 80 % of the total foulant resistance. 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 TABLE OF CONTENTS Ill LIST OF FIGURES VII LIST OF ABBREVIATIONS AND ACRONYM X ACKNOWLEDGEMENTS 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 THE RESEARCH 22 CHAPTER 4 EXPERIMENTAL APPARATUS AND METHODS OF ANALYSIS 24 4.1 EXPERIMENTAL APPARATUS 24 4.1.1 Membrane Biological Reactor System 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 6 4.1.1.4 Instrumentation 27 4.1.1.5 Feeding Tank 2 g VlATERIALS 2 g 4.2.1 Wastewater Feed 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 42 5.1 PHASES 1 AND 4 42 5.1.1 Methanol Removal. 42 5.1.2 Monoterpenes Removal 52 5.1.3 TOC Removal 61 5.1.4 Sludge Production 70 5.2 PHASE 2 71 5.2.1 Permeate Flux 71 5.2.2 Fouling Mechanisms 76 5.3 PHASE 3 79 IV C H A P T E R 6 C O N C L U S I O N S A N D R E C O M M E N D A T I O N S 85 6.1 C O N C L U S I O N S 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 R E F E R E N C E S 91 A P P E N D I X 1 D A T A C O L L E C T E D DURING P H A S E 1 98 A l . 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 98 A 1.2 R E M O V A L K I N E T I C S F O R T O C 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 , T U R P E N T I N E , 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 A P P E N D I X 2 D A T A C O L L E C T E D DURING P H A S E 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 A P P E N D I X 3 D A T A C O L L E C T E D DURING P H A S E 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 mi l l aerated lagoons 9 Table 2.2 Typical concentrations oi the main contaminants of concern 10 Table 4.1 Specifications and operating limits of 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 of 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 R2 during Phase 1 71 Table 6.1 Summary of 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 MBR (Membralox 1T-70) 26 Figure 4.3 Schematic of the cleaning system 36 Figure 5.1 Concentration of methanol in MBR during a typical batch feed cycle 43 Figure 5.2 Estimated contributions of methanol striping 45 Figure 5.3 Average MLVSS concentrations during Phase 1 47 Figure 5.4 Methanol specific biological utilization coefficients ( K u m ) during Phase 1 47 Figure 5.5 Influents and effluents methanol concentrations for RI and R2 48 Figure 5.6 Methanol removal efficiencies for RI and R2 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) 50 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 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) 51 Figure 5.12 Concentration of monoterpenes in MBR 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 RI (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) 72 Figure 5.33 Permeate flux with time for R2 (Phase 2, Run 2: SRT =15 d, HRT= 10 hrs, M L V S S =2670 mg/L) 72 Figure 5.34 Permeate flux with time for R2 (Phase 2, Run 3: SRT =10 d, HRT= 10 hrs, M L V S S =2060 mg/L) 73 Figure 5.35 Permeate flux with time for R2 (Phase 2, Run 4: SRT =10 d, HRT= 8 hrs, M L V S S =380 mg/L) 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 RI (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 of serial resistances with time for R I 77 Figure 5.40 Variation of serial resistances with time for R2 77 Figure 5.41 Percentages of R m , R p p , and R c p o f the total resistance with time for R I 78 Figure 5.42 Percentages of R m , R p p , and R c P o f the total resistance with time for R2 78 Figure 5.43 Variation of overall methanol removal rates with the sequence o f spiked batch feed cycles for R I during Phase 3 (SRT =15 days, HRT=10 hours) 82 Figure 5.44 Variation of overall methanol removal rates with the sequence o f spiked batch feed cycles for R2 during Phase 3 (SRT =15 days, HRT=12 hours) 82 Figure 5.45 Variation of monoterpenes overall removal rates with the sequence o f spiked 83 batch feed cycles for R I during Phase 3 (SRT =15 days, HRT=10 hours) 83 Figure 5.46 Variation o f monoterpenes overall removal rates with the sequence o f spiked batch feed cycles for R2 during Phase 3 (SRT =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 (SRT =15 days, HRT=10 hours) 84 Figure 5.48 Variation of overall T O C removal rates with the sequence o f spiked batch 84 feed cycles for R2 during Phase 3 (SRT =15 days, HRT=12 hours) 84 i x List of Abbreviations and Acronym u Dynamic Viscosity (N.sec/m2) AP Trans-membrane pressure (N/m2) ASB Aerated stabilization basin AST Activated sludge treatment ATP Adenosine triphosphate BCTMP Bleached chemi-thermomechanical pulp BOD Biochemical oxygen demand (mg/L) CFV Cross flow velocity 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 (m3/m2-sec) Ji Pure water flux for the cleaned membrane (m3/m2-sec) Jv Flux with real evaporator condensate (m3/m2-sec) Kbio.t First order coefficient for biological removal of monoterpenes (/minute) Kbio.TOC First order coefficient for biological removal of TOC (/minute) Zero order coefficient for methanol removal (mg/L minute) K m i First order coefficient for methanol removal (/minute) K-s.turp Half saturation concentration for monoterpenes (mg/L) K s MeOH Half saturation concentration for methanol (mg/L) Kstrip.Me First order coefficient for stripping of methanol (/minute) 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) S F M 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 Mot ivat ion of 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 of 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 of 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 of 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 permeate flux were 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 wood fibre is 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 originates from the 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 (Adapted from Tai, 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 R E L I E F g TUHREtLTJtl! Figure 1.2 Typical turpentine recovery systems (Adapted from Smook, 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 odour-contributing 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 vary from almost 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 foul fraction of 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 foul fraction of 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 digester vent condensate Batch digester blow condensate Continuous digester condensate Evaporator multiple condensate Evaporator condenser condensate Stripper feed Methanol mg/L 1300-12000 250-9100 670-8900 180-700 180-1200 140-10000 Terpenes mg/L 0.1-5500 0.1-1100 100-25000 0.1-150 0.1-620 1-9600 TOC (mg/L as BOD) 800-11500 720-9200 1950-8800. 