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A.“7\.P.1VH.:‘&. . ..‘w.._’.0...04040_*r x; u‘..r~. 0. \0.«.. .- u ..m... ‘ . ...1..?.~........... 0.1. r” '0 .0— $1.. .. ......am. .. ...- 1-: ......e............. . . 0 n0“ I0 .0 .0 .. . . 0.0 0.0.0 . . . . ..0.” 0 .U0" A 0 0 .. 0... . . 2.31%.... askifinsfiwanh. “may.” 0 ..u0‘.fl -.. . 0 ~ 3 0A- 0 co . 0 . u _ r . . . . . .. .0??? a . THESIS This is to certify that the thesis entitled RECONSTITUTION OF DEWATERED FOOD PROCESSING RESIDUALS WITH MANURE TO INCREASE ENERGY PRODUCTION FROM ANAEROBIC DIGESTION presented by David M. Wall has been accepted towards fulfillment of the requirements for the Master of degree in Biosystems Engineering Science éflm L29 JA/“M Major Profess’br’s Signature Angus?" z 4, 2010 Date MSU is an Affinnative Action/Equal Opportunity Employer w LIBRARY Michigan State University o-onn----u—-—.q.-.—.—.—.—.-.-.-.-.-—.--._4.4:L-.A-._.'.-.-.-.-.— PLACE IN RETURN BOX to remove this checkout from your record. TO AVOID FINES return on or before date due. MAY BE RECALLED with earlier due date if requested. DATE DUE DATE DUE DATE DUE 5108 KzlProleoc8Pres/ClRC/DateDue.indd RECONSTITUTION OF DEWATERED FOOD PROCESSING RESIDUALS WITH MANURE TO INCREASE ENERGY PRODUCTION FROM ANAEROBIC DIGESTION By David M. Wall A THESIS Submitted to Michigan State University in partial fulfilment of the requirements for the degree of MASTER OF SCIENCE Biosystems Engineering 2010 ABSTRACT RECONSTITUTION OF DEWATERED FOOD PROCESSING RESIDUALS WITH MANURE TO INCREASE ENERGY PRODUCTION FROM ANAEROBIC DIGESTION By David M. Wall A potentially effective wastewater treatment strategy for a food processor is to concentrate high carbon solid wastes by segregation and dewatering of bulk flow. This solid-liquid separation process results in a weaker wastewater fraction that can be economically disposed to sewer or potentially land applied with minimum surcharge, while remaining solids are collected and applied to landfill. An alternative to the landfill is to anaerobically digest the waste. This technology involves the degradation of organic matter in the absence of free oxygen. A byproduct is biogas that contains a substantial amount of methane which can be used to generate energy. The following study evaluates the reconstitution of dewatered food processing waste with manure to gain increases in energy produced per unit volume in a farm digester, and thereby increase profitability for the farmer. Two batch digestion studies were conducted on different blends of food waste and manure to determine if a synergistic relationship existed in gas production. A further semi-continuous study provided a more realistic interpretation of real-life co-digestion. Although gas production appeared additive in the batch studies, the semi-continuous digestion of an optimized food waste and manure blend was found to produce over twice as much methane as manure digested alone in reactors of same working volume. Copyright by DAVID WALL 2010 ACKNOWLEDGEMENTS First and foremost I would like to offer my sincerest thanks to my supervisor, Dr. Steve Safferman, for his continuous support and without whom, none of this would have been possible. I am forever grateful for his encouragement, patience and assistance throughout my two years at Michigan State University. My deepest gratitude is also due to the members of my supervisory committee, Dr. Wei Liao and Dr. Chris Saffron, whose knowledge and advice was invaluable in completing the study. I would like to give a special word of thanks to my colleagues at the Anaerobic Digestion Research and Education Center, Dr. Dana Kirk, Louis Faivor, Wei Wu-Haan, Jason Smith, Corey Scheffler and Matthew Ong, for the immense work they contributed to the study. I am forever indebted to you all for your support throughout this research. Finally I would like to thank my parents, Michael and Aileen, and my sisters, Elaine and Emma, for all their love and support while I have been abroad. There is no doubt that without your encouragement and support I would not be in the position I am today. Le chrol agus lamh. TABLE OF CONTENTS LIST OF TABLES ..................................................................................... vii LIST OF FIGURES ................................................................................... x Chapter 1 Introduction and Objective ..................................................... 1 Chapter 2 Literature Review ................................................................... 3 2.1 Solid Food Waste to Landfill ................................................... 3 2.2 Anaerobic Digestion for Waste Management ......................... 4 2.3 Biological Process of Anaerobic Digestion ............................. 5 2.4 Important Parameters in Anaerobic Digestion ........................ 5 2.4.1 pH .............................................................................. 5 2.4.2 Ammonia ................................................................... 6 2.4.3 Temperature .............................................................. 6 2.4.4 Solid Retention Time ................................................. 7 2.4.5 Mixing ........................................................................ 8 2.4.6 Nutrients .................................................................... 8 2.5 Anaerobic Digestion of Manure .............................................. 9 2.6 Benefits of Technology ........................................................... 10 2.6.1 Odour Control and Greenhouse Gas Emissions ....... 10 2.6.2 Ammonia Control ...................................................... 11 2.6.3 Environmental Protection .......................................... 11 2.6.4 Energy Generation .................................................... 12 2.7 Co-digestion and the Potential to Enhance Biogas Yields ...... 12 2.7.1 Food Waste Segregation ........................................... 13 2.7.2 Polymer Waste Studies ............................................. 14 2.8 Centralized Digesters ............................................................. 14 2.9 Biochemical Methane Potential .............................................. 15 2.9.1 lnoculum-to-Waste Ratio ............................................... 15 2.10 Semi-Continuous Digestion Studies ..................................... 16 Chapter 3 Methods and Materials .......................................................... 18 3.1 Food Processing Sludge Waste ............................................ 18 3.2 lnoculum ................................................................................ 22 3.3 Cow Manure .......................................................................... 23 3.4 Respirometer Assay Design .................................................. 24 3.4.1 Volume of Diluted Sludge and Cow Manure ............. 25 3.4.2 Volume of Seed ........................................................ 26 3.4.3 Respirometer Assay Setup ....................................... 26 3.5 Serum Bottle Assay Design ................................................... 27 3.5.1 Volume of Diluted Sludge and Cow Manure ............. 28 3.5.2 Volume of Seed ........................................................ 29 V 3.5.3 Serum Bottle Assay Setup .......................................... 29 3.5.4 Biogas Production Measurement ............................... 31 3.6 Semi-Continuous Systems .................................................... 32 3.6.1 Evaluating Specific Gravity ......................................... 32 3.6.2 Optimization Study ..................................................... 34 3.6.3 Semi-Continuous Start-Up .......................................... 37 3.6.4 Removal and Feeding of Reactors ............................. 38 Chapter 4 Results and Discussion ......................................................... 42 4.1 Batch Systems ....................................................................... 42 4.1.1 Respirometer Assay Results ....................................... 42 4.1.2 Serum Bottle Assay Results ........................................ 46 4.1.3 Discussion of Batch Assays ........................................ 52 4.2 Semi-Continuous System ....................................................... 53 4.2.1 Semi-Continuous Study Results and Discussion ......... 55 Chapter 5 Conclusions and Future Research ........................................ 66 Appendix A: RESPIROMETER STUDY .................................................. 69 Appendix B: SERUM BOTTLE STUDY .................................................... 75 Appendix C: SEMI-CONTINUOUS STUDY .............................................. 85 Bibliography ............................................................................................. 107 vi Table 3.1 Table 3.2 Table 3.3 Table 3.4 Table 3.5 Table 3.6 Table 3.7 Table 3.8 Table 3.9 Table 3.10 Table 4.1 Table 4.2 Table 4.3 Table 4.4 Table 4.5 Table 4.6 Table 4.7 Table 4.8 Table 4.9 Table 4.10 Table 4.11 Table 4.12 Table 4.13 Table 4.14 LIST OF TABLES Respiromteter Assay Initial Characteristics ........................... Serum Bottle Assay Initial Characteristics ............................. Semi-Continuous Study Initial Characteristics ....................... Respirometer Flask Compositions ......................................... Serum Bottle Compositions ................................................... Serum Bottle Values for Equation 1 ...................................... Serum Bottle Values for Equation 2 ...................................... Digestion Parameters ............................................................ Specific Gravity Values for each Substrate ........................... Semi-Continuous Reactor Compositions .............................. Ammonia and COD/Ammonia Before and After Digestion Respirometer COD and VS Destruction ............................... Respirometer Biogas per g COD and 9 VS Destroyed .......... Normalized Respirometer Energy Potential ........................... Respirometer Biogas Potential .............................................. CODzNzP Before and After Digestion .................................... Serum Bottle COD and VS Destruction ................................. Serum Bottle Biogas per g COD and 9 VS Destroyed ........... Statistical Output ................................................................... Normalized Serum Bottle Energy Potential ......................... Serum Bottle Biogas Potential ............................................. Reactor 1 Analysis .............................................................. Reactor 2 COD and VS Destruction .................................... Reactor 3 COD and VS Destruction .................................... vii 23 23 23 24 28 29 29 31 33 36 43 43 44 46 46 47 48 50 51 51 52 55 61 62 Table 4.15 Reactor 4 COD and VS Destruction .................................... 63 Table 4.16 Reactor Biogas per g COD Destroyed ................................ 64 Table 4.17 Reactor Biogas per 9 VS Destroyed .................................... 64 Table 4.18 Reactor Values for Equation 8 ............................................. 65 Table A1 Respirometer Concentrations before Digestion .................... 70 Table A2 Respirometer Concentrations after Digestion ....................... 70 Table A3 Respirometer pH Change during Digestion .......................... 71 Table A4 Respirometer Alkalinity Change during Digestion ................. 71 Table A5 Respirometer Total Solids Destruction .................................. 71 Table A6 Respirometer Total Suspended Solids Destruction ............... 72 Table A7 Respirometer Volatile Suspended Solids Destruction ........... 72 Table A8 Respirometer Hydrogen Sulfide Concentrations ................... 72 Table A9 Respirometer Soluble COD Destruction ............................... 73 Table A.10 Respirometer Normalized Energy Potential per COD ......... 73 Table A.11 Respirometer Normalized Energy Potential per VS ............ 73 Table B.1 Serum Bottle Concentrations before Digestion ..................... 76 Table B.2 Serum Bottle Concentrations after Digestion ........................ 77 Table B.3 Serum Bottle pH Change during Digestion ........................... 77 Table B.4 Serum Bottle Alkalinity Change during Digestion .................. 78 Table B.5 Serum Bottle Total Solids Destruction .................................. 78 Table 8.6 Serum Bottle Ammonia Change during Digestion ................. 79 Table B.7 Serum Bottle Soluble COD Destruction ............................... 79 Table 88 Serum Bottle Normalized Energy Potential per COD ............ 80 Table 89 Serum Bottle Normalized Energy Potential per VS ............... 80 Table B.10 Serum Bottle Hydrogen Sulfide Concentrations .................. 80 viii Table B.11 Daily Biogas Yields for Controls .......................................... 82 Table 8.12 Daily Biogas Yields for Blends ............................................ 83 Table B.13 Individual Treatment Gas Production and Averages ........... 84 Table 0.1 Removal and Feeding of Substrate Data .............................. 86 Table 0.2 Wet-Tip Gas Meter Data ....................................................... 101 Table 0.3 pH for 3 SRT’s ...................................................................... 102 Table 0.4 Alkalinity (mg/L CaCOa) for 3 SRT’s ..................................... 102 Table 0.5 COD (mg/L) for 3 SRT’s ....................................................... 103 Table 0.6 Reactor 2 TSNS for 3 SRT’s ................................................ 103 Table 07 Reactor 3 TSNS for 3 SRT’s ................................................ 104 Table C.8 Reactor 4 TSNS for 3 SRT's ................................................ 104 Table C.9 Reactor 5 TSNS for 3 SRT’s ................................................ 105 Table 010 Percentage (%) Methane Content for 3 SRT's .................... 105 Table 0.11 Reactor 5 COD and VS Destruction ................................... 106 Table 0.12 Characteristics of Substrate Feeds between SRT’s ............ 106 Figure 3.1 Figure 3.2 Figure 3.3 Figure 3.4 Figure 3.5 Figure 3.6 Figure 4.1 Figure 4.2 Figure 4.3 Figure 4.4 Figure 4.5 Figure 4.6 Figure 4.7 Figure 4.8 Figure 4.9 Figure 4.10 Figure A.1 Figure 31 LIST OF FIGURES Cyclone System at Food Processing Facility ....................... 19 Belt-Press Filter .................................................................... 20 Food Processing Sludge Waste ........................................... 21 Serum Bottle Assay Setup ................................................... 30 Semi-Continuous Reactor Setup .......................................... 40 Tubing Connections to Wet-Tip Gas Meters ........................ 41 Respirometer Biogas Methane Content ............................... 44 Respirometer Cumulative Biogas Volume ............................ 45 Serum Bottle Biogas Methane Content ................................ 49 Serum Bottle Cumulative Biogas Volume ............................ 49 Decision Flow Chart ............................................................. 54 Semi-Continuous Cumulative Biogas Volume ...................... 57 SRT 1 Biogas Production ..................................................... 58 SRT 2 Biogas Production ..................................................... 58 SRT 3 Biogas Production ..................................................... 59 Semi-Continuous Biogas Methane Content ....................... 60 Respirometer Biogas Production Rate ................................. 74 Serum Bottle H28 Concentrations ....................................... 81 Chagter1 Introduction and Objective Anaerobic digestion involves the degradation of organic matter in the absence of free oxygen with a byproduct of biogas that contains a substantial amount of methane. Much time and research has been devoted to improve the performance of anaerobic digestion systems. One technique often considered is the co-digestion of substrates in order to maximize biogas production. The technology has been widely applied for treatment of organic wastes that biodegrade easily. Food processing sludge waste (FPSW) can have a tremendous amount of imbedded energy and is theoretically an excellent co-substrate when reconstituted with manure at a farm digester. These high carbon wastes are produced at food processing facilities by segregation and dewatering of bulk flow. This solid-liquid separation produces a weaker wastewater that can potentially be cost-effectively disposed in a sewer or irrigated. The collected solids fraction offers a source of feedstock for the digester at the dairy farm that could potentially boost biogas production and profitability for the farmer. Other key benefits include savings in transportation costs and potential tipping fees for the food processor. If the reconstitution of the FPSW with manure co-digests successfully, then an increase in energy production per unit volume in the digester will be obtained. The production of a lower-strength wastewater at the food processing facility will also result. The majority of previous co-digestion studies have looked at organic wastes with the objective of enhancing biogas production; however the concept of thickening a FPSW and then reconstituting with manure at the digester, is novel. The evaluation of the FPSW involved the following four distinct stages, . An initial respirometer study to determine the F PSW’s energy potential, if any synergistic or antagonistic relationships resulted when digested with dairy manure, and if toxicity results. . A biogas potential screening assay of the FPSW blended with manure to determine specific optimum blending ratios. . The evaluation of the reconstituted FPSW using semi-continuous digester systems based on the most promising conditions established in the previous batch assays. Analysis from this stage provides a more realistic interpretation of real-life co-substrate digestion as no dilutions of the FPSW are required. . A report on findings, and recommendations on the potential of the FPSW as a feedstock. Chapter 2 Literature Review A number of issues need to be addressed when considering anaerobic digestion. Factors such as the nature of the waste, the biological processes and the critical process parameters all need to be assessed. Any potential benefits or difficulties associated with anaerobic systems must also be considered. This chapter provides some background to these topics while providing a brief outline of previous research undertaken in the anaerobic co- digestion of substrates. 