Waste Biomass Bioassay Project - Michigan · 2016-02-25 · 1 Waste Biomass Anaerobic Digestion Biogas Potential in Support of Renewable Energy Development Project PLA-09-34 Final

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Waste Biomass Anaerobic Digestion Biogas Potential in Support of

Renewable Energy Development

Project PLA-09-34

Final Report – October 1, 2008 - July 31, 2009 Submitted on September 15, 2009

Submitted to:

Tania M. Howard, Biomass Energy Program Coordinator Department of Energy, Labor & Economic Growth (DELEG) Bureau of Energy Systems 611 W. Ottawa, P.O. Box 30004 Lansing, MI 48909

Submitted from:

Steven I. Safferman, Associate Professor Department of Biosystems and Agricultural Engineering Michigan State University 212 Farrall Hall East Lansing, MI 48824 [email protected] 517-432-0812 517-432-2892

Prepared by: Steven Safferman, Louis Faivor, David Wall, and Wei Wu-Hann

A. Implementation Plan The objective of the project, as originally presented in the project proposal, follows.

MSU and the participating organizations will identify locations of large amounts of waste agricultural residuals and conduct biogas assays to determine if further consideration of establishing a renewable energy system is warranted for that specific material. Results will be reported to all involved stakeholders.

Tasks completed follow.

1. Identified diverse agricultural facilities located throughout the state, including farms and food processors, with substantial amounts of waste biomass that has the potential to be aerobically digested resulting in biogas formation.

2. Collected biomass from several of the identified facilities and screened for digestion potential using MSU’s biogas potential assay, Appendix A.

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3. Reported results to stakeholders so appropriate next steps can be taken. A total of 20 assays were conducted from 13 facilities. Several of the facilities had multiple waste streams that were tested. The proposal projected 16 to 24 assays would be completed. Reports for each assay are located in Appendix B. Two assays are continuing (12 and 24); however, preliminary data is reported. Deviations from the original project plan entailed minor variations associated with the specific steps in the protocol (Appendix A) as each assay represented a unique, customized design. Delays in the timeline also resulted due to equipment failure and a late project initiation resulting from contractual issues. Neither of these issues changed the outcome of the project. B. Accomplishments The objective of the project was fully realized. Twenty assays were initiated with 18 completely finished. Appendix B contains the reports, including the preliminary data associated with the final 2 ongoing assays (12 and 24). The associated reports were sent to the organizations that represented the facility; Sali Group, LLC, Phase 3 Development and Investments, LLC, and Michigan State University. The organizations are currently examining the data and results in preparation of working with the facilities on the next step of considering digestion. This is a lengthy complex procedure as commitment to a digester is substantial and requires much deliberation and the wealth of data must be carefully interpreted. Problems experienced in carrying out the project primarily entailed delays resulting from a late start caused by contractual issues and a water bath failure. Hence 2 assays are still ongoing but preliminary results are included. Interpreting the wealth of data is also proving to be time consuming and challenging. Although the project is complete, the impact is still being realized. The results are being further interpreted to determine if further consideration of digestion is warranted. A manuscript is being prepared for publication in a peer reviewed journal on the assay. Results are being generalized, beyond that already completed in this report. Of importance is blending of biomass to produce optimized feed stocks. C. Coordinated Efforts with other Organizations Close coordination between Sali Group, LLC, Phase 3 Development and Investments, LLC occurred. These two organizations made the initial contacts with each facility, collected the samples, delivered them to MSU, are participating in the interpretation of results, and are explaining the results to the original facility managers. All 13 facilities where samples were collected are also involved in the project. D. Impacts In all, 13 agricultural related facilities were involved, with follow-up planned at several sites. Quantification of these follow-up steps is not possible as the process of investing

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in a digester is substantial and results from the assays are still being interpreted and discussed. One additional purpose for this project was the evaluation and adaptation of the current protocol for conducting biogas assays. With each additional biogas assay conducted in the laboratory, new findings arise. These findings include not only the intended data, but also challenges that were not initially expected, equipment malfunctions and failures, as well as revelations concerning methods for collecting the data. The need to analyze 16 to 24 different samples during this project in a limited amount of time tested the current protocol and the purpose of the biogas assays; mainly, to be a rapid prescreening tool for the initial evaluation of potential feeds tocks in anaerobic digestion. Specific lessons learned follow.

• Although the protocol explicitly stated it was not the intent, many individuals have a desire to use the results of the biogas assays to go directly into anaerobic digester design. This is strongly discouraged by the research team and is stressed to clients. These results are not intended to make decisions on possible loadings, feeding schedules or any other design implications. This point will need to continue to be stressed as future work is conducted.

• In the current protocol, there are several analytic tests that are conducted on each individual flask or sample. Currently, the volume of work associated with these tests is a limiting factor in providing a rapid prescreening tool. Thus, it is vital that the tests that are run in the lab are quick, reliable, repeatable, and relevant. For that reason, it has been decided that total suspended solids and volatile suspended solids will not be conducted unless specifically requested by a client for a specific purpose. Due to the variability in composition of these tests and the high level of precision needed, it proved difficult to gather consistent results. It was not uncommon to spend more time conducting those tests than any other test on the samples. Additionally, it was found that clients were rarely using the data from these tests.

• Because the biogas assay is intended to be a tool for providing evaluation of potential feed stocks, it is necessary to analyze and compare results on a comparable scale. The gathered data needs to be organized and arranged in units that can be compared regardless of how the sample was setup. When comparing samples, total gas production alone cannot be used for comparing feed stocks because the amount of COD is not equal for all biogas assays. After looking at the literature, it has been decided that samples will be compared using mainly two numbers; mL of gas production per mg COD destroyed, and mL gas production per mg volatile solids destroyed. Finding and using these numbers provides a quick and meaningful tool for comparison.

• Although not specified in the protocol, gas analysis through gas chromatography is currently conducted once a week on each sample. Further discussions with the research team and clients will lead to a decision on exactly how often the gas should be analyzed. Under normal digestion, the percentage of methane in the sample will be relatively consistent once digestion has stabilized. However, the percentage of methane is vital for determining if a feedstock is viable for biogas

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use in electrical generators or boilers. Additionally, the current gas chromatograph has the capability to analyze biogas for nitrogen, methane, and carbon dioxide. The need and desire to provide clients with data on hydrogen sulfide will soon be met with the purchase of a new gas chromatograph. Currently, to measure hydrogen sulfide 300 mL of the biogas is collected from each sample in gas bags and tested them using Gastec tubes. This method provides a general idea of how concentrated the hydrogen sulfide might be but is not as accurate as a gas chromatograph.

• Most often, the biogas assay is conducted until gas production ceases. Determining when this might happen during the design of the respirometer run can be difficult. Acclimation periods and slow or fast rates of gas production can dramatically change the time frame in which a biogas assay takes place. For this to be an effective tool, it is important to produce enough biogas to provide meaningful results yet have the test end in a reasonable amount of time for the client. Currently, a target COD of 3000 mg from the waste being researched is used. Assuming ideal conditions where 50% COD destruction took place, approximately 590 mL of methane gas would be produced. However, this does not take into account the amount of COD added by the manure or seed during blending. Consequently, it was not uncommon to have assays take much longer than desired. Most likely, this will be changed in future assays to account for the COD added by the manure and seed.

• The current protocol calls for a nutrient solution to be used to optimize anaerobic digestion. There is a listed nutrient solution as well as a desired ratio of COD to nitrogen. The intention was to use this nutrient solution to meet this ratio. However, there are issues with this current procedure. A test for nitrogen is not part of the current procedure so determining how much additional nitrogen is actually needed is difficult. Assuming that the samples contain zero nitrogen can lead to nutrient toxicity. In an effort to avoid this, it was assumed that manure provides most of the necessary nutrients for anaerobic digestion. However, manure collected from feedstock operations is not consistent and does not always contain all of the trace metals recommended by the literature. Thus, a large portion of future work will be dedicated to finding both a method for determining the nutrient needs of a sample and a method of implementation.

• Seed used for the biogas assays was collected from a running pilot-scale digester on campus. In an effort to maintain consistency it was decided to collect enough seed at the start of this project and store it in a freezer until needed. The question of whether the seed used at the end of the project was viable in terms of providing an acclimated community of anaerobic microbes has since been asked. This question will be addressed in further work.

MSU is now recognized for conducting the biogas assay and is providing services for 3 organizations with agreements with 3 additional companies planned. All of these projects either examine the potential of specific biomass blends for biogas production and/or the optimization of digestion.

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E. Financial Expenditures A separate financial report has been prepared and submitted by MSU Contracts and Grants Office.

F. Applying Project Products The application of the results from each assay is the critical next step. Each assay, biomass, and facility is unique. The 3 participating organizations are now in the process of results interpretation in preparation to work with each facility to plan the next step. Additionally, a manuscript for peer-review publication is being prepared. The emphasis is on the utility of the assay and generalizations concerning biomass blending produce an optimized feed stock. Further, the predictive nature of the assays will be assessed by monitoring progress in initiating digestion at the facilities from where samples were collected. Preliminary general conclusions follow.

• Current studies demonstrated that co-digestion of cow manure with chicken manure likely increased biogas production up to 57% and co-digestion of cow manure with MSU breakfast waste could enhance biogas production 2 fold.

• Ammonia varied between treatments, however, no effect of ammonia on cumulative biogas yield was observed which indicated that no ammonia inhibition occurred during most trial periods.

• Biogas yield from cow manure digestion ranged from 30 mL/g VS destroyed to 1,880 ml/g VS destroyed (average 770 mL/g VS destroyed). This varied biogas production is likely related to various seed activity.

• The percentage of methane in the biogas ranged from 20% to 80% (an average of 50-60% methane in the biogas was observed across all trials). It is difficult to calculate methane potential of substrates due to highly variable methane content during experimental periods and equipment limitation.

• Manure usually provided buffering capacity and a wide range of nutrients. Substrate used for co-digestion with manure should contain high carbon content which could balance the carbon to nitrogen (C/N) ratio of the feedstock, thereby increasing biogas yields and decreasing the risk of ammonia inhibition.

G. Budget

A separate financial report has been prepared and submitted by MSU Contracts and Grants Office.

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Appendix A

Biogas Potential Screening and Anaerobic System Monitoring

Introduction Michigan State University, Department of Biosystems and Agricultural Engineering (BAE), will conduct anaerobic treatment screening assays on waste samples that may be feed stocks for anaerobic digesters. Sources may include manure, ethanol production byproducts, and food processing wastewater. The assays are designed simply to determine if further development studies are warranted in terms of the anaerobic biodegradability of the wastewater under the tested conditions. Results may also provide characteristics of the waste useful in such future studies. Assay conditions will not represent proposed on-site treatment techniques as the assay is strictly designed to serve as a screening tool. Sample Collection and Shipment Samples will be collected by Client (unless other arrangements are made for the University or another organization to collect the samples), immediately chilled, stored near 4oC, and shipped to Michigan State University (at a chilled temperature) with 24 hours. A total sample size of 2 L is required. The shipping information is provided below.

Michigan State University Department of Biosystems and Agricultural Engineering 212 Farrall Hall East Lansing, MI 48824 Attn: Steven Safferman Phone: 517-432-0812 or 355-4720 Fax: 517-432-2892

Client will inform BAE by phone or in writing of the characteristics of the samples including the name of the facilities where the waste originated from (that will be kept confidential), the process(es) that generated the waste, special safety precautions, waste constituents that may inhibit anaerobic digestion, and any other relevant information. Specific constituents of concern include the following.

• Oxidizing sanitizers o Hyperchlorites, chlorine, chloramines o Organic bromine o Iodine, alcohol-iodine, iodophors o Hydrogen peroxide, peroxy acids

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• Biocides and non-oxidizing sanitizers

o Organic acids (e.g. acetic acid, propionic acid, formic acid, carboxylic acids)

o Acid anionic sanitizers o Acid-quat sanitizers o Quaternary ammonium compounds

• Polyphenols • Long Chain Fatty Acids

Only samples that can be disposed of by flushing down the sink into the sanitary sewer can be accepted unless arrangements are made to return the samples back to the original facilities. BAE will hold the samples at 4oC before processing, for up to 7 days, before initiating the respirometry assay. If Client collects a sample from a facility that does not wish to be identified to the University, the identifying company information, such as name, location, and unique features that may identify the facility, can be excluded provided that Client provides the other needed information listed. Pre Respirometry Analysis Table 1 contains the pre-respirometry analysis that will be conducted for each sample, including the method and suggested ranges for idealized digestion, where applicable. Table 1. Pre Respirometry Analysis Analysis Method Suggested Range Source

pH pH meter 6.5 to 8.2 Speece, 1996 Alkalinity* Hach 8203 2000 to 3000 mg/L CaCO3 Speece, 1996

COD Hach 8000 (EPA approved) > 1000 mg/L COD Speece, 1996

Soluble COD HACH 8000 after Filtering with TSS Filter

Total Solids (TS)

Hach 8271 (EPA approved) < 10% for batch tests Carucci et al., 2005

Total Volatile Solids (TVS)

Hach 8271 (EPA approved)

High Percent of Total Solids

Total Suspended Solids (TSS)

Hach 8271 (EPA approved)

Relatively Low Percent of Total Solids

Total Volatile Suspended Solids (TVSS)

Hach 8158, 8164 Relatively Low Percent of Total Solids

*Colorimetric test, may not be possible to analyze for all samples All but the alkalinity will be duplicated to ensure quality.

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Respirometry Set Up One respirometry unit, containing 8 vessels, will be used for each assay. Four conditions will be tested. For each condition, 2 vessels will be used. One will measure the total biogas produced and the other will measure biogas produced after carbon dioxide has been removed. Assuming that the biogas is composed of only carbon dioxide and methane, the carbon dioxide scrubbed biogas is an estimate of the amount of methane produced. The carbon dioxide will be removed by passing the biogas through an approximately 500 mg/L potassium hydroxide solution with a pH indicator. Each vessel is 675 mL. Of this volume, 600 mL will be filled with liquid with the balance serving as head space based on recommendations by the respirometer manufacturer. The four conditions (2 vessels for each condition) proposed for testing includes the following. However, plant-specific alternatives can be designed.

• Seed • Seed/Nutrient • Feed Stock/Seed • Feed Stock/Nutrients/Seed (optimal)

Seed will be digester content obtained from a locally operational anaerobic digester (most likely digesting manure). This digester may be a bench-scale experimental unit or a field-scale system, depending on availability at the time analysis is run. Each vessel will receive 100 mL of seed, determined based on previous experience. The volume of wastewater in each vessel will be based on the dilution expected in a theoretical plug flow reactor with a HRT of 15 days as the dilution would be equivalent to a batch reactor. Consequently, 40 mL will be used. However, the volume of substrate should never result in a total solids concentration greater than 10% for a typical assay. Nutrients, where applicable, will be added as a solution containing the constituents shown in Table 2 (Shelton and Tiedje, 1984). The volume of the nutrient solution will be based on the COD of the feed stock. Specifically, a COD/Total Nitrogen (as added from the NH4Cl) weight ratio of 100/4 will be used (Bouallagui et al., 2004). From this ratio, the mg of NH4Cl will be calculated that can then be converted to a volume for the vessel. The other nutrients will be added in proportion. Because of the low concentration of the metals, a stock solution will be prepared and the appropriate amount transferred into each vessel. The media will be autoclaved for 5 minutes before use to drive off oxygen (Shelton and Tiedje, 19984). This level of nutrients assumes no nutrient value form the feed stock and seed although realistically, there would be a contribution. However, the excess should not have a negative influence and can be examined in the feed stock/seed vessel. Thus, the volume of the nutrient solution will be 6000 mL subtracted from the other applicable volumes (wastewater and/or seed).

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Table 2. Nutrient Solution

Parameter mg/L KH2PO4 270 K2HPO4 350 (adjusted to pH 7) NH4Cl 530 CaCl2 • 2H2O 75 MgCl2 6 •H2O 100 FeCl2 • 4 H2O 20 MnCl2 • 4H2O 0.5 H3BO3 0.05 ZnCl2 0.05 CuCl2 0.03 Na2Mo4 • 2H2O 0.01 CoCl2 • 6H2O 0.5 NiCl2 • 6H2O 0.05 Na2SeO3 0.05

Additionally, 1 mg/L of resazurin dye will be added to each vessel. Specifically, a 1,000 mg/L solution will be prepared and 0.6 mL will be added to each flask. If oxygen is present, the color of the solution will be bright pink. If the color is dark maroon, the condition is anaerobic. Once all constituents are in the respirometry vessels, the head space will be flushed with nitrogen for 5 minutes. The vessels are then sealed and placed atop the magnetic stirrer within the water bath. Respirometry Operation The temperature within the water bath will be set at 350C, unless an alternative temperature is a variable to be tested. Gas production rates and cumulative gas volume are measured continuously and recorded every 3 hours. To supplement the gas volume measurements with and without CO2 scrubbing, gas grab samples will be collected directly from the head space of each treatment vessel and analyzed for methane and carbon dioxide using a gas chromatograph (GC). Specifically, a Supelco SCOTT MX 216 packed primary and reference column will be used in a Shimazdu GC8. The oven temperature is run isothermally at a temperature of 100oC. Helium is the carrier gas. A 3 to 5 point standard curve will be used to calibrate a linear regression curve. Once all of the vessels reach their maximum gas volume, as indicated by a horizontal cumulative biogas production curve, the assay will be considered complete and post respirometry analysis will be conducted. Post Respirometry Analysis The same parameters measured pre respirometry analysis will be repeated for each vessel. All analysis will be repeated for one randomLy picked vessel to ensure quality.

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Data Presentation A letter report will provide a detailed summary of the operational protocol. Assay operational issues, if any, will also be reported. A plot of the cumulative gas production with time and another with the gas production rate with time will be provided. Methane and total biogas potential of the wastewater over the course of the batch assay will be provided. These plots will be calculated by subtracting the optimal vessel results from the seed/nutrients vessel results and the feed stock/seed results from the seed vessel. A table containing the ultimate methane and biogas volumes and all of the pre and post respirometry analysis for each vessel will be provided. Calculated values of the ultimate methane potential will be included by subtracting out the appropriate control. The methane potential will be normalized to the COD removed and to the volatile solids removed. Based on the stoichiometry, 395 mL CH4 at 35°C is produced per 1000 mg COD. The values obtained in the assays will be compared to this theoretical standard. Results from the duplicates and GC analysis will be reported. References Borja, R., B. Rincón, F. Raposo, J. R. Dominguez, F. Millan, and A. Martín. 2004. “Mesophilic anaerobic digestion in a fluidized-bed reactor of wastewater from the production of protein isolates from chickpea flour.” Process Biochemistry 39(12): 1913-1921. Carucci, G., F. Carrasco, K. Trifoni, M. Majone, and M. Beccan. 2005. “Anaerobic Digestion of Food Industry Wastes: Effect of Codigestion on Methane Yield.” Journal of Environmental Engineering 131(7): 1037-1045. Gunaseelan, V. N. (1997). "Anaerobic digestion of biomass for methane production: A review." Biomass & Bioenergy 13(1-2): 83-114. Shelton, D. R. and J. M. Tiedje. 1984. “General Method for Determining Anaerobic Biodegradation Potential.” Applied and Environmental Microbiology 47(4): 850-857.

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Appendix B

Biogas Assay Reports

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Waste Biomass Anaerobic Digestion Biogas Potential in Support of Renewable Energy Development

Phase 3

1. Poll Farms Swine Finish Manure Hamilton, MI

Submitted to Phase 3 Renewables

Date Sample Collected: January 26, 2009 Date Assay Conducted: January 30 – February 23, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems

Phase 3 Renewables Sali Group

Michigan State University MSU Principal Investigator: Steven Safferman ([email protected], 517‐432‐0812)

mailto:[email protected]

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Goal This assay determined the anaerobic biodegradability and biogas recovery potential of swine finish manure collected from Poll Farms. The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993 Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).