60-1100 450-2500 800-13000 Suspended solids mg/L 30-70 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/m3*day) could 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/ m3*day achieved COD and methanol removal efficiencies of 85 and 99 % 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 / m3*day (Carpenter and Berger, 1984). Another study 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/ m3-day 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/m3*day by increasing the influent TOC concentrations from 800 to 2500 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 Al-Sharekh, 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 and from 73.6 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 alpha-terpineol), 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 biomass from the 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 membrane filtration combined 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 (Rm), pore plugging (Rpp), and concentration polarization (Rc P ) . Each one could be c orrelated w ith flux d ecline. F lux d ecline c aused b y R m is usually governed by the membrane material and solute interactions. R p P is determined by the relative sizes of the solutes and pores as well as the operating conditions. R c P is the formation of a 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 shear-induced lift, the diffusivity increases with increasing particle size (above 10 pm) (Wiesner and Chellam, 1992). Therefore, membranes are most susceptible to fouling by particles of 0.01-10 pm in size since the influence of both diffusive forces is small (Ramamurthy et al, 1995). Membrane resistances (Rpp and R c P ) are affected by operating conditions, namely the 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 2 1 p ( R m + R p p + R c p ) where: AP is the trans-membrane pressure (N/m2) , u is the dynamic viscosity (Nsec/m2), R m , R p p ,andR c p are membrane resistances (/m), and J v is the membrane flux (m3/m2- sec). Serial resistances due to multiple fouling mechanisms are correlated with flux loss under specified operating parameters (TMP, CFV 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 (Jv) is the flux with the real evaporator condensate. From Equation 2.1, the equations used to estimate each individual resistance are as follows: R m from Equation 2.1 (pure water permeability for R m only) Ji R P p = ( T — i ) R m 2.3 J f Rep =(j— l)R m- Rpp ; ; 2.4 Then each resistance is often expressed as a function of the total resistance (Rt) as follows: %R m =^ xlOO, %R p p =^LxlOO, %R c p =--3Lxl00 2.5 K t R t R 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 / J j and J v / J i 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 i I 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 membrane fouling encountered in the previous studies that dealt with evaporator J-J 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 m2. Other specifications and operating limits of the membrane module as provided by the manufacturer are given in Table 4.1. Figure 4.2 illustrates this unit and its accessories. |Solenoid valve Ultrafiltration Membrane t Treated effluent Recycling pump Temperature controller Heating coil Feeding tank Condensate feed pump Solenoid valve Nutrient feed pump Float T switcRTZT" 0 pH Probe Diffuser Reactor Heating plate Time controller I I pH controller NaOH feed Air 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 ceramic filter Tl-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 m2 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 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 re-heated 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 mixture from five condensers (personal communication, Taylor, J., Western Pulp Limited Partnership, Squamish, B.C, Canada). At the Western Pulp Limited Partnership mill, the evaporator condensate from the 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 non-limiting 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 i i Table 4.3 Characteristics of nutrient solution Nutrients Approximate nutrient concentration per litre of i » evaporator condensate (mg/L) NH4NO3 200 i i KH 2 P0 4 150*(300) Tl MgS04.7H20 25 1 k CaCl2.7H20 70 n i i FeCl3.6H20 20 * Due to precipitation of K H 2 P 0 4 , the dosage was doubled. 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 * with the precipitate, the amount of K H 2 P 0 4 added to the nutrient solution was doubled. • i . t 7 4.2.3 Biomass 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 from a pilot scale activated sludge system treating municipal wastewater (UBC Civil r 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 Acclimatization Sampling Reactor 1 (RI) Reactor 2 (R2) Other number Dates Dates SRT (days) HRT (hours) SRT (days) HRT (hours) 1 25-Nov-Ol To 27-Dec-01 27-Dec-01 To 8-Jan-02 15 12 15 12 2 9-Jan-02 To 20-Jan-02 20-Jan-02 To l-Feb-02 '15 '10 15 10 1 2 3 2-Feb-02 To ll-Feb-02 ll-Feb-02 To 2l-Feb-02 10 12 10 10 4 22-Feb-02 To 06-Mar-02 6-Mar-02 To 18-Mar-02 15 8 10 8 5 19-Mar-02 To 06-Apr-02 6-Apr-02 To 20-Apr-02 15 10 15 12 TMP was as presented in Table 4.5 23 1 - 25-Apr-02 15 10 15 12 JS= 300 mg/L 2 - 30-Apr-02 15 10 15 12 'S=750 mg/L 3 - 2-May-02 15 10 15 12 'S=1500mg/L 4 1 5-May-02 15 10 10 12 inactivated biomass test I T , , , 2 & 3 5-May-02 clean water test RI failed during Phasel, Run 2 as indicated in Section 4.3.2 2Foaming problems occurred during Phase 3 3S 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 membrane from the 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 require filtration before analysis. For each batch cycle selected, 15 mL samples were collected in fired glass 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 sampled from the 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 monoterpenes from the 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 106 mm Hg 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: d C M e O H = K u m ( CJ^OH ) X 5 1 d t CM e O H+ K S M e O H where — [ s the rate of biological removal of methanol (mg/L' minute), C M e O H dt is the concentration of methanol in the MBR (mg/L), K s M e O H is the half saturation concentration for methanol uptake (mg/L), K u m i s the specific methanol utilization 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 a first order relationship as presented in Equation 5.2 (Berube, 2000): dC MeOH dt ~ K strip Me C MeOH .5.2 where K s t r i p M e 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 M e O H + K S MeOH •)X + ^ s t r i p M e • ^"MeOH .5.3 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. cn E c o —. TO —' C CD O c o O o c CD J= "5 80 70 • overall test A abiotic test - • 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 apart from Run 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 significant fraction of 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. The first order 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 44 100 Run 1 Run 2&5 Run 4 nol 90 -ca .c c: 80 -o5 CL Q . 70 -X I -w CO 60 ima o •o 50 -H—» 40 -LU o x> 30 -0 TO < 20 -CO c val 10 -0) o o E 0 -0) a> 0_ or Run 3 Run 3 Run 4 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 5.2 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 - K u m X ~ K m 0 ' .5.4 where K m 0 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 (Ku m), for the combinations of the operational 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 (Km 0) observed during Phase 1, Runs 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 decreased from approximately 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 3 0 0 0 • 2 5 0 0 -D) E 2 0 0 0 -CO CO > 1 5 0 0 -1 0 0 0 -5 0 0 -0 -JEuinJL BunJ2&5_ -RunA. JRiinJL JRunJL JBuoA. r 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) 1.2 c o CO N 5^  CO X I o 0) Q. CO 0 . 8 0 . 6 + 0 . 4 0 . 