2.1 Solid Food Waste to Landfill Improper food industry waste management including the collection, treatment, processing and disposal of residuals is a source of concern due to its negative impact on the environment (Dutta and Das, 2010; Mohan et al., 2006). In 2007, the amount of food waste generated in the US alone was estimated at 28.8 million metric tons with only 2.6% of this waste recovered and diverted from landfill (Levis et al., 2010). Methane, a dangerous greenhouse gas, is generated by the degradation of solid waste in landfills. Approximately 23% of the total US methane emissions originate from landfills, the second largest contributor in the country (US-EPA, 2008). An estimated 57 million tons of methane were emitted to the atmosphere as a result of worldwide landfills in 2000 (Themelis and Ulloa, 2007). The hazards associated with solid waste landfill application and the relatively few methane capture initiatives in operation have encouraged the development of alternative technologies. The introduction of carbon credit gains has further reinforced the push for sustainable energy development. Treatment methods such as anaerobic digestion, composting and fluidized bed combustion are attractive alternatives, depending on the food waste of concern (Arvanitoyannis and Varzakas, 2008). 2.2 Anaerobic Digestion for Waste Management Anaerobic digestion is a mature biological treatment method that can be cost effective, environmentally sound and a source of renewable energy when implemented correctly (Mata-Alvarez et al., 2000). Successful anaerobic digestion results in the production of methane gas which subsequently can be used for power generation (Chynoweth et al., 2001). From a farmer’s perspective, correct implementation of an anaerobic digestion system offers advantages such as heat production, electricity generation, reduced odors and increased flexibility in manure management (Tafdrup, 1995). Food processing companies benefit from pollution reduction and revenue gains from carbon credits and renewable energy credits. Currently in the United States there are estimated to be 151 agricultural digesters in operation with the majority farm owned and having livestock manure as the only feedstock (AgStar, 2010a). The development of the technology in Europe has been more prominent with countries such as Germany, Denmark, Austria and Sweden leading the way in agricultural biogas plant development (Holm-Nielsen et al., 2009). The implementation of government initiatives, for example, the European Union (EU) Landfill Directive (1999/31/EC), and the participation in regulations such as the United Nations Framework Convention on Climate Change (UNFCCC) among EU member states has encouraged the diversion of biodegradable waste from landfill in pursuit of alternative technologies such as anaerobic digestion (Clarke and Alibardi, 2010; Zglobisz et al., 2010). 2.3 Biological Process of Anaerobic Digestion Anaerobic digestion involves the microbial decomposition of organic waste in the absence of free oxygen. Bacterial hydrolysis occurs first, where the waste’s complex organics are broken down into simple sugars, amino acids and peptides. Subsequently, these products of hydrolysis are converted to volatile acids through biological acidogenesis. Acetogen bacteria then convert the fatty acids to acetic acid, carbon dioxide and hydrogen. Finally, methanogenic bacteria convert the products of these reactions in a process known as methanogenesis where as a result methane and carbon dioxide are produced (Grady Jr et al., 1999; Speece, 1996b; US-EPA, 2006). 2.4 Important Parameters in Anaerobic Digestion There are a number of parameters that must be accounted for to avoid inhibition and provide stability in the digestion process. The microorganisms associated with the acid forming and methane forming stages of the anaerobic digestion process have different requirements in terms of nutrients available and the conditions of their environment. Reactor failure can originate from an unbalanced microbial population. Inhibition of a system is evident through declining rates in methane production and a buildup of organic acids (Chen et al., 2008). 2.4.1 pH A key variable in the digestion process is the pH of the liquid waste. The suggested optimum pH range of anaerobic digestion is between 6.5 and 8.2 (Liu et al., 2008; Speece, 1996b). Regulation of pH in anaerobic systems leads to process stability. Growth rate of methanogens is significantly diminished below the optimum range while a high pH hinders system stability 5 through the breakup of microbial granules (Ward et al., 2008). By maintaining adequate pH, the likelihood of toxicity due to free ammonia levels is reduced as levels will be lower (Bhattacharya and Parkin, 1989). Hydrolysis of lipids contained in certain food wastes feedstocks can result in the accumulation volatile fatty acids (VFA). The build up of VFA’s can cause a reduction in pH and subsequently, inhibition of methanogenesis (Griffin et al., 1998). 2.4.2 Ammonia When nitrogenous matter is degraded ammonia is released (Chen et al., 2008). Specifically, anaerobic degradation of animal manure proteins into amino acids releases ammonia to the surrounding environment (Uludag- Demirer et al., 2008). Previous literature has suggested that ammonia toxicity levels are in the region of 700 and 1200 mg /L N (Hansen et al., 1998). Sung and Liu, 2003, demonstrated reductions in specific methanogenic activity by 39% and 64% in completely stirred tank reactors (CSTR) of a synthetic wastewater when total ammonia nitrogen concentrations were 4.92 and 5.77 g/L, respectively. Studies relating to the digestion of dairy manure have indicated that small increases in ammonia during digestion can improve biogas production while high increases can result in reductions of approximately 50% (Sterling et al., 2001). 2.4.3 Temperature The temperature inside the digester is usually operated at a mesophilic or thermophilic range. Mesophilic temperature, corresponding to 35°C, allows for process stability, high methane yields and maximum energy output (\Nenxiu and Mengjie, 1989). However, the thermophilic range, corresponding to 55°C, has often shown superior performance in volatile solids (VS) 6 destruction and lower VFA’s although a much higher energy input is required (Kim et al., 2002). In the thermophilic range, inhibition by ammonia is more common (Campos et al., 1999). Maintaining the optimum temperature is a key component of manure digestion as indicated in a mesophilic study of swine manure by Chae et al., 2008, where a fall in temperature from 35°C to 30°C decreased methane yield by 3% while a fall to 25°C caused a 17.4% reduction. Approximately 60% of the anaerobic digesters in Europe with capacity for solid waste operate with the mesophilic temperature range. The remaining 40% have systems using a thermophilic process (Mata-Alvarez et al., 2000). Mesophilic digestion is less expensive to maintain than thermophilic as less energy is required (Gerardi, 2003). 2.4.4 Solid Retention Time The solids retention time (SRT), expressed in days, is average time the solids spend in the digester and a characteristic that can affect the performance of a digester (Appels et al., 2008). Shortening the SRT is sometimes favorable as studies have indicated that a reduction from 30 to 12 days, coinciding with an increase in organic loading rate, can potentially triple the biogas production when dealing with dewatered sewage sludge in CSTR’s (Nges and Liu, 2010). The SRT must be sufficient enough to allow the anaerobic bacteria to complete the digestion process. For a digestion system operating at 35°C, it is recommended that the minimum SRT is 10 days to avoid washout of the microorganisms (Appels et al., 2008). Less than 10 days will result in the rate of bacterial loss exceeding the rate of bacterial growth in the system. The recommended SRT for animal wastes is between 10 and 20 days (Keshtkar et al., 2003). Since hydrolysis is the rate-limiting step in the anaerobic digestion, it is essential to optimize the SRT especially when dealing with wastes containing high paniculate matter (Burke, 2001). 2.4.5 Mixing For optimal performance, mixing must ensure that the entire digester volume is being utilized, there is extensive contact between the bacteria and the substrate and that heat is being transferred effectively (Kaparaju et al., 2008). Otherwise methane production may be limited (Keshtkar et al., 2003). For wastes with higher solids content, the implementation of efficient mixing becomes ever more important in terms of producing higher biogas yields (Karim et al., 2005). The cost of mixing for a CSTR digester can be high especially when the feedstock contains materials that must be suspended throughout the digestion period (Burke, 2001). 2.4.6 Nutrients Methanogenesis is a highly sensitive process and a deficiency in certain nutrients has been shown to result in inefficient substrate removal and lower gas production (Kayhanian and Hardy, 1994). Optimizing the nutrients in anaerobic digestion enables microbial stability resulting in the maximum methane production being achieved (Hills, 1979). The main macronutrlents involved are carbon (C), nitrogen (N) and phosphorus (P). Each of the macronutrients are essential in specific quantities. In an anaerobic digestion study of fruit and vegetable wastes, the most suitable ratio of C:N:P for microbial growth was found in the range of 100:4.3:0.9 (Bouallagui et al., 2004). Apart from these macronutrients, a number of micronutrients are also important to the digestion process (Wilkie et al., 1986). Previous literature has shown that the biodegradable organic fraction of municipal solid wastes often 8 requires nutrient supplementation of nitrogen and phosphorus, and that the addition of dairy manure as a nutrient-rich source can substantially improve gas production rates (Kayhanian and Rich, 1995). Likewise, the addition of a high carbon waste to manure digestion can enhance the process by providing a more optimal C:N ratio overall (El-Mashad and Zhang, 2010; Ward et al., 2008). Organic fractions of municipal solid wastes have been successfully blended with manure with the aim of finding optimized co-digestion ratios that produce stable systems with high biogas yields (Hartmann and Ahring, 2005). 2.5 Anaerobic Digestion of Manure The potential to capture methane from manure comes from the degradation of its organic materials primarily carbohydrates, proteins and lipids (Moller et al., 2004). Previous studies of broiler manure, cattle manure and their mixtures conducted in batch reactors showed that the cattle manure alone led to a highest methane production (Gilngdr—Demirci and Demirer, 2004). The higher nitrogen content of poultry wastes can lead to ammonia inhibition in a digester. Swine manure and chicken manure have also been investigated as a potential methane sources with some encouraging results comparable to other wastes, however ammonia inhibition has also been detected (Chae et al., 2008; Hansen et al., 1998; Huang and Shih, 1981). The digestion of livestock wastes is well established with dairy being the most common, representing 82% of all digesters located in the US (AgStar, 2010b). Problems associated with manure-only digesters include the struggle to be economically feasible due to low financial returns for farmers from energy generation and lower methane yields due to inhibition by free ammonia (Hansen et al., 1998; Salminen and Rintala, 2002). However, for large farms, manure still remains a plentiful source of feedstock for anaerobic digestion and its conversion to biogas moderates the quantity of harmful greenhouse gas (GHG) emissions being released to the surrounding environment (Ward et al., 2008). 2.6 Benefits of Technology The utilization of anaerobic digestion for waste management of livestock manures introduces a number of benefits. The most significant of these advantages are discussed below. 2.6.1 Odor Control and Greenhouse Gas Emissions Farms producing large quantities of livestock manure are often a source of pollution with regards to offensive odors. In fact, according to Holm- Nielsen et al., 2009, “65% of anthropogenic nitrous oxide and 64% of anthropogenic ammonia emissions originates from the world-wide animal production sector”. The implementation of an anaerobic digester ensures significantly less odors than conventional manure management systems and is more favorable on a cost basis compared to other odor reducing alternatives (EPA, 2002). Harmful GHG emissions can also be cutback by the installation of a digester. This was verified in a study by Kaparaju and Rintala, 2010, where anaerobic systems mitigated GHG emissions on dairy, sow and swine farms. Methane originating from livestock manure is considered a major contributor to agricultural GHG emissions and is deemed 21 times more potent than carbon dioxide on a molecule to molecule basis (Steed Jr and Hashimoto, 1994; Thelen et al., 2010). Anaerobic Digesters capture the harmful gas 10 using it for energy purposes, and subsequently off-set energy that would originate from fossil fuels (EPA, 2002). 2.6.2 Ammonia Control The largest source of ammonia emissions in the United States originates from livestock with manure storage being one of the most contributing factors (Pinder et al., 2003). The control of ammonia emissions from livestock manure is usually prevented using a storage tank cover. However, the release of ammonia has become ever more serious in recent times through the impact of eutrophication and acidification of the natural environment. Emissions of ammonia are controlled in a digester system. Additionally, technologies such as chemical precipitation and stripping/absorption can further reduce ammonia losses post digestion (Wilkie, 2000). 2.6.3 Environmental Protection Pathogens, viruses and parasites contained in the feedstock will be eliminated once sufficient digester holding times and temperatures are ensured (Tafdrup, 1995). Operating in the thermophilic range, anaerobic digestion removes microbial pathogens present in the waste (Smith et al., 2005). The destruction of such organisms eradicate the possibility of contamination to surrounding groundwater and hence, human and animal health risks are reduced (EPA, 2002). Mesophilic digestion does not eradicate pathogens directly since the growth and survival of bacteria is in this temperature range. Characteristics such as the retention time are more important for pathogen removal in the mesophilic range (Smith et al., 2005). 11 2.6.4 Energy Generation In 2009, it was estimated that approximately 374 million kilowatt-hours (kWh) of energy were produced from on-farm digester systems (AgStar, 2010a). However, the estimation of yields from such biological degradation processes is very much dependent on the particular type of substrate being digested (Mata-Alvarez et al., 2000). Different substrates are often co- digested in order to increase biogas yields and in turn, generate more energy. 