Table 1. Submitted Sample Analysis

Submitted Sample pH TS (mg/L)

VS (mg/L)

COD (mg/L)

Swine Manure Used in Lab* 7.87 12,336 8,477 18,050 Swine Manure Corrected For Dilution NA 49,344 33,908 72,200

*Data was collected on a diluted sample because only a 250 mL sample of the finial manure was available. To make this dilution 250 mL of the original sample was diluted into 1 liter.

Table 2. Flask Composition

Flask Seed (mL)

Manure(mL)

Swine (mL)

D.I. Water(mL)

Seed (1.1 Seed) 143 0 0 507

Seed, Cow Manure (1.2 Seed, MSU Manure) 143 182 0 325

Seed, Swine Manure (1.3 Seed, Poll Finish Manure) 143 0 182 325

Seed, 1:1 Cow:Swine Manure (1.4 Seed, 1:1 MSU Manure:Poll Finish Manure) 143 182 182 143

Swine Manure (1.5 Poll Finish Manure) 0 0 182 468

Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended

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solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not shown in Table 3 are also provided in the Appendix. Figures 1-3 are graphs of the cumulative, total biogas production, biogas production rate, and biogas methane content, respectively.

Table 3. Constituents Before and After Anaerobic Digestion Assay

COD Soluble COD Volatile Solids

Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 5,558 4,761 797 14 3,088 3,429 -341 -11 3,974 3,171 803 20Seed, Cow Manure 15,909 11,009 4,900 31 8,483 8,084 399 5 8,412 7,204 1,208 14

Seed, Swine Manure 8,954 7,256 1,698 19 4,664 5,533 -869 -19 5,392 4,410 981 18

Seed, 1:1 Cow:Swine Manure 17,721 14,463 3,258 18 10,758 8,889 1,869 17 10,856 8,785 2,071 19

Swine Manure 3,632 2,949 683 19 2,210 2,543 -333 -15 1,793 1,494 299 17

Figure 1. Cumulative Biogas Volume

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Figure 2. Biogas Production Rate

Figure 3. Biogas Methane Content

Table 4 shows biogas production and provides a comparison to the amount of COD and volatile solids destroyed.

Table 4. Biogas Produced per COD and Volatile Solids

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Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 235 NA 797 0.29 803 0.29Seed, Cow Manure 2,271 NA 4,900 0.46 1,208 1.88

Seed, Swine Manure 743 508 1,698 0.44 981 0.76Seed, 1:1 Cow:Swine Manure 2,549 278 3,258 0.78 2,071 1.23

Swine Manure 259 259 638 0.38 299 0.87 **Calculated using the Seed and Seed, Cow Manure flasks. Note: Can only be used for flasks where the seed and cow manure volumes are the same.

Discussion and Conclusions Alkalinity and pH were adequate at the beginning and end of digestion (Appendix A. B., and C.). Ammonia varied substantially between treatments (Appendix A. and B.), however, the discrepancies in ammonia content relating to biogas production as well as COD and VS destruction were not evident (Table 4 and Appendix H). This result suggested that ammonia inhibition was not observed in current study. Soluble COD (Table 3) increased after digestion for the seed flask and those with swine manure. This may have resulted from the breakdown of organic solids into soluble COD, however the microbial community was not acclimated to degrading those available soluble COD. The relatively low COD and VS destructions (Table 3), compared to that reported in the literature, may relate to the relatively short period assay which likely cause lacking of microbial acclimation to the specific substrates. As equivalent volumes of both manures were used, swine manure appears to produce substantially less biogas per volatile solids destroyed than cow manure but produced similar levels based on COD destroyed (Table 4). Since cow manure utilized in current assay was obtained after manure separation process, relatively greater biogas production per volatile solids destroyed were expected. The percentage of methane in the biogas (Figure 3) was very similar for all treatments. However, swine manure produced substantially less biogas than cow manure, on an equivalent volume basis (Table 4). Consequently, the energy potential for swine manure is substantially less compared with cow manure utilized in current assay. Interestingly, this does not appear to be related to ammonia as the levels in flasks with swine manure were not higher than those with cow manure (data in the Appendix). The mixture of the cow and swine manure did not produce an amount of gas that is additive of the individual sources during the assay period (after accounting for the gas produced by the seed). However, at the end of the assay the rate of gas production appears to be increasing beyond the flasks with just the cow manure and seed indicating that acclimation may have occurred (Figure 2). This increasing

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trend was not observed for the vessel with only swine manure indicating the maximum biogas potential may have been realized by the end of the assay. Comparing the amount of COD destroyed to the stoichiometric volume of methane produced , ,approximately 390 mL/g COD destroyed (Speece,1996), is difficult as the percent methane in the biogas is highly variable. However, considering the assay in its entirety and an average of 50% methane in the biogas, the actual methane potential is fairly close to that expected for the amount of COD destroyed in all flasks. From the assay, it is projected that there is no advantage to mixing this specific swine and cow manure in equal proportions if the objective is energy production. However, the biogas assay does not use acclimated microbial communities. Inhibition does not appear to be occurring and if a primary objective is environmental protection and mixing enables economies of scale, additional testing using a prototype more representative of the proposed digester system, such as a semi-continuous bench-scale treatability study, is warranted.

Reference: Chynoweth, D.P.; C.E. Turick, J. M. Owens, D. E. Jerger, and M. W. Peck. 1993. Biochemical Methane Potential of Biomass and Waste Feedstocks. Biomass & Bioenergy 5(1): 95-111. Speece, R. E. 1996. Anaerobic Biotechnology for Industrial Wasters.

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Appendix

Appendix A. Constituents Concentrations in Flasks Before Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)

Seed 7.96 2,900 8,551 4,751 9,626 5,360 6,114 4,105 391 Seed, Cow Manure 7.08 5,420 24,475 13,051 19,549 13,831 12,942 10,760 777

Seed, Swine Manure 7.98 4,140 13,775 7,175 12,889 6,751 8,295 5,560 735 Seed, 1:1 Cow Manure:Swine Manure 7.74 6,420 27,263 16,551 25,926 15,540 16,702 11,771 1,114

Swine Manure 8.17 1,820 5,588 3,400 4,314 1,225 2,758 1,225 352

Appendix B. Constituents Concentrations in Flasks After Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Swine Manure 7.56 5,200 11,163 8,512 11,318 6,500 6,785 6,500 814 Seed, 1:1 Cow:Swine Manure 7.75 7,920 22,251 13,675 21,923 12,100 13,515 10,500 1,343

Swine Manure 7.38 2,140 4,538 3,913 3,579 1,500 2,299 1,500 389

Appendix C. pH Change During Digestion Flask Initial pH Final pH pH Change Seed 7.96 7.33 -0.63

Seed, Cow Manure 7.08 7.39 0.31 Seed, Swine Manure 7.98 7.56 -0.42

Seed, 1:1 Cow:Swine Manure 7.74 7.75 0.01 Swine Manure 8.17 7.38 -0.79

19

Appendix D. Alkalinity Change During Digestion

Flask Initial Alkalinity (mg CaCO3)

Final Alkalinity (mg CaCO3)

Alkalinity Change (mg CaCO3)

Seed 1,885 2,171 286 Seed, Cow Manure 3,523 4,641 1,118

Seed, Swine Manure 2,691 3,380 689 Seed, 1:1 Cow:Swine Manure 4,173 5,148 975

Swine Manure 1,183 1,391 208

Appendix E. Total Solids Destruction During Digestion

Flask Initial TS (mg)

Final TS (mg)

TS Destruction (mg)

Destruction (%)

Seed 6,257 5,121 1,136 18 Seed, Cow Manure 12,707 12,073 634 5

Seed, Swine Manure 8,378 7,357 1,021 12 Seed, 1:1 Cow:Swine Manure 16,852 14,250 2,602 15

Swine Manure 2,804 2,326 479 17

Appendix F. Total Suspended Solids Destruction During Digestion

Flask Initial TSS (mg)

Final TSS (mg)

TSS Destruction (mg)

Destruction (%)

Seed 3,484 2,470 1,014 29 Seed, Cow Manure 8,990 6,565 2,425 27

Seed, Swine Manure 4,388 4,225 163 4 Seed, 1:1 Cow:Swine Manure 10,101 7,865 2,236 22

Swine Manure 796 975 -179 -22

Appendix G. Volatile Suspended Solids Destruction During Digestion

Flask Initial VSS (mg)

Final VSS (mg)

VSS Destruction (mg)

Destruction (%)

Seed 2,668 2,470 198 7 Seed, Cow Manure 6,994 5,135 1,859 27

Seed, Swine Manure 3,614 4,225 -611 -17 Seed, 1:1 Cow:Swine

Manure 7,651 6,825 826 11

Swine Manure 1,225 975 250 20

Appendix H. Ammonia Change During Digestion

Flask Initial Ammonia (mg NH3)

Final Ammonia (mg NH3)

Ammonia Change (mg NH3)

Seed 254 279 25 Seed, Cow Manure 505 582 76

Seed, Swine Manure 478 529 51 Seed, 1:1 Cow:Swine Manure 724 873 149

Swine Manure 229 253 24 Note: feedstocks containing high levels of protein break down to ammonium bicarbonate, increasing alkalinity and ammonia concentrations (Metcalf and Eddy, 2003).

20

Appendix I. Hydrogen Sulfide Concentration

Flask H2S Concentration** (PPM)

Seed NSG* Seed, Cow Manure 2,400

Seed, Swine Manure 900 Seed, 1:1 Cow:Swine Manure 2,050

Swine Manure 100 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

21


Phase 3

2. Deweerdt Farms Chicken Manure Hamilton, MI


Date Sample Collected: January 26, 2009 Date Assay Conducted: January 30 – February 23, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems


Michigan State University MSU Principal Investigator: Steven Safferman ([email protected], 517-432-0812)


22

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of dry chicken manure collected from Deweerdt Farms. The sample was collected by Norma McDonald, Phase 3 Renewables LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Deweerdt Chicken Manure Used in Lab* 7.96 97,156 58,678 61,250 * Data for the above parameters was collected on a diluted sample. Dry chicken manure was submitted and was diluted with water and blended until a consistency was produced that allowed for laboratory use.

. Table 4. Flask Composition

Flask Seed (mL)

Cow Manure

(mL)

Chicken Manure

(mL)

DI Water (mL)

Seed (2.1 Seed) 300 0 0 350


Seed, Chicken Manure (2.3 Seed, Deweerdt Chicken Manure) 300 0 55 295

Seed, 1:1 Cow Manure:Chicken Manure (2.4 Seed, 1:1 MSU Manure:Deweerdt Chicken Manure) 300 55 55 240

Chicken Manure (2.5 Deweerdt Chicken Manure) 0 0 55 595



Seed, 1:1 Cow Manure:Chicken Manure DUP (2.8 Seed, 1:1 MSU Manure:Deweerdt Chicken Manure) 300 55 55 240

23

Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not shown in Table 3 are also provided in the Appendix. Figures 1-3 are graphs of the cumulative, total biogas production, biogas production rate, and biogas methane content, respectively.



Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 10,058 9,328 731 7 5,980 5,956 24 0 8,052 5,989 2,063 26

Seed, Cow Manure 12,732 11,351 1,382 11 5,883 7,378 -1,495

-25 9,640 7,360 2,280 24

Seed, Chicken Manure 15,129 11,180 3,949 26 6,663 6,931 -268 -4 10,952 6,960 3,994 36Seed, 1:1 Cow

Manure:Chicken Manure 15,697 12,294 3,405 22 8,141 7,881 260 3 13,066 7,651 5,415 41

Chicken Manure 2,877 2,283 594 21 1,641 1,991 -349 -21 3,642 1,486 2,155 59

Seed, 2:1 Cow Manure:Chicken Manure 17,866 15,885 1,983 11 9,458 9,238 219 2 14,120 9,743 4,378 31

Seed, 1:2 Cow Manure:Chicken Manure 13,812 11,660 2,154 16 7,264 7,394 -130 -2 11,548 7,398 4,149 36

Seed, 1:1 Cow Manure:Chicken Manure

DUP 15,357 13,025 2,332 15 7,556 6,630 926 12 11,955 8,018 3,935 33

24



25




Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 458 NA 731 0.63 2,063 0.22Seed, Cow Manure 859 NA 1,382 0.62 2,280 0.38

Seed, Chicken Manure 1,950 1,492 3,949 0.49 3,994 0.49Seed, 1:1 Cow Manure:Chicken Manure 2,741 1,882 3,405 0.80 5,415 0.51

Chicken Manure 852 852 594 1.43 2,155 0.40Seed, 2:1 Cow Manure:Chicken Manure 3,368 NA 1,983 1.70 4,378 0.77Seed, 1:2 Cow Manure:Chicken Manure 1,777 NA 2,154 0.82 4,149 0.43

Seed, 1:1 Cow Manure:Chicken Manure DUP 2,102 1,243 2,332 0.90 3,935 0.53**Calculated using the Seed and Seed, Cow Manure flasks. Note: Can only be used for flasks where the seed and cow manure volumes are the same.

Discussion and Conclusions:

26

Alkalinity and pH of all treatments were adequate at the beginning and end of 24-d digestion period with the exception of chicken manure without seed (Appendix A.B. and C). The alkalinity of chicken manure without seed was relatively lower compared with other treatments at the beginning of current assay. Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix H). Soluble COD decreased after 24 day digestion period for treatments co-digested cow manure and chicken manure at varied ratio. While soluble COD of treatments contained only cow manure or sole chicken manure increased after this digestion period this may have resulted from the breakdown of organic solids into soluble COD. However with the limited incubation time (24 day) the microbial community was not acclimated to degrading those available soluble COD. The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, cow manure co-digested with chicken manure at 2:1 ratio had the greatest methane yield (770 mL/g VS destructed) followed by the 1:1 ratio of cow manure and chicken manure DUP (530 mL/g VS destructed) treatment and the 1;1 ratio of cow manure and chicken manure (510 mL/g VS destructed) treatment. However, co-digestion of cow manure with chicken manure at 1:2 ratio did not produce more biogas compared with digestion of chicken manure alone. These results suggested that co-digestion of cow manure with chicken manure likely increase biogas yield and potentially enhance energy production, however, the ratio of mixing those two substrate is still needed to be determined in future study to optimize biogas yield. Comparing the amount of COD destroyed to the stoichiometric volume of methane produced (390 mL/g COD; Speece 1996) is difficult as the percent methane in the biogas is highly variable. However, an average of 40% methane in biogas during the entire digestion period, the actual methane potential is fairly close to the expected amount. From the assay, it is projected that there is an advantage to mixing this specific cow and chicken manure at 2:1 ratio if the objective is energy production. However, in order to optimize biogas production, determining the ideal ratio is still needed in future studies. In addition, no ammonia inhibition was observed during this trial. Reference: Chynoweth, D.P.; C.E. Turick, J. M. Owens, D. E. Jerger, and M. W. Peck. 1993. Biochemical Methane Potential of Biomass and Waste Feedstocks. Biomass & Bioenergy 5(1): 95-111.

27

Appendix Appendix A. Constituent Concentrations in Flasks Before Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Su

spen

ded

Solid

s

(mg/

L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s

(mg/

L)

Am

mon

ia

(mg/

L N

)

Seed 8.08 5,740 15,474 9,200 17,597 12,900 12,388 6,400 715Seed, Cow Manure 8.01 4,180 19,588 9,051 20,928 11,100 14,831 5,600 831

Seed, Chicken Manure 7.73 5,500 23,275 10,251 25,511 18,200 16,849 10,300 920Seed, 1:1 Cow

Manure:Chicken Manure 7.78 5,320 24,149 12,525 30,048 16,600 20,102 12,000 935

Chicken Manure 6.96 620 4,426 2,525 7,538 5,300 5,603 2,000 43Seed, 2:1 Cow

Manure:Chicken Manure 7.85 5,760 27,486 14,551 34,097 13,700 21,723 9,600 1,035

Seed, 1:2 Cow Manure:Chicken Manure 7.85 4,760 21,249 11,175 26,997 13,600 17,766 10,300 845

Seed, 1:1 Cow Manure:Chicken Manure

DUP 7.83 5,160 23,626 11,625 26,966 18,400 18,392 12,900 926

Appendix B. Constituent Concentrations in Flasks After Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Su

spen

ded

Solid

s

(mg/

L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s

(mg/

L)

Am

mon

ia

(mg/

L N

) Seed 7.49 6,380 14,351 9,163 15,080 7,800 9,214 6,900 775

Seed, Cow Manure 7.53 7,640 17,463 11,351 18,308 10,300 11,323 7,600 958Seed, Chicken Manure 7.66 7,800 17,200 10,663 18,651 13,200 10,708 9,700 997

Seed, 1:1 Cow Manure:Chicken

Manure 7.67 10,100 18,914 12,125 20,409 11,400 11,771 7,300 1,197

Chicken Manure 6.71 1,900 3,512 3,063 4,128 3,800 2,286 2,900 171Seed, 2:1 Cow

Manure:Chicken Manure

7.71 11,880 24,438 14,212 25,512 14,600 14,989 8,700 1,468


Manure 7.70 8,360 17,938 11,375 20,017 13,300 11,382 8,700 991


Manure DUP 7.72 11,680 20,038 10,200 21,332 13,600 12,337 8,900 1,100

28

Appendix C. pH Change During Digestion

Flask Initial pH

Final pH

pH Change

Seed 8.08 7.49 -0.59 Seed, Cow Manure 8.01 7.53 -0.48

Seed, Chicken Manure 7.73 7.66 -0.07 Seed, 1:1 Cow Manure:Chicken Manure 7.78 7.67 -0.11

Chicken Manure 6.96 6.71 -0.25 Seed, 2:1 Cow Manure:Chicken Manure 7.85 7.71 -0.14 Seed, 1:2 Cow Manure:Chicken Manure 7.85 7.70 -0.15

Seed, 1:1 Cow Manure:Chicken Manure DUP 7.83 7.72 -0.11

Appendix D. Alkalinity Change During Digestion


Final Alkalinity

(mg CaCO3)

Alkalinity Change

(mg CaCO3) Seed 3,731 4,147 416

Seed, Cow Manure 2,717 4,966 2,249 Seed, Chicken Manure 3,575 5,070 1,495

Seed, 1:1 Cow Manure:Chicken Manure 3,458 6,565 3,107 Chicken Manure 403 1,235 832

Seed, 2:1 Cow Manure:Chicken Manure 3,744 7,722 3,978 Seed, 1:2 Cow Manure:Chicken Manure 3,094 5,434 2,340

Seed, 1:1 Cow Manure:Chicken Manure DUP 3,354 7,592 4,238

Appendix E. Total Solids Destruction During Digestion


Final TS

(mg)

TS Destruction

(mg)

Destruction (%)

Seed 11,438 9,802 1,637 14Seed, Cow Manure 13,603 11,900 1,703 13

Seed, Chicken Manure 16,582 12,123 4,458 27Seed, 1:1 Cow Manure:Chicken Manure 19,531 13,266 6,265 32

Chicken Manure 4,900 2,683 2,215 45Seed, 2:1 Cow Manure:Chicken Manure 22,163 16,583 5,580 25Seed, 1:2 Cow Manure:Chicken Manure 17,548 13,011 4,537 26Seed, 1:1 Cow Manure:Chicken Manure

DUP 17,528 13,866 3,663 21

29

Appendix F. Total Suspended Solids Destruction During Digestion


Final TSS (mg)

TSS Destruction

(mg) Destruction

(%)

Seed 8,385 5,070 3,315 40Seed, Cow Manure 7,215 6,695 520 7

Seed, Chicken Manure 11,830 8,580 3,250 27Seed, 1:1 Cow Manure:Chicken Manure 10,790 7,410 3,380 31

Chicken Manure 3,445 2,470 975 28Seed, 2:1 Cow Manure:Chicken Manure 8,905 9,490 -585 -7Seed, 1:2 Cow Manure:Chicken Manure 8,840 8,645 195 2

Seed, 1:1 Cow Manure:Chicken Manure DUP 11,960 8,840 3,120 26

Appendix G. Volatile Suspended Solids Destruction During Digestion


Final VSS (mg)

VSS Destruction

(mg) Destruction

(%)

Seed 4,160 4,485 -325 -8Seed, Cow Manure 3,640 4,940 -1,300 -36

Seed, Chicken Manure 6,695 6,305 390 6Seed, 1:1 Cow Manure:Chicken Manure 7,800 4,745 3,055 39

Chicken Manure 1,300 1,885 -585 -45Seed, 2:1 Cow Manure:Chicken Manure 6,240 5,655 585 9Seed, 1:2 Cow Manure:Chicken Manure 6,695 5,655 1,040 16

Seed, 1:1 Cow Manure:Chicken Manure DUP 8,385 5,785 2,600 31

Appendix H. Ammonia Change During Digestion

Flask Initial

Ammonia (mg NH3)


Ammonia Change

(mg NH3) Seed 465 504 39

Seed, Cow Manure 540 623 83 Seed, Chicken Manure 598 648 50

Seed, 1:1 Cow Manure:Chicken Manure 608 778 171 Chicken Manure 28 111 84

Seed, 2:1 Cow Manure:Chicken Manure 673 954 281 Seed, 1:2 Cow Manure:Chicken Manure 549 644 95

Seed, 1:1 Cow Manure:Chicken Manure DUP 602 715 113 Note: feedstocks containing high levels of protein break down to ammonium bicarbonate, increasing alkalinity and ammonia concentrations (Metcalf and Eddy, 2003).