2 -RunJ_ Run R u n 3 -RunJL S R T = 1 5 d H R T = 1 2 h r S R T = 1 5 d H R T = 1 0 h r S R T = 1 0 d H R T = 1 2 h r S R T = 1 0 d 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 E c o i _ -*—' <v o c o O o ro —^• 1000 900 800 700 600 500 400 300 1 200 100 0 27-Dec-01 30-Dec-01 2-Jan-02 Dates 5-Jan-02 8-Jan-02 Figure 5.5 Influents and effluents methanol concentrations for RI and R2 (Phase 1, Run 1: SRT=15 days, HRT=12 hours) -± -R1 - « - R 2 27-Dec-01 30-Dec-01 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 •Effluent • Efficiency _ l 1000 j 13) 900 -E c o 800 -ro 700 -c 600 a 0) 500 j ( o c o O 400 -o 300 -c TO 200 --C 0> 100 -2 0 ¥ 6-Apr-02 10-Apr-02 15-Apr-02 Dates 20-Apr-02 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) CD -A—Influent •Effluent • Efficiency 0 6-Mar-02 0 10-Mar-02 15-Mar-02 Dates 18-Mar-02 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 E c o CO c Q) O c o O o c ro J : 1000 100 99.8 4- 99.6 99.4 99.2 99 98.8 98.6 + 98.4 98.2 11-Feb-02 14-Feb-02 18-Feb-02 Dates 21-Feb-02 >> o c 0) o i t Ul ro > o • E ' 0 tr ~o tz ro sz a) 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) =d 1000 i 900 •Influent •Effluent •Efficiency 11-Feb-02 14-Feb-02 18-Feb-02 Dates 21-Feb-02 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 •Efficiency E c o o c o O o c CO 1000 100 ^ 6-Mar-02 10-Mar-02 Dates 15-Mar-02 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 a first order relationship as follows: dC MeOH dt ~ K m l ' C M e 0 H .5.5 where: K m l is the first order 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 by fitting Equation 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 m l ) for Phase 1, Run 4 are presented in Table 5.1. Table 5.1 Methanol removal coefficients during Phase 1 SRT (day) I W T T T I r 15 15 15 10 10 10 HR  (hours) 12 10 12 10 KmO (mg/L- minute) 0.88 ±0.175 0.86 ± 0.0945 0.783 ±0.169 0.627 ± 0.068 Kml (/minute) 0.0009 ±0.00013 0.00082 ±0.00022 1 K m 0 is the zero order coefficient for the biological removal of methanol (mg/L' minute) 2 K m l is the first order 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 c t u r P —V f t^urp w , v n Ht ^ " t V " —— -i-J^ strip.turp • t^urp 5.6 U l Murp+JS^turp 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 the rate of removal of monoterpenes (mg/L* minute), K . is the specific dt monoterpenes biological utilization coefficient (/minute), Ks^^ is the half saturation concentration for monoterpenes uptake (mg/L), K s t r i ^ is the first order 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 t u i p ) . 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 ~ ~ (Kbio.t + K s t r i P . t ) - C , u r p = K t o t , . C t u r p 5.7 where: K b i o t is the first order coefficient for the biological removal of monoterpenes (/minute), K t o t t is the first order coefficient for the total removal of monoterpenes (/minute). Equation 5.7 was fitted to the concentrations of monoterpenes measured with time in the MBRs during Phase 1. The estimates of the first order 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 by fitting the 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 ranged from 16 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 and from 0.006 ± 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 decreased from 15 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 c? o '5. c a. o c 100 90 80 -70 60 T> O <U ~ LU £ <1) CO D) > CO o c E d) CD (j or <D 0_ W 50 40 30 20 10 0 Run 1 Run 2&5 Run 4 Run 3 Run 3 Run 4 • I ISSlV H R ^ SHS=l5hd S R T = 1 ° d S R T = 1 ° « SRT=10d hr h r R T = 8 h r H R T = 1 2 H R T = 1 0 HRT=8 hr h r hr 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 1 fluctuated between 10 and 30 mg/L. Although the evaporator condensate was always collected from the 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 (d-limonene 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 decreased from 10 to 8 hours for both SRTs 56 0 . 0 1 2 Run 1 Run 2&5 Run 4 Run 3 Run 3 Run 4 c o r o M >> CO w d CL -*-> <D C O .«> c o s i o 0) Q L C O 0 . 0 1 + 0 . 0 0 8 0 . 0 0 6 -0 . 0 0 4 -0 . 0 0 2 S R T = 1 5 d S R T = 1 5 d S R T = 1 5 d S R T = 1 0 d S R T = 1 0 d S R T = 1 0 d H R T = 1 2 h r H R T = 1 0 h r H R T = 8 h r H R T = 1 2 hr H R T = 1 0 h r H R T = 8 h r Figure 5.14 Monoterpene specific biological utilization coefficients (Kut) during Phase 1 (error bars represent 90 % confidence interval for measurement) —A—R1 i n f l u e n t -m- R 2 i n f l u e n t - + - R 1 e f f l u e n t R 2 e f f l u e n t e 3 0 - , o 2 25 c: 2 7 - D e c - 0 1 3 0 - D e c - 0 1 2 - J a n - 0 2 6 - J a n - 0 2 8 - J a n - 0 2 D a t e s 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 Dates 6-Jan-02 8-Jan-02 Figure 5.16 Monoterpenes removal efficiencies for RI and R2 (Phase 1, Run 1: SRT= 15 days, HRT=12hours) 30 M | 2 5 a> E | . i 2 0 8 c o O c o 10 -Influent •Effluent • Efficiency 0 6-Apr-02 9-Apr-02 12-Apr-02 15-Apr-02 18-Apr-02 Dates 100 90 80 + 70 60 50 40 30 + 20 10 0 ro > O v P E ^ or g o .3> c o ro i E •B UJ 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 -* -Ef f luent - • - 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 • Effluent •Efficiency e o r o c a) o tz o O w cu c <D CL i— a> o 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 •Effluent •Efficiency 6-Mar-02 9-Mar-02 12-Mar-02 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 adapted from Berube (2000) as follows: dS d t - K t o t . T O c ( S - S N ' ) - K u T 0 C X ( S - S N ) + K s t r i p T 0 C (S-Snv) 5.8 dS where: — is the rate of removal of TOC (mg/L-minute), K u T O C is the first order dt biological TOC specific utilization coefficient (/mg/L.day), X is MLVSS concentration (mg/L), S is the concentration of the multi-component substrate (mg/L as TOC), S N is the non-biodegradable component of the multi-component substrate (mg/L as TOC), S N 1 is non-volatile, non-biodegradable component of the TOC (mg/L), K s t r i p T Q C 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 non-biodegradable TOC component are presented in Tables A1.22 To A1.40. First and zero order overall removal coefficients for TOC and methanol-TOC, respectively (Ktot.Toc and Kmo) are presented in Table 5.2. 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 E c o 80 T 70 60 ro 50 c <u o c o O O O 40 30 4 20 10 A • abiotic test A overall test • MeOH as TOC A - -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 removed from the 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. The first order coefficient for the biological TOC removal was estimated by subtracting the first order stripping ro > o E O c n O c t- CL TJ .9-<D tt ro w •I ^  "(?J TJ o J cn tt ro < -*-» c Q) CD Q . 100 90 80 70 60 50 40 30 20 10 0 Run 1 Run 2&5 Run 4 1 Run 3 Run 3 Run 4 1 11 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 HRT from 10 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 (Ktot.Toc and io-TOc) and zero order for methanol-TOC (Kmo ) during Phase 1 SRT HRT Ktot.TOC KbioTOC KmO (day) (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 lowered from 10 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 ro N 0.035 0.03 0.025 a 0.02 Run 1 Run 2&5 Run 4 5 ^0 .015 4-o D . co o.oi 4-0.005 0 Run 3 Run 3 Run 4 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 h r hr hr hr 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 Dates 5-Jan-02 8-Jan-02 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 - R 1 - » - R 2 27-Dec-01 30-Dec-01 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 §400 03 £300 §200 o O o Q 100 100 80 60 40 20 0 6-Apr-02 9-Apr-02 12-Apr-02 15-Apr-02 18-Apr-02 Dates >, o c <u 'o se UJ "CO v P > tf-o 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 -A— I n f l u e n t •Effluent •Efficiency ch 450 -E 400 * c - -o 350 - w — (1 2 300 - A --£ 250 < E J k £ 200 -O 150 • O 100 -O c n , , • • II 0 -1 1 100 90 80 70 60 50 20 10 11-Feb-02 