2.7 Co-digestion and the Potential to Enhance Biogas Yields A variety of wastes have been investigated for anaerobic co-digestion purposes. Certain food wastes can be desirable under anaerobic conditions due to high biodegradability characteristics (Zhang et al., 2007). Blending manure with organic wastes has been shown to be beneficial in terms of increasing cumulative biogas yield (Callaghan et al., 1999). This concept of co-digestion is relatively mature. The addition of organic wastes with high carbon content can overcome the problems of digesting activated sludge or manure alone (Habiba et al., 2009). Previous literature concerning organic vegetable wastes co-digested with sewage sludge at four different retention times showed increased methane yields and high degradability of such wastes (Mata-Alvarez et al., 1992). Studies co-digesting cattle slurry with fruit and vegetable waste and chicken manure in a continuously stirred tank reactors revealed that by increasing the fraction of food and vegetable waste from 20% to 50% methane yields could be improved almost two-fold (Callaghan et al., 2002). The co-digestion performance of a fruit-vegetable- municipal solid mixture that included waste from banana, apple, orange, cabbage, potatoes, bread and paper processing have also been tested with a 12 primary sludge. Under different mixing conditions and loading rates the system was found to be stable and produced more biogas than the primary sludge due to higher volatile solids content (deez et al., 2006). Alvarez and Lidén, 2008, demonstrated that the mes0phi|ic co-digestion of slaughterhouse waste, fruit vegetable waste and manure gave higher methane yields and productivity as compared to the digestion of the individual wastes alone or mixtures of two wastes. Biogas methane yields of over 60% can be achieved through the co-digestion of food waste and dairy manure (El-Mashad and Zhang,2010) 2.7.1 Food Waste Segregation Onsite segregation of food wastes at processing plants facilitates initiatives such as byproduct recovery, recycling and improved waste treatment performance. The idea hinges on technical and economic issues as well as the nature of the waste in terms of the quantity, biodegradability and the location of the processing facility (Zaror, 1992). The concept of thickening food wastes and reconstituting with manure at the digester is a novel co- digestion proposal and so there is only a small amount of relevant literature. For instance, Tsukahara et al., 1999, examined the separated liquid fraction of food waste in an upflow anaerobic sludge blanket (UASB). With the solids removed, the reactor was found to be suitable for efficient digestion of the liquidized food waste. The recovery of food residuals through energy generation is a primary constituent in any food industry’s waste management hierarchy (Bates and Phillips, 1999). By reconstituting concentrated food wastes in a digester, a potential waste-to-energy system is generated. The success demonstrated in 13 the co-digestion of organic materials from food industries with manure has given confidence to the concept of joint biogas plants and centralized digesters on a larger scale (Holm-Nielsen et al., 2009). 2.7.2 Polymer Waste Studies The onsite addition of polymers for solid-liquid separation of food waste introduces a unique feature when contemplating co-digestion with manure. Literature directly related to the effect of polymers in anaerobic digestion systems has been limited and contrasting. In the past, the addition of organic fiocculants to municipal wastewater has resulted in a sludge that was not digestible in anaerobic systems showing indications of reduced methane content, chemical oxygen demand (COD) destruction and VS destruction (Gossett et al., 1978). Chu et al., 2003, investigated the effect of three polyelectrolyte flocculants on the digestion of waste activated sludge in terms of methane generation. Gas production was found to increase in the early stages of digestion but depending on the polymer type, could inhibit digestion at later stages. A more recent study involved the use of a polyacrylamide flocculent for improving separation of solid fractions of pig waste for anaerobic digestion. The polymer was not readily degradable by anaerobic bacteria, however, it was not found to be toxic (Campos et al., 2008). 2.8 Centralized Digesters Constructing an anaerobic digestion system on every dairy farm is impractical and unrealistic. A centralized digester is a facility that allows for the collection of wastes from small clusters of farms within a certain distance (Ma et al., 2005). Such systems also offer a strategy for areas where food processing wastes are mass produced. Co-digestion of livestock manure and 14 food waste residuals in a centralized digester can generate revenue for the farmer through better biogas production and reduce waste handling costs for the food processor (Dagnall, 1995). Transportation costs are the main obstacle when planning centralized digesters. Effective shipping varies on the distance per unit volume transported (Flotats et al., 2009). Currently there are 9 centralized digestion projects in operation in the US (Roos, 2010). 2.9 Biochemical Methane Potential A batch biochemical methane potential (BMP) study is an inexpensive technique used in the laboratory to determine how biodegradable substrates are under anaerobic treatment processes (Owen et al., 1979). Literature on the BMP of various fruit and vegetable wastes with the purpose of obtaining ultimate methane yields has been well documented (Gunaseelan, 2004). Likewise, BMP tests have also been demonstrated on various other food wastes and dairy manure (Chen et al., 1988; Cho et al., 1995; El-Mashad and Zhang, 2010). Conducting initial biogas screening assays allows for estimations of the wastes energy potential and general indications of whether further study of the feedstock is warranted. However, the use of a BMP as an indicator to full-scale digestion is challenging and should be avoided as some studies have indicated over prediction of biogas production by as much as 51% (Bishop et al., 2009). The validity of a BMP assay depends on factors such as the inoculum used and the ratio of inoculum-to-waste on a VS basis. The latter parameter will now be looked at in more detail. 2.9.1 Inoculum-to-Waste Ratio For a BMP study it is essential to begin with the correct amount of acclimated inoculum with respect to quantity of waste being added. lnoculum- 15 to-waste ratios on a VS basis using domestic sewage sludge from an active digester have been examined with different feedstocks such as cellulose, napiergrass and energycane. Various ratios were tested with an inoculum-to- waste ratio of 2:1 showing the maximum conversion rates (Chynoweth et al., 1993). Another study examining inoculum-to-waste importance tested ratios of 2, 1, 0.74 and 0.43 (VS basis) on a restaurant kitchen waste. Production of methane and biodegradability potential decreased significantly for the inoculum-to-waste ratio of 0.43 (Neves et al., 2004). Further literature using ratios of 3, 2, 1.5 and 1 (VS basis) were compared in the study of maize. Digester sludge from a municipal wastewater treatment plant was used as inoculums. The results showed that the percentage of methane in the total biogas volume was very similar irrespective of ratio. This corresponded well with larger batch-scale fermentations (Raposo et al., 2006). In 2009, a similar study was developed examining methane production from the anaerobic digestion of sunflower oil cake. Numerous inoculum-to-feed ratios (3, 2, 1.5, 1, 0.8, and 0.5) were compared using granular sludge inoculum from an anaerobic reactor treating brewery wastewater. High stability was reported for all ratios between 3 and 0.8. The highest concentration of total volatile fatty acids (TVFA) was found at the ratio of 0.5 resulting in an extremely negative effect on methane production (Raposo et al., 2009). 2.10 Semi-Continuous Studies Semi-continuous operations are often used to analyze wastes in co- digestion. Cuetos et al., 2008, operated 3 L working volume semi-continuous reactors at a mesophilic temperature to examine the blend of slaughterhouse wastes and municipal solid waste. Reactors were fed via side inlet each day 16 and the system was allowed run for two SRT’s. A similar study investigating the co-digestion of slaughterhouse waste, fruit-vegetable waste and manure utilized stainless steel semi-continuous digesters with total volume of 2 L at 35°C with gas production measured via a water displacement method (Alvarez and Lidén, 2008). Glass reactors of 5 L total volume and 4 L working volume have been used previously in co-digestion studies of meat processing byproducts and sewage sludge (Luste and Luostarinen, 2010). Magnetic stir bars operating at 300 rpm provided the adequate mixing effect in the reactors. Gas produced was collected in aluminum gas bags. An alternative approach using 15 L glass reactors was conducted in a study examining the digestion of cattle slurry mixed with fruit and vegetable waste (Misi and Forster, 2002). The semi-continuous reactor had an 8.8 L working volume with the remainder comprising as headspace. An external water jacket provided maintained the heat at 35°C. The single stage digester as described by Lafitte-Trouqué and Forster, 2000, consisted of a pyrex bottle with fitted stopper on top of a magnetic stir plate. Fresh feed was pumped into the reactor daily. A wet-tip gas meter was used to provide gas measurement. Small semi-continuous systems, as mentioned above, represent continuously stirred tank reactors (CSTR). Operations such as this give a more realistic interpretation of full-scale anaerobic digestion than batch BMP studies (Owen et al., 1979). Results obtained from semi-continuous reactors can be used to observe the reaction of different substrates in co-digestion. 17 Chapter 3 Methods and Materials This chapter provides a detailed account of the respirometer, serum bottle and semi-continuous studies. Information regarding the origin of each substrate used and the different procedures for each assay are described in detail. Any calculations involved in the experimental setup are also discussed. 3.1 Food Processing Sludge Waste The FPSW was obtained from a large food processing facility on March 1, 2010. Manufactured foodstuffs at the facility included a variety of sauces (mustard, relish, barbeque), Vinegars (white, wine, cider) and pickles (kosher, fresh, sweet). Item production at the plant resulted in leftover food waste, cleaning waste and chemicals which are was washed to drain. The drainage system collects all the waste material from the production line. This wastewater is pumped over screens to remove larger particulates that are collected in a large open-top container outside of the building. A large storage tank (250,000 gallons) is used to hold the remaining wastewater. While stored the wastewater is chlorinated. This effluent is then taken from the storage tank and filtered by means of a cyclone system (Figure 3.1). This system allows for the separation/removal of finer particulates. Calcium hydroxide (Ca(OH)2), otherwise known as slaked lime, is added in order to regulate the pH of the wastewater as it enters the cyclone. Furthermore, polymers (unspecified for proprietary reasons) are added to help enhance solid separation. The final stage of waste treatment involves removing the coagulated solids from the cyclone and utilization of a belt-press filter for further dewatering (Figure 3.2). The solids that emerge at the end of the belt-press filter are known as “sludge waste’ and are ready to be Iandfilled (Figure 3.3). Remaining wastewater that 18 was generated throughout the waste management process is allowed to be injected to a well in close proximity to the plant. F,- “l ‘# m. ' I ‘1 A)” a} t ' H I I! 3m: ‘3;- ' I .. .1. 5’% Ir. 1 03/01/2010 Figure 3.1 Cyclone System at Food Processing Facility 19 Figure 3.2 Belt-Press Filter 20 . . I! - 'd'fi*’ - 1 "r1- ’3' 3..." I. er‘er"; 1: is ,. - A 03/01/2010 Figure 3.3 Food Processing Sludge Waste 21 Currently about 1,600 ton/year of FPSW is produced. The costs involved with the waste are estimated at $75-85 per ton, not including hauling costs to the landfill. Since consumer demand on certain foodstuffs varies depending on the time of year, the make-up of the F PSW itself is therefore subject to some variability. Consequently, in researching the FPSW, consistency of the sample was an important factor. The first biogas respirometer assay conducted on the F PSW was carried out on a sample collected on February 17, 2009. Subsequently, the sample for the serum bottle study was collected almost exactly a year later on March 1, 2010. This F PSW sample was used for both the serum bottle and semi-continuous systems. The pH, COD, total solids (TS) and VS of the F PSW were analyzed between studies to ensure characteristics had not changed. Only minimal differences were found in testing. 3.2 lnoculum The inoculums used for the respirometer and serum bottle assays were collected from a membrane bioreactor (MBR) located on Michigan State University campus, East Lansing, MI. The manure inoculum was digestate from the MBR that was collected in the days preceding start-up of each assay and was stored at 4°C prior to use. For the semi-continuous systems, the digestate from the batch assay was used as the seed inoculum. All remaining digestate not used for chemical analysis testing were mixed thoroughly and refrigerated until time of use. 22 3.3 Cow Manure The manure used for both the respirometer and serum bottle assays was collected from Minnis Farms, Williamston, MI and stored at 4°C prior to use. Any manure held for more than one week was stored in a freezer at -17°C. The same location supplied the manure for the semi-continuous operation. This allowed for consistency between all three studies. Tables 3.1, 3.2 and 3.3 show the initial characteristics of each constituent for the three studies. Table 3.1 Respirometer Assay Initial Characteristics Seed Diluted Sludge | pH NA 4.70 TS m /L) NA 27,612 vs m IL) 21,577 20,393 coo (mg/L) NA 46,725 Table 3.2 Serum Bottle Assay Initial Characteristics Seed Cow Manure Diluted Sludge pH 7.44 6.95 5.81 TS (mg/L) 57,600 39,893 35,607 VS (mg/L) 34,300 26,112 20,581 COD (mg/L) 81,100 59,250 38,425 Table 3.3 Semi-Continuous Study Initial Characteristics FPSW/DI Seed "2:39 FPSW 1:12;: FPsvgellgsnure pH 7.60 7.34 6.91 7.58 7.50 TS (mg/L) 16,875 27,008 321,690 95,075 112,820 vs (mg/L) 9,613 18,697 176,310 50,580 61,938 coo (mg/L) 17,188 30,763 427,130 93,550 125,550 23 Seed characteristics between the serum bottle and semi-continuous studies are shown to have significantly different values in terms of TS, V8 and COD. This can be attributed to the origin of the inoculums as mentioned in section 3.2. pH values of the diluted sludge samples appeared to have slight differences between studies. The reason for this variation remains unclear. 3.4 Respirometer Assay Design The initial biogas assay for co-digestion of the F PSW and cow manure was conducted from March 20 - April 17, 2009 with a goal of determining the anaerobic biodegradability and biogas recovery potential of co-digestion. Table 3.4 shows the compositions of the flasks used in the assay. Table 3.4 Respirometer Flask Compositions Seed Cow Diluted DI Treatment (mL) Manure Sludge Water (le (ml-l (mL) Seed 136 0 0 514 Seed, Cow Manure 136 72 0 442 Seed, Diluted Sludge 136 0 72 442 Seed, 1:1 Cow Manure: Diluted Sludge 136 72 72 370 Seed, 2:1 Cow Manure: Diluted Sludge 136 144 72 298 Seed, 1:2 Cow Manure: Diluted Sludge 136 36 72 406 The “Seed” treatment was run as a control. “Seed, Cow Manure” and “Seed, Diluted Sludge” treatments were run so that the normalized gas of the individual components (manure and F PSW) could be established by subtracting out the gas produced by the “Seed”. This method allowed for the calculation of the individual levels of gas production of each constituent. The sludge used in each treatment was diluted in the ratio of 1 part sludge to 10 parts de-ionized (DI) water so as to allow for a homogenous and consistent product that was suitable for conducting analytical tests. This was achieved by weighing 100 g of FPSW in a beaker on a ScoutTM Pro 4000 9 scale and 24 diluting the sludge to 1000 9 total with DI water. The “diluted sludge” was blended for 1 minute using a Waring® Commercial Blender. This mixture was blended several times until enough substrate was prepared for the assay. 3.4.1 Volume of Diluted Sludge and Cow Manure The volume of diluted sludge and cow manure was made on a COD basis. According to Speece, 1996, the conversion of 1 g COD destruction is equal to 395 mL CH4 at 35°C. This represents the maximum theoretical yield of methane. Therefore, to produce at least 1,000 mL methane, 2,531 mg COD was required. Past literature has shown percentage COD reductions to vary substantially depending on the waste (Chinnaraj and Venkoba Rao, 2006; Telles Benatti et al., 2002; Wilkie et al., 2004). A 50% destruction of COD was assumed based on previous BMP’s conducted and hence the amount used was 5,063 mg COD. The total volume of each treatment initially prepared was 1 L. Each respirometer bottle had a working volume of 650 mL while the remaining 350 mL was used to conduct analytical testing. Therefore, 5,063 mg was the desired amount of COD required in the initial 1 L treatment sample prepared. With the COD of the sludge calculated at 46,725 mg/L (Table 3.1), the volume of diluted sludge required for 1 L was obtained using Equation 1. Calculating for a 650 mL bottle, it was determined that 72 mL was needed. The volume of cow manure was based around the volume of diluted sludge required and the chosen blending ratios (discussed in section 3.5.1). Desired mg COD x Working Volume (mL) 000 ofSludge (91:3) x 1L Diluted Sludge Volume (mL) = Equation 1. 25 3.4.2 Volume of Seed An inoculum-to-waste ratio of 2:1 (VS basis) was chosen for this study (Chapter 2, Section 2.9.1). The diluted Sludge volume for 1 L was calculated to be 110 mL. The VS of the diluted sludge and seed were 20,393 mg/mL and 21,577 mg/mL, respectively (Table 3.1). Consequently, the seed volume was calculated by Equation 2 as 208 mL. Accounting for the 650 mL respirometer bottle the amount of seed required was 136 mL. Seed Volume (mL) = ( 2 x Diluted Sludge Volume mm x VS Sludge (%)) 28 VS Seed (mL) Equation 2. 