30

Appendix I.Table 5. Hydrogen Sulfide Concentration


Seed 1,000 Seed, Cow Manure 1,400

Seed, Chicken Manure 2,400 Seed, 1:1 Cow Manure:Chicken Manure 1,900

Chicken Manure 2,800 Seed, 2:1 Cow Manure:Chicken Manure 4,000 Seed, 1:2 Cow Manure:Chicken Manure 2,000

Seed, 1:1 Cow Manure:Chicken Manure DUP 2,700 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but as a general indicator.

31


Phase 3

3. MSU Breakfast Waste East Lansing, MI

Submitted to Biosystems and Agricultural Engineering

Date Sample Collected: January 26, 2009 Date Assay Conducted: February 23 – March 20, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems


Michigan State University MSU Principal Investigator: Steven Safferman ([email protected], 517-432-0812)


32

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of breakfast waste collected from the Brody Dormitory Complex on the campus of Michigan State University. The sample was collected by Dana Kirk, Michigan State University on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

MSU Breakfast Used in Lab* 4.93 203,096 156,469 222,500 *Data for the above parameters was collected on a blended sample. The

sample contained both dry and liquid components. This sample was blended for several minutes until a homogenous product was produced.

. Table 7. Flask Composition

Flask Seed (mL)

Manure (mL)

MSU Breakfast

(mL)

DI Water (mL)

Seed (3.1 Seed) 236 0 0 414


Seed, MSU Breakfast (3.3 Seed, MSU Breakfast) 236 0 16 398

Seed, 1:1 Cow Manure: MSU Breakfast (3.4 Seed, 1:1 MSU Manure: MSU Breakfast) 236 16 16 382




Seed, 20:1 Cow Manure: MSU Breakfast DUP (3.8 Seed, 20:1 MSU Manure: MSU Breakfast) 236 325 16 73

33




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 7,012 6,362 650 9 4,550 3,876 674 15 5,097 3,907 1,190 23Seed, Cow Manure 8,271 6,931 1,340 16 4,648 4,006 642 14 5,632 4,122 1,510 27

Seed, MSU Breakfast 11,489 8,604 2,885 25 6,500 5,566 934 14 7,782 4,889 2,893 37Seed, 1:1 Cow Manure:

MSU Breakfast 12,261 8,669 3,592 29 6,614 4,404 2,210 33 7,887 5,044 2,843 36

Seed, 2:1 Cow Manure: MSU Breakfast 13,683 9,401 4,282 31 7,946 4,810 3,136 39 8,357 5,610 2,747 33



Seed, 20:1 Cow Manure: MSU Breakfast DUP 26,569 21,962 4,607 17 16,575 13,138 3,437 21 17,109 12,464 4,645 27

34





35


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 473 NA 650 0.73 1,190 0.40Seed, Cow Manure 737 NA 1,340 0.55 1,510 0.49

Seed, MSU Breakfast 1,637 1,164 2,885 0.57 2,893 0.57Seed, 1:1 Cow Manure: MSU Breakfast 2,463 1,726 3,592 0.69 2,843 0.87Seed, 2:1 Cow Manure: MSU Breakfast 2,344 NA 4,282 0.55 2,747 0.85Seed, 5:1 Cow Manure: MSU Breakfast 3,783 NA 4,648 0.81 3,279 1.15

Seed, 10:1 Cow Manure: MSU Breakfast 2,350 NA 4,436 0.53 3,588 0.65Seed, 20:1 Cow Manure: MSU Breakfast DUP 3,641 NA 4,607 0.79 4,645 0.78

**Calculated using the Seed and Seed, Cow Manure flasks. Note: Can only be used for flasks where the seed and cow manure volumes are the same.

Discussion and Conclusions: Alkalinity and pH were adequate for all treatments at the beginning and end of digestion (Appendix A. B., and C.). An increase in the ratio of cow manure vs. MSU breakfast in the mixture from 1:1 to 20:1 resulted in increasing of COD, soluble COD, total solid (TS), volatile solid (VS), and ammonia content at the beginning and end of digestion trial.

The percentage of methane in the biogas (Figure 3) was very similar for all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate VS destroyed, cow manure mixed with MSU breakfast at 5:1 ratio had the greatest methane yield (1,150 mL/g VS destructed) followed by 1:1 ratio and 2:1 ratio of cow manure mixed with MSU breakfast (870 and 850 mL/g VS destroyed, respectively). While, cow manure mixed with MSU breakfast at 10:1 ratio and 20:1 ratio had relatively lower biogas yield compared with those at 1:1 ratio, 2:1 ratio and 5:1 ratio, likely due to ammonia inhibition when cow manure mixed at higher level. Biogas yield from co-digestion of manure and breakfast mixture were consistently higher than those from digestion manure or breakfast separately. This result suggested that co-digestion of manure and MSU breakfast could potentially enhance energy production as the result of increased biogas yield.

Methane potential is fairly close to the stoichiometric methane volume (390 mL/g COD destroyed) considering an average of approximately 45% methane in the biogas during the digestion period.

From the assay, it is projected that there is a great advantage to mixing cow manure and MSU breakfast and the largest biogas yield was obtained when cow manure and MSU breakfast

36

mixed at 5:1 ratio. In addition, containing higher level of cow manure (cow manure vs. breakfast >10: 1) likely reduce biogas yield as the result of ammonia inhibition.

37

Appendix Appendix A. Constituent Concentrations in Flasks Before Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Su

spen

ded

Solid

s

(mg/

L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s

(mg/

L)

Am

mon

ia

(mg/

L N

)


Seed, MSU Breakfast 7.04 4,051 17,675 10,000 15,814 8,600 11,972 7,000 483Seed, 1:1 Cow Manure:

MSU Breakfast 7.04 4,200 18,863 10,175 17,051 10,400 12,134 7,800 498

Seed, 2:1 Cow Manure: MSU Breakfast 7.19 4,700 21,051 12,225 19,072 10,000 12,857 7,100 563



Seed, 20:1 Cow Manure: MSU Breakfast DUP 7.14 9,200 40,875 25,500 39,935 21,000 26,322 15,600 1,143

Appendix B Constituent Concentrations in Flasks After Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Su

spen

ded

Solid

s

(mg/

L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s

(mg/

L)

Am

mon

ia

(mg/

L N

)


Seed, MSU Breakfast 7.42 5,100 13,237 8,563 12,045 4,600 7,522 3,600 677Seed, 1:1 Cow Manure:

MSU Breakfast 7.50 5,600 13,337 6,775 12,595 6,800 7,760 6,300 618



Seed, 10:1 Cow Manure: MSU Breakfast 7.60 8,500 23,937 15,125 23,026 13,900 13,462 10,300 1,142

Seed, 20:1 Cow Manure: MSU Breakfast

DUP 7.73 11,450 33,788 20,213 33,005 21,400 19,175 13,500 1,592

38

Appendix C pH Change During Digestion

Flask Initial pH

Final pH

pH Change

Seed 7.88 7.46 -0.42 Seed, Cow Manure 7.81 7.47 -0.34

Seed, MSU Breakfast 7.04 7.42 0.38 Seed, 1:1 Cow Manure: MSU Breakfast 7.04 7.50 0.46 Seed, 2:1 Cow Manure: MSU Breakfast 7.19 7.56 0.37 Seed, 5:1 Cow Manure: MSU Breakfast 7.12 7.60 0.48

Seed, 10:1 Cow Manure: MSU Breakfast 7.10 7.60 0.50 Seed, 20:1 Cow Manure: MSU Breakfast DUP 7.14 7.73 0.59

Appendix D Alkalinity Change During Digestion

Flask Initial

Alkalinity (mg CaCO3)

Final Alkalinity

(mg CaCO3)

Alkalinity Change

(mg CaCO3) Seed 3,510 3,510 0

Seed, Cow Manure 3,218 3,510 292 Seed, MSU Breakfast 2,633 3,315 682

Seed, 1:1 Cow Manure: MSU Breakfast 2,730 3,640 910 Seed, 2:1 Cow Manure: MSU Breakfast 3,055 3,900 845 Seed, 5:1 Cow Manure: MSU Breakfast 3,445 4,485 1,040

Seed, 10:1 Cow Manure: MSU Breakfast 4,225 5,525 1,300 Seed, 20:1 Cow Manure: MSU Breakfast

DUP 5,980 7,442 1,462

Appendix E Total Solids Destruction During Digestion

Flask Initial

TS (mg)

Final TS

(mg)

TS Destruction

(mg)

Destruction (%)


Seed, MSU Breakfast 10,279 7,829 2,450 24Seed, 1:1 Cow Manure: MSU Breakfast 11,083 8,187 2,896 26Seed, 2:1 Cow Manure: MSU Breakfast 12,397 9,433 2,964 24Seed, 5:1 Cow Manure: MSU Breakfast 14,604 11,284 3,320 23

Seed, 10:1 Cow Manure: MSU Breakfast 18,424 14,967 3,457 19Seed, 20:1 Cow Manure: MSU Breakfast

DUP 25,958 21,453 4,505 17

39

Appendix F Total Suspended Solids Destruction During Digestion


Final TSS (mg)

TSS Destruction

(mg) Destruction

(%)


Seed, MSU Breakfast 5,590 2,990 2,600 47Seed, 1:1 Cow Manure: MSU Breakfast 6,760 4,420 2,340 35Seed, 2:1 Cow Manure: MSU Breakfast 6,500 4,940 1,560 24Seed, 5:1 Cow Manure: MSU Breakfast 7,475 6,890 585 8

Seed, 10:1 Cow Manure: MSU Breakfast 9,620 9,035 585 6Seed, 20:1 Cow Manure: MSU Breakfast

DUP 13,650 13,910 -260 -2

Appendix G Volatile Suspended Solids Destruction During Digestion


Final VSS (mg)

VSS Destruction

(mg) Destruction

(%)

Seed 3,965 3,575 390 10Seed, Cow Manure 4,550 3,640 910 20

Seed, MSU Breakfast 4,550 2,340 2,210 49Seed, 1:1 Cow Manure: MSU Breakfast 5,070 4,095 975 19Seed, 2:1 Cow Manure: MSU Breakfast 4,615 3,380 1,235 27Seed, 5:1 Cow Manure: MSU Breakfast 4,420 5,200 -780 -18

Seed, 10:1 Cow Manure: MSU Breakfast 7,020 6,695 325 5Seed, 20:1 Cow Manure: MSU Breakfast DUP 10,140 8,775 1,365 13

Appendix H Ammonia Change During Digestion

Flask Initial

Ammonia (mg NH3)


Ammonia Change

(mg NH3) Seed 378 418 40

Seed, Cow Manure 413 426 13 Seed, MSU Breakfast 314 440 126

Seed, 1:1 Cow Manure: MSU Breakfast 324 402 78 Seed, 2:1 Cow Manure: MSU Breakfast 366 499 133 Seed, 5:1 Cow Manure: MSU Breakfast 430 588 158

Seed, 10:1 Cow Manure: MSU Breakfast 581 742 161 Seed, 20:1 Cow Manure: MSU Breakfast DUP 743 1,035 292

Note: feedstocks containing high levels of protein break down to ammonium bicarbonate, increasing alkalinity and ammonia concentrations (Metcalf and Eddy, 2003).

40

Appendix I.Table 8. Hydrogen Sulfide Concentration


Seed 200 Seed, Cow Manure 200

Seed, MSU Breakfast 1,400 Seed, 1:1 Cow Manure: MSU Breakfast 1.900 Seed, 2:1 Cow Manure: MSU Breakfast 760 Seed, 5:1 Cow Manure: MSU Breakfast 1,200

Seed, 10:1 Cow Manure: MSU Breakfast 850 Seed, 20:1 Cow Manure: MSU Breakfast DUP 3,200

*Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but as a general indicator.

41


Phase 3

4. Poll Farms Swine Gestation Manure Hamilton, MI






42

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of swine gestation manure collected from Poll Farms. The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Gestation Manure Used in Lab* 7.22 9,027 5,919 11,750 Gestation Manure Corrected for Dilution NA 36,108 23,676 47,000

*Data for the above parameters was collected on a blended sample. This sample was blended for several minutes until a homogenous product was produced.


Flask Seed (mL)

Cow Manure

(mL)

Gestation Manure

(mL)

D.I. Water (mL)

Seed (4.1 Seed) 135 0 0 515


Seed, Gestation Manure (4.3 Seed, Poll Gestation Manure) 135 0 247 268

Seed, 1:1 Cow:Gestation Manure (4.4 Seed, 1:1 MSU Manure:Poll Gestation

Manure) 135 247 247 21


43




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 4,469 5,068 -599 -13 3,055 2,795 260 9 3,305 2,472 833 25Seed, Cow Manure 17,193 12,967 4,226 25 9,685 7,784 1,901 20 10,479 7,785 2,694 26

Seed, Gestation Manure 11,359 5,038 6,321 56 3,803 3,088 715 19 4,720 3,321 1,399 30

Seed, 1:1 Cow:Gestation

Manure 19,224 14,471 4,753 25 11,586 7,564 4,022 35 13,192 8,593 4,599 35


44



45



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 219 NA -599 NA 833 0.26Seed, Cow Manure 1,665 NA 4,226 0.39 2,694 0.62

Seed, Gestation Manure 491 272 6,321 0.08 1,399 0.35Seed, 1:1 Cow:Gestation Manure 2,438 773 4,753 0.51 4,599 0.53


Discussion and Conclusions

Alkalinity and pH were adequate at the beginning and end of digestion (Appendix A. B., and C.). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix H).

The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from digestion only cow manure (620 mL/g VS destroyed) were greater than co-digestion of cow manure with gestation swine manure (530 mL/g VS destroyed). Digestion of only gestation swine manure produced the lowest amount of biogas (350 mL/g VS destroyed). From the assay, it is projected that there is no advantage to mixing this specific gestation swine manure and cow manure in equal proportions if the objective is energy production.

46

Appendix

Appendix A Constituents Concentrations in Flasks Before Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Gestation Manure 7.91 4,300 17,475 5,851 11,700 8,200 7,262 5,200 637Seed, 1:1 Cow:Gestation Manure 7.74 7,951 29,575 17,825 32,172 20,300 20,295 13,000 1,094

Appendix B Constituents Concentrations in Flasks After Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 7.58 2,949 7,825 4,300 6,820 4,100 3,803 3,600 386Seed, Cow Manure 7.56 8,200 19,963 11,975 20,246 12,100 11,977 8,200 1,083

Seed, Gestation Manure 7.46 4,500 7,751 4,751 9,140 4,800 5,109 4,000 663Seed, 1:1 Cow:Gestation Manure 7.73 9,549 22,263 11,637 22,297 14,500 13,220 9,800 1,380

Appendix C pH Change During Digestion Flask Initial pH Final pH pH Change Seed 7.93 7.58 -0.35

Seed, Cow Manure 7.77 7.56 -0.21 Seed, Gestation Manure 7.91 7.46 -0.45

Seed, 1:1 Cow:Gestation Manure 7.74 7.73 -0.01

Appendix D Alkalinity Change During Digestion




Seed 1,690 1,917 227 Seed, Cow Manure 4,583 5,330 747

Seed, Gestation Manure 2,795 2,925 130 Seed, 1:1 Cow:Gestation Manure 5,168 6,207 1,039

47

Appendix E Total Solids Destruction During Digestion


Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Gestation Manure 7,605 5,941 1,664 22 Seed, 1:1 Cow:Gestation Manure 20,912 14,493 6,419 31

Appendix F. Total Suspended Solids Destruction During Digestion Flask Initial TSS

(mg) Final TSS

(mg) TSS Destruction

(mg) Destruction

(%) Seed 3,445 2,665 780 23

Seed, Cow Manure 9,555 7,865 1,690 18 Seed, Gestation Manure 5,330 3,120 2,210 41

Seed, 1:1 Cow:Gestation Manure 13,195 9,425 3,770 29

Appendix G Volatile Suspended Solids Destruction During Digestion


Final VSS (mg)


Destruction (%)

Seed 2,275 2,340 -65 ‐3 Seed, Cow Manure 6,825 5,330 1,495 22

Seed, Gestation Manure 3,380 2,600 780 23 Seed, 1:1 Cow:Gestation

Manure 8,450 6,370 2,080 25

Appendix H Ammonia Change During Digestion





Seed, Gestation Manure 414 431 17 Seed, 1:1 Cow:Gestation Manure 711 897 186


48

Appendix I Hydrogen Sulfide Concentration Flask H2S Concentration**

(PPM) Seed 200

Seed, Cow Manure 4,000 Seed, Gestation Manure 400

Seed, 1:1 Cow:Gestation Manure 4,800 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

49


Phase 3

5. Poll Farms Swine Farrowing Manure Hamilton, MI






50

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of swine farrowing manure collected from Poll Farms. The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Poll Farrowing Manure Used in Lab* 7.57 14,797 8,273 10,100 Poll Farrowing Manure Corrected for Dilution NA 59,188 33,092 40,400

*Data for the above parameters was collected on a diluted sample because only a 250 mL sample of the finish manure was submitted. To make this dilution 250 mL of original sample was diluted into 1 liter.


Flask Seed (mL)

Manure(mL)

Farrowing Manure

(mL)

D.I. Water (mL)

Seed (5.1 Seed) 174 0 0 476


Seed, Farrowing Manure (5.3 Seed, Poll Farrowing Manure) 174 0 228 248

Seed, 1:1 Cow: Farrowing Manure (5.4 Seed, 1:1 MSU Manure:Poll Farrowing

Manure) 174 228 228 21


51




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 6,996 5,826 1,170 17 3,689 3,486 203 6 4,095 3,473 622 15Seed, Cow Manure 17,542 13,845 3,697 21 10,254 8,799 1,455 14 10,849 8,392 2,457 23

Seed, Farrowing Manure 9,458 6,728 2,730 29 3,770 3,664 106 3 6,912 4,357 2,555 37

Seed, 1:1 Cow:Farrowing Manure 21,288 16,575 4,713 22 10,286 9,133 1,153 11% 17,898 9,882 8,016 45


52




53


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 261 NA 1,170 0.22 622 0.42Seed, Cow Manure 1,850 NA 3,697 0.50 2,457 0.75

Seed, Farrowing Manure 473 212 2,730 0.17 2,555 0.19Seed, 1:1 Cow:Farrowing Manure 1,514 -336 4,713 0.32 8,016 0.19



Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix).