14-Feb-02 17-Feb-02 Dates 20-Feb-02 o c a) o it UJ ro > o E 0) a: o O r-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 —•—Effluent —•—Efficiency 6-Mar-02 9-Mar-02 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 (Y0bS) is particularly useful to determine the ratio of the mass 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: Mass of VSS formed during a run Yobs = - 5.9 Mass of methanol consumed during a run 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 5 (Metcalf and Eddy, 1991). The differences in the observed growth yield values obtained in the present study from those 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 R2 — — . . — ' 3 10 10 0.304 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 96 144 192 240 288 336 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 Time hours 240 288 336 Figure 5.36 Permeate flux with time for RI (Phase 2, Run 5: SRT =15 d, HRT= 10 hrs, MLVSS =2500 mg/L) 48 96 Time hours 144 192 Figure 5.37 Permeate flux with time for RI (Phase 2, Run 4: SRT =15 d, HRT= 8 hrs, MLVSS =450 mg/L) 74 1.2 tz 0.2 A 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 less frequently when 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/m2'minute 75 and 270 to 315 mg/m2-minute for R2 and RI, respectively) that affected the fouling of the 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 P) resistances with time during Phase 2, Run 5 for RI and R2 respectively. During Phase 2, Run 5, Figures 5.39 and 5.40 show that the filtration resistance was mainly attributed to R p p rather than to Rc P or R m for both membranes investigated. The contributions of R p p 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, RpP and R<;p ranged from 39 x 1012 to 52 x 1012 /m and 4.8 x 1012 to 8.11 x 1012 /m respectively. While, for R2 in which the TMP and MLVSS concentration were 66 kPa (10 psi) and 1820 mg/L, respectively, RpP and R^ ranged from 9 x 1012 to 22.7 x 1012 An and 1.45 x 1012 to 2.86 x 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) - • - R m -4—Rpp - » - R c p 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_ 50 100 150 200 250 300 350 400 Time hours TMP= 30 psi Figure 5.41 Percentages of R m , Rp p, and Rc P of the total resistance with time for R I (Phase 1, Run 5: SRT= 15 days, HRT=10 hours, MLVSS concentration = 2500 mg/L) 0) o c ro S2 'OT <D CC "ro o OJ O ) •JS c 0) £ Q. 100 90 80 70 60 -{ 50 40 -I 30 20 10 0 0 •Rm •Rpp •Rep 100 150 200 Time hours 250 300 350 TMP = 10 psi Figure 5.42 Percentages of Rm, RpP, and R^of the total resistance with time for R2 (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 the five-spiked batch feed cycles of each Run within Phase 3. Results from non-linear regression analysis for the first order 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 the five-spiked batch 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 a first order 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 non-biodegradable 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) 1.05 -, c E 0.9 1 E 0.75 -' c (D 0.6 -o SE <D 0.45 -O o 0.3 t_ <D "D i _ O 0.15 -o a> 0 -N •1st Run -2nd Run —•—3rd Run 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) 0.009 0.008 -: 0.007 0.006 0.005 c o i t 0 0.004 | 0.003 6 0.002 -I 1 0.001 LL 0 0 1 st Run -4— 2 nd Run - • - 3rd Run 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) cu 0.009 .1 0.008 |j 0.007 § 0.006 H 0.005 c3 0.004 -0.003 -1 3 0.002 -o -4-> 0.001 0 •1st Run —4—2 nd Run • 3rd Run 1 2 3 4 5 6 Order of batch feed cycle 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 a> 0.075 c E 0.06 A a D 0.045 i t o O 0.03 •p O 0.015 ] •1st Run •2 nd Run • 3rd Run 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) 0.075 cu | 0.06 c 0) 'o it o O 0.045 ^ 0.03 -i CD •E O ii. r 0.015 i •1st Run •2 nd Run -3rd Run 1 2 3 4 Order of batch feed cycle —r— 5 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 drawn from the 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 than from lowering the operational HRT. 85 Table 6.1 Summary of the results obtained in the present study and the previous studies Study Overall removal efficiency (%) Specific biological utilization coefficient (/day for methanol and TOC for Berube (2000) study, and /mg/L.day for monoterpenes and TOC for present study Methanol 'Turp TOC Methanol 'Turp TOC Present HRT=12 hrs 98 86.2 83 0.70±0.17 0.0083±0.0015 0.027±0.0035 study HRT=10 hrs 98 85.3 78 0.49±0.05 0.006±0.0011 0.0078±0.002 SRT=15 days HRT=8 hrs 38 47.3 35.85 2 0.0048±0.0022 0.009±0.0021 Present study HRT=12 hrs 97.5 81.5 79.4 0,83±0.17 0.0025±0.0013 0.0186±0.014 HRT=10 hrs 97 80 76.75 0.43±0.04 0.00193±0.0007 0.007±0.002 SRT=10 days HRT=8 hrs 34 34.9 28.3 2 0.00384±0.0025 0.0076±0.001 Berube (2000) SRT=20days HRT=12 hrs 99 93 0.59±01 0.66±0.05 Jen (2002) SRT=38 days HRT=9hrs 95 64 1.03±0.13 to 1.47±0.15 0.51±0.072 to 0.74±0.06 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 the first shockload 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 part from the 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. (1998) Application of nanofiltration for recycling of paper regeneration wastewater and characterization of filtration resistance, Desalination, 119, 169-176. Alvarez F. R., and Shaul M. (1999) Fate of terpene compounds in activated sludge wastewater treatment systems, Journal of Air and Waste Management Association, 49, 734-739. American Public Health Association (APHA), American Water Works Association (A WW A) and Water Environment Federation (WEF) (1995) Standard Methods for the Examination of Wastewater, 19th edition, Washington, USA. Barton D.A., Matthews K.O., Hickman G.T., and Tielbaard M.H. (1998) Stand-alone biological treatment of kraft mill condensate-pilot plant studies, Proceedings TAPPI International Environmental Conference, 521-537. Ben Aim R. (1999) Membrane bioreactors with submerged hollow fibre from lab scale wastewater treatment plants, Presented at IAWQ Symposium on Membrane Technology in Environmental Management, Tokyo, Japan. Berube P. (2000) High Temperature Biological Treatment of Foul Evaporator Condensate for Reuse, Ph.D. Thesis, Department of Civil Engineering, University of British Columbia, Vancouver, Canada. Blackwell B.R., MacKay W.B., Murray F.E., and Oldham W.K. (1979) Review of kraft foul condensates, TAPPI Journal, 62 (10), 33-37. 91 Bohman B., Heyman M. Ek. W., and Frostell B. (1991) Membrane filtration combined with biological treatment for purification of bleach plant effluents, Water S cience a nd Technology, 24 (3/4), 219-228. Carpenter W.L, and Berger H.F. (1984) A laboratory investigation of the applicability of anaerobic treatment to selected pulp mill effluents, P roceedings T APPIE nvironmental Conference, 173-178. Cook W.H., Farmer F.A., Kristiansen O.E., Reid K., Reid J., and Rowbottom R. (1973) The effect of pulp and paper mill effluents on the taste and odour of the receiving water and the fish therein, Pulp and Paper Magazine of Canada, Convention Issue, 97-106. Dal-Cin M.M., McLellan F., Striez C.N., Tarn C M . , Tweddle T.A., and Kumar A. (1996) Membrane performance with a pulp mill effluent: relative contributions of fouling mechanisms, Journal of Membrane Science 120, 273-285. Dorica J. (1986) Ultrafiltration of bleach plant effluents-a bleach plant study, Journal of Pulp and Paper Science, 12 (6), 172-177. Dufrense R., Lavallee H. C , Lebrun R. E., and Lo S. N. (1996) Comparison of performances between membrane bioreactor and activated sludge system for the treatment of pulping process wastewaters, Proceedings TAPPI International Environmental Conference, 1, 323-330. Fan X.J., Urbain Y., and Manem J. (2000) Ultrafiltration of activated sludge with ceramic membranes in a cross-flow membrane bioreactor process, Water Science and Technology, 41 (10-11), 234-250. Hough G.W. and Sallee R.W. (1977) Treatment of contaminated condensates, TAPPI Journal, 60 (2), 83-86. 