3.4.3 Respirometer Assay Setup An anaerobic respirometer (Challenge Technology AER-200, Springdale, AR) was used for the biogas assay. The treatment flasks had total capacity of 725 mL of which 650 mL was used for liquid sample while the remaining 75 mL was left as headspace. Using the volumes calculated in section 3.4.2, the constituents of each treatment flask (Table 3.4) were added precisely. All flasks were sealed tightly with a cap and septum. An adhesive was applied to the inside of the cap to ensure a gas tight fit. The headspace in each treatment flask was flushed with 100% N2 gas for 10 minutes at a flow rate of 0.5 L/min before start-up (Owen et al., 1979). This was performed using a B-D 20 gauge needle that purged the bottle septum introducing the N2 gas, while a second needle allowed for the initial headspace gases to be flushed out. The flasks were then positioned in a water-bath that was held at mesophilic temperature (35°C). The water-bath sat on a large magnetic stir 26 plate with each flask containing a stir bar that provided adequate mixing (50 rpm). Wires with attached gauge-needles were inserted through the septum of each reaction flask and subsequently connected to individual gas counter cells. Each individual cell was then connected directly to a stand-alone computer. Real-time gas production rates and cumulative gas volumes were measured for each flask using Challenge Technology AER computer software. Biogas from each vessel was analyzed weekly for methane and carbon dioxide using a Shimazdu GC8 gas chromatograph. This was accomplished using a syringe that extracted 2 mL of biogas from the headspace which was injected into the GC column to be analyzed. Once the vessels reach maximum gas production, as indicated by a sharp reduction in the cumulative biogas production curve, the assay is considered complete. However, due to strict time constraints it was not possible for all treatments to reach this stage (discussed in Chapter 4, section 4.1.3). Hydrogen sulfide (H28) analysis was conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastec tube sampling methods. This is a rapid analysis where 100 mL of gas is pulled from the gas bag and direct measurement of H28 concentrations is read off the scale on the tube. The H28 numbers do not represent precise concentrations, but to serve as a general indicator (Appendix A, Table A8). 3.5 Serum Bottle Assay Design Table 3.5 shows the constituents of each treatment assessed are in the serum bottle assay. Each treatment was run in triplicate for QAIQC purposes. The “Seed” treatment was run as a control. “Seed, Cow Manure” and “Seed, 27 Diluted Sludge” treatments were run so that the normalized gas of the individual component (manure and diluted sludge) could be established by subtracting out the gas produced by the “Seed”. This method allowed for the calculation of the individual levels of gas production of each constituent. The sludge used in each treatment was diluted in the ratio of 1 part sludge to 10 parts water so as to allow for a homogenous and consistent product that was suitable for conducting analytical tests. The diluted Sludge was prepared in an identical fashion as to that already discussed in section 3.4. Table 3.5 Serum Bottle Compositions Seed Cow Diluted Dl Treatment (mL) Manure Sludge Water (mL) it“; (mL) Seed 30 0 0 120 Seed, Cow Manure 30 25 0 95 Seed, Diluted Sludge 30 0 25 95 Cow Manure 0 25 0 125 Diluted Sludge 0 0 25 125 Seed, 2:1 Cow Manure: Diluted Sludge 30 50 25 45 Seed, 1:1 Cow Manure: Diluted Sludge 30 25 25 70 Seed, 1:2 Cow Manure: Diluted Sludi 30 12 25 83 Seed, 1:4 Cow Manure: Diluted Sludge 30 6 25 89 Seed, 1:6 Cow Manure: Diluted Sludge 30 4 25 91 3.5.1 Volume of Diluted Sludge and Cow Manure The constituents of each bottle were determined in a similar fashion to the respirometer study discussed in section 3.4.1; however, the smaller working volume of the serum bottles were accounted for and a COD destruction of 40% was now assumed based on the results of the previous assay. Using Equation 1 and the values listed in Table 3.6, the volume of diluted sludge for the serum bottles was calculated to be 25 mL. The amount of diluted sludge remained constant for each treatment it appeared in. The blending ratios were developed in relation to the diluted sludge volume of 25 28 mL. For example, a 2:1 ratio consisted of 50 mL of cow manure to 25 mL diluted sludge. A ratio of 1:4 consisted of 6 mL of cow manure to 25 mL diluted sludge etc. The volume of diluted sludge did not change between treatments. Table 3.6 Serum Bottle Values for Equation 1 Parameter Value Desired COD (mg) 6,239 Amount to be Prepared (L) 1 COD of Sludge (mg/L) 38,425 Serum Bottle volume (mL) 150 COD Destruction (%) 40 3.5.2 Volume of Seed The determination of seed volume for the serum bottles was calculated Similarly to that presented for the respirometer study in section 3.4.2. Using Equation 2 and the values listed in Table 3.7 the volume of diluted sludge for the serum bottles was calculated to be 30 mL. Table 3.7 Serum Bottle Values for Equation 2 Parameter Value Reference Inoculum-to-Waste (VS basis) 2:1 Section 3.4.2 Sludge Volume (mL) 25 Section 3.5.1 VS Sludge (mg/L) 20,581 Table 3.2 V8 Seed (mg/L) 34,300 Table 3.2 3.5.3 Serum Bottle Assay Setup Borosilicate glass - aluminum seal, Kimble Chase serum bottles of 225 mL liquid capacity were used for all treatments in the assay. The bottles were sealed with septa and covered tightly with septa caps. Once the constituents of each co—digestion treatment were made and the subsequent bottles sealed, 29 the headspace was flushed with 100% nitrogen as described in section 3.4.3. All treatment bottles were placed in a VWR SignatureTM Forced Air Safety Oven which was held constantly at 35°C (Figure 3.4). Initially the serum bottles were incubated for two hours in the oven. After two hours, the internal pressure was returned to atmospheric by following the Biogas Production Measurement method (Section 3.5.4) and thus the assay had begun. The assay ran from March 10 — May 25, 2010. “"T:‘ . *-'mf_ ~- '.‘ 13w.” ** *1 . ~ .3! ~ ," . H... 4‘ .' . ."- e, .‘ 1: "t . >01. --~ ‘ ' ' ' Q. 4 -" . - ~WH ' “m i - r - ' . ‘ ... "'M— -k—~— #bu-h- 3 . 0018-2010 1 111.3 1. Figure 3.4 Serum Bottle Assay Setup The wastes were first analyzed for pH, COD, TS and V8 to ensure suitability for digestion as characterized in Table 3.8. Table 3.8 Digestion Parameters (Szczegielniak, 2007) Parameters Method Suggested Range Source pH pH meter 6.5 to 8.2 Speece, 1996 2000 to 3000 mg/L Alkalini Hach 8203 , 1996 W CaCO3 Speece Hach 8000 COD (EPA approved) > 1000 mg/L COD Speece, 1996 HACH 8000 after Soluble COD Filtering with TSS Filter . Hach 8271 < 10% for batch (Carucci et al., Total SONS (TS) (EPA approved) tests 2005) Volatile Solids Hach 8271 High Percent of (VS) (EPA approved) Total Solids Ammonia l-lach 10031 200 to 700 mg/L-N (Hang): 3'" Nitrogen (N) Hach 10072 Phosphorus (P) Hach 10127 3.5.4 Biogas Production Measurement To measure the biogas, the serum bottles were held at a 45° angle. A glass syringe (30 mL or 100 mL capacity) with an attached ED 20 gauge needle was inserted through the serum bottle septum. Acetone and DI water were applied to the inside of the glass syringe case and plunger before use allowing for the syringe plunger to move freely. Once the needle was inserted the biogas under pressure in the serum bottle came to atmospheric pressure in the syringe. The volume of the biogas could then be measured on the syringe scale. After removing the syringe and biogas, the internal pressure of the serum bottle was back at atmospheric. The contents of the serum bottle 31 were mixed daily by inverting the bottle slowly five times. Measuring the biogas of the serum bottles started on a daily basis. Once the biogas production began to decrease the measurement process was performed on a less regular basis (between 2 — 5 days). Biogas composition analysis was performed on a weekly basis using an SRI 86100 Gas Chromatograph along with Peaksimple computer software. Biogas was extracted from the headspace of the serum bottles as previously described in section 3.4.3 and analyzed for methane, carbon dioxide, nitrogen and hydrogen sulfide content. 3.6 Semi-Continuous Systems The final stage of research involved the implementation of five semi- continuous digestion reactors to test the FPSW. The working volume of each reactor was 2 L. Based on previous literature, the SRT of a digester involving animal wastes should be between 10-20 days and so an SRT of 15 days was chosen for this study (section 2.4.4). Using this information, the flow rate to and from the reactors was calculated using Equation 3 as 0.130 Uday. Working Reactor Volume (L) SRT (days) L = Flow Rate (—) day Equation 3. This meant that 0.130 L of sample was removed and 0.130 L of fresh sample was fed every day to the reactors. 3.6.1 Evaluating Specific Gravity An important factor of this study was to test the specific gravity of each substrate used in the semi continuous reactors (i.e. cow manure, FPSW/DI 32 and FPSW/manure). By calculating the specific gravity it could be assumed that 1 mL of cow manure, F PSW/Dl water (blended) or FPSW/manure (blended) was equivalent to 1 g in weight allowing for the removal and feeding of substrates to be conducted on both a weight and volume basis. The results of the specific gravity tests are shown in Table 3.9. Tests were conducted by placing a beaker on a ScoutTM Pro 40009 scale and zeroing the weight, measuring the weight in grams of 130 mL of each substrate three times, measuring the weight in grams of 130 mL of water once and calculating the specific gravity based on Equation 4. Table 3.9 Specific Gravity Values for each Substrate Sample Wight Averag(;)Weight $6me Cow Manure 0.130 L A 131.6 Cow Manure 0.130 L B 128.8 130.3 1 Cow Manure 0.130 L C 130.4 Water 0.130 L 130.0 130.0 FPSW/DI Water 0.130 L A 132.4 FPSW/DI Water 0.130 L B 132.2 132.5 1.019 3 1 FPSW/DI Water 0.130 L C 132.9 Water 0.130 L 130.0 130.0 FPSW/Manure 0.130 L A 132.8 FPSW/Manure 0.130 L B 132.9 133.2 1.024 g 1 FPSW/Manure 0.130 L C 133.8 Water 0.130 L 130.0 130.0 Specific Gravity = . Weight of the Substance Weight of an Equal Volume of Water Equation 4. 33 3.6.2 Optimization Study The five semi-continuous reactors contained the following constituents: 1. Seed 2. Seed, Cow Manure 3. Seed, FPSW 4. Seed, Cow Manure, FPSW 5. Seed, Cow Manure, FPSW (Duplicate) Straight reconstitution of the F PSW with manure was achieved using the semi-continuous operation. No blending ratio seemed ideal from the batch studies as indicated by the purely additive results of combining diluted sludge and manure. A study with optimum COD:N ratio for the FPSW/manure was deemed the best approach (refer to Chapter 4, section 4.2 and Figure 4.5). Chemical analysis tests were run on the cow manure and FPSW so that a COD:N ratio of approximately 20:1 could be obtained. Iterative calculations were made for Equation 5 and Equation 6. (000 Cow Manure (%) x M(Kg)) (0.45) + (000 FPSW (E?) x S(Kg)) (0.81) (M(Kg) + 80(8)) Equation 5. (Nitrogen Cow Manure (112% N) x M(Kg)) + (Nitrogen FPSW (13:13 N) x S(Kg)) (mm + 50(8)) Equation 6. COD of Cow Manure = 27,763 mg/Kg M = mass of manure in Kg 34 COD of FPSW = 427,130 mg/Kg S = mass of FPSW in Kg 0.45 is a representative figure for the percentage of undestroyed COD resulting from the “Manure” treatment in the serum bottle assay. It was calculated by subtracting the percentage COD destroyed (100%-55%). This is the quantity of COD that is relevant to the inside of the semi-continuous reactors to keep the optimum COD:N ratio. Similarly, 0.81 is a representative figure for the percentage of undestroyed COD resulting from the “Diluted Sludge” treatment in the serum bottle assay. It was calculated by subtracting the percentage COD destroyed (100%-19%). This is the quantity of COD that is relevant to the inside of the semi- continuous reactors to keep the optimum COD:N ratio. Nitrogen Cow Manure = 1,975 mg/Kg - N Nitrogen FPSW = 14,910 mg/Kg -N The COD:N ratio is optimized at approximately 20:1 (Chapter 2, section 2.4.6). Using an iterative process of entering values, coinciding with the already fixed 2 L working volume, the values of M and S were resolved to be 1.1 Kg and 0.5 Kg, respectively, using Equation 7. Equation 5 _ Equation 6 Equation 7. The COD:N:P ratio of the cow manure alone was approximately 140:10:1. The COD:N:P ratio of the FPSW alone was 219:7.5z1. Combining 1,100 g manure and 500 g FPSW was found to give an optimum COD:N ratio of approximately 20:1. For the “Seed, FPSW" treatment, 1,100 g of DI water 35 was used to comprise the full 2 L volume of the reactor. DI water does not contribute to gas production. Therefore the compositions of the semi- continuous reactor flasks could be made as shown in Table 3.10. Table 3.10 Semi-Continuous Reactor Compositions Treatment 8&9)“ Mgzme ”298;” Wgtler (9) (9) Reactor 1 Seed 400 0 0 1,600 Reactor 2 Seed, Cow Manure 400 1,600 0 0 Reactor 3 Seed, FPSW 400 0 500 1 ,100 Reactor 4 Seed, Cow Manure F PSW 400 1,100 500 0 Reactor 5 Seed, Cow Manure F PSW 400 1,100 500 0 Borosil 3 L Erlenmeyer Flasks were used for the five semi-continuous reactors. The flasks were fitted with size 11 rubber stoppers and tied tightly using metal wire. Each reactor was placed on magnetic stir plates with 3.5 Inch magnetic stir bars providing the mixing effect (350 rpm). Two holes were drilled through each stopper. Glass tubing (1 cm diameter) was fitted tightly through the holes in the stoppers. The first tube was 18 inches in length and used for removal and feeding of substrate. A valve fitting connected at the top of the glass tubing allowed access for both pumping and Shutting off of the line when not in use. The other glass tube was shorter at approximately 6 inches. This tubing was left in the headspace so that the gas generated was free to move to the wet-tip gas meters (Wet Tip Gas Meter Company, Nashville, TN) for volume measurement. Each wet-tip gas meter was calibrated to tip every 100 mL. The reactors were held in a constant temperature room at 35°C. Tubing from the top of the reactors led to the wet- tip gas meters which were held outside of the constant temperature room. 36 Dual-Valve Tedlar PVF Bags were connected via Y-fitting outside of the constant temperature room on the tubing lines connecting the reactors to the wet-tip gas meters. 3.6.3 Semi-Continuous Start Up Each reactor was set up one week before the start of the first SRT. Reactor 1 was started with the full amount of seed and DI water and connected to the wet-tip gas meter. No substrate was removed or fed throughout the entire run of Reactor 1. Reactor 2 was started with full amount of seed. In order to not ‘shock’ the system, only 500 mL of manure was added initially. The remaining manure was added gradually in the week preceding the start of the first SRT. Until the full 2 L reactor volume was reached, the gas produced was collected in a dual valve Tedlar Gas Bag. This allowed for the reactor to build up an initial amount of biogas that was later used to counteract any negative vacuum created in the system when sample was being extracted via the Masterflex® pump. Reactor 3 was started with full amount of seed. In order to not ‘shock’ the system, only 500 mL of FPSW/DI water was added initially. The F PSW/Dl water mixture consisted of 500 g of FPSW and 1,100 mL of DI water blended until homogeneous sample was obtained. Reactor 3 was gradually fed to the full 2 L reactor volume in a similar manner as that previously mentioned for Reactor 2. Reactors 4 and 5 (duplicates) were started with full quantity of seed. In order to not ‘shock’ the system, only 500 mL of FPSW/manure was added initially. The sludge/manure mixture consisted of 500 g of FPSW and 1,100 37 mL of manure blended until homogeneous sample was obtained. Reactors 4 and 5 were gradually fed to their full 2 L reactor volumes in a similar manner as that previously mentioned for Reactor 2. On the first day of the first SRT, reactors 2, 3, 4 and 5 were connected to the wet-tip gas meters. The wet-tip gas meters were continuously connected to the reactors for the remainder of the study. Figure 3.5 shows the semi-continuous reactor setup. Figure 3.6 shows the tubing that connected the reactors to the wet-tip gas meters located outside of the constant temperature room. 3‘ 9° 9" 3.6.4 Removal and Feeding of Reactors Reactors 2 - 5 were fed everyday in the following manner: Record number of tips before feeding process, Close gas line to wet-tip gas meter by switching valve off, Open gas line to Tedlar gas bag, Document date and time of feeding, Carefully place reactor on ScoutTM Pro 4000 9 scale, Attach Masterflex pump lines to the reactor, Record initial weight on the scale, Open stopcock valve on the pump line and switch pump on, Remove 130 g of sample into graduated cylinder (this allowed for removal to be conducted on a weight and volume basis), 10. Close stopcock valve once sample is removed, 11. Record weight of reactor after removal of sample, 12. Pour feed into graduated cylinder (usually over 130 mL to account for sample in the feed lines), 38 13. Open stopcock valve on the pump line and switch on pump, 14. Feed until weight is equal to the initial weight of the reactor recorded at the start of the removal/feeding process, 15. Close stopcock valve once appropriate weight is achieved, 16. Record weight of reactor after feeding of sample, 17. Carefully place reactor back on to magnetic stir plate and adjust rpm, 18. Record number of tips after feeding process (should be the same), 19. Open gas line to wet-tip gas meter by switching valve on, 20. Close gas line to Tedlar gas bag. The reactors were fed everyday for the 3 SRTS’s as accurately as possible (Appendix C, Table C.1). Stock solutions of each sample (i.e. feed for Reactor 3 and feed for Reactors 4 and 5) were prepared on a weekly basis and stored at 4°C until time of use. The number of tips on the gas meters was accounted for at the end of each day for each reactor (Appendix C, Table C.2). For safety purposes, all gas bags were inspected every day to ensure that maximum capacity had not been reached. If close to maximum capacity, gas was released slowly into the tip meter until the bag was approximately half full. Reactor mixing speeds were also checked every day to ensure it was within the specified optimum range. The gas lines were drained of any water build-up as required. This water build-up occurred due to overflow from the submerged wet-tip gas meter. Chemical analysis tests were performed on the effluent of each reactor approximately 3 times a week. The tests run comprised of pH, alkalinity, COD and TSNS, and were carried out using the same methods as discussed earlier for the batch assays (Chapter 3, Table 3.6). The substrate being fed to 39 each reactor was tested for pH, COD and TSNS at the beginning of the first SRT and was not expected to change throughout. This was confirmed by running additional characteristics tests during the second and third SRT’s (Appendix C, Table 0.12) Figure 3.5 Semi-continuous Reactor Setup 40 Figure 3.6 Tubing Connections to Wet-Tip Gas Meters 41 Chapter 4 Results and Discussion The evaluation of a dewatered FPSW reconstituted with manure in an anaerobic digester was accomplished using three separate studies. The following sections discuss the results obtained from the respirometer, serum bottle and semi-continuous systems. All the data collected throughout the studies are also reported. 