The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from digestion only cow manure (750 mL/g VS destroyed) were greater than co-digestion of cow manure with farrowing swine manure (190 mL/g VS destroyed) and only farrowing swine manure (190 mL/g VS destroyed). From the assay, it is projected that there is no advantage to mixing this specific gestation swine manure and cow manure in equal proportions if the objective is energy production.

Appendix

54

Constituents Concentrations in Flasks Before Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Farrowing Manure 7.89 5,251 14,551 5,800 16,938 15,900 10,634 9,700 723Seed, 1:1 Cow:Farrowing Manure 7.66 8,851 32,751 15,825 43,838 27,300 27,535 17,600 1,094

Constituents Concentrations in Flasks After Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)


Seed, Farrowing Manure 7.55 5,500 10,351 5,637 11,763 9,600 6,703 3,400 797Seed, 1:1 Cow:Farrowing Manure 7.77 10,549 25,500 14,051 25,757 14,300 15,203 7,800 1,592

pH Change During Digestion Flask Initial pH Final pH pH Change Seed 7.98 7.50 -0.48

Seed, Cow Manure 7.79 7.62 -0.17 Seed, Farrowing Manure 7.89 7.55 -0.34

Seed, 1:1 Cow:Farrowing Manure 7.66 7.77 0.11

Alkalinity Change During Digestion




Seed 2,665 2,600 -65 Seed, Cow Manure 4,615 5,687 1,072

Seed, Farrowing Manure 3,413 3,575 162 Seed, 1:1 Cow:Farrowing Manure 5,753 6,857 1,104

55

Total Solids Destruction During Digestion


Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Farrowing Manure 11,010 7,646 3,364 31 Seed, 1:1 Cow:Farrowing Manure 28,495 16,742 11,753 41

Total Suspended Solids Destruction During Digestion


Final TSS (mg)


Destruction (%)


Seed, Farrowing Manure 10,335 6,240 4,095 40 Seed, 1:1 Cow:Farrowing Manure 17,745 9,295 8,450 48

Volatile Suspended Solids Destruction During Digestion


Final VSS (mg)


Destruction (%)


Seed, Farrowing Manure 6,305 2,210 4,095 65 Seed, 1:1 Cow:Farrowing

Manure 11,440 5,070 6,370 56

Ammonia Change During Digestion





Seed, Farrowing Manure 470 518 48 Seed, 1:1 Cow:Farrowing Manure 711 1,035 324


Hydrogen Sulfide Concentration


Seed 200 Seed, Cow Manure 2,200

Seed, Farrowing Manure 900 Seed, 1:1 Cow:Farrowing Manure 4,400 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

56


Phase 3

6. Beaver Creek Dairy Coopersville, MI


Date Sample Collected: January 26, 2009 Date Assay Conducted: May 15 ‐ June12, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems




57

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of dairy manure collected from Beaver Creek Dairy of Coopersville, MI. The sample was collected by Norma McDonald, Phase 3 Renewables LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).

Table 13. Submi57tted Sample Analysis


VS (mg/L)

COD (mg/L)

Beaver Creek Dairy Used in Lab* 7.54 37,697 24,376 32,250 * Data for the above parameters was collected on a sample diluted to 1L and then blended.


Flask Seed (mL)

Cow Manure

(mL)

Beaver Creek Dairy (mL)

DI Water (mL)

Seed (6-8.1 Seed) 260 0 0 390

Seed, Cow Manure (6.1 Seed, Cow Manure) 260 117 0 273

Seed, Dairy Manure (6.2 Seed, Beaver Creek Dairy) 260 0 117 273

Seed, 1:1 Cow Manure:Dairy Manure (6.3 Seed, 1:1 MSU Manure:Beaver Creek Dairy) 260 117 117 156



58




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 8,978 8,564 414 5 5493 5704 -211 -4 5,418 5,157 261 5Seed, Cow Manure 14,268 12,147 2,121 15 8174 7069 1105 14 8,854 7,269 1,585 18Seed, Dairy Manure 12,984 10,944 2,040 16 7036 6078 958 14 8,004 6,840 1,164 15

Seed, 1:1 Cow Manure:Dairy Manure 18,038 16,811 1,227 7 9734 8239 1495 15 11,802 9,724 2,078 18

Seed, 2:1 Cow Manure:Dairy Manure 23,563 24,359 -796 -3 12724 14430 -1706 -13 15,215 13,593 1,622 11

Seed, 1:2 Cow Manure:Dairy Manure 15,413 12,943 2,470 16 8905 7036 1869 21 9,642 7,799 1,843 19


59



60



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 693 NA 414 1.67 261 2.66Seed, Cow Manure 1,480 NA 2,121 0.70 1,585 0.93Seed, Dairy Manure 1,668 975 2,040 0.82 1,164 1.43

Seed, 1:1 Cow Manure:Dairy Manure 2,164 684 1,227 1.76 2,078 1.04Seed, 2:1 Cow Manure:Dairy Manure 680 NA 3,120 0.22 1,622 0.42Seed, 1:2 Cow Manure:Dairy Manure 1,353 NA 2,470 0.55 1,843 0.73**Calculated using the Seed and Seed, Cow Manure flasks. Note: Can only be used for flasks where the seed and cow manure volumes are the same.

Discussion and Conclusions: Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied substantially between treatments (Appendix).

The percentage of methane in the biogas from co-digestion MSU cow manure with Beaver Creek dairy manure at 2:1 ratio was relatively low (average 35%; Figure 3). As shown in Table 4, after normalized as mL biogas per g of substrate VS destroyed, biogas yield from cow manure mixed with Beaver Creek dairy manure at 1:1, 2:1, and 1:2 ratios were consistently lower than those from beaver creek dairy manure (1,430 mL/g VS destroyed).

From the assay, it is projected that there is no advantage to mixing this specific dairy manure and cow manure in 1:1, 2:1 or 1:2 ratios if the objective is energy production.

61

Appendix Constituent Concentrations in Flasks Before Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Su

spen

ded

Solid

s

(mg/

L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s

(mg/

L)

Am

mon

ia

(mg/

L N

)

Seed 7.84 5,850 13,813 8,438 13,698 9,400 8,335 6,100 716Seed, Cow Manure 7.71 7,900 21,950 12,375 21,930 15,000 13,622 9,200 900Seed, Dairy Manure 7.93 7,450 19,975 10,800 19,280 14,600 12,313 10,800 915

Seed, 1:1 Cow Manure:Dairy Manure 7.80 9,400 27,750 14,938 28,032 16,400 18,157 10,500 1,209



Constituent Concentrations in Flasks After Digestion

Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Su

spen

ded

Solid

s

(mg/

L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s

(mg/

L)

Am

mon

ia

(mg/

L N

)

Seed 7.59 6,300 13,175 8,775 14,068 9,700 7,933 5,000 761Seed, Cow Manure 7.73 8,700 18,688 10,875 19,517 13,000 11,183 7,600 1,135Seed, Dairy Manure 7.60 8,500 16,838 9,350 17,665 12,300 10,523 9,100 1,033




pH Change During Digestion

Flask Initial pH

Final pH

pH Change

Seed 7.84 7.59 -.25 Seed, Cow Manure 7.71 7.73 .02 Seed, Dairy Manure 7.93 7.60 -.33

Seed, 1:1 Cow Manure:Dairy Manure 7.80 7.83 .03 Seed, 2:1 Cow Manure:Dairy Manure 7.46 7.41 -.05 Seed, 1:2 Cow Manure:Dairy Manure 7.80 7.71 -.09

62


Flask Initial

Alkalinity (mg CaCO3)

Final Alkalinity

(mg CaCO3)

Alkalinity Change

(mg CaCO3) Seed 5,850 4,095 -1,755

Seed, Cow Manure 7,900 5,655 -2,245 Seed, Dairy Manure 7,450 5,525 -1,925

Seed, 1:1 Cow Manure:Dairy Manure 9,400 6,890 -2,510 Seed, 2:1 Cow Manure:Dairy Manure 11,450 7,572.5 -3,877.5 Seed, 1:2 Cow Manure:Dairy Manure 8,550 6,077.5 -2,472.5


Flask Initial

TS (mg)

Final TS

(mg)

TS Destruction

(mg)

Destruction (%)

Seed 8,904 9,144 -240 3Seed, Cow Manure 14,255 12,686 1,569 11Seed, Dairy Manure 12,532 11,482 1,050 8

Seed, 1:1 Cow Manure:Dairy Manure 18,221 15,633 2,588 14Seed, 2:1 Cow Manure:Dairy Manure 23,151 20,986 2,165 9Seed, 1:2 Cow Manure:Dairy Manure 15,369 13,131 2,238 15



Final TSS (mg)

TSS Destruction

(mg) Destruction

(%)

Seed 6,110 6,305 -195 -3Seed, Cow Manure 9,750 8,450 1,300 13Seed, Dairy Manure 9,490 7,995 1,495 16

Seed, 1:1 Cow Manure:Dairy Manure 10,660 10,725 -65 -1Seed, 2:1 Cow Manure:Dairy Manure 12,740 13,650 -910 -7Seed, 1:2 Cow Manure:Dairy Manure 9,685 6,760 2,925 30



Final VSS (mg)

VSS Destruction

(mg) Destruction

(%)

Seed 3,965 3,250 715 18Seed, Cow Manure 5,980 4,640 1,340 22Seed, Dairy Manure 7,020 5,915 1,105 16

Seed, 1:1 Cow Manure:Dairy Manure 6,630 7,670 -1,040 -16Seed, 2:1 Cow Manure:Dairy Manure 10,465 9,750 715 7Seed, 1:2 Cow Manure:Dairy Manure 6,825 4,550 2,275 33

63


Flask Initial

Ammonia (mg NH3)


Ammonia Change

(mg NH3) Seed 466 495 29

Seed, Cow Manure 585 738 153 Seed, Dairy Manure 595 671 76

Seed, 1:1 Cow Manure:Dairy Manure 786 899 113 Seed, 2:1 Cow Manure:Dairy Manure 991 1,181 190 Seed, 1:2 Cow Manure:Dairy Manure 699 757 58


Table 15. Hydrogen Sulfide Concentration


Seed 200 Seed, Cow Manure 1.650 Seed, Dairy Manure 3,600

Seed, 1:1 Cow Manure:Dairy Manure 4,500 Seed, 2:1 Cow Manure:Dairy Manure 4,500 Seed, 1:2 Cow Manure:Dairy Manure 3,200

*Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but as a general indicator.

64


Phase 3

7. Slaughterhouse Paunch, RIP Farms (West Michigan Beef) Hudsonville, MI


Date Sample Collected: January 26, 2009 Date Assay Conducted: April 15 – May 15, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems




65

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of slaughterhouse paunch collected from RIP Farms. The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Paunch Used in Lab* 5.28 13,323 8,834 13,750 *Data for the above parameters was collected on a sample diluted to 1L.

An amount of 250 mL was diluted to 1 L.


Flask Seed (mL)

Manure(mL)

Paunch (mL)

D.I. Water (mL)

Seed (7-9-10-11.1 Seed) 211 0 0 439 Seed, Cow Manure

(7.1 Seed, MSU Manure) 211 211 0 228 Seed, Paunch

(7.2 Seed, RIP Paunch) 211 0 211 228 Seed, 1:1 Cow Manure: Paunch

(5.4 Seed, 1:1 MSU Manure:RIP Paunch) 211 211 211 16 Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not shown in Table 3 are also provided in the Appendix. Figures 1-3 are graphs of the cumulative, total biogas production, biogas production rate, and biogas methane content, respectively.

66



Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 7,629 6,151 1,478 19 4,501 3,916 585 13 5,916 3,794 2,122 36Seed, Cow Manure 17,176 13,187 3,989 23 9,165 8,856 309 34 10,938 8,007 2,931 27

Seed, Paunch 10,051 7,548 2,503 25 4,778 4,420 358 8 8,597 5,339 3,258 38Seed, 1:1 Cow Manure:

Paunch 19,321 16,372 2,949 15 9,750 9,441 309 3 13,714 9,800 3,914 29


67




68


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 429 NA 1,478 0.29 2,122 0.20Seed, Cow Manure 1,977 NA 3,989 0.50 2,931 0.67

Seed, Paunch 1,277 848 2,503 0.51 3,258 0.39

Seed, 1:1 Cow Manure: Paunch 1,793 -184 2,949 0.61 3,914 0.46



Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix).

The percentage of methane in the biogas (Figure 3) was similar across all treatments (average approximately 50%). As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, cow manure had the greatest methane yield (670 mL/g VS destroyed), followed by the co-digestion of cow manure with RIP paunch (460 mL/g VS destroyed). Digestion of RIP paunch alone produced the least amount of methane (390 mL/g VS destroyed). From the assay, it is projected that there is no significant advantage to mixing this specific cow manure and RIP paunch at in equal proportions if the objective is energy production. However, co-digestion of cow manure and RIP paunch could improve digestion efficiency comparing with digestion RIP paunch only. Therefore, if the objective is to utilize RIP paunch, co-digestion may be applied to improve digestibility.

69

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Paunch 7.71 4,550 15,463 7,325 20,218 13,900 13,227 8,500 554Seed, 1:1 Cow Manure: Paunch 7.56 7,950 29,725 14,800 32,757 21,700 21,098 14,200 936


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Paunch 7.37 5,150 11,613 6,800 13,453 7,500 8,213 5,400 654Seed, 1:1 Cow Manure: Paunch 7.64 9,300 25,188 14,525 23,852 15,700 15,077 11,000 1,335


Seed, Cow Manure 7.67 7.56 -0.11 Seed, Paunch 7.71 7.37 -0.34

Seed, 1:1 Cow Manure: Paunch 7.56 7.64 0.08






Seed, Paunch 2,958 3,348 390 Seed, 1:1 Cow Manure: Paunch 5,168 6,045 877

70



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Paunch 13,142 8,745 4,397 33 Seed, 1:1 Cow Manure: Paunch 21,292 15,504 5,788 27



Final TSS (mg)


Destruction (%)


Seed, Paunch 9,035 4,875 4,160 46 Seed, 1:1 Cow Manure: Paunch 14,105 10,205 3,900 28



Final VSS (mg)


Destruction (%)


Seed, Paunch 5,525 3,510 2,015 36 Seed, 1:1 Cow Manure:

Paunch 9,230 7,150 2,080 23





Seed 370 358 -12 Seed, Cow Manure 587 742 155

Seed, Paunch 360 425 65 Seed, 1:1 Cow Manure: Paunch 609 868 259





Seed, Paunch 850 Seed, 1:1 Cow Manure: Paunch 4,500 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

71


Phase 3

8. MSU Dairy Farm Manure with Sawdust East Lansing, MI

Submitted to Michigan State University

Date Sample Collected: January 26, 2009 Date Assay Conducted: May 18 – June 12, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems




72

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of Dairy Manure from the MSU Dairy Farm in East Lansing. The sample was collected by Dana Kirk, Michigan State University, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

MSU Dairy Manure 8.29 110,611 88,005 86,400


Flask Seed (mL)

Cow Manure

(mL)

Dairy Manure

(mL) D.I. Water

(mL)

Seed (6-8.1 Seed) 260 0 0 390


Seed, Dairy Manure (8.2 Seed, MSU Dairy Manure) 260 0 33 358 Seed, 1:1 Cow:Dairy Manure

(8.3 Seed, 1:1 MSU Manure:MSU Dairy Manure) 260 33 33 325 Seed, 2:1 Cow:Dairy Manure

(8.4 Seed, 2:1 MSU Manure:MSU Dairy Manure) 260 65 33 293 Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not

73

shown in Table 3 are also provided in the Appendix. Figures 1-3 are graphs of the cumulative, total biogas production, biogas production rate, and biogas methane content, respectively.



Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 8,978 8,564 414 5 5493 5704 -211 -4 5,418 5,157 261 5

Seed, Cow Manure 10,749 8,710 2,039 19 10,749 5,476 5,273 49 6,669 5,505 1,164 17

Seed, Dairy Manure 11,887 11,115 772 6 11,887 6,378 5,509 46 9,415 7,128 2,287 24Seed, 1:1 Cow:Dairy

Manure 13,528 11,570 1,958 14 13,528 6,037 7,491 55 9,242 7,472 1,770 19

Seed, 2:1 Cow:Dairy Manure 14,633 12,935 1,698 12 14,633 6,533 8,100 55 10,507 8,381 2,126 20


74




75


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 693 NA 414 1.67 261 2.66 Seed, Cow Manure 787 NA 2,039 0.39 1,164 0.68 Seed, Dairy Manure 1,069 376 772 1.38 2,287 0.47

Seed, 1:1 Cow:Dairy Manure 1,704 917 1,958 0.87 1,770 0.96 Seed, 2:1 Cow:Dairy Manure 2,160 NA 1,698 1.27 2,126 1.02



Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, MSU cow manure co-digested with dairy manure at 2:1 ratio had the greatest methane yield (1,020 mL/g VS destroyed); followed by the 1:1 ratio of combination of cow manure with dairy manure (960 mL/g VS destroyed). Digestion dairy manure alone produced the least amount of biogas (470 mL/g VS destroyed) during this trial. From the assay, it is projected that there is an advantage to mixing these two specific cow manures if the objective is energy production. In order to optimize biogas production, determining the ideal mixing ratio is needed in future studies.

76

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, 1:1 Cow:Dairy Manure 7.81 6,900 20,813 11,288 21,328 13,300 14,218 9,300 783Seed, 2:1 Cow:Dairy Manure 7.80 7,800 22,513 12,588 24,482 17,900 16,165 11,500 920


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, 1:1 Cow:Dairy Manure 7.60 7,350 17,800 9,288 18,633 10,200 11,495 7,100 864Seed, 2:1 Cow:Dairy Manure 7.83 8,500 19,900 10,050 20,212 13,700 12,893 10,900 996

pH Change During Digestion Flask Initial pH Final pH pH Change Seed 7.84 7.59 -.25

Seed, Cow Manure 7.92 7.59 -.33 Seed, Dairy Manure 7.84 7.73 -.11

Seed, 1:1 Cow:Dairy Manure 7.81 7.60 -.21 Seed, 2:1 Cow:Dairy Manure 7.80 7.83 .03

77





Seed 5,850 4,095 -1,755 Seed, Cow Manure 4,095 4,615 520 Seed, Dairy Manure 4,128 4,387.5 260

Seed, 1:1 Cow:Dairy Manure 4,485 4,777.5 293 Seed, 2:1 Cow:Dairy Manure 5,070 5,525 455



Final TS (mg)

TS Destruction (mg)

Destruction (%)

Seed 8,904 9,144 -240 3 Seed, Cow Manure 10,785 9,570 1,215 11 Seed, Dairy Manure 13,781 11,172 2,609 19

Seed, 1:1 Cow:Dairy Manure 13,863 12,112 1,751 13 Seed, 2:1 Cow:Dairy Manure 15,913 13,138 2,775 17



Final TSS (mg)


Destruction (%)

Seed 6,110 6,305 -195 -3 Seed, Cow Manure 8,840 6,240 2,600 29 Seed, Dairy Manure 11,245 6,955 4,290 38

Seed, 1:1 Cow:Dairy Manure 8,645 6,630 2,015 23 Seed, 2:1 Cow:Dairy Manure 11,635 8,905 2,730 23



Final VSS (mg)


Destruction (%)

Seed 3,965 3,250 715 18 Seed, Cow Manure 5,330 3,900 1,430 27 Seed, Dairy Manure 9,685 4,875 4,810 50

Seed, 1:1 Cow:Dairy Manure 6,045 4,615 1,430 24 Seed, 2:1 Cow:Dairy Manure 7,475 7,085 390 5





Seed 466 495 29 Seed, Cow Manure 483 548 65 Seed, Dairy Manure 463 582 119

Seed, 1:1 Cow:Dairy Manure 509 561 52 Seed, 2:1 Cow:Dairy Manure 598 648 50


78



Seed 200 Seed, Cow Manure 800 Seed, Dairy Manure 1,000

Seed, 1:1 Cow:Dairy Manure 1,400 Seed, 2:1 Cow:Dairy Manure 1,100 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

79


Phase 3

9. Slaughterhouse Blood, RIP Farms (West Michigan Beef) Hudsonville, MI






80

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of slaughterhouse blood collected from RIP Farms. The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Slaughterhouse Blood Used in Lab* 7.34 46,146 44,707 51,300 * Data for the above parameters was collected on a diluted sample. An

amount of 250 mL was diluted to 1 L.