92 Hamoda M. F., and Al-Sharekh H. A. (1999) Sugar wastewater treatment with aerated fixed-film biological systems, Water Science and Technology, 40, 313-321. Jen R. (2002) High Temperature Membrane Bioreactor Treating Kraft Evaporator Condensate Under Steady and Transient Conditions, M.A.Sc. Thesis, Department of Civil Engineering, University of British Columbia, Vancouver, Canada. Jurgensen S.L., Benjamin M.N., and Ferguson J.F. (1985) Treatability of thermomechanical pulping process effluents with anaerobic biological reactors, Presented at the TAPPI Environmental Conference, Mobile, Al, USA, 83-92. Johnson R. (1994) Miller and Freunds Probability and Statistics for Engineers, 5th edition, Prentice Hall Publications, USA. Lu S.G., Imai M., Ukita M., Sekine M., Fukagawa M., and Nakanishi H. (2000) The performance of fermentation wastewater treatment in ultrafiltration membrane bioreactor by continuous and intermittent aeration processes, Water Science and Technology, 42 (3-4), 323-329. Lubbecke S., Vogelpohl A., and Dewjanin W. (1995) Wastewater treatment in a biological high-performance system with high biomass concentration, Water Research, 29 (3), 793-802 Magara Y., and Itoh M. (1991) The effects of operational factors on solid/liquid separation by ultramembrane filtration in a biological denitrification system for collected human excreta treatment plants, Water Science and Technology, 23, 1883-1590. Manttari M., Nuortila-Jokkinen J., Nystorm M. (1997) Influence of filtration conditions on the performance of nanofiltration membranes in the filtration of paper mill total effluent, Journal of Membrane Science, 137,187-199. 93 Metcalf and Eddy (1991) Wastewater Engineering: Treatment, Disposal, and Reuse, 3rd edition, McGraw-Hill Publications, NY, USA. Misra G., Pavlostathis S.G., Perdue E. M., and Araujo R. (1996) Aerobic biodegradation of selected monoterpenes, Applied Microbiology and Biotechnology, 45, 831-838 Nagaoka H., Ueda S., and Miya A. (1996) Influence of bacterial extracellular polymers on the membrane separation activated sludge process, Water Science Technology, 34 (9), 165-172. Orr P., Mooney B., Owen M., and Yazer M. (1997) Effect of chemical spills on treatment system microorganisms, Proceedings TAPPI Environmental Conference and Exhibit, Minneapolis, USA, 2, 709-715. Paul G.S., Martha W., Dolones S. (1968) The Merck Index: An Encyclopaedia of Chemicals and Drugs, 8th edition, Merck & Co inc. Publication, New Jersey, USA. Pekkanen M., Kiiskila E. (1996) Options to close the water cycle of pulp and paper mills using evaporation and condensate reuse, Proceedings TAPPI Minimum Effluent Mills Symposium, 229-243. Pinder A. R. (1960) Chemistry of the Terpenes, 2nd edition, London Chapman & Hall Publications, London, England. Ragona C , and Hall E.R (1998) Parallel operation of ultrafiltration and aerobic membranes bioreactor treatment systems for mechanical newsprint mill Whitewater at 55 °C, Water Science and Technology, 38 (4-5), 307-314. Ramamurthy P., P oole R., a nd D orica J. G. (1995) F ouling o f u ltrafiltration m embrane during treatment of CTMP screw press filtrates, Journal of Pulp and Paper Science, 21 (2), 50-54. 94 Ronnholm A.A.R. (1974) Steam stripping removes BOD compounds from condensates of continuous pulp mill, Pulp and Paper International, February 1974, 45-49. Sarlin T., Halttunen S., Vuoriranta P., and Puhakka J. (1999) Effects of chemical spills on activated sludge treatment performance of pulp and paper mills, Water Science and Technology, 40 (11), 319-325. Schwartz S.M., Boethling R.S., and Leighton T. (1990) Fate of terpenes anethole and dipentene in a bench scale activated sludge system, Chemosphere, 21 (10-11), 1153-1160. Sebbas E. (1987) Reuse of kraft mil secondary condensates, TAPPI Journal, 70 (7), 53-58. Shimizu Y., Shimodera K., and Watanabe A. (1993) Cross flow microfiltration of bacterial cells, Journal of Fermentation and Bioengineering, 76 (6), 493-500. Smook G.A. (1992) Handbook for Pulp and Paper Technologists, 2nd edition, Angus Wild Publications, Vancouver, Canada. Tai J. Y. W. (1994) High Temperature Biological Treatment of Kraft Pulping Effluent, M.A.Sc. Thesis, Department Chemical and Biological Engineering, University of British Columbia, Vancouver, Canada. Tardieu E., Grasmick A., Geaugey V., and Manem J. (1996) Fouling mechanisms in membrane bioreactors applied to wastewater treatment, Proceedings of the 7th World Filtration Congress, Budapest, Hungary. Tardif O. (1996) Aerobic Membrane Biological Reactor Treatment of Recirculated Mechanical Newsprint Whitewater at High Temperatures. M.AS.c. Thesis, Department of Civil Engineering, University of British Columbia, Vancouver, B.C., Canada. 95 Templeton W. (1969) An Introduction to the Chemistry of the Terpenoids and Steroids, 3rd edition, London Butterworths Publications, London, England. Towers M.T., and Wearing J.T. (1994) Closed Cycle Design in Technology and Environmental Enhancement Pulp and Paper Mills, Technology Development and Programs Resource Processing Industries Branch, 30-30, Ottawa, Canada. U.S Filter (1996) Ceramic Membrane User Manual, Ceramic Membrane Products, Deland, Fl, USA. Welander T., Morin R., and Nylen B.(1999) Biological removal of methanol from kraft pulp mill condensate, Proceedings TAPPI International Environmental Conference, 783-794. Wiesner M.R., and Chellam S. (1992) Mass transfer considerations for pressure-driven membrane processes, Journal of American Water Works Association, 84 (1), 88-95. Wijmans J.G., Nakao S., and Smolders C A . (1984) Flux limitation in ultrafiltration: osmotic pressure model and gel layer model, Journal of Membrane Science, 20, 115-124. Wijmans J.G., Nakao S., Van den Berg J.W.A., Toelstra F.R., and Smolders C A . (1985) Hydrodynamic resistance of concentration polarization boundary layers in ultrafiltration membrane, Journal of Membrane Science, 22, 117-135. Wilson D.F. (1974) Monoterpenes: Their Fate and Analysis in Kraft Mill Aerated Lagoon and Kraft Processing, Ph.D. Thesis, University of Washington, Washington, USA. Wilson D.F., Hrutfiord B.F. (1971) Formation of volatile organic compounds in the kraft pulping process, TAPPI Journal, 54 (7), 1094-1098. 96 Wilson D.F., Hrutfiord B.F. (1975) The fate of turpentine in aerated lagoons, Pulp and Paper Canada, 76 (6), 91-93. Wiseman C , Biskovich V., Garber R., Tielbaard M., and Wilson T. (1998) Anaerobic treatment of kraft foul condensates, Proceedings TAPPI Environmental Conference and Exhibit, 539-546. 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 Al . 