4.1 Batch Systems The respirometer assay was started on March 29, 2009, and ran for 29 days in total. The serum bottle assay was initiated on March 10, 2010, and was discontinued after 77 days. 4.1.1 Respirometer Assay Results Although pH of the diluted sludge was relatively low (pH 4.7), after mixing with seed and manure, it was adequate at the beginning and end of for all treatments (Appendix A, Table A3). Alkalinity was also adequate at the beginning and end of digestion (Appendix A, Table A. 1, Table A2, Table A4). Ammonia varied between treatments; however, no effect on cumulative biogas yield is expected based on the literature as levels are adequate but not toxic (Table 4.1 and Appendix A, Table A. 1, Table A. 2). The amount of ammonia in the “Seed, Cow Manure” flask was higher than needed for the COD but not toxic. However, this level was near optimal for several of the manure, diluted sludge blends. COD and VS destruction ranged from 22-27% when cow manure and sludge were combined and was lower when only manure was digested (Table 4.2). Trends associated with soluble COD destruction were not observed (Appendix A, Table A9). 42 Table 4.1 Ammonia and COD/Ammonia Before and After Digestion Ammonia (mg) COD/Ammonia T'eatment Initial Final Initial Final Seed 235 259 20:1 17:1 Seed, Cow Manure 323 390 24:1 16:1 Seed, Diluted Sludge 229 299 31:1 19:1 Seed, 1:1 Cow Manure: Diluted Sludge 340 449 30:1 17:1 Seed, 2:1 Cow Manure: Diluted Sludge 413 544 34:1 19:1 Seed, 1:2 Cow Manure: Diluted Sludge 285 365 30:1 19:1 Table 4.2 Respirometer COD and VS Destruction coo vs 2 = 2" = Treatment 3 ’5 ~— 32 3 ‘51 v .3 E— 5 3 9 E 5 g 3 I! - N - :g .2 g E 2g .E 3 E - ‘L 8 .\° - “' 8 32 D 0 Seed 4,591 4,428 163 4 3,378 2,891 487 14 Seed, Cow Manure 7,613 6,346 1,267 17 5,410 4,2121,198 22 Seed, Diluted Sludge 7,166 5,753 1,413 20 4,704 3,6151,089 23 Seed, 1:1 Cow Manure: muted Sludge 10,294 7,564 2,730 27 6,728 4,865 1,863 28 seed?” C°w Mame: I14,235 10,351 3,884 27 8,546 6,280 2,266 27 Dlluted Sludge Seed 1:2 Cow Manure: ’ | Di'uted smge l8,678 6,809 1,869 22 5,689 4,1701,519 27 The percentage of methane in the biogas (Figure 4.1) was similar across all treatments (average approximately 68 - 78%). However, the “Seed and “Seed 2:1 Cow Manure: Diluted Sludge” showed an obvious delay. Table 4.3 shows the biogas production represented as mL of biogas per gram of substrate VS destructed. Cow manure co-digested with diluted sludge at a 1:2 and 2:1 ratio produced more biogas per 9 VS destroyed than the digestion of manure alone. However, biogas yield from co-digestion of cow manure and diluted sludge at a 1:1 ratio did not produce more biogas compared with the 43 digestion of manure or diluted sludge alone. Figure 4.2 shows a graph of the total biogas production over time. 90 80 70 60 50 40 30 20 1 0 0 Methane % 0 100 200 ——Seed —0 - Seed, Diluted Sludge 300 ------- Seed, Cow Manure 400 Hours 500 600 700 —)( -Seed, 1:1 Cow Manure: Diluted Sludge ----Seed, 2:1 Cow Manure: Diluted Sludge — - Seed, 1:2 Cow Manure: Diluted Sludge Figure 4.1 Respirometer Biogas Methane Content Table 4.3 Respirometer Biogas per g COD and 9 VS Destroyed 11; A .. 36 .. a 1‘; E’ 8 E 3 8 3 T § " '§ 6‘ E. E E reatment E g t '5 2 3: 2 a 1 8 8 g. 8 g l 9 8 '9 8 9 19 g o l- o l- a: I- a: Seed 135 163 830 487 280 Seed, Cow Manure 897 1,267 710 1,198 750 Seed, Diluted Sludge 911 1,413 640 1,089 840 Seed, 1:1 Cow Manure: Diluted Sludge , 1,291 2,730 470 1,863 690 Seed, 2:1 Cow Manure: Diluted Sludge 1,839 3,884 470 2,266 810 Seed, 1:2 Cow Manure: Diluted Sludge 1,459 1,869 780 1,519 960 44 2000 1800 1600 1400 1200 1000 800 600 400 200 Gas Production (mL) 0 200 400 600 800 Hours — - Seed — -Seed, Cow Manure -- — Seed, Diluted Sludge ----Seed, 1:1 Cow Manure: Diluted Sludge ------- Seed, 2:1 Cow Manure: Diluted Sludge Seed, 1:2 Cow Manure: Diluted Sludge Figure 4.2 Respirometer Cumulative Biogas Volume Both the diluted sludge and manure showed a very similar amount of normalized gas production (Table 4.4). However, accounting for the 10 fold dilution, the energy potential from the F PSW was an order of magnitude higher than the manure. In the manure and diluted sludge blended flasks, the “Seed 1:1 Cow Manure: Diluted Sludge” and “Seed 2:1 Cow Manure: Diluted Sludge” flasks produced 23% and 24%, respectively, less biogas than predicted by adding the individual levels of each constituent (seed, cow manure and diluted sludge). This may indicate that the higher level of manure resulted in an antagonistic impact (Table 4.5). However, the “Seed, 1:2 Cow Manure: Diluted Sludge” flask had an actual gas production that was 13% higher than the addition of the individual components indicating a synergistic relationship. Interestingly, this trend matches the quantity of manure. The worst, middle, 45 and best gas production resulted in the flasks with 144, 72, and 36 mL of manure, respectively. Table 4.4 Normalized Respirometer Energy Potential Original _ 3 Normalized Volume Blogasl Brogasl Gas after Dilute Dilution Original Component Produced , _ + Sample Ratio Sample (mL) Dllutlon (ms/L) (m3’L) (le Cow Manure 762 72 0.011 1:1 0.011 Diluted Sludge'k 776 72 0.01 1 1021 0.108 * Based on “Seed, Diluted Sludge” minus “Seed” +At experimental Temperature (35°C) and Standard Pressure Table 4.5 Respirometer Biogas Potential Diluted Seed Manure Expected Measured % Treatment (mL) (mL) 8:31? Gas (mL) Gas (mL) Difference Seed, 2:1 Blend 135 1,524 776 2,435 1,839 -24 Seed, 1:1 Blend 135 762 776 1,673 1,291 -23 Seed, 1:2 Blend 135 381 776 1,292 1,457 13 Results from this assay indicated that blending FPSW with manure has the potential to significantly increase gas production. However, the ratio of the blend appears to be important. 4.1.2 Serum Bottle Assay Results Although pH of the sludge was relatively low (pH 5.81), once the treatments were mixed with seed and manure, it was adequate at the beginning and end of digestion (Appendix B, Table 83). The “Diluted Sludge” treatment had a slightly low pH before and after digestion of 5.76 and 6.25, respectively. Alkalinity was adequate at the beginning and end of digestion (Appendix B, Table 8.1, Table 3.2, Table 8.4). Ammonia varied between treatments; however, no effect on cumulative biogas yield is expected based on the literature as levels are adequate but not 46 toxic (Appendix B, Table 81, Table B2 and Table B6). The “Seed, 2:1 Cow Manure: Diluted Sludge” treatment had a slightly high post-digestion ammonia value of 813 mg/L-N although no toxicity issues were suspected. The optimum C to N ratio for anaerobic digestion is 20-30:1 (Bouallagui et al., 2004). Taking COD as a representative value of C, all of the blended treatments were initially in this range apart from the 1:1 blend ratio which was slightly low . However, after digestion, C to N ratio values were all lower than recommended in literature for the blended treatments as shown in Table 4.6. Table 4.6 COD:N:P Before and After Digestion Nitrogen Phosphorus COD:N:P Treatment (mg) (mg) Initial Final Initial Final Initial Final Seed 105 106 36 29 75:3:1 57:4:1 Seed, Cow Manure 161 153 42 41 73:4:1 52:4:1 Seed, Diluted Sludge 135 143 36 38 90:4:1 60:4:1 Cow Manure 69 65 6 7 199:12:1 77:9:1 Diluted Sludge 33 20 3 4 309:10:1 232:6:1 Seed, 2:1 Cow Manure: Diluted Sludge Seed, 1:1 Cow Manure: Diluted Sludge Seed, 1:2 Cow Manure: Diluted Sludge Seed, 1:4 Cow Manure: Diluted Sludge Seed, 1:6 Cow Manure: Diluted Sludge 223 255 70 64 762311 50:4:1 255 190 53 48 79:5:1 56:4:1 144 176 47 41 772321 64:4:1 154 150 43 38 80:4:1 62:4:1 1 05 145 44 38 NA 66:4: 1 COD destruction increased when cow manure and diluted sludge were combined in the 2:1 and 1:1 blended treatments compared to when manure- only was digested. The “Seed, 1:2 Cow Manure: Diluted Sludge” and “Seed, 1:4 Cow Manure: Diluted Sludge” treatments were not statistically different from manure alone. The “Seed, 1:6 Cow Manure: Diluted Sludge” treatment 47 data was not available due to an error in COD testing. It is suspected that an error also occurred for the initial COD of the “Seed” treatment (2,685 mg) as it resulted in a high destruction value in relation to the quantity of gas produced. VS destruction for the “Seed, 2:1 Cow Manure: Diluted Sludge” and “Seed, 1:1 Cow Manure: Diluted Sludge" treatments were higher than when manure was digested alone. The 1:2, 1:4 and 1:6 treatments were not statistically different compared to manure—only digestion (Table 4.7). Trends associated with soluble COD destruction were not observed (Appendix B, Table B.7). Table 4.7 Serum Bottle COD and VS Destruction coo vs a C a C 1 a 3 1 ‘1 1 3 1 Treatment : :E, E. g 1' : a g 1 1 1 1 1 1 .E u- g 32 .5 IL 3 32 D 0 Seed 2,685 1,624 1,061 40 1,356 979 377 28 Seed, Cow Manure 3,058 2,135 923 30 1,8141,242 572 32 Seed, Diluted Sludge 3,214 2,266 948 29 1,8761,210 666 36 Cow Manure 1,193 540 653 55 584 344 240 41 Diluted Sludge 1,044 843 201 19 572 280 292 51 seed’.2:I C°w Mam”: 5,312 3,222 2,090 39 3,085 1,953 1,132 37 Dlluted Sludge seed’.131C°WMa””'e‘ 4,179 2,669 1,510 36 2,4821,517 965 39 Dlluted Sludge seed'IZZ C°WMa"“'e: 3,606 2,619 987 27 2,0841,415 669 32 Dlluted Sludge ‘ seed'.1:4 CWMaM'e: 3,437 2,388 1,049 31 1,9151,343 572 30 Dlluted Sludge seed'.1‘6 C°w Manure‘ 1,877 2,496 NA NA 1,977 1,347 630 32 Dlluted Sludge The percentage of methane in the biogas (Figure 4.3) was similar across alt blended treatments (average 57 - 59%). The “Seed, Cow Manure”, “Seed, Diluted Sludge” and “Cow Manure” treatments had similar biogas 48 methane content. The “Diluted Sludge” treatment had low methane content. Figure 4.4 shows a graph of the total biogas production over time. 8O Methane % 0 T I 1 0 1000 1500 2000 Hours ------- Seed - - -Seed, Cow Manure —‘ - Seed, Diluted Sludge ----Cow Manure Diluted Sludge — - Seed, 2:1 Cow Manure: Diluted Sludge -+ - Seed, 1:1 Cow Manure: Diluted Sludge - - Seed, 1:2 Cow Manure: Diluted Sludge -— ~ Seed, 1:4 Cow Manure: Diluted Sludge — -Seed, 1:6 Cow Manure: Diluted Sludgg Figure 4.3 Serum Bottle Biogas Methane Content 1500 A ..- II" .. - . .7... ..I .. a’ E [or z 1000 v 4. airl- ° / +-+ + +""'+ ° :3 0' + U ‘I M f I 3 ‘ + on“— D d. “I, --" ' 1 A W“? ”5:: T 0 ...-fl '7 'i' _— fl . 0': 500 1’14“ /-" 33%;- - -— "" '7 g '7 ‘4? .' - .— I— u— 0 I ’------------------- 1000 1500 2000 Hours ------- Seed — -Seed, Cow Manure - - Seed, Diluted Sludge ----Cow Manure —Diluted Sludge --0-- Seed, 2:1 Cow Manure: Diluted Sludge) —+ - Seed, 1:1 Cow Manure: Diluted Sludge — - Seed, 1:2 Cow Manure: Diluted Sludge --—-. - Seed, 1:4 Cow Manure: Diluted Sludge - - -SeecL 1:6 Cow Manure: Diluted Sludg_e_ Figure 4.4 Serum Bottle Cumulative Biogas Volume 49 Total biogas production represented as mL of biogas per gram of substrate VS destructed is shown in Table 4.8. A one-way ANOVA, using Tukey HSD with 95% confidence limits, was run in order to see if there were any significant differences in individual treatment blend ratios and between blend ratios and the digestion of manure alone. The analysis was run on both a total gas produced per g COD destroyed (ng) basis and total gas produced per 9 VS destroyed (mL/g) basis. For both COD and VS parameters, there was no statistical difference found between the different treatment blends and the digestion of manure alone. Similar results were found in the comparison of individual treatment blends with again no statistical difference found. Table 4.9 shows a portion of the statistical output. Table 4.8 Serum Bottle Biogas per g COD and 9 VS Destroyed Diluted Sludge u a \ A ‘ o 13 at g E. 5 g, E g B 3 o "' 3 >4 8 3 1g a .. 13 3 o A Treatment a .l g a o 3 3 a. 3 3 g 5 t; a a E :3 a o E Q a a V n (B v 0 O 0 o R (D (D '5 o '5 o 3 3 2 o 1- 8 3 °’ > .2 Seed _ 246 1,061 230 377 650 Seed, Cow Manure 656 923 710 572 1,150 Seed, Diluted Sludge 602 948 640 666 900 Cow Manure 308 653 470 240 1,280 Diluted Sludge 80 201 400 292 270 Seed, 2:1 Cow Manure: Diluted Sludge 1,312 2,090 630 1,132 1,160 Seed, 1:1 Cow Manure: Diluted Sludge 990 1,510 660 965 1,030 Seed, 1:2 Cow Manure: Diluted Sludge 769 987 780 669 1,150 Seed, 1:4 Cow Manure: Diluted Sludge 695 1,049 660 572 1,220 Seed, 1:6 Cow Manure: 660 NA NA 630 1,050 50 Table 4.9 Statistical Output Treatment Mean Mean 3:: 3:" E9113 3:: Va r. Var. Blend 9 VS 9 COD 9 VS 9 COD 9 VS 9 COD 9 VS 9 COD Me— 1.123 0.687 0.093 0.100 0.024 0.029 0.009 0.010 2:1 1.160 0.627 0.036 0.021 0.021 0.012 0.001 0.000 1 :1 1.027 0.657 0.045 0.015 0.026 0.009 0.002 0.000 1 :2 1.153 0.797 0.070 0.159 0.041 0.092 0.005 0.025 1 :4 1.223 0.667 0.107 0.060 0.062 0.035 0.011 0.004 1 :6 1.050 0.010 0.006 0.000 Once again, both the sludge and manure showed a somewhat similar amount of normalized biogas production (Table 4.10). However, accounting for the 10 fold dilution, the energy potential from the Sludge was significantly higher than the manure. Table 4.10 Normalized Serum Bottle Energy Potential Normalized Original Biogas! Biogas] C om on ent Gas Volume at?" Dilute Dilution Original p Produced Dilution Sample Ratio Sample (le (mL) (m’ILl (m’ILl Cow Manure 410 25 0.062 1:1 0.062 Diluted Sludge* 356 25 0.054 10:1 0.539 Diluted Sludge** 334 25 0.051 10:1 0.506 * Based on “Seed, Sludge” minus “Seed” "Based on “Seed, 1:1 Cow Manure: Diluted Sludge” minus “Seed, Manure” +At experimental Temperature (35 °C) and Standard Pressure Table 4.11 shows the biogas predicted by adding the individual levels of each constituent (seed, cow manure, and diluted sludge) and the actual measured biogas from the study. The co-digestion treatment effects seem to be additive, showing no true synergistic or antagonistic response as the differences between the expected and measured gas are minimal overall. 51 Table 4.11 Serum Bottle Biogas Potential Seed Manure Slud e Ex ected Measured T'“""°"t (mL) (mL) (ng Ga: (mL) Gas (mL) % Seed, 2:1 246 820 356 1,422 1,312 -8% Seed, 1:1 246 410 356 1,012 990 -2% Seed, 1:2 246 205 356 807 769 -5% Seed, 1:4 246 103 356 704 695 -1% Seed, 1:6 246 68 356 670 660 -2% 4.1.3 Discussion of Batch Assays For the respirometer study, further examination of Figure 4.2 deemed that the assay was not run for a sufficient amount of time as gas production was still increasing when the flasks were discontinued. Therefore, the true effect of the diluted sludge in co-digestion was not realized. However the respirometer study did indicate that the reconstitution of FPSW with manure could possibly offer a synergistic relationship at certain blended ratios and so further examination was warranted. The serum bottle assay ran for over 70 days with the intention of finding the optimum blend ratio of the FPSW with cow manure in co-digestion to give a possible synergistic effect as already indicated by the respirometer assay. Initially, the optimum ratio was thought to be related to the quantity of the manure present in the mixture, with the lowest amount providing the best biogas potential. Therefore, the objective of the serum bottle assay involved investigating even lower manure-to-diluted sludge ratios (1 :4, 1:6) while also looking at the conditions already tested (2:1, 1:1 and 1:2). Gas production results of the serum bottle assay did not show evidence of a synergistic or antagonistic relationship in co-digestion. Results showed that the methane produced from the diluted sludge when mixed with cow manure is additive. However, by volume, the FPSW has approximately 52 10 times the energy potential of manure. Further, the FPSW alone does not have the addition of nutrients and a buffering system. The addition of manure provides an adequate amount of both. 4.2 Semi-continuous System The results from the batch assays Showed that the FPSW contained a great deal of embedded energy; however no optimum blend in co-digestion was recognized. This was signified by finding no statistical difference between treatment blends in terms of g COD and 9 VS destruction and also by the relatively small difference between predicted and measured gas production levels. To verify the utility of the F PSW’s reconstitution with manure it was important to examine the substrate in a semi-continuous operation that would more accurately represent real-life digestion. The semi-continuous digesters were implemented in the form of continuously stirred tank reactors (CSTR) as might occur on a real-life centralized farm digester. Since gas production was found to be additive, the best approach to the semi-continuous analysis was optimizing the carbon to nitrogen ratio (CzN). The rationale behind this decision was based on the decision flow chart illustrated in Figure 4.5. This flow chart was carefully created based on past experience of running laboratory-scale batch BMP assays of various wastes. Since no significant statistical difference was found for biogas produced per 9 VS destroyed for the different blends, it was advocated that the optimization of C:N should be made for a further semi-continuous study. Although the decision flow chart shown in Figure 4.5 was developed for the purposes of this research, it can be used for any potential co-substrate BMP study to make well informed, educated decisions. 