Flask Seed (mL)

Manure(mL)

Blood (mL)

D.I. Water(mL)


(9-10.1 Seed, MSU Manure) 211 52 0 387 Seed, Blood

(9.1 Seed, RIP Blood) 211 0 52 387 Seed, 1:1 Cow Manure: Blood

(9.2 Seed, 1:1 MSU Manure:RIP Blood) 211 52 52 335 Seed, 2:1 Cow Manure: Blood

(9.3 Seed, 2:1 MSU Manure:RIP Blood) 211 104 52 283 Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not

81




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion


Seed, Blood 12,813 8,060 4,753 37 8,060 4,290 3,770 47 8,419 4,593 3,826 45Seed, 1:1 Cow Manure:

Blood 14,154 10,294 3,860 27 8,775 6,199 2,576 29 9,584 5,892 3,692 39

Seed, 2:1 Cow Manure: Blood 15,730 12,196 3,534 22 9,458 7,296 2,126 22 10,636 6,694 3,942 37

SPECIAL NOTE FOR THIS SAMPLE ONLY: DURING DIGESTION, A CRACK DEVELOPED IN THE FLASK OF SAMPLE 9-10.1 SEED, MSU MANURE. RESULTING INACCURATE GAS PRODUCTION RESULTS.


82



83



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 429 NA 1,478 0.29 2,122 0.20Seed, Cow Manure 488 NA 3,266 0.15 2,463 0.20

Seed, Blood 1,360 931 4,753 0.29 3,826 0.36Seed, 1:1 Cow Manure: Blood 1,384 896 3,860 0.36 3,692 0.37Seed, 2:1 Cow Manure: Blood 1,899 NA 3,534 0.54 3,942 0.48



Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments (average approximately 60%). As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, cow manure co-digested with blood at 2:1 ratio had the greatest biogas yield (480 mL/g VS destroyed). Biogas yield from co-digestion of cow manure with blood in equal proportions (1:1 ratio) was similar as digestion of blood alone (370 and 360 mL/g VS destroyed, respectively). From the assay, it is projected that is an advantage to mixing this specific cow manure and blood at 2:1 ratio if the objective is energy production.

84

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)


Seed, Blood 8.04 4,450 19,713 12,388 18,388 8,500 12,952 4,100 603Seed, 1:1 Cow Manure: Blood 7.92 5,550 21,775 13,588 21,647 10,700 14,745 7,100 688Seed, 2:1 Cow Manure: Blood 7.87 6,350 24,200 14,700 23,580 14,600 16,363 8,800 753


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)


Seed, Blood 7.70 6,900 12,400 6,600 11,663 7,100 7,067 5,400 1,169Seed, 1:1 Cow Manure: Blood 7.57 8,000 15,838 9,538 14,370 8,700 9,065 5,800 1,368Seed, 2:1 Cow Manure: Blood 7.79 8,950 18,763 11,225 16,782 10,900 10,298 6,000 1,508


Seed, Cow Manure 7.93 7.43 -0.50 Seed, Blood 8.04 7.70 -0.34

Seed, 1:1 Cow Manure: Blood 7.92 7.57 -0.35 Seed, 2:1 Cow Manure: Blood 7.87 7.79 -0.08






Seed, Blood 2,893 4,485 1,592 Seed, 1:1 Cow Manure: Blood 3,608 5,200 1,592 Seed, 2:1 Cow Manure: Blood 4,128 5,818 1,690

85



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Blood 11,952 7,581 4,371 37 Seed, 1:1 Cow Manure: Blood 14,070 9,340 4,730 34 Seed, 2:1 Cow Manure: Blood 15,327 10,908 4,419 29



Final TSS (mg)


Destruction (%)


Seed, Blood 5,525 4,615 910 16 Seed, 1:1 Cow Manure: Blood 6,955 5,655 1,300 19 Seed, 2:1 Cow Manure: Blood 9,490 7,085 2,405 25



Final VSS (mg)


Destruction (%)


Seed, Blood 2,665 3,510 -845 -32 Seed, 1:1 Cow Manure:

Blood 4,615 3,770 845 18

Seed, 2:1 Cow Manure: Blood 5,720 3,900 1,820 32





Seed 370 358 -12 Seed, Cow Manure 411 498 87

Seed, Blood 392 760 368 Seed, 1:1 Cow Manure: Blood 447 889 442 Seed, 2:1 Cow Manure: Blood 489 980 491


86




Seed, Blood 1,400 Seed, 1:1 Cow Manure: Blood 2,400 Seed, 2:1 Cow Manure: Blood 3,800

*Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

87


Phase 3

10. Slaughterhouse Blood with Fat, RIP Farms (West Michigan Beef)

Hudsonville, MI






88

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of slaughterhouse blood with fat from RIP Farms (West Michigan Beef). The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Slaughterhouse Blood with Fat used in Lab* 7.30 50,939 45,570 85,900 * Data for the above parameters was collected on a diluted sample. An amount of 250 mL was diluted to 1 L. NOTE: This sample contained fat tissue; efforts were made to blend the

tissue. Most of fat was blended into small particulates; however large chunks were removed from sample.


Flask Seed (mL)

Manure(mL)

Blood w/fat (mL)

D.I. Water(mL)


(9-10.1 Seed, MSU Manure) 211 52 0 387 Seed, Blood with fat

(10.1 Seed, RIP Blood with fat) 211 0 52 387 Seed, 1:1 Cow Manure: Blood with fat

(10.2 Seed, 1:1 MSU Manure:RIP Blood with fat) 211 52 52 335 Seed, 2:1 Cow Manure: Blood with fat

(10.3 Seed, 2:1 MSU Manure:RIP Blood with fat) 211 104 52 283 Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not

89




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion


Seed, Blood w/fat 8,702 13,163 -4,461 -51 4,924 4,087 837 17 9,284 9,039 245 3

Seed, 1:1 Cow Manure: Blood w/fat 10,733 14,170 -

3,437 -32 5,574 5,176 398 7 11,399 9,425 1,974 17

Seed, 2:1 Cow Manure: Blood w/fat 14,073 14,812 -739 -5 6,500 5,777 723 11 9,952 8,381 1,571 16

SPECIAL NOTE FOR THIS SAMPLE ONLY: DURING DIGESTION, A CRACK DEVELOPED IN THE FLASK OF SAMPLE 9-10.1 SEED, MSU MANURE. RESULTING INACCURATE GAS PRODUCTION RESULTS.


90



91



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 429 NA 1,478 0.29 7,629 0.03Seed, Cow Manure 488 NA 3,266 0.15 10,871 0.03Seed, Blood w/fat 3,878 3,449 -4,461 NA 8,702 0.21

Seed, 1:1 Cow Manure: Blood w/fat 3,949 3,461 -3,437 NA 10,733 0.18Seed, 2:1 Cow Manure: Blood w/fat 4,325 NA -739 NA 14,073 0.15


Discussion and Conclusions Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from digestion only blood w/fat (210 mL/g VS destroyed) were greater than co-digestion of cow manure and blood w/fat at 1:1 ratio (180 mL/g VS destroyed) as well as 2:1 ratio (150 mL/g VS destroyed). Digestion of cow manure alone had the least amount of biogas produced. From the assay, it is projected that there is no advantage to mixing this specific cow manure and blood w/fat if the objective is energy production.

92

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)

Seed 8.00 4,750 11,738 6,988 14,818 12,900 9,102 8,200 569Seed, Cow Manure 7.93 5,500 16,725 8,000 17,392 12,300 10,702 6,500 633Seed, Blood w/fat 8.02 4,450 13,388 7,375 19,472 12,600 14,283 9,600 506

Seed, 1:1 Cow Manure: Blood w/fat 7.93 5,550 16,513 8,525 23,985 1,200 17,537 9,400 620Seed, 2:1 Cow Manure: Blood w/fat 7.77 6,300 21,650 10,088 22,963 14,100 15,310 10,600 668


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)

Seed 7.46 4,750 9,463 6,025 10,310 5,200 5,837 3,700 551Seed, Cow Manure 7.43 5,950 11,700 7,700 12,430 6,300 6,912 3,900 766Seed, Blood w/fat 7.18 3250 20,250 6,288 10,700 18,278 9,500 13,907 634

Seed, 1:1 Cow Manure: Blood w/fat 7.36 5100 21,800 7,963 12,800 20,085 8,400 14,500 641Seed, 2:1 Cow Manure: Blood w/fat 7.49 6600 22,788 8,888 11,900 18,850 8,200 12,893 915


Seed, Cow Manure 7.93 7.43 -0.50 Seed, Blood w/fat 8.02 7.18 -0.84

Seed, 1:1 Cow Manure: Blood w/fat 7.93 7.36 -0.57 Seed, 2:1 Cow Manure: Blood w/fat 7.77 7.49 -0.28





Seed 3,088 3,088 0 Seed, Cow Manure 3,575 3,868 293 Seed, Blood w/fat 2,893 2,113 -781

Seed, 1:1 Cow Manure: Blood w/fat 3,608 3,315 -293 Seed, 2:1 Cow Manure: Blood w/fat 4,095 4,290 195

93



Final TS (mg)

TS Destruction (mg)

Destruction (%)

Seed 9,632 6,702 2,930 30 Seed, Cow Manure 11,305 8,080 3,225 29 Seed, Blood w/fat 12,657 11,881 776 6

Seed, 1:1 Cow Manure: Blood w/fat 15,590 13,055 2,535 16 Seed, 2:1 Cow Manure: Blood w/fat 14,926 12,253 2,673 18



Final TSS (mg)


Destruction (%)

Seed 8,385 3,380 5,005 60 Seed, Cow Manure 7,995 4,095 3,900 49 Seed, Blood w/fat 8,190 6,955 1,235 15

Seed, 1:1 Cow Manure: Blood w/fat 7,800 8,320 -520 -7 Seed, 2:1 Cow Manure: Blood w/fat 9,165 7,735 1,430 16



Final VSS (mg)


Destruction (%)

Seed 5,330 2,405 2,925 54 Seed, Cow Manure 4,225 2,535 1,690 40 Seed, Blood w/fat 6,240 6,175 65 1

Seed, 1:1 Cow Manure: Blood w/fat 6,110 5,460 650 11

Seed, 2:1 Cow Manure: Blood w/fat 6,890 5,330 1,560 23





Seed 370 358 -12 Seed, Cow Manure 411 498 87 Seed, Blood w/fat 329 412 83

Seed, 1:1 Cow Manure: Blood w/fat 403 417 14 Seed, 2:1 Cow Manure: Blood w/fat 434 595 161


94



Seed 300 Seed, Cow Manure 700 Seed, Blood w/fat 800

Seed, 1:1 Cow Manure: Blood w/fat 3,200 Seed, 2:1 Cow Manure: Blood w/fat 2,000


95


Phase 3

11. Liquid Industrial Waste Holland, MI






96

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of food processing waste collected from Liquid Industrial Waste. The sample was collected by Norma McDonald, Phase 3 Renewables, LLC, on January 26, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Liquid Industrial Waste Used in Lab* 5.61 173,180 140,629 190,100 * Data for the above parameters was collected on a diluted sample. The sample was diluted and blended until a consistency was produced that was usable in the lab. This

dilution ended up 1:1.33 by mass.


Flask Seed (mL)

Manure(mL)

LIW (mL)

D.I. Water(mL)


(11.1 Seed, MSU Manure) 211 16 0 423 Seed, Liquid Industrial Waste

(11.2 Seed, Liquid Industrial Waste) 211 0 16 423 Seed, 1:1 Cow Manure: Liquid Industrial Waste

(10.2 Seed, 1:1 MSU Manure: Liquid Industrial Waste) 211 16 16 406 Seed, 2:1 Cow Manure: Liquid Industrial Waste

(10.3 Seed, 2:1 MSU Manure: Liquid Industrial Waste) 211 33 16 390 Seed, 1:2 Cow Manure: Liquid Industrial Waste

(10.3 Seed, 1:2 MSU Manure: Liquid Industrial Waste) 211 8 16 414 Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended

97




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 7,629 6,151 1,478 19 4,501 3,916 585 13 5,916 3,794 2,122 36Seed, Cow Manure 9,482 6,622 2,860 30 5,200 3,811 1,389 27 5,855 4,292 1,563 27

Seed, Liquid Industrial Waste 10,457 7,174 3,283 31 4,534 3,892 642 14 7,901 4,497 3,404 43

Seed, 1:1 Cow Manure: Liquid Industrial Waste 10,278 7,109 3,169 31 4,826 4,136 690 14 7,564 4,293 3,271 43

Seed, 2:1 Cow Manure: Liquid Industrial Waste 12,285 7,597 4,688 38 5,086 4,696 390 8 8,263 4,701 3,562 43

Seed, 1:2 Cow Manure: Liquid Industrial Waste 10,896 6,971 3,925 36% 4,469 4,648 -179 0 8,200 4,222 3,978 49


98




99


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 429 NA 1,478 0.29 2,122 0.20Seed, Cow Manure 577 NA 2,860 0.20 1,563 0.37

Seed, Liquid Industrial Waste 1,906 1,477 3,283 0.58 3,404 0.56Seed, 1:1 Cow Manure: Liquid Industrial Waste 2,030 1,453 3,169 0.64 3,271 0.62Seed, 2:1 Cow Manure: Liquid Industrial Waste 1,364 NA 4,688 0.29 3,562 0.38Seed, 1:2 Cow Manure: Liquid Industrial Waste 1,556 NA 3,925 0.40 3,978 0.39



Alkalinity and pH were adequate at the beginning and end of digestion after mixing with seed (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments at the end of this trial (average approximately 65%). As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from cow manure mixed with liquid industrial waste at 1:1 ratio (620 mL/g VS destroyed) was slightly greater than those from liquid industrial waste alone (560 mL/g VS destroyed). However, biogas yield from co-digestion of cow manure mixed with liquid industrial waste at 1:2 ratio (390 mL/g VS destroyed) and 2:1 ratio (380 mL/g VS destroyed) did not produce more biogas compared with digestion of liquid industrial waste alone. From the assay, it is projected that there is no significant advantage to mixing this specific cow manure and liquid industrial waste if the objective is energy production.

Appendix

100


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 8.00 4,750 11,738 6,988 14,818 12,900 9,102 8,200 569Seed, Cow Manure 8.05 4950 14,588 8,150 14,910 11,100 9,008 6,700 596

Seed, Liquid Industrial Waste 7.96 4550 16,088 7,175 17,850 11,100 12,155 8,300 554Seed, 1:1 Cow Manure: Liquid Industrial

Waste 7.88 4850 15,813 7,400 17,255 11,000 11,637 8,300 544

Seed, 2:1 Cow Manure: Liquid Industrial Waste 7.89 4800 18,900 7,800 18,668 11,300 12,712 7,500 536

Seed, 1:2 Cow Manure: Liquid Industrial Waste 7.94 4600 16,763 6,888 18,357 12,400 12,615 8,800 526


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)


Seed, Liquid Industrial Waste 7.45 5,750 11,038 5,988 11,280 5,900 6,918 3,900 790Seed, 1:1 Cow Manure: Liquid Industrial

Waste 7.49 5,800 10,938 6,363 11,413 6,100 6,605 3,50 800

Seed, 2:1 Cow Manure: Liquid Industrial Waste 7.47 6,450 11,688 7,225 12,375 7,400 7,232 4,600 855

Seed, 1:2 Cow Manure: Liquid Industrial Waste 7.44 5,850 10,725 7,150 10,842 4,900 6,495 3,800 821


Seed, Cow Manure 8.05 7.42 -0.63 Seed, Liquid Industrial Waste 7.96 7.45 -0.51

Seed, 1:1 Cow Manure: Liquid Industrial Waste 7.88 7.49 -0.39 Seed, 2:1 Cow Manure: Liquid Industrial Waste 7.89 7.47 -0.42 Seed, 1:2 Cow Manure: Liquid Industrial Waste 7.94 7.44 -0.50


101





Seed, Liquid Industrial Waste 2,958 3,738 780 Seed, 1:1 Cow Manure: Liquid Industrial Waste 3,153 3,770 617 Seed, 2:1 Cow Manure: Liquid Industrial Waste 3,120 4,193 1,073 Seed, 1:2 Cow Manure: Liquid Industrial Waste 2,990 3,803 813



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Liquid Industrial Waste 11,603 7,332 4,271 37 Seed, 1:1 Cow Manure: Liquid Industrial Waste 11,216 7,419 3,797 34 Seed, 2:1 Cow Manure: Liquid Industrial Waste 12,134 8,044 4,090 34 Seed, 1:2 Cow Manure: Liquid Industrial Waste 11,932 7,047 4,885 41



Final TSS (mg)


Destruction (%)


Seed, Liquid Industrial Waste 7,215 3,835 3,380 47 Seed, 1:1 Cow Manure: Liquid Industrial Waste 7,150 3,965 3,185 45 Seed, 2:1 Cow Manure: Liquid Industrial Waste 7,345 4,810 2,535 35 Seed, 1:2 Cow Manure: Liquid Industrial Waste 8,060 3,185 4,875 60



Final VSS (mg)


Destruction (%)


Seed, Liquid Industrial Waste 5,395 2,535 2,860 53 Seed, 1:1 Cow Manure: Liquid

Industrial Waste 5,395 2,275 3,120 58 Seed, 2:1 Cow Manure: Liquid

Industrial Waste 4,875 2,990 1,885 39 Seed, 1:2 Cow Manure: Liquid

Industrial Waste 5,720 2,470 3,250 57

Ammonia Change During Digestion Flask Initial Ammonia Final Ammonia Ammonia Change

102

(mg NH3) (mg NH3) (mg NH3) Seed 370 358 -12

Seed, Cow Manure 388 411 23 Seed, Liquid Industrial Waste 360 514 154

Seed, 1:1 Cow Manure: Liquid Industrial Waste 353 520 167 Seed, 2:1 Cow Manure: Liquid Industrial Waste 349 556 207 Seed, 1:2 Cow Manure: Liquid Industrial Waste 342 534 192





Seed, Liquid Industrial Waste 2,000 Seed, 1:1 Cow Manure: Liquid Industrial Waste 1,250 Seed, 2:1 Cow Manure: Liquid Industrial Waste 2,000 Seed, 1:2 Cow Manure: Liquid Industrial Waste 1,000


103


Phase 3

12. Glycerine Bangor, MI

DRAFT

Submitted to

Date Sample Collected: 2007 Date Assay Conducted: July 31 – , 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems


Michigan State University

104

MSU Principal Investigator: Steven Safferman ([email protected], 517‐432‐0812)


105

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of a glycerine sample that was donated to Michigan State University in 2007. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Glycerine Used in Lab* 8.58 1,046,941 1,037,196 1,751,000


Flask Seed (mL)

Manure(mL)

Glycerine (mL)

D.I. Water(mL)