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 2 values presented in these tables 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 Table Al.2 MeOH and turp removal 2nd set 1st set RI R2 2nd set 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 4.715 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 0 80 0 2.118 K 1.59 0.0107 0.67 0.00953 K 0.63 0.014 1.06 / R 0.91 0.92 0.78 0.95 R2 0.98 0.64 0.95 / 98 Table A l .3 MeOH and turp removal 3rd set Table A l .4 MeOH and turp removal 4th set 3rd set RI R2 Time MeO H Turp MeOH Turp min mg/L mg/L mg/L mg/L 0 47.43 7.114 29.44 3.971 10 35.11 4.798 21.22 20 26.76 3.64 11.4 30 21.26 2.978 3.143 40 13 2.564 60 0.13 1.985 70 2.482 80 K 0.76 0.014 0.902 0.012 R2 0.98 0.77 0.99 0.97 4th set RI R2 Time MeOH Turp MeOH Turp min mg/L mg/L mg/L mg/L 0 39 5.46 30.17 3.971' 10 34.5 3.805 15.46 3.193 20 24.5 3.292 12.7 2.151 30 14.7 3.226 5.88 2.498 40 5.3 60 70 80 1.936 K 0.87 0.017 0.75 0.008 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 32.7 10 92 17 20 86 6.948 9.9 30 85.2 6.75 40 72.8 60 62 K 0.54 0.012 1.052 R2 0.93 0.93 0.97 99 Run 2 R2only( SRT =15 days, HRT= 10 hrs) Table A1.6 MeOH and turp removal l s l set Table A1.7 MeOH and turp removal 2nd set 1st set R2 Time MeOH Turp min mg/L mg/L 0 90.55 15.22 10 77.9 20 76.4 14.062 30 34.9 8.7683 40 60 29.2 70 25.3 K 0.95 0.0163 Rz 0.84 0.699 2nd set R2 Time MeOH Turp min mg/L mg/L 0 51 10 44.4 10.754 20 38 30 29.2 10.092 40 19.84 8.3547 60 0 70 0 6.783 K 0.85 0.0081 R2 0.99 0.94 Table A1.8 MeOH and turp removal 3 set 3rt set R2 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 4.46688 70 0 K 1.04 0.014 R2 0.94 0.906 100 Run3 [SRT (Rl=10d,R2=10d), HRT (Rl=12hrs,R2=10hrs)] Table A 1.9 MeOH and turp removal 1st set Table ALIO MeOH and turp removal 2nd set 1st set RI R2 2nd set RI R2 MeOH Turp MeOH Turp MeOH Turp MeOH Turp Time mg/L mg/L mg/L mg/L Time mg/L mg/L mg/L mg/L min min 0 55 7.61 82.4 0 45.8 5.625 59.1 10 44 80 2.7794 10 45 48.23 3.6 20 28.7 5.96 72.35 2.7463 20 40.5 5.4595 30.7 30 21.8 5.64 61.3 2.6636 30 36.74 5.1286 24 3.59 40 14.4 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 2.8456 K 0.911 0.64 0.0029 K 0.61 0.0034 0.69 0.0044 R2 0.974 0.98 0.98 R1 0.95 0.85 0.82 0.86 Table A l . l 1 MeOH and turp removal 3rd set Table A 1.12 MeOH and turp removal 4th set 3ra set RI R2 4th set 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 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 4.7812 3.9209 30 24 6.3198 22 3.8051 30 20.8 4.7316 23.5 3.7389 40 8.34 5.8069 21.2 40 17 22.2 60 0 5.1286 19 3.6231 60 0 20 ' 70 0 4.9797 0 70 0 4.682 0 3.6231 K 0.89 0.0045 0.55 0.0047 K 0.72 0.0026 0.63 0.0025 R2 0.97 0.89 0.81 0.86 R5 0.97 0.57 0.84 0.81 101 Run 4 [SRT (Rl=15d,R2=10d), HRT (Rl=8hrs,R2=8hrs)] Table A1.13 MeOH and turp removal first set Table A1.14 MeOH and turp removal 2nd set 1st set RI R2 2nd set RI R2 MeOH Turp MeOH Turp MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L Time min mg/L mg/L mg/L mg/L 0 664 17.43 121 0 449 16.766 402 9 10 664 11.952 120 6.308 10 427 16 409 20 643 10.906 120 5.312 20 394.6 7.304 30 640.8 11.786 30 40 • 40 430 418.7 7.2542 60 640 13.612 119 5.5776 60 14.442 404 6.142 70 623.9 113 70 447 13.446 397 8.4162 K 0.0008 0.0019 0.001 0.0033 K 0.0008 0.0028 0.0003 0.0022 R 2 0.79 0.058 0.6 0.6 R 2 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 3ra set RI R2 4th set RI R2 MeOH Turp MeOH Turp MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L Time min mg/L mg/L mg/L mg/L 0 384 13.197 250 0 693 9.628 10 13.048 257 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 2 0.56 0.99 0.81 0.23 R 2 0.96 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 1st set Table A 1.18 MeOH and turp removal 2nd set 1st set RI R2 MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L 0 51.4 10 28.28 10.7 20 21.04 9.3 30 13.9 40 5.6 9.9 60 0 8.3 70 0 7.8 K 0.797 0.0045 R 2 0.873 0.806 Table A 1.19 MeOH and turp removal 3rd set . 5mset RI R2 MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L 0 55.4 12.8 56.17 10 58 8.6 48.37 11.8 20 50.77 9.1 43.95 11.2 30 9.9 11 40 34.28 8.049 26.6 10.2 60 16.27 4.8 17.19 10.08 70 7 7.2 11.56 7.8 K 0.75 0.0094 0.64 0.0057 R 2 0.96 0.63 0.99 0.802 2nd set RI R2 MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L 0 66.5 4.4 10 63.5 20 54.4 12.9 4.5 30 46.37 10.7 3.2 40 34.5 10.7 3.7 60 16.5 7.4 70 3.2 11.1 3.3 K 0.92 0.0055 0.0045 R2 0.98 0.307 0.532 Table A 1.20 MeOH and turp removal 4th 4th set RI R2 MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L 0 63.7 8.6 71.4 8.7 10 58 63.9 7.7 20 56.1 7.5 58.25 7.6 30 43.3 7.6 55.15 40 32 8.5 52.2 60 13.64 5 40 7.1 70 3.8 4.9 36 6.3 K 0.89 0.0085 0.48 0.0035 R* 0.98 0.733 0.98 0.857 Table A1.21 MeOH and turp removal 5th set 3rd set 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 0.49 R2 0.97 0.631 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 2 values presented in the following tables are the correlation index square for non-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 non-biodegradation components respectively. 104 Runl [(RI SRT =15 days, HRT= 12 hrs, R2 the same as RI)] Table A1.22 TOC removal for the first set 1st set Reactor RI 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 2 0.91 - 0.94 0.78 - 0.85 Table A1.23 TOC removal for the second set 2nd set Reactor RI 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 - 0 51.5 K 0.237 - 0.065 0.4 - 0.065 R2 0.98 - 0.86 0.95 - 0.96 Table A1.24 TOC removal for the third set 3rd set Reactor RI 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 R2 0.98 - 0.76 0.9 - 0.63 Table A 1.25 TOC removal for the fourth set 4 th set Reactor RI 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 0 8.8 K 0.286 - 0.066 0.33 - 0.063 R2 0.985 0.74 0.99 - 0.94 Table A1.26 TOC removal for the fifth set 5m set Reactor RI 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 R2 0.93 - 0.83 0.95 - 0.98 Run 2 [R2 only SRT =15 days, HRT= 10 hrs] Table A l .27 TOC removal for second set Table Al .28 TOC removal for the third set 2nd set Reactor R2 3rd set Reactor R2 Time min MeOH** mg/L TOC mg/L TOC* Sp=58 MeOH** mg/L TOC mg/L TOC* Sp=32 Time min 0 19.125 0 19.5 59.5 22.5 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 2 0.99 - 0.5755 R2 0.94 - 0.91 Run 3 [ SRT(Rl=10d,R2=10d),HRT(Rl=12hrs,R2=10hrs] Table A 1.29 TOC removal for the first set 1st set Reactor RI Reactor R2 MeOH** mg/L TOC mg/L TOC* Sp=58 MeOH** mg/L TOC mg/L TOC* Sp=49 Time min 0 20.625 - 30.9 69.1 19.6 10 16.5 79 21 30 20 10.7625 27.1313 30 8.175 69.9 11.9 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 R2 0.97 - 0.98 0.98 - 0.97 108 Table A1.30 TOC removal for the second set 2nd set Reactor RI 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 3rd set Reactor RI 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 Rz 0.98 - 0.89 0.814 - 0.83 109 Table A1.32 TOC removal for the forth set 4th set Reactor RI 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 20 45.5 13.5 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 R2 0.935 - 0.98 0.84 - 0.78 Run 4 [SRT (Rl=15d,R2=10d), HRT (Rl=8hrs,R2=8hr] Table A1.33 TOC removal for the first set 1st set Reactor RI 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 45 20 241.125 281.22 19.22 45 30 240.3 279.93 17.93 40 92 2.5 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 R2 0.79 - 0.78 0.6 - 0.96 110 Table Al.34 TOC removal for the second set 2nd set 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 40 161.25 223 6 157.013 172 3.2 60 227 149.25 169 0.2 70 167.625 146.25 172 3.2 K 0.128 - 0.041 0.0477 - 0.037 R 2 0.35 - 0.92 0.117 - 0.51 Table Al.35 TOC removal for the third set 3rd set Reactor RI 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 10 211 10 96.375 136 13 20 142.875 91.8113 138 15 30 89.625 130 7 40 144.375 202 1 92.25 132 9 60 132.375 178 86.25 128 5 70 137.25 202 1 85.5 124 1 K 0.13 - 0.038 0.138 - 0.032 R2 0.56 - 0.83 0.806 - 0.76 Table A 1.36 TOC removal for the fourth set 4th set Reactor RI Reactor R2 MeOH** TOC TOC* MeOH** TOC 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 R2 0.96 - 0.72 Run 5 [RI only SRT 15 days, HRT =10hrs, repeat run 2nd] Table A l .37 TOC removal for the 2nd set Table Al.38 TOC removal for the 3rd set 2nd set Reactor RI 3rd set Reactor RI MeOH** TOC 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 T 0.34 - 0.04 K 0.247 - 0.053 R 0.98 - 0.67 R2 0.97 - 0.83 112 Table Al .39 TOC removal for fourth set 4th set Reactor RI MeOH** TOC TOC* Time min mg/L mg/L Sp=53 0 23.8875 80 27 10 21.75 75.5 22.5 20 21.0375 71 18 30 16.2375 67 14 40 12 65 12 60 5.115 53.5 0.5 70 1.425 56 3 K 0.33 - 0.046 R 2 0.98 - 0.98 Table A1.40 TOC removal the fifth set 5th set Reactor RI MeOH** TOC TOC* Sp=46 Time min mg/L mg/L 0 20.775 65 18.8 10 21.75 57 10.8 20 19.0388 63 16.8 30 40 12.855 58.5 12.3 60 6.10125 53 6.8 70 2.625 46.5 0.3 K 0.282 - 0.042 R z 0.964 - 0.58 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 TOC eff mg/L 65 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 MeOH eff mg/L 0 MeOH eff mg/L 0 MeOH eff mg/L 16 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 TOC eff mg/L 51.5 TOC eff mg/L TOC efficiency % 78.95 TOC efficiency % 85.89 TOC efficiency % MeOH ifl mg/L 668 MeOH ifl mg/L 720 MeOH ifl mg/L 790 MeOH eff mg/L 75 MeOH eff mg/L 0 MeOH eff mg/L 0 MeOH efficiency% 88.77 MeOH efficiency% 100 MeOH efficiency% 100 Turp.inf mg/L 10.2 Turp.inf mg/L 15.66 Turp.inf mg/L 9.18 Turp.eff mg/L 1.5 Turp.eff mg/L 2.65 Turp.eff mg/L 0.72 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 fficiency fifth set 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 efficiency0/" 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% 100 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 115 Run 3, [SRT (Rl=10d,R2=10d), HRT (Rl=12hrs,R2=10hrs)] Tabel Al .43 MeOH, turpentine, and TOC and solids measurements for sets 2 and 3 Efficiency 1st set Run 3 Efficiency 2nd set Run 3 Reactor one (RI) Reactor one (RI) 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% 100 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 2380 MLVSS mg/L 2089 116 Tabel A1.44 MeOH, turpentine, and TOC and solids measurements for sets 3 and 4 Efficiency 3rd set Run 3 Efficiency 4th set Run 3 Reactor one (RI) Reactor one (RI) 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 Is' set Run 4 Efficiency 2nd set Run 4 Reactor one (RI) Reactor one (RI) 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 % 37 MLVSS mg/L 630 MLVSS mg/L 510 Reactor two (R2) 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 % 36 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% 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 480 MLVSS mg/L 310 118 Tabel A1.46 MeOH, turpentine, and TOC and solids measurements for sets 3 and 4 Efficiency 3rd set Run 4 Efficiency 4th set Run 4 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% 39 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 % 50 Turp.eff % 55 MLVSS mg/L 310 MLVSS mg/L 350 Reactor two (R2) 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 1st set Run 5 = repeat l s t&2 n d run Efficiency 2nd set Run5 =repeat lst&2ndrun Reactor one (RI) Reactor one (RI) TOC inf mg/L 230 TOC inf mg/L 290 TOC eff mg/L 60 TOC eff mg/L 58 TOC efficiency % 73.9 TOC efficiency % 80 MeOH ifl mg/L 595 MeOH ifl mg/L 760 MeOH eff mg/L 25 MeOH eff mg/L 40 MeOH efficiency% 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 TOC eff mg/L 44 TOC efficiency % TOC efficiency % MeOH ifl mg/L 710 MeOH ifl mg/L 708 MeOH eff mg/L 0 MeOH eff mg/L 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 3ra set, Run 5th =repeat 1st &2 n d run Efficiency 4m set, Run 5m r^epeat 1st & 2nd run 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 % 80.6 TOC efficiency % 80 MeOH ifl mg/L 798 MeOH ifl mg/L 827 MeOH eff mg/L 17 MeOH eff mg/L 0 MeOH efficiency% 97.8 MeOH efficiency% 100 Turp.inf mg/L 25.2 Turp.inf mg/L Turp.eff mg/L 3.2 Turp.eff mg/L Turp.eff % 86.6 Turp.eff % MLVSS mg/L 2200 MLVSS mg/L 2093 Reactor two (R2) Reactor two (R2) TOC inf mg/L 265 TOC inf mg/L 254 TOC eff mg/L 70 TOC eff mg/L 58 TOC efficiency % TOC efficiency % MeOH ifl mg/L 675 MeOH ifl mg/L 670 MeOH eff mg/L 1.4 MeOH eff mg/L 0 MeOH efficiency% 99.2 MeOH efficiency% 100 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 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, HRT = 12 hrs) Reactor volume =(1475+295)= 1770 ml Dates Set Cumulative CO Influent Flux Time of Total K m MeOH MLVSS Sludge Cumulative Cumulative Time mg/L flow (ml/min) filter (mg/L.min) consumed (mg/L) wasted MeOH solids day effluent mg/cycle ml/d (mg) (mg) ml/hr (min) 27-Dec- 1 0 80 147.5 6 49.2 1.59 141.60 1610 118 0 0 01 30-Dec- 2 3 47 147.5 6 49.2 0.63 82.84 2000 118 2982.229 708 01 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 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 Time day CO mg/L Influent flow (ml /hr) Flux (ml/min) Time of filter effluent (min) Total K m (mg/L.min) MeOH consumed mg/cycle MLVSS (mg/L) Sludge wasted (ml/d) Cumulative MeOH (mg) Cumulative solids (mg) 27-Dec-01 1 0 32 110 6.25 35.2 0.67 42.24 2200 88 0 0 30-Dec-01 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 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 Flux Time of Total K m MeOH MLVSS Sludge Cumulative Cumulative Time mg/L flow (ml/min) filter (mg/L. min) consumed (mg/L) wasted MeOH solids day ml/hr effluent (min) mg/cycle (ml/d) (mg) (mg) 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 Flux Time of Total K m MeOH MLVSS Sludge Cumulative Cumulative Time mg/L flow (ml/min) filter (mg/L. min) consumed (mg/L) wasted MeOH solids day (ml effluent mg/cycle (ml/d) (mg) (mg) /hr) (min) ll-Feb-02 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 Flux Time of Total K,,, MeOH MLVSS Sludge Cumulative Cumulative Time mg/L flow (ml/min) filter (mg/L.min) consumed (mg/L) wasted MeOH solids day (ml /hr) effluent (min) mg/cycle (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 Flux Time of Total K r a MeOH MLVSS Sludge Cumulative Cumulative Time mg/L flow (ml/min) fdter (mg/L.min) consumed (mg/L) wasted MeOH solids day (ml /hr) effluent (min) mg/cycle (ml/d) (mg) (mg) 6-Apr-02 1 0 0.00 2850 0 0 10-Apr-02 2 4 66.5 118.5 2.9 81.7 0.92 75.23 2850 79 3610.948 900.6 15-Apr-02 3 9 55.4 118.5 5.5 43.1 0.75 65.76 2910 79 7556.536 2050.05 18-Apr-02 4 12 63.7 118.5 3.15 75.2 0.89 72.78 2200 79 10176.77 2571.45 20-Apr-02 5 14 50.2 118.5 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 the first, 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 1st run, 1st batch cycle run, 2nd batch cycle Time minute Reactor RI Reactor R2 Time minute Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L 0 77 35 68 41 0 58.81 46.94 66.79 -10 69.74 29.7 59.98 40.07 10 53.8 43.97 61.75 34.28 20 62.5 28.74 55.17 38.2 20 44.19 43.28 51.38 32.4 30 51.65 26.79 50.72 25.5 30 37.43 40.19 45.3 30.45 40 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 R2 0.99 0.95 0.98 0.93 R1 0.97 0.934 0.89 0.99 125 Table A2.3 MeOH and turp removal for Table A2.4 MeOH and turp removal for 1 1st run, 3rd batch cycle run, 4th batch cycle Time min Reactor RI Reactor R2 Time min Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L 0 60.73 41.9 65.53 43.513 0 44.38 42.2 68.63 10 56.51 41.1 58.81 35.49 10 51.84 44.88 63.22 27.3 20 51.45 36.29 56.78 20 43.25 39.61 60.09 26.31 30 42.65 