53 fiewfiéU EBEoEom . . IV . . .€3w . oZ . II 2.98.2 92.0 mzozczcou-_Eom “oz 00 > mo> 82530 38:0 .7 23m «mom _ mo> 800:0 2x0... 0 Z mo> mdotzm E2532 2?. _ J €2on EoEoE Eng—no.5 a_=oEE< 5:58.? In muoxobmoa wEflEoi “mo—2 “Coachmen m>w ..8 x025 ..8 0.820 do.“ x026 m>w dog cones—OPE 9 0931 03mm 2: 26th Log 55385 28502 30 8:3. 50253 .80 Swami e\e 52?: oocodota EmoEcwa _ .r a 1 1 - QEmcozflom - F 9:20:29; oszowS=< _ _ 03:22 22.5 _ ouflcowficsoummwdoim _ 3:25:23. ocflwdocxm _ - > - 283 ”23:32 w; 1 1w owcam E 2.3— 3655 88:85 .3 5533.050 ”33m ...—zom EEom seam :28 26E .3368 3 2:9“. 54 4.2.1 Semi-Continuous Study Results and Discussion The semi-continuous reactors were started on June 17, 2010 and ran for three SRT's, 45 days in all. The study ceased on August 1, 2010. On day 13 of the first SRT, Reactor 1, containing just seed inoculum, was discontinued as gas production had ceased. This signified that the addition of seed in the start up of the other reactors was negligible in terms of contributing to gas production. The initial and final analysis characteristics of Reactor 1 are shown in Table 4.12. Table 4.12 Reactor 1 Analysis Reactor 1 Day 1 Day 13 pH 7.60 7.42 TS (mg) 33,750 6,834 VS (mg) 19,226 3,830 COD (mg) 34,376 7,300 Reactor 2, containing manure with acclimated seed, was replaced with a substitute reactor of same composition on day 13 of the first SRT due to a malfunction. No effect on pH, COD, alkalinity, TSNS or gas production was evident as a result of the changeover. The reactor was fed on a daily basis without disruption. The COD and VS destruction of the new Reactor 2 returned to normal after the first few days of the new start-up. Reactors 3 and 4, containing FPSW/DI water with seed and FPSW/manure with seed, respectively, ran for the 3 SRT’s uninterrupted. Both reactors were fed daily for the entirety of the operational run. From day 12 of the second SRT and onwards, no sample was removed or fed from Reactor 5 that contained FPSW/manure with seed. This reactor was a duplicate to be run in conjunction with Reactor 4, comprising of 55 the same constituents. Concerns over the quantity of FPSW remaining to complete the study, as it unexpectedly was no longer available, forced the decision to discontinue feeding of the reactor. However, the reactor was left to run for the remainder of the second and third SRT’s and gas production was recorded. The pH of all reactors were within the acceptable range at the beginning and end of their respective digestion run times (Appendix C, Table C.3). However, the pH of reactor 3 was slightly low throughout. This can be attributed to the FPSW’S initial pH being low (Chapter 3, Table 3.1, Table 3.2, Table 3.3). The alkalinity of each reactor was also measured for the 3 SRT’s. Reactors 2 and 4 showed no imminent problems as values remained at a suitable high range throughout (Appendix C, Table C4). The possibility of denitrification was suspected for Reactor 3. This was illustrated by increasing alkalinity and a corresponding rise in pH, both of which characterized the denitrification process (Henze et al., 2002). Measurements of COD and TSNS were made on the effluent approximately three times a week (Appendix C, Table 0.5 and Table C3, C7, C8 and C9). Figure 4.6 Shows the overall gas production for the full 45 days of operation. The graph shows that Reactor 4, containing the optimum blended C:N ratio of manure and FPSW, significantly outperformed the rest of the reactors. In fact, Reactor 4 (106,600 mL) generated more than twice as much biogas as Reactor 2 (45,500 mL) that contained cow manure alone. Reactor 3, containing just F PSW, performed poorly in terms of gas production although this was to be as expected due to deficiencies in nutrient content. As anticipated, only a very small quantity of biogas was produced by Reactor 1 56 containing just seed inoculum. Reactor 5, a duplicate of Reactor 4 which was discontinued in the second SRT, showed promising Signs of high gas production although it did seem to have a longer lag time than its replicate. 120000 1 00000 80000 60000 40000 Gas Production (mL) 20000 0 . . 0 5 10 15 20 25 30 35 40 45 Days - - -Seed - - Manure — -FPSW — FPSW/Manure ------ FPSW/Manure Dup. Figure 4.6 Semi-Continuous Cumulative Biogas Volume Examining the biogas produced per individual SRT, similar results were observed. Figures 4.7, 4.8 and 4.9 Show the gas production for the first, second and third SRT’s, respectively. With identical 2 L reactor working volumes, the blend of FPSW/manure produced 2.36 times as much biogas as the reactor containing only manure for the third SRT. Again, this third SRT represented a stabilized system. For the first and second SRT’s, the FPSW/manure also outperformed the manure digester producing 1.82 and 2.84 times as much biogas. Reactor 3 containing FPSW consistently produced the lowest yield of biogas for each SRT. 57 35000 30000 25000 20000 1 5000 1 0000 Gas Production (mL) 5000 Days — -Seed - - Manure — - FPSW — FPSW/Manure ------ FPSW/Manure Dup. Figure 4.7 SRT 1 Biogas Production _EJ / s / 'o 8 o. ' ----- ‘0 ' 7": 8 ...;I'f ’ ’ ’ 10 15 - - Manure -- . FPSW —FPSW/Manure ------ FPSW/Manure Dup. Figure 4.8 SRT 2 Biogas Production 58 35000 30000 / AANN 001001 0000 COCO 0000 Gas Production (mL) ’ ’ ’ 5000 / 1’ ’ ‘ ...... "" 0'1 “- 1 l I 0 5 1 0 1 5 Days - - Manure — ~FPSW —FPSW/Manure Figure 4.9 SRT 3 Biogas Production The percentage methane of each reactor from day 26 to day 45 is represented in Figure 4.10. Average values for methane content are determined in Table C10 in Appendix C. The reactor containing manure-only had the highest percentage methane in the biogas averaging 62%. This was followed closely by the F PSW/manure reactor that contained 58% methane in the biogas. Reactor 3, containing FPSW alone, had substantially lower methane content at approximately 35%, yet again showing the system lacked the sufficient nutrients. Although discontinued at an earlier stage, Reactor 5 had already reached a promising biogas methane content of 58%. 59 7O 65 ...: ............. 60 ......... .-A: .......... N o ._ - ...—— ‘1— a—I- ' -— _ ~ ~ 55 a: S 50 :5 o 2 45 \ 0 e\ \ I 40 \ I \ I - - - - \ 35 \ l \ 30 fi~_ .. .. ..a— 5-‘l 25 r . 1 a 25 30 35 40 45 Day ------ Manure - - FPSW — ~FPSW/Manure Figure 4.10 Semi-Continuous Biogas Methane Content COD and VS destruction for the manure reactor (Reactor 2), the F PSW reactor (Reactor 3) and the FPSW/manure reactor (Reactor 4) were examined for all 3 SRT’s (Table 4.13, Table 4.14, Table 4.15). Using the third SRT as that representing a steady and stabilized system, the destruction rates could be compared. For COD destruction, Reactor 2, containing manure and Reactor 4, containing FPSW/manure, were very similar averaging at 33% and 34%, respectively. Reactor 3, containing F PSW alone, was drastically lower at averaging at approximately 7%. Destruction data concerning Reactor 5 is Shown in Appendix C, Table C.11, although the relevant percentages are lower as it did not reach the third SRT. 60 Taking the third SRT as representing a steady and stabilized system, the VS destruction was highest in Reactor 4, containing the optimized FPSW/manure blend, averaging approximately 45%. Reactor 2, containing manure, and Reactor 3, containing FPSW alone, were similar in terms of VS destruction averaging 31 and 33% respectively. VS destruction for Reactor 5 averaged approximately 41% for the duration of its run (Appendix C, Table 0.11). Table 4.13 Reactor 2 COD and VS Destruction COD VS Reazctor a ’15 1: 5 ‘3 3 'o .6 Day 3% E E g E 3% E E g I? - .\° " .\° 2 3,999 3,250 749 19 2,431 1,235 1,195 49 6 3,999 3,663 336 8 2,431 1 ,932 498 20 8 3,999 3,757 242 6 2,431 1,975 456 19 12 3,999 3,094 905 23 2,431 1,818 612 25 16 3,999 4,212 NA NA 2,431 2,002 429 18 19 3,999 3,985 15 0 2,431 2,051 380 16 21 3,999 3,549 450 11 2,431 1,827 604 25 23 3,999 3,403 596 15 2,431 1,821 610 25 26 3,999 2,860 1,139 , 28 2,431 1,698 732 30 28 3,999 2,678 1,321 33 2,431 1,606 824 34 ' 30 3,999 2,782 1,217 30 2,431 1,600 831 34 - 33 3,999 2,623 1,376 34 2,431 1,541 889 37 35 3,999 2,545 1,454 36 2,431 1,520 910 37 37 3,999 2,603 1,396 35 2,431 2,003 428 18 40 3,999 2,880 1,120 ' 28 2,431 1 1,894 537 22 42 3,999 2,545 1 .454 36 2,431 1 .608 823 34 44 3,999 2,730 1,269 l 32 2,431 1,617 814 33 61 Table 4.14 Reactor 3 COD and VS Destruction COD VS Reactor ... A u 8 A A '0 S 3 2’ E’ 2... '3 ‘e” E’ 2.- a ‘5 E £3 § :‘5 =5 +2.33 1?. Day E E 3 n: E E 8 m " =2 ' .\° 2 12,162 11,141 1,021 8 6,575 3,760 2,816 43 6 12,162 11,564 598 5 6,575 4,074 2,502 38 8 12,162 12,220 NA NA 6,575 4,264 2,312 35 12 12,162 11,323 839 7 6,575 4,230 2,345 36 16 12,162 11,291 871 7 6,575 4,141 2,434 37 19 12,162 11,388 774 6 6,575 4,449 2,126 32 21 12,162 11,518 644 5 6,575 4,734 1,842 28 23 12,162 12,766 NA NA 6,575 4,629 1,946 30 26 12,162 12,188 NA NA 6,575 4,356 2,219 34 28 12,162 11,408 754 6 6,575 4,249 2,327 35 30 12,162 12,162 0 0 6,575 4,470 2,105 32 33 12,162 11,538 624 5 6,575 4,342 2,233 34 35 12,162 11,063 1,099 9 6,575 4,534 2,041 31 37 12,162 11,720 442 4 6,575 4,268 2,308 35 40 12,162 11,499 663 5 6,575 4,389 2,186 33 42 12,162 11,148 1,014 8 6,575 4,335 2,241 34 44 12,162 10,277 1,885 ' 16 6,575 4,435 2,140 33 62 Table 4.15 Reactor 4 COD and VS Destruction COD VS Reactor c c i i 35’ 13 E i 3.3 i Day 2 t: 8 g s t: a g, 2 16,322 12,233 4,089 25 8,052 4,173 3,879 48 6 16,322 12,747 3,575 22 8,052 4,841 3,211 40 8 16,322 13,176 3,146 19 8,052 4,732 3,320 41 12 16,322 11,863 4,459 27 8,052 4,953 3,099 38 16 16,322 12,428 3,894 24 8,052 4,719 3,333 41 19 16,322 12,877 3,445 21 8,052 4,797 3,255 40 21 16,322 11,778 4,544 28 8,052 4,739 3,313 41 23 16,322 10,849 5,473 34 8,052 4,395 3,657 45 26 16,322 1 1,869 4,453 27 8,052 4,616 3,436 43 28 16,322 10,738 5,584 34 8,052 4,332 3,720 46 30 16,322 10,355 5,967 37 8,052 4,018 4,034 50 33 16,322 11,518 4,804 29 8,052 4,447 3,605 45 35 16,322 10,712 5,610 34 8,052 4,495 3,557 44 37 16,322 10,446 5,876 36 8,052 4,271 3,781 47 40 16,322 10,810 5,512 34 8,052 4,373 3,679 46 42 16,322 1 1 ,362 4,960 30 8,052 5,047 3,005 37 44 16,322 10,602 5,720 35 8,052 4,511 3,541 44 Tables 4.16 and 4.17 show the reactors’ biogas produced per g COD and 9 VS destroyed, respectively. Figures were based on the data collected over the final SRT to ensure analysis was relevant for a stabilized system. Reactor 2, containing only manure, had the highest gas production on both a g COD and 9 VS destruction basis. Interestingly, the optimized blend of FPSW/manure (Reactor 4) demonstrated the lowest gas production per g COD destroyed. On a 9 VS destruction basis, Reactor 4 was only half as efficient as Reactor 2 in terms of gas production. However; although less efficient, Reactor 4 was still vastly outperforming Reactor 2 in terms of overall 63 biogas production. This signifies that hydrolysis of some of the solids associated with the FPSW was not possible in the chosen SRT of 15 days. Though evidence suggests a low rate conversion, Reactor 4 still produced a quantity of biogas that indicated a synergistic relationship. Table 4.16 Reactor Biogas per g COD Destroyed Average Total Average COD Total Gas SRT 3 Gas per day Destroyed per Produced per 9 over SRT day over SRT COD Destroyed (mL) (9) (ng) Reactor 2 Manure 868.75 1.33 653 Reactor 3 FPSW 387.50 0.82 473 Reactor 4 FPSW/Manure 2062.50 5.49 376 Table 4.17 Reactor Biogas per 9 VS Destroyed Average Total Average VS Total Gas SRT 3 Gas per day Destroyed per Produced per 9 over SRT day over SRT VS Destroyed (mL) (9) (must) Reactor 2 Manure 868.75 0.75 1,158 Reactor 3 FPSW 387.50 2.18 178 Reactor 4 FPSW/M a nu r e 2062.50 l 3.60 573 In evaluating the results of the semi-continuous reactors the percentage of the maximum theoretical methane yield was calculated using Equation 8. Equation 8 is based on the principle that 1 gram of COD destruction equals 395 mL CH4 (Speece, 1996b). Table 4.18 shows the relevant values for each reactor as pertains to Equation 8. All the values 64 presented were based on the third SRT to ensure estimates were made on a stabilized system. Reactor 2, containing manure, had a methane yield minimally greater than the calculated maximum theoretical methane available. Experimental error in COD analysis during digestion was allowed within a 10% range. Accounting for this, the actual methane yield was within range of maximum theoretical yield, however, Reactor 2 showed almost complete efficiency. Reactor 3, containing F PSW-alone, produced a smaller percentage yield of maximum theoretical of approximately 44%. This can be contributed to the higher carbon dioxide content existing in the biogas. Finally, the optimized blend in Reactor 4 was estimated to be yielding approximately 58% of the maximum theoretical methane available. More capacity, for example, increasing reactor SRT, may be required to enhance efficiency. Total Gas Production (mL) x Methane Content (%) COD Destoyed (g) x 395 (%) % Yield = Equation 8. Table 4.18 Reactor Values for Equation 8 Average COD TOW Gas Methane SRT 3 Destroyed Production" Content (9) (mL) (%) Manure 1.33 907 62 FPSW 0.82 405 35 FPSW/ Manure 5.49 2,153 58 * Corrected for standard temperature (35°C) and pressure (STP) 65 Chapter 5 Conclusions and Future Research Conducting the two initial batch BMP assays provided the starting point in the assessment of reconstituting the FPSW with manure. Results projected that digestion of substrates was additive and that the FPSW could potentially be an excellent co-substrate if reconstituted with manure at a farm digester. Culmination of the BMP studies resulted in the formation of a decision flow chart, Figure 4.5, to establish optimum co-substrate blending ratios and deciding if further studies of certain wastes are warranted. From this chart, a semi-continuous reactor study was designed based on an optimized C:N ratio. The FPSW and manure blend with optimized C:N ratio performed exceptionally well in a semi-continuous system. With identical working volumes of 2 L, the blend of FPSW/manure produced approximately 2.19 times more methane than the reactor containing manure alone. The digestion of FPSW alone was found to be unsuccessful without the incorporation of additional nutrients, further advocating the concept of adding manure. Although perceived to be additive in the second BMP study, the reconstitution of the FPSW with manure showed true synergistic signs when studied at the semi-continuous phase. This was signified by the biogas production from the FPSW/manure blend being almost 1.6 times higher than the combination of the manure and F PSW reactors. Introducing FPSW can generate greater revenue from higher energy production with no alteration to an existing digester’s working volume. For the food processor, possible carbon credit gains may be obtained depending on district regulations. Renewable energy certificates can also be attained. 66 Tipping fees between farmer and food processor may also transpire although this benefit is currently market driven. The digestion of the FPSW/manure optimized blend was shown to have a low conversion rate, in terms of biogas produced per g COD and 9 VS destroyed, as compared to that of the manure alone. Three potential reasons were identified as to why this low efficiency occurred. Initially, a problem was suspected in the hydrolysis of certain solids of the FPSW as pertaining to a short SRT of 15 days. With a longer retention time, better conversion rates may have been achieved. Another possibility was toxicity issues arising from the polymers in the FPSW which would have led to poor system performance and inhibition. Finally, sorption of trace nutrients may have occurred, again, through the presence of the polymers. The removal of minerals and micronutrients from the system would ensure lower conversion efficiency. The research conducted in this study looked at the reconstitution of the FPSW with manure in a very applied manner, focusing on the science and microbiology behind the concept. However, logistical questions still remain unanswered. Future research should focus on an in-depth analysis of the costs associated with dewatering food wastes onsite. Concepts such as the cost benefits associated with shipping dewatered solids as opposed to the transportation of a slurry must be considered. By answering these logistical questions and providing an evaluation of the energy produced per volume of the food waste inserted in the digester, the feasibility of reconstitution at a digester can be determined. 67 APPENDICES 68 APPENDIX A RESPIROMETER STUDY 69 Table A1 Respirometer Concentrations before Digestion 'E‘éof-I‘US a 5 a 3’ 52 Treatment fi'fio 031%?) g E, g .5. 