Seed (12.1 Seed) 312 0 0 338


Seed, Glycerine (12.3 Seed, Glycerine) 312 0 3 335

Seed, 1:1 Cow Manure: Glycerine (12.4 Seed, 1:1 MSU Manure: Glycerine) 312 3 3 332


Seed, 1:2 Cow Manure: Glycerine (12.6 Seed, 1:1 MSU Manure: Glycerine) 312 1.5 3 333.5



106




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 8,751 3,868 6,099 Seed, Cow Manure 10,132 4,144 6,123

Seed, Glycerine 16,234 7,719 9,272 Seed, 1:1 Cow Manure: Glycerine 17,046 8,564 8,119 Seed, 2:1 Cow Manure: Glycerine 17,989 8,678 9,556 Seed, 1:2 Cow Manure: Glycerine 15,104 8,060 7,549

Seed, 50:1 Cow Manure: Glycerine 26,163 11,765 14,166

Seed, 100:1 Cow Manure: Glycerine 29,933 14,381 17,130

107



108


109



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed Seed, Cow Manure

Seed, Glycerine Seed, 1:1 Cow Manure: Glycerine Seed, 2:1 Cow Manure: Glycerine Seed, 1:2 Cow Manure: Glycerine

Seed, 50:1 Cow Manure: Glycerine Seed, 100:1 Cow Manure: Glycerine



110

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Cheese Whey 7.95 6,350 24,975 11,875 21,310 12,100 14,265 7,500 511 Seed, 1:1 Cow Manure: Glycerine 7.94 6,100 26,225 13,050 18,780 8,600 12,490 6,500 504 Seed, 2:1 Cow Manure: Glycerine 7.90 6,650 27,675 13,400 21,565 14,300 14,702 10,300 481 Seed, 1:2 Cow Manure: Glycerine 7.94 6,650 23,238 12,325 17,288 5,500 11,613 4,500 508 Seed, 50:1 Cow Manure: Glycerine 7.73 9,000 40,250 18,175 32,352 20,100 21,793 14,000 868 Seed, 100:1 Cow Manure: Glycerine 7.57 11,250 46,050 22,413 39,183 23,300 26,353 15,700 1,168


Flask pH

Alk

alin

ity

(mg/

LC

aCO

3)C

OD

(m

g/L)

So

lubl

e C

OD

(m

g/L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s(m

g/L)

Vola

tile

Solid

s (m

g/L)

Susp

ende

d So

lids

Am

mon

ia

(mg/

L N

)


Seed, Cheese Whey Seed, 1:1 Cow Manure: Glycerine Seed, 2:1 Cow Manure: Glycerine Seed, 1:2 Cow Manure: Glycerine Seed, 50:1 Cow Manure: Glycerine Seed, 100:1 Cow Manure: Glycerine

pH Change During Digestion Flask Initial pH Final pH pH Change Seed 7.93

Seed, Cow Manure 8.00 Seed, Cheese Whey 7.95

Seed, 1:1 Cow Manure: Glycerine 7.94 Seed, 2:1 Cow Manure: Glycerine 7.90 Seed, 1:2 Cow Manure: Glycerine 7.94 Seed, 50:1 Cow Manure: Glycerine 7.73 Seed, 100:1 Cow Manure: Glycerine 7.57

111






Seed, Cheese Whey 4,128 Seed, 1:1 Cow Manure: Glycerine 3,965 Seed, 2:1 Cow Manure: Glycerine 4,323 Seed, 1:2 Cow Manure: Glycerine 4,323 Seed, 50:1 Cow Manure: Glycerine 5,850 Seed, 100:1 Cow Manure: Glycerine 7,313



Final TS (mg)

TS Destruction (mg)

Destruction (%)





Final TSS (mg)


Destruction (%)





Final VSS (mg)


Destruction (%)


Seed, Cheese Whey 4,875 Seed, 1:1 Cow Manure: Glycerine 4,225 Seed, 2:1 Cow Manure: Glycerine 6,695 Seed, 1:2 Cow Manure: Glycerine 2,925

Seed, 50:1 Cow Manure: Glycerine 9,100

Seed, 100:1 Cow Manure: Glycerine 10,205

112






Seed, Cheese Whey 332 Seed, 1:1 Cow Manure: Glycerine 327 Seed, 2:1 Cow Manure: Glycerine 313 Seed, 1:2 Cow Manure: Glycerine 330 Seed, 50:1 Cow Manure: Glycerine 564 Seed, 100:1 Cow Manure: Glycerine 759





Seed, Cheese Whey 200 Seed, 1:1 Cow Manure: Glycerine 1500 Seed, 2:1 Cow Manure: Glycerine 1200 Seed, 1:2 Cow Manure: Glycerine 900 Seed, 50:1 Cow Manure: Glycerine - Seed, 100:1 Cow Manure: Glycerine 1400


113


Phase 3

13. Request Foods Hamilton, MI

Submitted to Sali Engineering

Date Sample Collected: January 26, 2009 Date Assay Conducted: March 20 – April 17, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems




114

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of food processing waste collected from Request Foods. The sample was collected by Jim Garber, Sali Engineering, on February 6, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Request Foods Used in Lab* 8.95 3,275 2,493 3,138 * Data for the above parameters was collected on the original submitted

sample.


Flask Seed (mL)

Manure(mL)

Request Foods (mL)

D.I. Water(mL)

Seed (13.1 Seed) 45 0 0 605


Seed, Request Foods (13.3 Seed, Request Foods) 45 0 195 410

Seed, 1:1 Cow Manure: Request Foods (13.4 Seed, 1:1 MSU Manure: Request Foods)

45 195 195 215

Seed, 2:1 Cow Manure: Request Foods (13.5 Seed, 2:1 MSU Manure: Request Foods)

0 0 195 455

Seed, 1:2 Cow Manure: Request Foods (13.6 Seed, 1:2 MSU Manure: Request Foods) 45 390 195 20


115




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 1,771 1,739 32 2 1,316 1,178 138 10 1,225 1,130 95 8Seed, Cow Manure 11,993 7,735 4,258 36 7,556 4,290 3,266 43 6,904 4,883 2,021 29

Seed, Request Foods 2,503 1,796 707 28 1,869 1,292 577 31 1,522 1,154 368 24Seed, 1:1 Cow

Manure: Request Foods

12,431 8,596 3,835 31 7,898 5,143 2,755 35 7,215 5,371 1,844 26

Seed, 2:1 Cow Manure: Request

Foods 20,995 20,621 374 2 13,488 12,456 1,032 8 12,853 11,063 1,790 14

Seed, 1:2 Cow Manure: Request

Foods 7,109 4,558 2,551 36 5,249 2,958 2,291 44 4,582 3,132 1,450 32


116



117



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)


Seed, Request Foods 207 158 707 0.29 368 0.56Seed, 1:1 Cow Manure: Request Foods 2,154 -156 3,835 0.56 1,844 1.17Seed, 2:1 Cow Manure: Request Foods 1,225 NA 374 3.28 1,790 0.68Seed, 1:2 Cow Manure: Request Foods 1,580 NA 2,551 0.62 1,450 1.09



Alkalinity and pH were adequate at the beginning and end of digestion (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments (average approximately 50%), except cow manure mixed with request foods at 2:1 ratio. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from cow manure mixed with request foods at 1:1 ratio (1,170 mL/g VS destroyed) was slightly greater than those from cow manure alone (1,140 mL/g VS destroyed). However, biogas yield from co-digestion of cow manure mixed with request foods at 1:2 ratio (1,090 mL/g VS destroyed) and 2:1 ratio (680 mL/g VS destroyed) did not produce more biogas compared with digestion of cow manure alone. Digestion of request foods alone produced the least amount of biogas (560 mL/g VS destroyed). From the assay, it is projected that there is no significant advantage to mixing this specific cow manure and request foods if the objective is energy production.

118

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)

Seed 8.23 950 2,725 2,063 3,073 1,600 1,885 1,600 135Seed, Cow Manure 7.53 4,050 18,450 11,600 16,370 9,700 10,622 8,200 510

Seed, Request Foods 7.78 950 3,850 2,850 3,602 2,100 2,342 1,700 80Seed, 1:1 Cow Manure: Request Foods 7.41 3,900 19,125 12,038 17,393 10,100 11,100 8,900 494Seed, 2:1 Cow Manure: Request Foods 7.50 8,150 32,300 20,688 31,935 18,500 19,773 13,500 924Seed, 1:2 Cow Manure: Request Foods 7.73 2,600 10,938 8,025 10,682 7,400 7,050 5,800 275


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 7.54 1,400 2,675 1,813 2,703 400 1,738 200 153Seed, Cow Manure 7.34 5,200 11,900 6,600 12,862 9,100 7,512 5,900 635

Seed, Request Foods 6.88 1,250 2,763 1,988 2,863 1,800 1,775 1,800 150Seed, 1:1 Cow Manure: Request Foods 7.25 5,500 13,225 7,913 13,727 7,000 8,263 3,900 670Seed, 2:1 Cow Manure: Request Foods 7.37 8,200 31,725 19,163 26,938 14,100 17,020 9,300 1,174Seed, 1:2 Cow Manure: Request Foods 7.19 3,400 7,013 4,550 8,000 6,000 4,818 3,700 413


Seed, Cow Manure 7.53 7.34 -0.19 Seed, Request Foods 7.78 6.88 -0.90

Seed, 1:1 Cow Manure: Request Foods 7.41 7.25 -0.16 Seed, 2:1 Cow Manure: Request Foods 7.50 7.37 -0.13 Seed, 1:2 Cow Manure: Request Foods 7.73 7.19 -0.54

119





Seed 618 910 292 Seed, Cow Manure 2,633 3,380 747

Seed, Request Foods 618 813 195 Seed, 1:1 Cow Manure: Request Foods 2,535 3,575 1,040 Seed, 2:1 Cow Manure: Request Foods 5,298 5,330 32 Seed, 1:2 Cow Manure: Request Foods 1,690 2,210 520



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Request Foods 2,341 1,861 480 21 Seed, 1:1 Cow Manure: Request Foods 11,306 8,922 2,384 21 Seed, 2:1 Cow Manure: Request Foods 20,758 17,510 3,248 16 Seed, 1:2 Cow Manure: Request Foods 6,943 5,200 1,743 25



Final TSS (mg)


Destruction (%)

Seed 1,040 260 780 75 Seed, Cow Manure 6,305 5,915 390 6

Seed, Request Foods 1,365 1,170 195 14 Seed, 1:1 Cow Manure: Request Foods 6,565 4,550 2,015 31 Seed, 2:1 Cow Manure: Request Foods 12,025 9,165 2,860 24 Seed, 1:2 Cow Manure: Request Foods 4,810 3,900 910 19



Final VSS (mg)


Destruction (%)

Seed 1,040 130 910 88 Seed, Cow Manure 5,330 3,835 1,495 28

Seed, Request Foods 1,105 1,170 -65 -6 Seed, 1:1 Cow Manure:

Request Foods 5,785 2,535 3,250 56

Seed, 2:1 Cow Manure: Request Foods 8,775 6,045 2,730 31

Seed, 1:2 Cow Manure: Request Foods 3,770 2,405 1,365 36

120






Seed, Request Foods 52 98 46 Seed, 1:1 Cow Manure: Request Foods 321 436 115 Seed, 2:1 Cow Manure: Request Foods 600 763 163 Seed, 1:2 Cow Manure: Request Foods 179 268 89





Seed, Request Foods 100 Seed, 1:1 Cow Manure: Request Foods 2,600 Seed, 2:1 Cow Manure: Request Foods 2,000 Seed, 1:2 Cow Manure: Request Foods 1,600


121


Phase 3

17.Michigan Turkey Producers Waste Meat Wyoming, MI


Date Sample Collected: February 16, 2009 Date Assay Conducted: June 12 – August 5, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems




122

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of waste meat collected from Michigan Turkey Producers. The sample was collected by Andy Austin, Phase 3 Renewables, on February 16, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

MTP waste meat Used in Lab* 7.42 17,652 16,943 38,325 * Data for the above parameters was collected on a diluted sample. A dry waste meat was submitted and it was diluted with water and blended until a consistency was produced that allowed for laboratory used. The above numbers reflect this dilution. Dilution made by

measuring 100 g of waste meat and dilution with DI water up to 1000 g.


Flask Seed (mL)

Manure(mL)

MTP Waste (mL)

D.I. Water (mL)

Seed (17-18.1 Seed) 202 0 0 448


Seed, MTP Waste (17.2 Seed, MTP Waste) 202 0 126 322

Seed, 1:1 Cow Manure: MTP Waste (17.3 Seed, 1:1 MSU Manure: MTP Waste) 202 126 126 196




123




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 6,321 5,070 1,251 2 2,389 2,088 301 13 3,896 3,753 143 4Seed, Cow Manure 11,635 8,028 3,607 31 2,860 2,828 32 0.1 7,208 5,958 1,250 17Seed, MTP Waste 11,099 5,988 5,111 46 2,616 1,983 633 24 5,657 4,027 1,630 29

Seed, 1:1 Cow Manure: MTP Waste 16,478 9,076 7402 45 3,640 2,706 934 26 9,025 6,432 2,593 29

Seed, 2:1 Cow Manure: MTP Waste 23,043 12,448 1,060 46 5,119 3,778 1,341 26 12,056 9,194 2,862 24

Seed, 1:2 Cow Manure: MTP Waste 14,308 7,548 6,760 47 3,380 2,503 877 26 8,305 5,359 2,946 36


124



125



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 415 NA 1,251 0.33 143 2.90 Seed, Cow Manure 1,663 NA 3,607 0.46 1,250 1.33Seed, MTP Waste 2,082 1,667 5,111 0.41 1,630 1.28

Seed, 1:1 Cow Manure: MTP Waste 3,582 1,919 7,402 0.48 2,593 1.38Seed, 2:1 Cow Manure: MTP Waste 3,514 NA 1,060 3.32 2,862 1.22Seed, 1:2 Cow Manure: MTP Waste 3,847 NA 6,760 0.57 2,946 1.31 **Calculated using the Seed and Seed, Cow Manure flasks. Note: Can only be used for flasks where the seed and cow manure volumes are the same.


Alkalinity and pH were adequate at the beginning and end of digestion after mixing with seed (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from co-digestion of cow manure and MTP Waste at 1:1 ratio (1,380 mL/g VS destructed) had greatest biogas production. However, biogas yield from co-digestion of cow manure mixed with MTP waste at 1:2 ratio (1,310 mL/g VS destroyed) and 2:1 ratio (1,220 mL/g VS destroyed) did not produce more biogas compared with digestion of cow manure alone (1,330 mL/g VS destroyed).

From the assay, it is projected that there is likely an advantage to mixing this specific cow manure and MTP waste in equal proportions if the objective is energy production.

126

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)

Seed 7.97 4,250 9,725 3,650 10,173 5,900 5,993 3,800 531Seed, Cow Manure 7.67 6,650 17,900 4,363 18,308 11,100 11,090 7,400 755Seed, MTP Waste 7.82 4,200 17,075 4,050 13,275 8,800 8,703 6,500 540

Seed, 1:1 Cow Manure: MTP Waste 7.63 6,600 25,350 5,550 21,368 13,400 13,885 9,800 853Seed, 2:1 Cow Manure: MTP Waste 7.54 8,600 35,450 7,675 28,855 19,000 18,548 14,200 1,160Seed, 1:2 Cow Manure: MTP Waste 7.64 5,300 22,013 5,188 17,648 12,100 12,777 9,900 680


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 7.38 4,450 7,800 3,213 9,503 4,400 5,773 2,300 424Seed, Cow Manure 7.51 6,800 12,350 4,350 15,337 7,700 9,208 5,300 711Seed, MTP Waste 7.40 4,700 9,213 3,050 10,115 4,400 6,195 3,000 554

Seed, 1:1 Cow Manure: MTP Waste 7.69 9,500 13,963 4,163 16,352 8,400 9,895 6,600 759Seed, 2:1 Cow Manure: MTP Waste 7.81 6,150 19,150 5,813 23,155 11,400 14,145 8,100 1,086Seed, 1:2 Cow Manure: MTP Waste 7.50 7,600 11,613 3,850 13,447 5,500 8,245 4,100 675


Seed, Cow Manure 7.67 7.51 -.16 Seed, MTP Waste 7.82 7.40 -.42

Seed, 1:1 Cow Manure: MTP Waste 7.63 7.69 .06 Seed, 2:1 Cow Manure: MTP Waste 7.54 7.81 .27 Seed, 1:2 Cow Manure: MTP Waste 7.64 7.50 -.14

127





Seed 2,763 2,893 130 Seed, Cow Manure 4,323 4,420 97 Seed, MTP Waste 2,730 3,055 325

Seed, 1:1 Cow Manure: MTP Waste 4,290 6,175 1,885 Seed, 2:1 Cow Manure: MTP Waste 5,590 3,998 -1,592 Seed, 1:2 Cow Manure: MTP Waste 3,445 4,940 1,495



Final TS (mg)

TS Destruction (mg)

Destruction (%)

Seed 6,613 6,177 436 7 Seed, Cow Manure 11,900 9,969 1,931 16 Seed, MTP Waste 8,629 6,575 2,054 24

Seed, 1:1 Cow Manure: MTP Waste 13,889 10,629 3,260 24 Seed, 2:1 Cow Manure: MTP Waste 18,756 15,051 3,705 20 Seed, 1:2 Cow Manure: MTP Waste 11,471 8,740 2,731 24



Final TSS (mg)


Destruction (%)





Final VSS (mg)


Destruction (%)



128





Seed 345 275 -70 Seed, Cow Manure 491 462 -29 Seed, MTP Waste 351 360 9

Seed, 1:1 Cow Manure: MTP Waste 554 493 -61 Seed, 2:1 Cow Manure: MTP Waste 754 706 -48 Seed, 1:2 Cow Manure: MTP Waste 442 439 -3




Seed 0 Seed, Cow Manure 0 Seed, MTP Waste 0

Seed, 1:1 Cow Manure: MTP Waste 0 Seed, 2:1 Cow Manure: MTP Waste 0 Seed, 1:2 Cow Manure: MTP Waste 0


129


Phase 3

18. Michigan Turkey Producers ‐ Blood Wyoming, MI






130

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of blood collected from Michigan Turkey Producers. The sample was collected by Andy Austin, Phase 3 Renewables, on February 16, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

MTP Blood Used in Lab* 6.19 160,982 133,032 222,000 * Data for the above parameters was collected the liquid blood provided. The tissue was

removed as it was not possible to blend.


Flask Seed (mL)

Manure(mL)

MTP Blood (mL)

D.I. Water(mL)

Seed (17-18.1 Seed) 202 0 0 448


Seed, MTP Blood (18.2 Seed, MTP Blood) 202 0 16 432

Seed, 1:1 Cow Manure: MTP Blood (18.3 Seed, 1:1 MSU Manure: MTP Blood) 202 16 16 416



Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not

131




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 6,321 5,070 1,251 20 2,389 2,088 301 13 3,896 3,753 143 4 Seed, Cow Manure 5,614 4,217 1,397 25 1,950 1,828 122 6 3,663 3,093 570 16Seed, MTP Blood 9,685 6,183 3,502 36 2,909 2,381 528 18 5,978 4,931 1,047 18

Seed, 1:1 Cow Manure: MTP Blood 10,717 6,679 4,038 38 2,616 2,462 154 6 6,628 5,144 1,484

22Seed, 2:1 Cow Manure:

MTP Blood 11,018 6,264 4,754 43 3,413 2,381 1,032 30 6,778 4,452 2,326 34

Seed, 1:2 Cow Manure: MTP Blood 10,400 6,549 3,851 37 2,746 2,226 520 19 6,412 4,583 1,829 29


132



133



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 415 NA 1,251 0.33 143 2.90Seed, Cow Manure 385 NA 1,397 0.28 570 0.68Seed, MTP Blood 1,793 1,378 3,502 0.51 1,047 1.71

Seed, 1:1 Cow Manure: MTP Blood 1,847 1,462 4,038 0.46 1,484 1.24Seed, 2:1 Cow Manure: MTP Blood 1,561 NA 4,754 0.33 2,326 0.67Seed, 1:2 Cow Manure: MTP Blood 1,249 NA 3,851 0.32 1,829 0.68



Alkalinity and pH were adequate at the beginning and end of digestion after mixing with seed (Appendix). Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, digestion of MTP blood alone had the greatest biogas yield (1,710 mL/g VS destroyed), followed by the 1:1 ratio of cow manure and MTP blood (1,240 mL/g VS destroyed). Biogas yield from digestion of cow manure alone as well as co-digestion of cow manure and MTP blood at 1:2 and 2:1 ratio was similar (average 680 mL/g VS destroyed).