33.66 47.99 34.58 30 37.12 41.79 52 25.67 40 34.51 33.55 43.41 31.8 40 27.8 36.98 48.54 24.61 K 0.66 0.0064 0.55 0.0065 K 0.47 0.0034 0.51 0.0039 R 2 0.97 0.91 0.97 0.8 R 2 0.709 0.53 0.98 0.99 Table A2.5 MeOH and turp removal for 1st run, 5th batch cycle Time min Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp 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 34.12 K 0.32 0.0014 0.52 0.0028. R 2 0.29 0.921 0.972 0.71 126 Table A2.6 MeOH and turp removal for Table A2.7 MeOH and turp removal for 2' 2na run, 1st batch cycle run, 2nd batch cycle Time min Reactor RI Reactor RI Time min Reactor RI Reactor RI MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L 0 97.8 70.19 46.7 57.7 0 106 100.53 38.9 71.21 10 87.16 72.44 37.72 56.6 10 104.72 95.41 57.93 64.26 20 88.6 66.87 34.9 50.66 20 90.8 93.78 31.44 63.45 40 62.3 58.05 19.8 45.57 40 81.3 85.42 23.33 54.96 K 0.847 0.0053 0.64 0.0063 K 0.66 0.0039 0.584 0.0061 R2 0.9 0.85 0.98 0.96 R2 0.93 0.98 0.46 0.95 Table A2.8 MeOH and turp removal for Table A2.9 MeOH and turp removal for 2' 2" run, 3r batch cycle run, 4 batch cycle Reactor RI Reactor RI Reactor RI Reactor RI MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH Turp mg/L MeOH mg/L Turp mg/L Time min Time min mg/L 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 20 97.9 95.614 33.48 69.7 20 104.91 103.51 41.26 69.84 40 87.8 89.88 21.4 60 40 101 97.1 27.73 65.64 K 0.619 0.0029 0.53 0.0038 K 0.44 0.0029 0.46 0.0039 R2 0.48 0.955 0.82 0.05 R2 0.52 0.85 0.83 0.98 127 Table A2.10 MeOH and turp removal for 2nd run, 5th batch cycle Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L Time min 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 R2 0.34 0.73 0.88 0.96 Table A2.11 MeOH and turp removal for Table A2.12 MeOH and turp removal for 31 3rd run, 1st batch cycle run, 2nd batch cycle Reactor RI Reactor R2 Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L Time min Time min 0 218 119 42 96.6 0 197.18 138 35.5 136.72 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 12.3 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 R2 0.78 0.958 0.977 0.82 R2 0.69 0.936 0.98 0.77 128 Table A2.13 MeOH and turp removal for Table A2.14 MeOH and turp removal for 4' 3rd run, 3rd batch cycle run, 4th batch cycle Reactor RI Reactor R2 Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L MeOH Turp mg/L MeOH mg/L Turp mg/L Time min Time min mg/L 0 204 154 41.13 139 0 191 53 154.1 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 39.3 142.43 K 0.49 0.0036 0.367 0.0028 K 0.29 0.0019 0.321 0.0024 R 2 0.43 0.74 0.64 0.64 R2 0.91 0.97 0.65 0.661 Table A2.15 MeOH and turp removal for 3rd run, 5th batch cycle Time min Reactor RI Reactor R2 MeOH mg/L Turp mg/L MeOH mg/L Turp mg/L 0 183 157 72 166.5 10 182.4 164 75.1 167.29 20 182.2 155 67.8 162.8 30 164 67.26 161.3 40 182.3 163 69.32 159.2 K 0.015 0.0007 0.132 0.0013 R 2 0.51 0.77 0.41 0.91 A2.2 Removal Kinetics for TOC 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 2 values presented in the following tables are the correlation index square for non-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 non-biodegradation components respectively. 130 Table A2.16 TOC removal for 1st run, 1st batch cycle Time Reactor one RI Reactor two R2 min 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 1st run, 2nd batch cycle Time min Reactor one RI Reactor two R2 MeOH** TOC TOC* MeOH mg/L TOC mg/L TOC* Sp=83 mg/L mg/L Sp=72 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 1st run, 3rd batch cycle Time min Reactor one RI Reactor two R2 MeOH** mg/L TOC mg/L TOC* Sp=77 MeOH mg/L TOC mg/L TOC* 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 1st run, 4th batch cycle Time Reactor one RI Reactor two R2 min 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 1st run, 5th batch cycle Time min Reactor one RI Reactor two R2 MeOH** mg/L TOC mg/L TOC* Sp=72 MeOH mg/L TOC mg/L TOC* 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 2nd run, 1st batch cycle Time Reactor one RI Reactor two R2 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 2nd run, 2nd batch cycle Time min Reactor one RI Reactor two R2 MeOH** mg/L TOC mg/L TOC* Sp=101 MeOH mg/L TOC mg/L TOC* 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 2nd run, 3rd batch cycle Time Reactor one RI Reactor two R2 min 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 2nd run, 4th batch cycle Time Reactor one RI Reactor two R2 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 2nd run, 5th batch cycle Time Reactor one RI Reactor two R2 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 3rd run, 1st batch cycle Time min Reactor one RI Reactor two R2 MeOH** mg/L TOC mg/L TOC* Sp=100 MeOH mg/L TOC mg/L TOC* 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 3rd run, 2nd batch cycle Time Reactor one RI Reactor two R2 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 3rd run, 3rd batch cycle Time Reactor one RI Reactor two R2 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 3rd run, 4th batch cycle Time Reactor one RI Reactor two R2 min MeOH** TOC TOC* MeOH TOC TOC* mg/L mg/L Sp=180 mg/L mg/L Sp=109 0 185 4.6 19.875 116 7 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 3rd run, 5th batch cycle 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 30 164 10 25.2225 120 2 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 results from the 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 R2 values, presented in the following tables, are the correlation index square for non-linear regression. Table A3.1 Methanol and turpentine removal in MBR (inactivated biomass test) Inactivated Biomass RI R2 MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L 0 74.1 10.7 72.56 9.95 10 10 71.95 8.48 20 80.98 11.5 72.98 9.57 30 75.7 12.6 70.47 40 78.12 11.5 70.12 9.58 60 73.12 10.04 68.9 K 0.0008 0.0018 0.0009 0.00141 R z 0.49 0.5 0.81 0.3126 139 Table A3.2 Methanol and turpentine removal in MBR (clean water test 1) Clean Water RI R2 MeOH Turp MeOH Turp Time min mg/L mg/L mg/L mg/L 0 73.84 4.81 3.3.9 10 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 Rz 0.0273 0.41 0.33 0.79 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 2.84 60 56 33.11 3.66 K 0.0006 0.0012 0.0014 0.0011 Rz 0.438 0.0265 0.578 0.0069 140 A3.2 Stripping Kinetics for TOC 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 non-biodegradation components respectively. Table A3.4 TOC removal in MBR (inactivated biomass test) Reactor one RI Reactor two R2 Time Minute MeOH** mg/L TOC mg/L TOC* Sp=100 MeOH** mg/L TOC mg/L TOC* Sp=100 0 28.3875 168 68 27.21 106 6 10 147 47 26.98125 103 3 20 29.295 161 61 27.3675 103 3 30 119 19 26.42625 102 2 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 R2 0.49 - 0.821 0.81 - 0.942 141 Table A3.5 TOC removal in MBR (clean water test 1) Time Minute Reactor one RI Reactor two R2 MeOH** TOC mg/L TOC* Sp=30 MeOH** mg/L TOC mg/L TOC* Sp=17.5 mg/L 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 R2 0.0273 - 0.93 0.33 - 0.884 Table A3.6 TOC removal in MBR (clean water test 2) Time Minute Reactor one RI Reactor two R2 MeOH** mg/L TOC mg/L TOC* Sp=29 MeOH** mg/L TOC mg/L TOC* P=22.5 0 33.375 34 5 29 6.5 10 32.77875 32 3 25.6125 26 3.5 20 31 2 25.21875 25 2.5 30 31.575 30 1 . 23.73375 25 2.5 40 30 1 23.94 24 1.5 60 32.2125 30 1 24 23 0.5 K 0.0006 - 0.0282 0.0014 - 0.0392 R2 0.43 - 0.79 0.578 - 0.954 142 

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0063616/manifest

Comment

Related Items