55", 5d°§=§ m w m to EE 42 g 3 1- ,‘2 > g < v Seed 8.15 2,600 7,063 4,750 8,503 6,100 5,197 4,400 361 Seed, Cow Manure 7.82 4,10011,713 7,27513,115 7,900 8,323 5,300 496 Seed, Diluted Sludge 7.77 2,95011,0254,97511,173 7,700 7,237 4,100 353 Seed, 1:1 Cow Manure: Diluted 7.61 4,250 15,838 7,125 15,755 10,100 10,350 6,900 523 Sludge Seed, 2:1 Cow Manure: Diluted 7.51 5,100 21,900 9,388 20,120 12,400 13,147 8,500 635 Sludge Seed, 1:2 Cow Manure: Diluted 7.77 345013.350 607513.467 9,100 8,752 5,800 439 Sludge Table A2 Respirometer Concentrations after Digestion 3.3. 8 " I j A j a A 'E‘éofi"? 5'3 '3'» a E2 Treatment fifiuofigfi g E, g .E, 5% §d°§=§ a, w a, «0 Es < E (:5, 1- ,‘2 > g,’ < v Seed 7.43 3,100 6,813 5,088 7,403 3,700 4,448 2,300 399 Seed, Cow Manure 7.314,850 9,753 6,225 10,752 6,900 6,480 4,400 600 Seed, Diluted Sludge 7.23 3,600 8,850 4,350 9,260 7,700 5,562 5,200 460 Seed, 1:1 Cow Manure: Diluted 7.40 5,05011,638 5,188 12,145 8,300 7,485 2,300 690 Sludge Seed, 2:1 Cow Manure: Diluted 7.44 6,350 15,925 8,675 15,833 11,600 9,662 5,900 836 Sludge Seed, 1:2 Cow Manure: Diluted 7.30 4,350 10,475 5,175 10,633 7,700 6,415 4,300 561 Sludge 70 Table A.3 Respirometer pH Change during Digestion Treatment Initial pH Final pH pH Change Seed 8.15 7.43 -O.72 Seed, Cow Manure 7.82 7.31 -0.51 Seed, Diluted Sludge 7.77 7.23 -O.54 Seed, 1:1 Cow Manure: Diluted Sludge 7.61 7.40 -0.21 Seed, 2:1 Cow Manure: Diluted Sludge 7.51 7.44 -0.07 Seed, 1:2 Cow Manure: Diluted Sludge 7.77 7.30 -0.47 Table A.4 Respirometer Alkalinity Change during Digestion Initial Final Alkalinity Treatment Alkalinity Alkalinity Change (mg CaCO3) (mg CaCO3) (mg CaCO3) Seed 1,690 2,015 325 Seed, Cow Manure 2,665 3,153 488 Seed, Diluted Sludge 1,918 2,340 422 Seed, 1:1 Cow Manure: Diluted Sludge 2,763 3,283 520 Seed, 2:1 Cow Manure: Diluted Sludge 3’315 4’128 813 Seed, 1:2 Cow Manure: Diluted Sludge 2’243 2'828 585 Table A.5 Respirometer Total Solids Destruction Initial . TS . Treatment TS “3:38 Destruction Destruction 0 (m9) (m9) Seed 5,527 4,812 715 13 Seed, Cow Manure 8,525 6,989 1,536 18 Seed, Diluted Sludge 7,263 6,019 1,244 17 Seed, 1:1 Cow Manure: Diluted Sludge 10,241 7,894 2,347 23 Seed, 2:1 Cow Manure: Diluted Sludge 13,078 10,292 2,786 21 Seed, 1:2 Cow Manure: Diluted Sludge 8,753 6,912 1,841 21 71 Table A.6 Respirometer Total Suspended Solids Destruction Initial Final TSS Destruction Treatment T88 T38 Destruction 0 (A) ("19) (m9) (m9) Seed 3,965 2,405 1 ,560 39 Seed, Cow Manure 5,135 4,485 650 13 Seed, Diluted Sludge 5,005 5,005 0 0 Seed, 1:1 Cow Manure: Diluted Sludge 6,565 5,395 1,170 18 Seed, 2:1 Cow Manure: Diluted Sludge 8’060 7’540 520 6 Seed, 1:2 Cow Manure: Diluted Sludge 5,915 5,005 910 15 Table A.7 Respirometer Volatile Suspended Solids Destruction Initial Final VSS Destruction Treatment V88 V88 Destruction (%) (m9) (m9) (m9) Seed 2,860 1 ,495 1 ,365 48 Seed, Cow Manure 3,445 2,860 585 17 Seed, Diluted Sludge 2,665 3,380 -715 -27 Seed, 1:1 Cow Manure: Diluted Sludge 4,485 1,495 2,990 67 Seed, 2:1 Cow Manure: Diluted Sludge 5,525 3,835 1,690 31 Seed, 1:2 Cow Manure: Diluted Sludge 3,770 2,795 975 26 Table A.8 Respirometer Hydrogen Sulfide Concentrations Treatment H28 Coggmtration Seed 0 Seed, Cow Manure 1,200 I Seed, Diluted Sludge 700 Seed, 1:1 Cow Manure: Diluted Sludge 1,600 Seed, 2:1 Cow Manure: Diluted Sludge 3,200 Seed, 1:2 Cow Manure: Diluted Sludge 1,000 72 Table A9 Respirometer Soluble COD Destruction Soluble COD 6 C Treatment 3 ’5 E .3 g E 'o o a g 9. 3 E .5 g g E 1.1. Is? °\. Seed 3,088 3,307 -219 -7 Seed, Cow Manure 4,729 4,046 683 14 Seed, Diluted Sludge 3,234 2,828 406 13 Seed, 1:1 Cow Manure: Diluted Sludge 4,631 3,372 1,259 27 Seed, 2:1 Cow Manure: Diluted Sludge 6,102 5,639 463 8 Seed, 1:2 Cow Manure: Diluted Sludge 3,949 3,364 585 15 Table A.10 Respirometer Normalized Energy Potential per COD N I' d G N al' edl it' I Biogas/Initial COD ormaize as am II 11 1a _ , + °°mp°"°"t Produced (mL) cop (mg) a“°"3"““°" (m IKQ) Cow Manure 762 3,022 0.252 Diluted s|udge* 776 2,575 0.301 Table A.11 Respirometer Normalized Energy Potential per VS N I' d G N l‘ d I it“ I Biogas/Initial VS orma Ize as orma rze n 1a , _ + °°mp°"e“t Produced (mL) vs (mg) 3“" 2"“t'°" (m 1ng Cow Manure 762 2,032 0.375 Diluted Sludge" 776 1,326 0.585 * Based on “Seed, Diluted Sludge” minus “Seed” +At experimental Temperature (35°C) and Standard Pressure 73 ’5? 12 o I :1 10 E o as 8 . ’ CE ! .5 6 *6 8 9 4 CL 8 2 L (D | - g 0 ‘ r 1 *" o 100 200 300 400 500 600 700 Hours Seed Seed, Cow Manure - - - Seed, Diluted Sludge - - - Seed, 1:1 Cow Manure: Diluted Sludge ----- Seed, 2:1 Cow Manure: Diluted Sludge Seed, 1:2 Cow Manure: Diluted Sludge Figure A.1 Respirometer Biogas Production Rate 74 W SERUM BOTTLE STUDY 75 Table 8.1 Serum Bottle Concentrations before Digestion ’3 o .. ... .58 .. 8 .. .1 g g 5', .g i. c a a {I d 3: o: E o _l Treatment :3 fi 0 O o: 2 or E g E .. E ~ £- 3 O E '2 .E. 3; (I) 7, to E g < E 3’, l- f’_’ > g’ < v Seed 7.78 2,90017,900 4,263 12,980 9,042 700 240 277 Seed, Cow Manure 7.54 3,750 20,388 6,950 17,375 12,092 1,075 280 384 Set-zsdlhggzted 7.61 2,750 21,425 4,913 18,405 12,508 900 238 253 Cow Manure 7.44 1,700 7,950 3,663 5,490 3,892 460 40 168 Diluted Sludge 5.76 100 6,963 875 6,185 3,815 220 23 6 Seed, 2:1 Cow Manure: Diluted 7.45 5,550 35,413 11,100 30,215 20,567 1,488 465 665 Sludge Seed, 1:1 Cow Manure: Diluted 7.50 4,300 27,863 8,225 24,310 16,545 1,700 353 485 Sludge Seed, 1:2 Cow Manure: Diluted 7.47 3,350 24,038 5,988 20,415 13,895 963 313 346 Sludge Seed, 1:4 Cow Manure: Diluted 7.52 2,900 22,913 5,375 18,768 12,763 1,025 288 313 Sludge Seed, 1:6 Cow T Manure: Diluted 7.59 3,00012,513 4,750 19,34213,182 700 293 284 Sludge 76 Table 8.2 Serum Bottle Concentrations after Digestion ’3 o A A 0 ’~ ..I A .l a A 9? 0 A 8 A " a " a 'E z c a o {I :1 a E E E O _' Treatment Ego 05121:: E v E . EA 5 d 0 g '3 g a w ,7; a) E g < E (:6) 1- ‘,L’ > g < v Seed 7.11 3,383 10,825 4,158 10,071 6,523 708 191 285 Seed, Cow Manure 7.26 5,383 14,233 4,608 13,636 8,279 1,017 274 572 seed' 9"“th 7.21 4,150 15,104 3,754 13,726 8,068 950 250 492 Sludge CowManure 7.15 2,333 3,600 1,129 2,844 2,291 433 47 223 Diluted Sludge 6.25 750 5,621 1,917 3,488 1,867 133 24 130 Seed, 2:1 Cow Manure: Diluted 7.45 8,100 21,479 4,563 22,424 13,020 1,700 426 813 Sludge Seed, 1:1 Cow Manure: Diluted 7.39 5,600 17,796 4,242 17,311 10,116 1,267 318 637 Sludge Seed, 1:2 Cow Manure: Diluted 7.23 5,050 17,463 4,192 16,052 9,433 1,175 273 533 Sludge Seed, 1:4 Cow Manure: Diluted 7.18 4,433 15,917 3,900 15,137 8,951 1,000 255 460 Sludge Seed, 1:6 Cow Manure: Diluted 7.16 4,467 16,642 4,075 15,142 8,981 967 253 448 Sludge Table 8.3 Serum Bottle pH Change during Digestion Treatment Initial pH Final pH pH Change Seed 7.78 7.11 -0.67 Seed, Cow Manure 7.54 7.26 -0.28 Seed, Diluted Sludge 7.61 7.21 -0.4 Cow Manure 7.44 7.15 -0.29 Diluted Sludge 5.76 6.25 0.49 Seed, 2:1 Cow Manure: Diluted Sludge 7.45 7.45 0 Seed, 1:1 Cow Manure: Diluted Sludge 7.50 7.39 -0.11 Seed, 1:2 Cow Manure: Diluted Sludge 7.47 7.23 -0.24 Seed, 1:4 Cow Manure: Diluted Sludge 7.52 7.18 -0.34 Seed, 1:6 Cow Manure: Diluted Sludgfi 7.59 7.16 -0.43 77 Table 3.4 Serum Bottle Alkalinity Change during Digestion Initial Final Alkalinity Treatment Alkalinity Alkalinity Change (mg CaCO3) (mg CaCO;) (mg CaCO;) Seed 435 508 73 Seed, Cow Manure 563 808 245 Seed, Diluted Sludge 413 623 210 Cow Manure 255 350 95 Diluted Sludge 15 113 98 Seed, 2:1 Cow Manure: Diluted Sludge 833 1'215 382 Seed, 1:1 Cow Manure: Diluted Sludge 645 840 195 Seed, 1:2 Cow Manure: Diluted Sludge 503 758 255 Seed, 1:4 Cow Manure: Diluted Sludge 435 665 230 Seed, 1:6 Cow Manure: Diluted Sludge 450 670 220 Table 8.5 Serum Bottle Total Solids Destruction Initial Final TS Destruction Treatment TS TS Destruction (%) (m9) (m9) (m9) Seed 1,947 1,51 1 436 22 Seed, Cow Manure 2.606 2,045 561 22 Seed, Diluted Sludge 2.761 2.059 702 25 Cow Manure 824 577 247 30 Diluted Sludge 928 523 405 44 Seed, 2:1 Cow Manure: Diluted Sludge 4,532 3,364 1168 26 Seed, 1:1 Cow Manure: Diluted Sludge 3,647 2,597 1050 29 Seed, 1:2 Cow Manure: Dilute d Sludge 3,062 2,408 654 21 Seed, 1:4 Cow Manure: Diluted Sludge 2’815 2’271 544 19 I Seed, 1:6 Cow Manure: l Diluted Sludgfie 2,901 2,271 630 22 78 Table 3.6 Serum Bottle Ammonia Change during Digestion Initial Final Change Treatment Ammonia Ammonia (mg) (mg) ("‘9’ Seed 41 43 2 Seed, Cow Manure 58 86 28 Seed, Diluted Sludge 38 74 36 Cow Manure 25 33 8 Diluted Sludge 1 20 19 Seed, 2:1 Cow Manure: Diluted Sluge 100 122 22 Seed, 1:1 Cow Manure: Diluted Sludge 73 96 23 Seed, 1:2 Cow Manure: Diluted Sludge 52 80 28 Seed, 1:4 Cow Manure: Diluted Sludge 47 69 22 Seed, 1:6 Cow Manure: Diluted Sludge 43 67 24 Table 8.7 Serum Bottle Soluble COD Destruction Soluble COD 6 a v .5 Treatment g g % 3 § .5 g a .E. 8 'E i: 3 °‘ - 32 Seed 639 624 15 2 Seed, Cow Manure 1,043 691 352 34 Seed, Diluted Sludge 737 563 174 24 Cow Manure f 549 169 380 69 Diluted Sludge 131 288 NA NA 1 Seed, 2:1 Cow Manure: Diluted Sludge 1.665 684 981 59 Seed, 1:1 Cow Manure: Diluted Sludge 1,234 636 598 48 Seed, 1:2 Cow Manure: Diluted Slugge 898 629 269 30 Seed, 1:4 Cow Manure: Diluted Slunge 806 585 221 27 Seed, 1:6 Cow Manure: Diluted Sludge 713 611 102 14 79 Table 8.8 Serum Bottle Normalized Energy Potential per COD Normalized . . . Bi asllnitial COD Component Gas Produced Norrgglg ed 'mt'a' ggter Dilution“ (mL) ("‘9’ (m3lKgl Cow Manure 410 373 1.1 Diluted Sludge* 356 529 0.67 Diluted Sludg" 334 1,121 0.30 Table 3.9 Serum Bottle Normalized Energy Potential per VS Normalized . . . Biogas/Initial VS Component Gas Produced Norm:érzemdgl)mtial after Dilution..- m Jm’lKg) Cow Manure 410 458 0.895 Diluted surge 356 520 0.685 Diluted Sludge" 334 668 0.500 * Based on “Seed, Diluted Sludge” minus “Seed” "Based on “Seed, 1:1 Cow Manure: Diluted Sludge” minus “Seed, Manure” +At experimental Temperature (35°C) and Standard Pressure Table B.10 Serum Bottle Hydrogen Sulfide Concentrations H Average H28 1 Treatment Concentration (PPM) Seed 665 Seed, Cow Manure 1548 Seed, Diluted Sludge 759 Cow Manure 1028 Diluted Sludge 329 Seed, 2:1 Cow Manure: Diluted Sludge 1856 Seed, 1:1 Cow Manure: Diluted Sludge 1303 Seed, 1:2 Cow Manure: Diluted Slugge 1018 Seed, 1:4 Cow Manure: Diluted Sludge 903 Seed, 1:6 Cow Manure: Diluted Sludge 829 80 6000 3. A 4000 '2, E .0 3 1r m l\ . N \ . I 2000 . \‘ - ‘lv- I 0 I I I I o 500 1000 1500 2000 Hours —o—Seed -I- Seed, Cow Manure ...... Seed, Diluted Sludge - x- Diluted Sludge —x -Cow Manure ...... Seed, 2:1 Cow Manure: Diluted Sludge‘ --+--Seed, 1:1 Cow Manure: Diluted Sludge - - -Seed, 1:2 Cow Manure: Diluted Sludge ~— - Seed, 1:4 Cow Mjanure: Diluted Sludge —O - Seed, 1:6 Cow Manure: Diluted Slud 8 Figure 8.1 Serum Bottle H28 Concentrations 81 Table 8.11 Daily Biogas Yields for Controls 9,... s... “32:53:” ““3832?“ M3222. News“... a b c a b c a b c a b c a b 1: 3/10/2010 3 4 3 6 5 5 6 5 9 3 3 3 3 2 1 3/11/2010 3 2 2 7 8 8 8 8 8 3 3 2 1 2 2 3/12/2010 2 2 2 10 9 10 10 10 10 2 2 3 2 2 2 3/13/2010 1 1 2 8 9 9 16 16 17 3 3 2 2 2 2 3/14/2010 2 l 2 8 8 8 16 16 17 2 2 2 1 l 1 3/15/2010 3 2 3 11 12 12 16 16 16 3 3 2 0 l 1 3/16/2010 5 3 5 12 13 13 12 13 13 3 2 2 2 3 2 3/18/2010 8 8 10 30 31 32 24 30 25 9 9 10 4 3 5 3/20/2010 9 7 10 38 39 40 34 30 34 21 21 22 3 1 2 3/22/2010 8 7 9 40 41 42 43 37 40 25 26 25 2 1 2 3/24/2010 12 ll 14 39 41 40 36 35 35 25 25 24 4 3 4 3/26/2010 15 10 14 35 37 38 23 23 23 20 21 20 6 4 10 3/28/2010 16 'l 1 16 37 38 4O 24 23 24 22 24 24 10 9 18 3/30/2010 14 9 12 29 31 30 18 19 18 20 22 22 7 9 9 4/01/2010 16 10 16 33 37 36 23 20 21 21 22 24 5 13 5 4/03/2010 13 10 14 26 28 27 25 18 20 13 11 1 l 2 8 4 4/05/2010 13 10 14 25 26 27 29 22 23 8 7 7 0 3 1 4/07/2010 15 13 16 30 31 30 3O 26 28 10 11 11 2 4 3 4/10/2010 19 14 22 43 43 42 34 26 27 18 20 18 0 2 0 4/13/2010 12 9 14 3O 31 30 ‘17 14 14 18 19 19 2 1 2 4/16/2010 10 8 12 24 24 25 14 14 11 10 12 12 3 1 1 4/19/2010 6 4 7 13 14 15 12 11 8 5 5 5 O 0 0 4/22/2010 7 7 9 14 14 16 12 24 12 7 7 8 2 2 2 4/25/2010 5 6 7 10 12 ll 9 22 10 4 5 6 1 2 1 4/28/2010 2 l 2 6 6 5 5 17 11 2 2 2 2 0 2 5/01/2010 7 6 8 10 11 ll 10 20 25 5 5 5 0 1 0 5/05/2010 5 4 6 8 10 10 12 18 24 6 6 6 2 l 2 5/10/2010 4 3 4 8 9 10 l3 141 25 4 4 4 0 0 0 5/15/2010 6 5 7 16 19 17 15 15 22 4 4 4 2 O 2 5/20/2010 6 7 8 14 16 21 16 22 21 4 4 4 2 O 2 5/23/2010 4 6 5 7 7 9 13 14 17 1 1 l O 0 0 5/25/2010 3 4 4 4 4 4 8 9 8 1 l 1 0 O O 82 Table 8.12 Daily Biogas Yields for Blends 2:1 1:1 1:2 1:4 1:6 Date a b c a b c a b c a b c a b c 3/10/2010 13 21 20 14 14 12 7 7 7 6 6 7 6 6 7 3/11/2010 27 22 23 20 19 20 18 17 17 13 13 13 12 13 12 3/12/2010 21 22 21 16 15 16 13 13 13 13 14 14 15 15 15 3/13/2010 15 17 16 13 14 13 12 13 13 13 14 14 14 15 15 3/14/2010 13 15 14 13 12 12 12 11 12 13 13 14 14 13 14 3/15/2010 12 15 14 16 16 17 16 16 16 17 18 18 18 17 18 3/16/2010 10 13 12 16 17 17 16 17 17 19 18 18 18 18 18 3/13/2010 23 36 33 48 51 50 39 41 4O 4O 35 37 33 35 36 3/20/2010 37 65 58 58 64 57 38 38 38 32 30 31 3O 31 32 3/22/2010 68 78 81 51 50 48 35 37 37 36 37 37 35 35 35 3/24/2010 89 87 84 52 54 49 40 39 39 46 45 44 40 41 41 3/26/2010 78 69 68 49 47 48 42 43 44 38 34 34 31 33 31 3/28/2010 66 63 65 56 56 52 43 45 45 34 35 31 30 3O 32 3/30/2010 65 58 60 4O 47 41 28 30 33 28 30 25 26 25 26 4/01/2010 87 67 73 47 50 51 29 3O 35 29 31 26 27 27 29 4/03/2010 60 48 52 36 39 42 25 26 31 24 26 23 23 21 22 4/05/2010 53 47 44 35 38 40 29 3O 34 25 28 25 23 22 23 4/07/2010 46 37 4O 34 35 37 31 32 36 30 33 32 27 26 27 4/10/2010 63 77 69 48 49 49 44 44 47 50 50 47 44 44 47 4/13/2010 71 100 89 6O 63 59 37 40 45 36 30 26 27 28 31 4/16/2010 105 79 . 89 60 63 62 20 24 27 20 18 17 16 17 19 4/19/2010 55 50 ' 41 28 32 27 14 14 15 10 10 11 8 9 9 4/22/2010 36 52 1 34 23 26 23 20 21 . 23 15 16 22 13 13 15 4/25/2010 22 38 34 16 18 16 17 17 17 18 18 24 12 12 14 4/23/2010 10 23 28 12 14 9 12 16 7 9 10 16 9 13 15 5/01/2010 16 25 33 20 15 12 21 25 l3 14 12 19 16 18 27 5/05/2010 16 22 26 20 15 14 20 25 10 10 11 16 10 15 24 5/10/2010 16 18 24 18 15 13 17 22 10 9 ll 15 8 10 18 5/15/2010 21 18 23 17 17 18 18 20 13 11 15 15 10 12 17 5/20/2010 28 24 30 21 19 27 16 19 15 12 24 15 12 18 18 5/23/2010 21 20 18 19 17 13 11 11 14 7 12 9 6 15 10 5/25/2010 6 13 11 9 12 8 7 10 5 6 6 5 5 12 7 83 Table 3.13 Individual Treatment Gas Production and Averages Total Gas Avera 9 Gas Treatment Production (mL) Productgon (mL) Seed a 254 Seed b 205 246 Seed c 279 Seed, Cow Manure a 631 Seed, Cow Manure b 664 656 Seed, Cow Manure c 673 Seed, Diluted Sludge a 583 Seed, Diluted Sludge b 607 602 Seed, Diluted Sludge c 616 Cow Manure a 302 Cow Manure b 312 308 Cow Manure c 311 Diluted Sludge a 72 Diluted Sludge b 81 80 Diluted Sludge c 88 2:1 a 1,269 2:1 b 1,339 1,312 2:1 c 1,327 1:1 a 985 1:1 b 1,013 990 1:1 c 972 1:2 a 747 1:2 b 793 769 1:2 c 768 1:4 3 683 1:4 b 703 695 1:4 c 700 1:6 a 618 1:6 b 659 660 1:6 c 704 84 APPENDIX C SEMI-CONTINUOUS STUDY 8S Table C.1 Removal and Feeding of Substrate Data SRT: 1 Day: 1 Time: 1 .45 pm Date: 6/1 7/201 0 Tips w'i'agt Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 9 3040 130 2901 3052 9 Reactor 3 7 31 16 130 2984 3120 7 Reactor 4 8 31 74 130 3040 31 74 8 Reactor 5 31 3098 130 2928 3100 31 SRT: 1 Day: 2 Time: 10.30 am Date: 6/1 8/201 0 Tips VI???“ Amount Wing ht Wight Tips Before elg (g) 8 er a er After (9) Removal (9) Feed (9) Reactor 2 19 3098 130 2954 3101 19 Reactor 3 9 3077 130 2938 3075 9 Reactor 4 12 3176 130 3038 3174 12 Reactor 5 47 3101 130 2970 3109 47 SRT: 1 Day: 3 Time: 4 pm Date: 6/1 9/201 0 Tips with?“ Amount Wig ht Wight Tips Before eg (9) a er a er After (9) Removal (9) Feed (9) Reactor 2 32 3107 130 2976 3104 32 Reactor 3 10 3081 130 2963 3088 10 Reactor 4 17 3106 130 2974 3106 17 Reactor 5 63 3085 130 2945 3080 63 86 Table 0.1 cont’d. SRT: 1 Day: 4 Time: 2 pm Date: 6/20/2010 Tips W'F'agt Amount Wight Wight Tips Before 819 (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 42 3085 130 2945 3084 42 Reactor 3 11 3065 130 2918 3071 11 Reactor 4 24 3099 130 2971 31 01 24 Reactor 5 65 3090 130 2959 3083 65 SRT: 1 Day: 5 Time: 9.30 am Date: 6/21/201 0 Tips ”marl“ Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 47 3084 130 2954 3084 47 Reactor 3 12 3077 130 2934 3084 12 Reactor 4 32 3100 130 2970 3098 32 Reactor 5 69 3096 130 2960 3098 69 SRT: 1 Day: 6 Time: 11 am Date: 6/22/201 0 Tips ”want Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 56 3084 130 2953 3081 56 Reactor 3 15 3080 130 2947 3080 15 Reactor 4 44 3095 130 2950 3102 44 Reactor 5 84 3071 130 2940 3070 84 87 Table C.1 cont’d. SRT: 1 Day: 7 Time: 11 am Date: 6/23/201 0 Tips vaarl‘t Amount Wight Wight Tips Before eig (g) a er 3 er After (9) Removal (9) Feed (9) Reactor 2 61 3065 130 2932 3066 61 Reactor 3 19 3022 130 2892 3020 19 Reactor 4 63 3091 130 2959 3089 63 Reactor 5 99 3070 130 2941 3064 99 SRT: 1 Dfli 8 Time: 11 am Date: 6/24/2010 Tips V'J'iFiaAt Amount Wight Wight Tips Before mg (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 71 3066 130 2948 3069 71 Reactor 3 22 3014 130 2880 301 3 22 Reactor 4 88 3080 130 2920 3079 88 Reactor 5 1 13 3048 130 2915 3051 1 13 SRT: 1 Day: 9 Time: 10.30 am Date: 6/25/201 0 Tips with}; Amount Wight Wight Tips Before 819 (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 84 3054 130 2925 3056 84 Reactor 3 25 3035 130 2913 3033 25 Reactor 4 120 3061 130 2930 3060 120 Reactor 5 118 3038 130 2908 3034 1 18 88 Table C.1 cont’d. SRT: 1 Day: 10 Time: 1 1 am Date: 6/26/201 0 Tips ”was“ Amount Wight Wight Tips Before eig (g) a er 8 er After (9) Removal (9) Feed (9) Reactor 2 100 3133 130 3004 3130 100 Reactor 3 28 2977 130 2848 2985 28 Reactor 4 1 54 3058 130 2924 3056 1 54 Reactor 5 121 3026 130 2986 3027 121 SRT: 1 Day: 11 Time: 1 pm Date: 6/27/2010 Tips VI; '18," t Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 1 12 3089 130 2955 3089 1 12 Reactor 3 32 2969 130 2838 2974 32 L Reactor 4 181 3055 130 2924 3055 181 1 Reactor 5 123 3015 130 2885 3012 123 SRT: 1 Day: 12 Time: 9. 