From the assay, it is projected that there is no significant advantage to mixing this specific cow manure and MTP blood if the objective is energy production.

134

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 7.97 4,250 9,725 3,650 10,173 5,900 5,993 3,800 531Seed, Cow Manure 7.90 4,250 8,638 3,013 9,157 5,300 5,635 3,300 564Seed, MTP Blood 7.84 5,100 14,900 4,538 13,703 6,200 9,197 4,800 576

Seed, 1:1 Cow Manure: MTP Blood 7.77 5,600 16,488 4,200 15,062 6,400 10,197 4,600 519Seed, 2:1 Cow Manure: MTP Blood 7.97 5,700 16,950 5,500 15,595 8,500 10,428 6,300 591Seed, 1:2 Cow Manure: MTP Blood 7.84 5,500 16,000 4,263 14,470 7,700 9,865 5,600 576


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)

Seed 7.38 4,450 7,800 3,213 9,503 4,400 5,773 2,300 424Seed, Cow Manure 7.39 4,000 6,448 2,813 8,117 2,700 4,758 2,500 434Seed, MTP Blood 7.64 5,950 9,513 3,663 10,578 5,100 7,587 3,100 676

Seed, 1:1 Cow Manure: MTP Blood 7.69 6,000 10,275 3,788 11,823 6,000 7,913 3,500 800Seed, 2:1 Cow Manure: MTP Blood 7.71 6,500 9,638 3,663 11,262 5,500 6,850 14,200 813Seed, 1:2 Cow Manure: MTP Blood 7.65 6,000 10,075 3,425 11,413 4,800 7,050 3,500 788


Seed, Cow Manure 7.90 7.39 -.51 Seed, MTP Blood 7.84 7.64 -.2

Seed, 1:1 Cow Manure: MTP Blood 7.77 7.69 -.08 Seed, 2:1 Cow Manure: MTP Blood 7.97 7.71 -.26 Seed, 1:2 Cow Manure: MTP Blood 7.84 7.65 -.19

135





Seed 2,763 2,893 130 Seed, Cow Manure 2,763 2,600 -163 Seed, MTP Blood 3,315 3,868 553

Seed, 1:1 Cow Manure: MTP Blood 3,640 3,900 260 Seed, 2:1 Cow Manure: MTP Blood 3,705 4,225 520 Seed, 1:2 Cow Manure: MTP Blood 3,575 3,900 325



Final TS (mg)

TS Destruction (mg)

Destruction (%)

Seed 6,613 6,177 436 7 Seed, Cow Manure 5,952 5,276 676 11 Seed, MTP Blood 8,907 6,876 2,031 23

Seed, 1:1 Cow Manure: MTP Blood 9,790 7,685 2105 22 Seed, 2:1 Cow Manure: MTP Blood 10,137 7,320 2,817 28 Seed, 1:2 Cow Manure: MTP Blood 9,405 7,419 1,986 21



Final TSS (mg)


Destruction (%)

Seed 3,835 2,860 975 25 Seed, Cow Manure 3,445 1,755 1,690 49 Seed, MTP Blood 4,030 3,315 715 18




Final VSS (mg)

VSS Destruction

(mg) Destruction

(%)

Seed 2,470 1,495 975 40 Seed, Cow Manure 2,145 1,625 520 24 Seed, MTP Blood 3,120 2,015 1,105 35



136




Seed 345 275 -70 Seed, Cow Manure 366 282 -84 Seed, MTP Blood 375 440 65

Seed, 1:1 Cow Manure: MTP Blood 337 520 183 Seed, 2:1 Cow Manure: MTP Blood 384 528 144 Seed, 1:2 Cow Manure: MTP Blood 375 512 137




Seed 0 Seed, Cow Manure 0 Seed, MTP Blood 1400

Seed, 1:1 Cow Manure: MTP Blood 1000 Seed, 2:1 Cow Manure: MTP Blood 1000 Seed, 1:2 Cow Manure: MTP Blood 900


137


Phase 3

21. Heinz Dry Cake Holland, MI






138

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of dry cake waste collected from Heinz Foods. The sample was collected by Dr. Steve Safferman, Michigan State University, on February 17, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Heinz Dry Cake Used in Lab* 4.70 27,612 20,393 46,725 Heinz Dry Cake Corrected for Dilution** NA 276,120 203,930 460,725

* Data for the above parameters was collected on a diluted sample. A dry cake was submitted and it was diluted with water and blended until a consistency was produced that

allowed for laboratory used. The above numbers reflect this dilution. ** Dilution made by measuring 100 g of Dry Cake and Dilution with DI water up to 1000 g.


Flask Seed (mL)

Manure(mL)

Heinz (mL)

D.I. Water(mL)

Seed (21-22.1 Seed) 136 0 0 514

Seed, Cow Manure (21-22.2 Seed, MSU Manure) 136 72 0 442

Seed, Heinz Dry Cake (21.1 Seed, Heinz Dry Cake) 136 0 72 442

Seed, 1:1 Cow Manure: Heinz Dry Cake (21.2 Seed, 1:1 MSU Manure: Heinz Dry Cake) 136 72 72 371



Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of

139

all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not shown in Table 3 are also provided in the Appendix. Figures 1-3 are graphs of the cumulative, total biogas production, biogas production rate, and biogas methane content, respectively.



Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 4,591 4,428 163 4 3,071 3,307 -236 -8 3,378 2,891 487 14Seed, Cow Manure 7,613 6,346 1,267 17 4,664 4,046 618 13 5,410 4,212 1,198 22

Seed, Heinz Dry Cake 7,166 5,753 1,413 20 3,266 2,828 438 13 4,697 3,615 1,082 23Seed, 1:1 Cow Manure:

Heinz Dry Cake 10,294 7,564 2,730 27 4,599 3,372 1,227 27 6,728 4,865 1,863 28

Seed, 2:1 Cow Manure: Heinz Dry Cake 14,235 10,351 3,884 27 6,126 5,964 162 3 8,545 6,280 2,265 27

Seed, 1:2 Cow Manure: Heinz Dry Cake 8,678 6,809 1,869 22 3,949 3,364 585 15 5,689 4,170 1,519 27


140



141



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 135 NA 163 0.83 487 0.28Seed, Cow Manure 897 NA 1,267 0.71 1,198 0.75

Seed, Heinz Dry Cake 911 776 1,413 0.64 1,082 0.84Seed, 1:1 Cow Manure: Heinz Dry Cake 1,291 394 2,730 0.47 1,863 0.69Seed, 2:1 Cow Manure: Heinz Dry Cake 1,839 NA 3,884 0.47 2,265 0.81Seed, 1:2 Cow Manure: Heinz Dry Cake 1,459 NA 1,869 0.78 1,519 0.96



pH of Heinz dry cake before dilution was relatively low (pH 4.7). After mixing with seed, pH was adequate at the beginning and end of digestion. Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments (average approximately 50%). As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, cow manure co-digested with Heinz dry cake at 1:2 ratio produced more biogas gas (960 mL/g VS destructed) than digestion of Heinz dry cake alone (840 mL/g VS destructed). However, biogas yield from co-digestion of cow manure mixed with Heinz dry cake at 1:1 ratio (690 mL/g VS destroyed) and 2:1 ratio (810 mL/g VS destroyed) did not produce more biogas compared with digestion of Heinz dry cake alone. From the assay, it is projected that there is likely advantage to mixing this specific cow manure and Heinz dry cake at 1:2 ratio if the objective is energy production.

142

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)


Seed, Heinz Dry Cake 7.77 2,950 11,025 4,975 11,173 7,700 7,227 4,100 353Seed, 1:1 Cow Manure:Heinz Dry Cake 7.61 4,250 15,838 7,125 15,755 10,100 10,350 6,900 523Seed, 2:1 Cow Manure:Heinz Dry Cake 7.51 5,100 21,900 9,388 20,120 12,400 13,147 8,500 635Seed, 1:2 Cow Manure:Heinz Dry Cake 7.77 3,450 13,350 6,075 13,467 9,100 8,752 5,800 439


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)


Seed, Heinz Dry Cake 7.23 3,600 8,850 4,350 9,260 7,700 5,562 5,200 600Seed, 1:1 Cow Manure:Heinz Dry Cake 7.40 5,050 11,638 5,188 12,145 8,300 7,485 2,300 463Seed, 2:1 Cow Manure:Heinz Dry Cake 7.44 6,350 15,925 9,175 15,833 11,600 9,662 5,900 690Seed, 1:2 Cow Manure:Heinz Dry Cake 7.30 4,350 10,475 5,175 10,633 7,700 6,415 4,300 836


Seed, Cow Manure 7.82 7.31 -0.51 Seed, Heinz Dry Cake 7.77 7.23 -0.54

Seed, 1:1 Cow Manure:Heinz Dry Cake 7.61 7.40 -0.21 Seed, 2:1 Cow Manure:Heinz Dry Cake 7.51 7.44 -0.07 Seed, 1:2 Cow Manure:Heinz Dry Cake 7.77 7.30 -0.47

143






Seed, Heinz Dry Cake 1,918 2,340 422 Seed, 1:1 Cow Manure:Heinz Dry Cake 2,763 3,283 520 Seed, 2:1 Cow Manure:Heinz Dry Cake 3,315 4,128 813 Seed, 1:2 Cow Manure:Heinz Dry Cake 2,243 2,828 585



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Heinz Dry Cake 7,263 6,019 1,244 17 Seed, 1:1 Cow Manure:Heinz Dry Cake 10,241 7,894 2,347 23 Seed, 2:1 Cow Manure:Heinz Dry Cake 13,078 10,292 2,786 21 Seed, 1:2 Cow Manure:Heinz Dry Cake 8,753 6,912 1,841 21



Final TSS (mg)


Destruction (%)


Seed, Heinz Dry Cake 5,005 5,005 0 0 Seed, 1:1 Cow Manure:Heinz Dry Cake 6,565 5,395 1,170 18 Seed, 2:1 Cow Manure:Heinz Dry Cake 8,060 7,540 520 6 Seed, 1:2 Cow Manure:Heinz Dry Cake 5,915 5,005 910 15



Final VSS (mg)


Destruction (%)


Seed, Heinz Dry Cake 2,665 3,380 -715 27 Seed, 1:1 Cow Manure:Heinz

Dry Cake 4,485 1,495 2,990 67

Seed, 2:1 Cow Manure:Heinz Dry Cake 5,525 3,835 1,690 31

Seed, 1:2 Cow Manure:Heinz Dry Cake 3,770 2,795 975 26

144





Seed 235 268 33 Seed, Cow Manure 323 259 -64

Seed, Heinz Dry Cake 229 390 161 Seed, 1:1 Cow Manure:Heinz Dry Cake 340 301 -39 Seed, 2:1 Cow Manure:Heinz Dry Cake 413 449 36 Seed, 1:2 Cow Manure:Heinz Dry Cake 285 544 259





Seed, Heinz Dry Cake 700 Seed, 1:1 Cow Manure:Heinz Dry Cake 1,600 Seed, 2:1 Cow Manure:Heinz Dry Cake 3,200 Seed, 1:2 Cow Manure:Heinz Dry Cake 1,000


145


Phase 3

22. Heinz Solids Holland, MI






146

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of solid waste collected from Heinz Foods. The sample was collected by Dr. Steve Safferman, Michigan State University, on February 17, 2009 Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Heinz Solids Used in Lab* 3.67 39,140 20,862 31,275 * Data for the above parameters was collected on a blended sample. Submitted sample was a mixture of solids and liquids. Submitted sample was blended until a homogenous

mixture was produced.


Flask Seed (mL)

Manure(mL)

Heinz Solids (mL)

D.I. Water(mL)

Seed (21-22.1 Seed) 136 0 0 514

Seed, Cow Manure (21-22.2 Seed, MSU Manure) 136 72 0 442

Seed, Heinz Solids (22.1 Seed, Heinz Solids) 136 0 72 442

Seed, 1:1 Cow Manure: Heinz Solids (22.2 Seed, 1:1 MSU Manure: Heinz Solids) 136 72 72 371




147




Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

Red

uctio

n

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 4,591 4,428 163 4 3,071 3,307 -236 -8 3,378 2,891 487 14Seed, Cow Manure 7,613 6,346 1,267 17 4,664 4,046 618 13 5,410 4,212 1,198 22Seed, Heinz Solids 6,435 5,029 1,406 22 3,315 3,567 -252 -8 4,809 3,142 1,667 35

Seed, 1:1 Cow Manure: Heinz Solids 9,523 6,817 2,706 28 4,631 3,876 755 16 6,809 4,484 2,325 34

Seed, 2:1 Cow Manure: Heinz Solids 12,911 9,742 3,169 25 6,614 6,923 -309 -5 8,944 6,127 2,817 31

Seed, 1:2 Cow Manure: Heinz Solids 8,881 6,183 2,698 30 3,998 2,836 1,162 29 6,109 3,874 2,235 37


148


Figure 3. Biogas Methane Content Table 4 shows biogas production and provides a comparison to the amount of COD and volatile solids destroyed.


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 135 NA 163 0.83 487 0.28Seed, Cow Manure 897 NA 1,267 0.71 1,198 0.75Seed, Heinz Solids 898 763 1,406 0.64 1,667 0.54

Seed, 1:1 Cow Manure: Heinz Solids 1,733 836 2,706 0.64 2,325 0.75Seed, 2:1 Cow Manure: Heinz Solids 1,767 NA 3,169 0.56 2,817 0.63Seed, 1:2 Cow Manure: Heinz Solids 1,041 NA 2,698 0.39 2,235 0.47



149

pH of Heinz solids was relatively low (pH 3.7). After mixing with seed, pH was adequate at the beginning and end of digestion. Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) was similar across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, biogas yield from co-digestion of cow manure and Heinz solids at 1:1 ratio (750 mL/g VS destructed) was similar as digestion of cow manure alone (750 mL/g VS destructed). However, biogas yield from co-digestion of cow manure mixed with Heinz solids at 1:2 ratio (470 mL/g VS destroyed) and 2:1 ratio (630 mL/g VS destroyed) did not produce more biogas compared with digestion of cow manure alone. From the assay, it is projected that there is no significant advantage to mixing this specific cow manure and Heinz solids if the objective is energy production.

150

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 8.15 2,600 7,063 4,750 8,503 6,100 5,197 4,400 361Seed, Cow Manure 7.82 4,100 11,713 7,275 13,115 7,900 8,323 5,300 496Seed, Heinz Solids 7.62 2,800 9,900 5,188 12,400 5,800 7,398 5,200 355

Seed, 1:1 Cow Manure: Heinz Solids 7.48 4,000 14,650 7,200 17,108 10,000 10,475 9,300 471Seed, 2:1 Cow Manure: Heinz Solids 7.28 5,100 19,863 10,250 22,367 13,700 13,760 9,100 650Seed, 1:2 Cow Manure: Heinz Solids 7.56 3400 13,663 6,138 15,458 8,700 9,398 6,100 425


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

Am

mon

ia

(mg/

L N

)

Seed 7.43 3,100 6,813 5,088 7,403 3,700 4,448 2,300 413Seed, Cow Manure 7.31 4,850 9,763 6,225 10,752 6,900 6,480 4,400 399Seed, Heinz Solids 7.13 3,300 7,738 5,488 9,618 4,600 4,833 4,100 414

Seed, 1:1 Cow Manure: Heinz Solids 7.26 4,750 10,488 5,963 12,925 7,200 6,898 4,400 588Seed, 2:1 Cow Manure: Heinz Solids 7.39 6,500 14,988 10,650 17,035 9,300 9,427 6,800 820Seed, 1:2 Cow Manure: Heinz Solids 7.22 4,100 9,513 4,363 11,565 6,900 5,960 5,800 488


Seed, Cow Manure 7.82 7.31 -0.51 Seed, Heinz Solids 7.62 7.13 -0.49

Seed, 1:1 Cow Manure: Heinz Solids 7.48 7.26 -0.22 Seed, 2:1 Cow Manure: Heinz Solids 7.28 7.39 0.11 Seed, 1:2 Cow Manure: Heinz Solids 7.56 7.22 -0.34

151





Seed 1,690 2,015 325 Seed, Cow Manure 2,665 3,153 488 Seed, Heinz Solids 1,820 2,145 325

Seed, 1:1 Cow Manure: Heinz Solids 2,600 3,088 488 Seed, 2:1 Cow Manure: Heinz Solids 3,315 4,225 910 Seed, 1:2 Cow Manure: Heinz Solids 2,210 2,665 455



Final TS (mg)

TS Destruction (mg)

Destruction (%)

Seed 5,527 4,812 715 13 Seed, Cow Manure 8,525 6,989 1,536 18 Seed, Heinz Solids 8,060 6,252 1,808 22

Seed, 1:1 Cow Manure: Heinz Solids 11,120 8,401 2,719 24 Seed, 2:1 Cow Manure: Heinz Solids 14,538 11,073 3,465 24 Seed, 1:2 Cow Manure: Heinz Solids 10,048 7,517 2,531 25



Final TSS (mg)


Destruction (%)

Seed 3,965 2,405 1,560 39 Seed, Cow Manure 5,135 4,485 650 13 Seed, Heinz Solids 3,770 2,990 780 21

Seed, 1:1 Cow Manure: Heinz Solids 6,500 4,680 1,820 28 Seed, 2:1 Cow Manure: Heinz Solids 8,905 6,045 2,860 32 Seed, 1:2 Cow Manure: Heinz Solids 5,655 4,485 1,170 21



Final VSS (mg)


Destruction (%)

Seed 2,860 1,495 1,365 48 Seed, Cow Manure 3,445 2,860 585 17 Seed, Heinz Solids 3,380 2,665 715 21

Seed, 1:1 Cow Manure: Heinz Solids 6,045 2,860 3,185 53

Seed, 2:1 Cow Manure: Heinz Solids 5,915 4,420 1,495 25

Seed, 1:2 Cow Manure: Heinz Solids 3,965 3,770 195 5

152





Seed 235 268 33 Seed, Cow Manure 323 259 -64 Seed, Heinz Solids 231 269 38

Seed, 1:1 Cow Manure: Heinz Solids 306 382 76 Seed, 2:1 Cow Manure: Heinz Solids 423 533 110 Seed, 1:2 Cow Manure: Heinz Solids 276 317 41




Seed 0 Seed, Cow Manure 1,200 Seed, Heinz Solids 400

Seed, 1:1 Cow Manure: Heinz Solids 2,600 Seed, 2:1 Cow Manure: Heinz Solids 3,600 Seed, 1:2 Cow Manure: Heinz Solids 1,400


153


Phase 3

24. MSU Dairy Cheese Whey East Lansing, MI

DRAFT


Date Sample Collected: February 25, 2009 Date Assay Conducted: July 31 – , 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems


Michigan State University

154

MSU Principal Investigator: Steven Safferman ([email protected], 517‐432‐0812)