30 am Date: 6/28/201 0 Tips VIC/“981:1 Amount Wight Wight Tips Before eng (9) a er a er After 1 (9) Removal (9) Feed (9) Reactor 2 12 ‘ 3126 130 2995 3125 12 Reactor 3 35 2956 130 2824 2962 35 Reactor 4 198 3065 130 2934 3068 198 Reactor 5 135 3040 130 2910 3040 135 89 Table C.1 cont’d. SRT: 1 Day: 13 Time: 9.00 am Date: 6/29/201 0 Tips ”was“ Amount Wight Wight Tips Before 819 (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 134 NA 130 NA NA - Reactor 3 41 NA 130 NA NA 41 Reactor 4 218 NA 130 NA NA 218 Reactor 5 139 NA 130 NA NA 139 SRT: 1 Day: 14 Time: 1.30 pm Date: 6/30/2010 Tips . . Tips Before Weight In (9) Weight Out (9) After Reactor 2 139 146 130 139 Reactor 3 46 140 130 46 Reactor 4 237 130 1 15 237 Reactor 5 147 130 130 147 SRT: 1 Day: 15 Time: 2.15 pm Date: 7/1/2010 Tips . . Tips Before Weight In (9) WeIth Out (9) After Reactor 2 147 160 170 147 Reactor 3 59 132 145 59 Reactor 4 266 130 1 30 266 Reactor 5 157 136 140 157 90 Table C.1 cont’d. SRT: 2 Day: 1 Time: 12.30 pm Date: 7/2/2010 Tips V's/wall“ Amount Wight Wight Tips Before elg (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 157 NA 130 NA NA 157 Reactor 3 63 NA 130 NA NA 63 Reactor 4 286 NA 130 NA NA 286 Reactor 5 167 NA 130 NA NA 167 SRT: 2 Day: 2 Time: 2 pm Date: 7/3/2010 Tips “was“ Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 173 3087 130 2961 3088 173 Reactor 3 69 3046 130 2914 3045 69 Reactor 4 316 3042 130 2910 3040 316 Reactor 5 179 3107 130 2968 3106 179 SRT: 2 Day: 3 Time: 8 am Date: 7/4/2010 Tips Vlcifiagt Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 187 3078 130 2948 3076 187 Reactor 3 73 3031 130 2901 3032 73 Reactor 4 342 3017 130 2890 3016 342 Reactor 5 186 3090 130 2960 3088 186 91 Table C.1 cont’d. SRT: 2 Day: 4 Time: 12 pm Date: 7/5/2010 Tips Vii/witial Amount Weight Weight Tips Before eight (9) after after After (9) Removal (9) Feed (9) Reactor 2 203 3103 130 2974 3104 203 Reactor 3 78 3005 130 2875 3005 78 Reactor 4 385 3022 130 2890 3021 385 Reactor 5 199 3057 130 2927 3055 199 SRT: 2 Day: 5 Time: 1.30 pm Date: 7/6/2010 Tips Vl‘;1itial Amount Weight Weight Tips Before eight (9) after after After (9) Removal (9) Feed (9) Reactor 2 212 3092 130 2958 3091 212 Reactor 3 84 2933 130 2804 3074* 84 Reactor 4 431 2961 130 2829 2961 431 Reactor 5 . 212 3039 130 2907 3037 212 *Added to ensure 2L volume SRT: 2 Day: 6 Time: 11.50 am Date: 7/7/2010 Tips VlJiitial Amount Weight Weight Tips Before eight (9) after after After (9) Removal (9) Feed (9) Reactor 2 221 3105 130 2975 3108 221 Reactor 3 91 3083 130 2953 3084 91 Reactor 4 468 2949 130 2816 2947 468 Reactor 5 227 3026 130 2895 3026 227 92 Table C.1 cont’d. SRT: 2 Day: 7 Time: 11.30 am Date: 7/8/2010 Tips ”was“ Amount Wight Wight Tips Before eig (g) 3 er a er After (9) Removal (9) Feed (9) Reactor 2 231 3108 130 2971 3108 231 Reactor 3 101 2984 130 2953 2984 101 Reactor 4 502 2907 130 2773 2909 502 Reactor 5 245 2994 130 2863 2996 245 SRT: 2 Day: 8 Time: 2 pm Date: 7/9/2010 Tips Vlcmatlit Amount Wight Wight Tips Before eig (g) 3 er a er After (9) Removal (9) Feed (9) Reactor 2 242 3068 130 2938 3070 242 Reactor 3 11 1 3037 130 2900 3039 1 1 1 Reactor 4 533 2940 130 2810 2942 533 Reactor 5 270 2988 130 2856 2985 270 SRT: 2 Day: 9 Time: 2J>m Date: 7/1 0l201 0 Tips xii'agt Amount Wight Wight Tips Before eig (9) a er a er After (9) Removal (9) Feed (9) Reactor 2 251 31 38 130 3006 31 36 251 Reactor 3 120 3014 130 2880 3017 120 Reactor 4 556 291 1 130 2780 2938 556 Reactor 5 286 2963 130 2834 2957 286 93 Table C.1 cont’d. SRT: 2 Day: 10 Time: 8 am Date: 7/1 1/2010 Tips $93,; Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 259 3076 130 2947 3076 259 Reactor 3 126 3000 130 2873 3003 126 Reactor 4 580 2917 130 2790 2921 580 Reactor 5 307 2953 130 2825 2959 307 SRT: 2 Day: 11 Time: 11 am Date: 7/12/2010 Tips Vcwarlit Amount Wight Wight Tips Before 819 (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 267 3097 1 30 2966 31 05 267 Reactor 3 133 2889 130 2758 2885 133 Reactor 4 61 5 2902 130 2774 2914 615 Reactor 5 329 2955 130 2825 2950 329 SRT: Day: 12 Time: 33me Date: 7/12/201 0 Tips W'i'arflt Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 279 3094 130 2965 3095 279 Reactor 3 136 2883 130 2756 2880 136 Reactor 4 648 2846 130 2721 2850 648 Reactor 5 - - 130 - - - 94 Table C.1 cont’d. SRT: 2 Day: 13 Time: 11.30 am Date: 7/1 3/2010 Tips leal'llt Amount Wight Wight Tips Before 9'9 (g) a e’ 3 er After (9) Removal (9) Feed (9) Reactor 2 288 3072 130 2946 3078 288 Reactor 3 139 2864 130 2735 2856 139 Reactor 4 667 2851 130 2722 2849 667 Reactor 5 - - 130 - - - SRT: 2 Day: 14 Time: 1 1 .BOam Date: 7/1 5/201 0 Tips VlcifiatIit Amount Wight Wight Tips Before 9'9 (g) a e' 3 er After (9) Removal (9) Feed (9) Reactor 2 298 3061 130 2933 3062 298 Reactor 3 143 2839 130 2709 2835 143 Reactor 4 689 2831 130 2706 2827 689 Reactor 5 - - 130 - - - SRT: 2 Day: 15 Time: 11.30 am Date: 7/16/2010 Tips chmatltt Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 306 3069 130 2941 3069 306 Reactor 3 147 2844 130 2716 2839 147 Reactor 4 712 2831 130 2701 2827 712 Reactor 5 - - 130 - - - 95 Table C.1 cont’d. SRT: 3 Day: 1 Time: 5 pm Date: 7/17/2010 Tips “was“ Amount Wight Wight Tips Before eng (9) a er a er After (9) Removal (9) Feed (9) Reactor 2 316 3072 130 2945 3072 316 Reactor 3 150 2835 130 2703 2831 150 Reactor 4 736 2837 130 2703 2840 736 Reactor 5 - - 130 - - - SRT: 3 Day: 2 Time: 1 pm Date: 7/1 8/201 0 Tips V's/Wall“ Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 323 3061 130 2930 3064 323 Reactor 3 154 2835 130 2707 2837 154 Reactor 4 752 2838 130 2708 2840 752 Reactor 5 - - 130 - - - SRT: 3 Day: 3 Time: 2.15 pm Date: 7/19/2010 Tips VIJ'FiaAt . Amount Wight Wight Tips Before elg (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 333 3067 130 2936 3066 333 Reactor 3 157 2857 130 2732 2854 157 Reactor 4 776 2845 130 2717 2845 776 Reactor 5 - - 130 - - - 96 Table C.1 cont’d. SRT: 3 Day: 4 Time: 2.30 PM Date: 7/20/201 0 Tips VIS't'at'“ Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 343 3068 130 2938 3066 343 Reactor 3 160 2833 130 2697 2844 160 Reactor 4 803 2810 1 30 2681 2809 803 Reactor 5 - - 130 - - - SRT: 3 Day: 5 Time: 12 PM Date: 7/21/2010 Tips Vlyitialit Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 352 3063 130 2933 3064 352 Reactor 3 163 2831 130 2701 2828 163 Reactor 4 828 2772 130 2640 2774 828 Reactor 5 - - 130 - - - SRT: 3 Day: 6 Time: 11.30 am Date: 7/22/201 0 Tips Vlcltlarfit Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 363 3032 130 2903 3031 363 Reactor 3 167 2780 130 2650 2780 167 Reactor 4 852 2758 130 2625 2759 852 Reactor 5 - - 130 - - - 97 Table C.1 cont’d. SRT: 3 Day 7 Time: 10.30 am Date: 7/23/201 0 Tips W'F'T‘t Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 373 3015 130 2886 3015 373 Reactor 3 170 2754 130 2624 2754 170 Reactor 4 876 2765 130 2634 2765 876 Reactor 5 - - 130 - - - SRT: 3 Day: 8 Time: 11.30 am Date: 7/24/201 0 Tips V939,; Amount Wight Wight Tips Before elg (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 382 3012 130 2884 301 1 382 Reactor 3 173 2775 130 2643 2775 173 Reactor 4 894 2770 130 2641 2772 894 Reactor 5 - - 130 - - - SRT: 3 Day: 9 Time: 3 pm Date: 7/25/201 0 Tips W'F'arljt Amount Wight Wight Tips Before 819 (g) a er 8 er After (9) Removal (9) Feed (9) Reactor 2 392 3008 130 2880 3006 392 Reactor 3 177 2755 130 2624 2755 177 Reactor 4 922 2766 130 2631 2768 922 Reactor 5 - - 130 - - - 98 Table C.1 cont’d. SRT: 3 Day: 10 Time: 12 pm Date: 7/26/201 0 Tips Vlcmal'it Amount Wight Wight Tips Before eig (g) 8 er a er After (9) Removal (9) Feed (9) Reactor 2 400 3012 130 2880 3015 400 Reactor 3 180 2760 130 2629 2768 180 Reactor 4 940 2750 130 2620 2749 940 Reactor 5 - - 130 - - - SRT: 3 Day: 11 Time: 2.30 pm Date: 7/27/2010 Tips Vir't'arl‘t Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 409 2992 130 2864 2993 409 Reactor 3 184 2756 130 2626 2757 184 Reactor 4 963 2737 130 2600 2727 963 Reactor 5 - - 130 - - - l SRT: 3 Day: 12 Time: 1.30 pm Date: 7/28/2010 f Tips Vllrmatltt Amount Wight Wight Tips Before etg (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 417 2981 130 2850 2982 417 Reactor 3 188 2716 130 2587 2714 188 Reactor 4 983 2734 130 2602 2736 983 Reactor 5 - - 130 - - - 99 Table C.1 cont’d. SRT: 3 Day: 1 3 Time: 2 pm Date: 7/29/201 0 Tips ”mar; Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 427 2994 130 2864 2994 427 Reactor 3 193 2689 130 2559 2690 193 Reactor 4 1004 2698 130 2566 2697 1004 Reactor 5 - - 130 - - - SRT: 3 Day: 14 Time: 2 pm Date: 7/30/201 0 Tips VIJ'mal‘llt Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 436 2959 130 2829 2962 436 Reactor 3 199 2651 130 2522 2651 199 Reactor 4 1023 2701 130 2571 2701 1023 Reactor 5 - ! - 130 - - - SRT: 7 3 Day: 15 Time: 11.30 am Date: 7/31/2010 Tips v1???“ Amount Wight Wight Tips Before eig (g) a er a er After (9) Removal (9) Feed (9) Reactor 2 446 2967 130 2739 2972 446 Reactor 3 206 2639 130 2507 2640 206 Reactor 4 1042 2682 130 2552 2682 1042 Reactor 5 - - 130 - - - 100 Table C.2 Wet-Tip Gas Meter Data Date SRT R1 R2 R3 R4 R5 06/18/2010 1 2 21 10 13 49 06/19/2010 1 2 32 10 17 63 06/20/2010 1 2 42 1 1 24 65 06/21/2010 1 2 50 12 36 74 06/22/2010 1 2 57 17 5O 89 06/23/2010 1 2 63 20 69 103 06/24/2010 1 2 73 23 94 1 16 06/25/2010 1 2 84 25 120 118 06/26/2010 1 2 100 28 154 121 06/27/2010 1 2 112 32 181 123 06/28/2010 1 2 128 37 204 139 06/29/2010 1 - 134 46 235 147 06/30/2010 1 - 139 46 237 147 07/01/2010 1 - 147 60 268 158 07/02/2010 2 - 158 64 288 168 07/03/2010 2 - 173 69 315 177 07/04/2010 2 - 187 73 342 186 07/05/2010 2 - 203 78 384 199 07/06/2010 2 - 215 86 440 215 07/07/2010 2 - 224 94 477 232 07/08/2010 2 - 234 104 511 251 07/09/2010 2 - 242 1 12 534 271 07/10/2010 2 - 251 1 19 556 286 07/1 1/2010 2 - 259 126 580 307 07/12/2010 2 - 269 134 621 335 07/13/2010 2 - 280 1 36 649 355 07/14/2010 2 - 288 139 665 357 07/15/2010 2 - 300 144 695 358 07/16/2010 2 - 306 147 712 358 07/17/2010 3 - 316 150 736 359 07/ 1 8/2010 3 - 323 1 54 752 364 07/ 1 9/2010 3 - 334 1 58 778 372 07/20/2010 3 - 344 161 805 372 07/21/2010 3 - 354 164 833 374 07/22/2010 3 - 362 167 851 374 07/23/2010 3 - 376 171 876 379 07/24/201 0 3 - 382 1 73 894 380 07/25/2010 3 - 392 177 922 384 07/26/2010 3 - 400 180 939 386 07/27/2010 3 - 410 185 964 389 07/28/2010 3 - 419 189 987 392 07l29/2010 3 - 428 1 94 1007 394 07/30/2010 3 - 438 200 1025 396 07/31/2010 3 - 447 208 1045 397 08/01/2010 3 - 455 212 1066 398 101 Table C.3 pH for 3 SRT’s SRT Day Date Reactor Reactor Reactor Reactor 2 3 4 5 1 2 6/18/2010 7.62 6.09 7.37 7.36 1 5 6/21/2010 7.50 6.25 7.39 7.48 1 6 6/22/2010 7.46 6.27 7.33 7.38 1 8 6/24/2010 7.43 6.23 7.51 7.36 1 12 6/28/2010 7.58 6.16 7.58 7.29 2 16 7/02/2010 7.41 6.26 7.50 7.20 2 19 7/05/2010 7.79 6.32 7.84 7.16 2 21 7/07/2010 7.62 6.38 7.73 7.29 2 23 7/09/2010 7.65 6.60 7.75 7.47 2 26 7/12/2010 7.57 6.79 7.77 7.60 2 28 7/14/2010 7.63 6.69 7.76 - 3 30 7/16/2010 7.92 6.63 8.06 - 3 33 7/19/2010 7.69 6.49 7.68 - 3 35 7/21/2010 7.64 6.38 7.63 - 3 37 7/23/2010 7.72 6.39 7.75 - 3 40 7/26/2010 7.67 6.38 7.76 - 3 42 7/28/2010 7.64 6.43 7.75 - 3 44 7/30/2010 7.59 6.60 7.72 - Table C.4 Alkalinity (mgIL CaCO3) for 3 SRT’s SRT Day Date Reactor Reactor Reactor Reactor 2 3 4 5 1 2 6/18/2010 6,300 4,800 9,100 10,000 1 5 6/21/2010 7,100 4,800 8,600 10,600 1 8 6/24/2010 6,900 6,800 10,200 1 1 ,800 1 12 6/28/2010 7,300 4,000 11,800 11,800 2 16 7/2/2010 6,400 5,200 1 1 ,200 9,400 2 19 7/5/2010 7,700 4,400 13,800 10,200 2 21 7/7/2010 7,100 5,200 12,200 9,800 2 23 7/09/2010 7,600 5,600 12,200 10,800 2 26 7/12/2010 7,900 6,800 13,800 12,200 2 28 7/14/2010 7,000 4,800 12,800 - 3 30 7/16/2010 7,900 6,200 13,800 - 3 33 7/19/2010 8,200 6,600 13,400 - 3 35 7/21/2010 7,900 6,000 13,000 - 3 37 7/23/2010 8,300 5,800 13,800 - 3 40 7/26/2010 8,600 7,400 14,800 - 3 42 7/28/2010 8,700 7,400 15,200 - 3 44 7/30/2010 8,200 7,400 15,000 - 102 Table c.5 coo (mg/L) for 3 SRT’s SRT Day Date Reactor Reactor Reactor Reactor 2 3 4 5 1 2 6/18/2010 25,000 85,700 94,100 91,600 1 5 6/21/2010 28,175 NA 119,250 133,350 1 6 6/22/2010 28,550 88,950 98,050 104,150 1 8 6/24/2010 28,900 94,000 101 ,350 99,050 1 12 6/28/2010 23,800 87,100 91,250 101,450 2 16 7/02/2010 32,400 86,850 95,600 88,400 2 19 7/05/2010 30,650 87,600 99,050 108,300 2 21 7/07/2010 27,300 88,600 90,600 103,400 2 23 7/09/2010 26,175 98,200 83,450 102,450 2 26 7/12/2010 22,000 93,750 91,300 - 2 28 7/14/2010 20,600 87,750 82,600 - 3 30 7/16/2010 21 .400 93,550 79,650 - 3 33 7/19/2010 20,175 88,750 88,600 - 3 35 7/21/2010 19,575 85,100 82,400 - 3 37 7/23/2010 20,025 90,150 80,350 - 3 40 7/26/2010 22,150 88,450 83,150 - 3 42 7/28/2010 19,575 85,750 87,400 - 3 44 7/30l2010 21 .000 79,050 81 .550 - Table C.6 Reactor 2 TSNS for 3 SRT’s SRT Day Date TS (mg/L) TS % VS (mg/L) VS % 1 2 6/18/2010 15,877 1.62 9,503 0.97 1 5 6/21/2010 22,680 2.27 14,865 1.49 1 8 6/24/2010 23,460 2.33 15,193 1.49 1 12 6/28/2010 21,797 2.18 13,987 1.40 2 16 7/02/2010 25,290 2.54 15,400 1.55 2 19 7/05/2010 25,758 2.59 15,777 1.59 2 21 7/07/2010 23,363 2.32 14,053 1 .40 2 23 7/09/2010 23,003 2.37 14,007 1.45 2 26 7/12/2010 21,970 2.17 13,065 1.29 2 28 7/14/2010 20,530 2.03 12,355 1.22 3 30 7/16/2010 21,130 2.09 12,308 1.22 3 33 7/19/2010 20,225 2.01 11,855 1.18 3 35 7/21/2010 20,280 2.00 11,693 1.15 3 37 7/23/2010 26,007 2.60 15,407 1.55 3 40 7/26/2010 24,402 2.47 14,570 1 .47 3 42 7/28/2010 20,828 2.09 12,368 1.24 3 44 7/30/2010 21,045 2.09 12,440 1.23 103 Table C.7 Reactor 3 TSNS for 3 SRT’s SRT Day Date Ts (mg/L) Ts °/. vs (mgIL) vs % 1 2 6/18/2010 64,400 6.64 28,922 2.98 1 5 6/21/2010 70,153 6.99 31,337 3.12 1 8 6/24/2010 72,835 7.02 31 ,337 3.13 1 12 6/28/2010 72,240 7.19 32,540 3.24 2 16 7/02/2010 69,857 7.02 31,855 3.20 2 19 7/05/2010 76,190 7.58 34,223 3.40 2 21 7/07/2010 78,483 7.74 36,412 3.59 2 23 7/09/2010 76,915 7.55 35,608 3.50 2 26 7/12/2010 73,047 7.14 33,508 3.28 2 28 7/14/2010 70,362 7.06 32,682 3.28 3 30 7/16/2010 74,862 7.47 34,385 3.43 3 33 7/19/2010 73,622 7.35 33,403 3.34 3 35 7/21/2010 78,547 7.59 34,877 3.37 3 37 7/23/2010 74,503 7.50 32,830 3.31 3 40 7/26/2010 77,652 7.73 33,762 3.36 3 42 7/28/2010 79,577 7.97 33,343 3.34 3 44 7/30/2010 83,048 8.14 34,112 3.35 Table C.8 Reactor 4 TSNS for 3 SRT’s SRT Day Date TS (mgIL) TS % VS (mg/L) VS % 1 2 6/18/2010 70,500 7.14 32,097 3.25 1 5 6/21/2010 80,825 7.96 37,238 3.67 1 8 6/24/2010 80,508 8.19 36,398 3.70 1 12 6/28/2010 82,628 8.23 38,097 3.90 2 16 7/02/2010 80,395 8.02 36,297 3.62 2 19 7/05/2010 81,740 8.19 36,900 3.70 2 21 7/07/2010 80,447 7.96 36,452 3.61 2 23 7/09/2010 77,905 7.64 33,805 3.32 2 26 7/12/2010 80,542 8.13 ‘ 35,508 3.58 2 28 7/14/2010 77,347 7.76 33,322 3.35 3 30 7/16/2010 75,145 7.49 30,910 3.09 3 33 7/19/2010 78,967 8.13 34,208 3.52 3 35 7/21/2010 82,862 8.17 34,578 3.41 3 37 7/23/2010 81 ,268 8.02 32,855 3.24 3 40 7/26/2010 78,067 7.68 33,637 3.31 3 42 7/28/2010 88,932 8.78 38,826 3.84 3 44 7/30/2010 84,842 8.28 34,700 3. 39 104 Table C.9 Reactor 5 TSNS for 3 SRT’s SRT Day Date TS (mg/L) TS % VS (mg/L) VS % 1 2 6/18/2010 73,882 7.42 32,440 3.26 1 5 6/21/2010 74,503 7.42 32,807 3.27 1 8 6/24/2010 79,318 7.88 34,353 3.41 1 12 6/28/2010 83,200 8.32 37,295 3.73 2 16 7/02/2010 77,383 7.68 34,735 3.45 2 19 7/05/2010 84,853 8.67 39,173 4.00 2 21 7/07/2010 87,043 8.86 39,942 4.07 2 23 7/09/2010 89,462 8.83 40,258 3.98 2 26 7/12/2010 80,557 8.30 36,330 3.74 2 28 7/14/201 0 - - - - 3 30 7/1 6/201 0 - - - - 3 33 7/1 9/201 0 - - - - 3 35 7/21/201 0 - - - - 3 37 7/23/201 0 - - - - 3 40 7/26/201 0 - - - - 3 42 7/28/201 0 - - - - 3 44 7/30/2010 - - - - Table C.10 Percentage (%) Methane Content Date Day 8 RT Rea1ctor Reazctor Rea3ctor Rea4ctor Reasctor 6/17/2010 1 1 NA 54 16 18 44 6/18/2010 2 1 3 49 15 24 40 6/21/2010 5 1 3 46 16 34 41 6/23/2010 7 1 1 50 26 47 41 6/28/2010 12 1 1 63 29 52 46 7/01/2010 15 1 - 34 14 39 29 7/02/2010 16 2 - 42 16 45 31 7/04/2010 18 2 - 45 25 56 38 7/06/2010 20 2 - 65 31 61 44 7/08/2010 22 2 - 60 37 59 50 7/12/2010 26 2 - 63 44 59 58 7/15/2010 29 2 - 62 36 57 - 7/19/2010 33 3 - 67 36 53 - 7/22/201 0 36 3 - 63 29 58 - 7/26/201 0 40 3 - 61 29 57 - 7/28/2010 42 3 - 60 31 57 - 7/31/2010 45 3 - 61 42 57 - 105 Table 0.11 Reactor 5 COD and VS Destruction COD VS Reasctor 3 ‘5 'o .9 ‘3 3 1: .5 g. 5 33’s ‘9 E 9 3:6 ‘3’ .9 9 9g :9 9 9 8g 9 DAY 5 E a °\. 5 it 0 °\. 2 16,322 11,908 4,414 27 8.052 4,217 3,835 48 6 16.322 13,540 2,782 17 8,052 4,265 3,787 47 8 16,322 12,877 3,445 21 8.052 4,466 3,586 45 12 16.322 13,189 3,133 19 8,052 4,848 3,204 40 16 16,322 11,492 4,830 30 8,052 4,516 3,536 44 19 16.322 14,079 2,243 14 8,052 5,092 2,959 37 21 16,322 13,442 2,880 18 8,052 5,192 2,859 36 23 16,322 13,319 3,003 18 8,052 5,234 2,818 35 26 16.322 12,324 3,998 24 8,052 4,723 3,329 41 28 - - - - - - - - 30 - - - - - - - - 33 - - - - - - - - 35 - - - - - - - - 37 - - - - - - - - 40 — - - - - - - - 42 - - - - - _ - - 45 - - - - — - - - Table C.12 Characteristics of Substrate Feeds between SRT’s SRT 1 Reactor 2 Feed Reactor 3 Feed Reactor 4 Feed ‘ COD (mg) 61.525 187,100 251,100 VS (mg) 37,394 101,160 123,876 SRT 2 Reactor 2 Feed Reactor 3 Feed Reactor 4 Feed COD m 62,675 192,400 246,900 VS m 30.700 99.386 117,910 SRT 3 Reactor 2 Feed Reactor 3 Feed Reactor 4 Feed ‘ COD (mg) 61,150 200,400 257,200 VS (mg) 41,340 91,686 107,396 106 BIBLIOGRAPHY 107 AgStar. 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