155

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of cheese whey collected from MSU Dairy. The sample was collected by Louis Faivor, Michigan State University in June 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Cheese Whey Used in Lab* 5.00 66,045 49,292 71,500


Flask Seed (mL)

Manure(mL)

Cheese Whey (mL)

D.I. Water(mL)

Seed (24.1 Seed) 208 0 0


Seed, Cheese Whey (24.3 Seed, Cheese Whey) 208 0 46 396

Seed, 1:1 Cow Manure: Cheese Whey (24.4 Seed, 1:1 MSU Manure: Cheese Whey) 208 46 46 350





156




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 5,818 2,210 3,549 Seed, Cow Manure 9,742 2,746 6,277

Seed, Cheese Whey 10,554 5,411 7,555 Seed, 1:1 Cow Manure: Cheese

Whey 13,796 5,785 8,206

Seed, 2:1 Cow Manure: Cheese Whey 13,479 6,663 9,375




157



158


159



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)


Seed, Cheese Whey Seed, 1:1 Cow Manure: Cheese Whey Seed, 2:1 Cow Manure: Cheese Whey Seed, 1:2 Cow Manure: Cheese Whey Seed, 5:1 Cow Manure: Cheese Whey Seed, 8:1 Cow Manure: Cheese Whey



160

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Cheese Whey 7.63 4,400 16,238 8,288 16,878 9,400 11,623 8,000 391 Seed, 1:1 Cow Manure: Cheese Whey 7.59 4,500 21,225 8,850 18,292 10,000 12,625 7,300 441 Seed, 2:1 Cow Manure: Cheese Whey 7.59 4,550 20,738 10,2,25 21,063 11,700 14,423 7,200 503 Seed, 1:2 Cow Manure: Cheese Whey 7.67 3,800 16,788 7,475 17,567 9,000 11,772 6,300 383 Seed, 5:1 Cow Manure: Cheese Whey 7.43 6,450 33,963 16,000 33,608 18,100 20,705 12,000 919 Seed, 8:1 Cow Manure: Cheese Whey 7.36 8,650 44,425 19,038 39,270 23,000 24,857 15,200 1,061


Flask pH

Alk

alin

ity

(mg/

LC

aCO

3)C

OD

(m

g/L)

So

lubl

e C

OD

(m

g/L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s(m

g/L)

Vola

tile

Solid

s (m

g/L)

Susp

ende

d So

lids

Am

mon

ia

(mg/

L N

)


Seed, Cheese Whey Seed, 1:1 Cow Manure: Cheese Whey Seed, 2:1 Cow Manure: Cheese Whey Seed, 1:2 Cow Manure: Cheese Whey Seed, 5:1 Cow Manure: Cheese Whey Seed, 8:1 Cow Manure: Cheese Whey

pH Change During Digestion Flask Initial pH Final pH pH Change Seed 7.95

Seed, Cow Manure 7.81 Seed, Cheese Whey 7.63

Seed, 1:1 Cow Manure: Cheese Whey 7.59 Seed, 2:1 Cow Manure: Cheese Whey 7.59 Seed, 1:2 Cow Manure: Cheese Whey 7.67 Seed, 5:1 Cow Manure: Cheese Whey 7.43 Seed, 8:1 Cow Manure: Cheese Whey 7.36

161






Seed, Cheese Whey 2,860 Seed, 1:1 Cow Manure: Cheese Whey 2,925 Seed, 2:1 Cow Manure: Cheese Whey 2,958 Seed, 1:2 Cow Manure: Cheese Whey 2,470 Seed, 5:1 Cow Manure: Cheese Whey 4,193 Seed, 8:1 Cow Manure: Cheese Whey 5,623



Final TS (mg)

TS Destruction (mg)

Destruction (%)





Final TSS (mg)


Destruction (%)




Flask Initial VSS (mg) Final VSS (mg) VSS Destruction

(mg) Destruction

(%) Seed 3,055

Seed, Cow Manure 4,680 Seed, Cheese Whey 5,200

Seed, 1:1 Cow Manure: Cheese Whey 4,745 Seed, 2:1 Cow Manure: Cheese Whey 4,680 Seed, 1:2 Cow Manure: Cheese Whey 4,095 Seed, 5:1 Cow Manure: Cheese Whey 7,800 Seed, 8:1 Cow Manure: Cheese Whey 9,880

162






Seed, Cheese Whey 254 Seed, 1:1 Cow Manure: Cheese Whey 287 Seed, 2:1 Cow Manure: Cheese Whey 327 Seed, 1:2 Cow Manure: Cheese Whey 249 Seed, 5:1 Cow Manure: Cheese Whey 597 Seed, 8:1 Cow Manure: Cheese Whey 690





Seed, Cheese Whey 600 Seed, 1:1 Cow Manure: Cheese Whey 1200 Seed, 2:1 Cow Manure: Cheese Whey 2500 Seed, 1:2 Cow Manure: Cheese Whey 1200 Seed, 5:1 Cow Manure: Cheese Whey 2000 Seed, 8:1 Cow Manure: Cheese Whey 2600


163


Phase 3

25. Smeltzers Orchard: Cherry Waste Stream Frankfort, MI

Submitted to Sali Group

Date Sample Collected: January 26, 2009 Date Assay Conducted: May 18 – June 12, 2009 Funding: Michigan Department of Energy, Labor & Economic Growth, Bureau of Energy Systems




164

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of cherry processing waste collected from Smeltzer Orchards of Frankfort, MI. The sample was collected by Jim Garber, on April 15, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Smeltzer Cherry Processing Waste* 4.24 6,982 6,442 11,850 * Data for the above parameters was collected on the original submitted sample.


Flask Seed (mL)

Manure(mL)

Smeltzer (mL)

D.I. Water(mL)

Seed (25.1 Seed) 107 0 0 543


Seed, Smeltzer (25.3 Seed, Smeltzer) 107 0 176 367

Seed, 1:1 Cow Manure: Smeltzer (25.4 Seed, 1:1 MSU Manure: Smeltzer) 107 111 176 192



Digestion Analysis Each flask was analyzed before and after digestion. Table 3 shows the pre and post digestion amount of COD, soluble COD, and volatile solids (VS). The amount of each constituent destroyed and the percent reduction is also shown in Table 3. Initial and final concentrations of all measured constituents including pH, alkalinity, total suspended solids, volatile suspended solids, and ammonia are provided in the Appendix. Tables of mass changes of constituents not

165




Vessel In

itial

(mg)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Seed 3,518 3,445 73 2 2,389 2,527 -138 -6 2,383 2,277 106 4Seed, Cow Manure 11,684 8,775 2,909 25 7,020 5,289 1,731 25 7,501 5,782 1,719 23

Seed, Smeltzer 6,118 5,411 707 12 3,218 3,039 179 6 3,002 2,913 89 3Seed, 1:1 Cow

Manure: Smeltzer 14,300 13,423 877 6 8,174 7,605 569 7 8,237 6,652 185 19

Seed, 2:1 Cow Manure: Smeltzer 20,727 17,534 3,193 15 12,496 12,919 -423 -3 12,459 11,317 1,142 9

Seed, 1:2 Cow Manure: Smeltzer 10,351 10,189 162 2 5,915 6,143 -228 -4 5,945 5,165 780 13


166



167



Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)


Seed, Smeltzer 128 -5 707 0.18 89 1.44Seed, 1:1 Cow Manure: Smeltzer 935 -972 877 1.07 185 5.05Seed, 2:1 Cow Manure: Smeltzer 670 NA 3,193 0.21 1,142 0.59Seed, 1:2 Cow Manure: Smeltzer 165 NA 162 1.02 780 0.21 **Calculated using the Seed and Seed, Cow Manure flasks. Note: Can only be used for flasks where the seed and cow manure volumes are the same.


pH of Smeltzer was relatively low (pH 3.7). After mixing with seed, pH was adequate at the beginning and end of digestion. Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix).

The percentage of methane in the biogas (Figure 3) was relative low across all treatments. As shown in Table 4, after normalized as mL biogas per g of substrate volatile solid (VS) destructed, Co-digestion of cow manure and Smeltzer at 1:1 ratio had the greatest biogas yield. However, co-digestion of cow manure and Smeltzer at 1:2 or 2:1 ratio did not produce more biogas compared with digestion of cow manure and Smeltzer separately. From the assay, it is projected that there is likely advantage to mixing this specific cow manure and liquid industrial waste at 1:1 ratio if the objective is energy production.

168

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Smeltzer 7.41 2,300 7,413 5,025 7,030 2,500 4,618 1,400 276Seed, 1:1 Cow Manure: Smeltzer 7.25 4,950 22,000 12,563 19,305 10,900 12,672 7,800 658Seed, 2:1 Cow Manure: Smeltzer 7.19 8,000 31,888 19,213 29,527 20,300 13,168 13,600 1,048Seed, 1:2 Cow Manure: Smeltzer 7.29 3,500 15,925 9,113 13,792 5,500 9,147 4,300 471


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Smeltzer 6.30 2,100 8,325 4,675 6,878 10,200 4,482 7,100 248Seed, 1:1 Cow Manure: Smeltzer 7.05 5,300 20,650 11,700 16,210 13,700 10,233 10,900 768Seed, 2:1 Cow Manure: Smeltzer 6.87 8,000 26,975 19,875 26,872 3,100 17,410 1,900 1,278Seed, 1:2 Cow Manure: Smeltzer 6.55 3,600 15,675 9,450 12,045 7,400 7,947 4,800 474


Seed, Cow Manure 7.50 7.61 0.11 Seed, Smeltzer 7.41 6.30 -0.11

Seed, 1:1 Cow Manure: Smeltzer 7.25 7.05 -0.20 Seed, 2:1 Cow Manure: Smeltzer 7.19 6.87 -0.32 Seed, 1:2 Cow Manure: Smeltzer 7.29 6.55 -0.74

169





Seed 1560 1787.5 227.5 Seed, Cow Manure 3510 4095 585

Seed, Smeltzer 1495 1365 -130 Seed, 1:1 Cow Manure: Smeltzer 3218 3445 227 Seed, 2:1 Cow Manure: Smeltzer 5200 5200 0 Seed, 1:2 Cow Manure: Smeltzer 2275 2340 65



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Smeltzer 4,570 4,471 99 2 Seed, 1:1 Cow Manure: Smeltzer 12,548 10,537 2,011 16 Seed, 2:1 Cow Manure: Smeltzer 19,192 17,467 1,725 9 Seed, 1:2 Cow Manure: Smeltzer 8,965 7,829 1,136 13



Final TSS (mg)


Destruction (%)

Seed 1,625 2,015 -390 -24 Seed, Cow Manure 7,670 4,810 2,860 37

Seed, Smeltzer 1,625 1,950 -325 -2 Seed, 1:1 Cow Manure: Smeltzer 7,085 6,045 1,040 15 Seed, 2:1 Cow Manure: Smeltzer 13,195 10,660 2,535 19 Seed, 1:2 Cow Manure: Smeltzer 3,575 4,810 -1,235 -35



Final VSS (mg)


Destruction (%)

Seed 910 1,235 -325 -36 Seed, Cow Manure 4,745 3,120 1,625 34

Seed, Smeltzer 910 1,560 -650 -71 Seed, 1:1 Cow Manure:

Smeltzer 5,070 4,225 845 17

Seed, 2:1 Cow Manure: Smeltzer 8,840 7,085 1,755 20

Seed, 1:2 Cow Manure: Smeltzer 2,795 2,990 -195 -7

170






Seed, Smeltzer 180 161 19 Seed, 1:1 Cow Manure: Smeltzer 427 499 72 Seed, 2:1 Cow Manure: Smeltzer 681 830 149 Seed, 1:2 Cow Manure: Smeltzer 306 308 2





Seed, Smeltzer 820 Seed, 1:1 Cow Manure: Smeltzer 2,600 Seed, 2:1 Cow Manure: Smeltzer 3,800 Seed, 1:2 Cow Manure: Smeltzer 100 *Non-sufficient gas production for H2S analysis **Conducted once during gas production by collecting gas in a 300 mL gas sampling bag. Concentrations were measured by Gastech sampling method. These numbers are not meant to represent precise or definite H2S concentrations, but to serve as a general indicator.

171


Phase 3

26. Swanson Pickle Company Inc Ravenna, MI

Submitted to Sali Group





172

Goal This assay determined the anaerobic biodegradability and biogas recovery potential of pickle brine wastewater collected from Swanson Pickle Company Inc. The sample was collected by Mike Winchester, Sali Group, on June 1, 2009. Procedure and Respirometer Design General details on the procedure and all analyses are in the document “Anaerobic Digester Feasibility Protocol for Fruit and Vegetable Processing Waste,” which can be found at the following website: www.egr.msu.edu/~safferma/Research/Greeen/Deliverables/Anaerobic%20Digester%20Protocol.pdf The volume of each constituent used in this assay was based on its initial chemical oxygen demand (COD) so that an adequate amount of biogas is produced to negate the impacts of the ambient gas in the 75 mL of flask headspace and to maximize differences between test conditions. Further, waste was blended with inoculated seed at a volatile solids ratio of approximately 2:1, inoculum to waste, selected based on the standard for biochemical methane potential assays presented by Chynoweth et al., 1993, "Biochemical Methane Potential of Biomass and Waste Feedstocks." Biomass & Bioenergy 5(1): 95-111. Substrate Characterization The substrate sample was characterized upon arrival as shown in Table 1. These parameters were used to design the assay (Table 2).



VS (mg/L)

COD (mg/L)

Swanson Pickle Used in Lab* 3.17 105,577 51,907 17,488 * Data for the above parameters was collected the sample provided.


Flask Seed (mL)

Manure(mL)

Swanson Pickle (mL)

D.I. Water(mL)

Seed (26.1 Seed) 394 0 0 256


Seed, Swanson Pickle (26.3 Seed, Swanson Pickle) 394 0 82 174

Seed, 1:1 Cow Manure: Swanson Pickle (26.4 Seed, 1:1 MSU Manure: Swanson Pickle) 394 82 82 92

Seed, 2:1 Cow Manure: Swanson Pickle (26.5 Seed, 2:1 MSU Manure: Swanson Pickle) 394 164 82 10


173



Vessel

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion

Initi

al (m

g)

Fina

l (m

g)

Des

troy

ed (m

g)

% R

educ

tion


Seed, Swanson Pickle 14,406 11,806 2,600 18 4,241 4,103 138 3 10,457 9,056 1,401 13Seed, 1:1 Cow Manure:

Swanson Pickle 17,152 15,600 1,552 9 5,574 4,542 1,032 19 11,414 10,587 827 7

Seed, 2:1 Cow Manure: Swanson Pickle 22,401 17,753 4,648 21 6,451 5,233 1,218 19 14,260 12,381 1,879 13


174




175


Vess

el

Tota

l Gas

Pro

duce

d (m

L)

Nor

mal

ized

Gas

Pro

duce

d (m

L)*

CO

D D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

CO

D D

estr

oyed

(mg)

Vola

tile

Solid

s D

estr

oyed

(mg)

Tota

l Gas

Pro

duce

d (m

L)/

Vola

tile

Solid

s D

estr

oyed

(mg)

Seed 944 NA 3,730 0.25 1,631 0.58Seed, Cow Manure 1,448 NA 4,055 0.36 1,230 1.18

Seed, Swanson Pickle 1,114 170 2,600 0.43 1,401 0.80Seed, 1:1 Cow Manure: Swanson Pickle 782 -666 1,552 0.50 827 0.95Seed, 2:1 Cow Manure: Swanson Pickle 911 NA 4,648 0.20 1,879 0.48



pH of Swanson pickle was relatively low (pH 3). After mixing with seed, pH was adequate at the beginning and end of digestion. Ammonia varied between treatments; however, no effect of ammonia on cumulative biogas yield was observed (Table 4 and Appendix). The percentage of methane in the biogas (Figure 3) from cow manure mixed with Swanson pickle at 1:1 ratio was relatively low (average less than 40%). Digestion of cow manure alone had greatest biogas production (1,180 mL/g VS destroyed). Co-digestion of cow manure with Swanson pickle at 1:1 ratio (950 mL/g VS destroyed) and 2:1 ratio (480 mL/g VS destroyed) did not produce more biogas compared with digestion of cow manure alone. From the assay, it is projected that there is no significant advantage to mixing this specific cow manure and Swanson pickle if the objective is energy production.

176

Appendix


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Swanson Pickle 7.48 9,050 22,163 6,513 32,545 16,600 16,088 10,300 1,080Seed, 1:1 Cow Manure: Swanson

Pickle 7.41 10,450 26,388 8,625 35,378 15,400 17,560 9,500 1,235Seed, 2:1 Cow Manure: Swanson

Pickle 7.41 11,800 34,463 9,938 42,118 21,300 21,938 15,300 1,685


Flask pH

Alk

alin

ity

(mg/

L C

aCO

3)

CO

D

(mg/

L)

Solu

ble

CO

D

(mg/

L)

Tota

l Sol

ids

(mg/

L)

Tota

l Sus

pend

ed

Solid

s (m

g/L)

Vola

tile

Solid

s (m

g/L)

Vo

latil

e Su

spen

ded

Solid

s (m

g/L)

A

mm

onia

(m

g/L

N)


Seed, Swanson Pickle 7.50 8,750 18,163 6,313 29,345 10,100 13,932 7,100 891Seed, 1:1 Cow Manure: Swanson

Pickle 7.30 9,600 24,000 6,988 32,798 11,200 16,288 7,000 1,179Seed, 2:1 Cow Manure: Swanson

Pickle 7.64 11,400 27,313 8,050 37,528 14,900 19,048 10,600 1,490


Seed, Cow Manure 7.87 7.71 -.16 Seed, Swanson Pickle 7.48 7.50 .02

Seed, 1:1 Cow Manure: Swanson Pickle 7.41 7.30 -.11 Seed, 2:1 Cow Manure: Swanson Pickle 7.41 7.64 .23

177





Seed 5,460 5265 -195 Seed, Cow Manure 6,143 5948 -195

Seed, Swanson Pickle 5,883 5688 -195 Seed, 1:1 Cow Manure: Swanson Pickle 6,793 6240 -553 Seed, 2:1 Cow Manure: Swanson Pickle 7,670 7410 -260



Final TS (mg)

TS Destruction (mg)

Destruction (%)


Seed, Swanson Pickle 21,154 19,074 2,080 10 Seed, 1:1 Cow Manure: Swanson Pickle 22,996 21,319 1,677 7 Seed, 2:1 Cow Manure: Swanson Pickle 27,377 24,393 2,984 11



Final TSS (mg)


Destruction (%)


Seed, Swanson Pickle 10,790 6,565 4,225 39 Seed, 1:1 Cow Manure: Swanson Pickle 10,010 7,280 2,730 27 Seed, 2:1 Cow Manure: Swanson Pickle 13,845 9,685 4,160 30



Final VSS (mg)

VSS Destruction

(mg) Destruction

(%)


Seed, Swanson Pickle 6,695 4,615 2,080 31 Seed, 1:1 Cow Manure: Swanson

Pickle 6,175 4,550 1,625 26

Seed, 2:1 Cow Manure: Swanson Pickle 9,945 6,890 3,055 31

178





Seed 646 547 -99 Seed, Cow Manure 763 659 -104

Seed, Swanson Pickle 702 579 -123 Seed, 1:1 Cow Manure: Swanson Pickle 803 766 -37 Seed, 2:1 Cow Manure: Swanson Pickle 1,095 969 -126





Seed, Swanson Pickle 1600 Seed, 1:1 Cow Manure: Swanson Pickle 1900 Seed, 2:1 Cow Manure: Swanson Pickle 1900


Documents

Waste Biomass Bioassay Project - Michigan · 2016-02-25 · 1 Waste Biomass Anaerobic Digestion Biogas Potential in Support of Renewable Energy Development Project PLA-09-34 Final