Advantages and Limitations with using Various Substrates in Manure Biogas Plants

Anna Crolla1, Chris Duke2, Chris Kinsley1 and Terrence Sauv2

1 2

Ontario Rural Wastewater Center at University of Guelph Campus dAlfred Ontario Ministry of Agriculture, Food and Rural Affairs

4th Annual Canadian Farm & Food Biogas Conference and Exhibition London Convention Center, London, ON March 5 7, 2012

Co-digestion of Manure
Addition of co-substrates to manure improves nutrient balance of carbon, nitrogen and phosphorus Manure dilutes high strength wastes Dairy manure has good buffering capacity with alkalinity as high as 9000 mg CaCO3/L Organic rich substrates improve methane yields Europe: A lot of interest in energy crops (e.g. grass, clover, cereals, corn) Ontario: Focus in using wastes (e.g. waste grease, stillage, food leftovers)
Mean Biogas Yields of Substrates (m
0 200 400 255 385 290 546 675 638 514 375 300 575 500 600 550 450 775 1000 600
3 gas /t

VSsubstrate )
1000 1200

800

Cow manure (9%TS) Pig manure (7%TS) Chicken manure (15%TS) Corn (whole Crop)* Wheat (grain)* Grass* Sugar beets* Harvest residues (straw, stems) Sewage sludge Expired animal feed Food Industry Waste Stillage from breweries Green wastes (markets) Biowastes (source separated) Flotation sludge/animal fat Waste fat

[Compilation of data from Braun et al. (2009), Braun and Wellinger (2003) and Weiland (2000)]

Sources of Possible Substrates

Compounds
Carbohydrates: Sugars Starch Cellulose Proteins

Sources
beets, corn, fruit potatoes, corn straw, grass, wood animals & animal products animals & animal products

Possible Inhibition
pH drop

pH drop ammonia increase VFA increase pH drop

Fats

Volatile Fatty Acids (VFA)

fats, oils, grease (FOG) pH drop inhibition of some bacteria

Parameters for Stable Digestion

Substrates will affect these values

pH Alkalinity IA/TA C:N:P C:N Ammonium (NH4+-N) VS/TS

6.8 to 7.2 1500 to 4000 mg CaCO3/L 0.1 to 0.2 (<0.4) 100 to 120:5:1 20 to 30:1 <1500 mg/L >45%

IA/TA = intermediate alkalinity to total alkalinity ratio (volatile acid-to-alkalinity ratio)

Sources: Sakar et al., 2009; US EPA, 2004; Gerardi (2003); Burke (2001)

Testing of Substrates
Substrate Characterization pH Alkalinity tCOD, sCOD VS, TS (VS/TS) VFAs (acetic, propionic, butyric) Ammonium Nitrogen (NH4+-N) C:N Digester Stability pH* IA/TA (at start of changing OLRs)* VFAs (at start of changing OLRs) Biogas production and composition

Important parameters to monitor pH monitoring alone may prove to be unreliable

VFA Analysis at ORWC Laboratory

BMP & ATA Batch Tests

500 mL Wheaton bottles Incubators for temperature control and agitation (120 rpm) Manometer for gas volume Acclimatized inoculum from on-farm manure digester Incubated for >30 days Biochemical Methane Potential (BMP)
Indication of biodegradability of substrate to produce CH4
Mesophilic Incubator Thermophilic Incubator Manometer

Anaerobic Toxicity Assay (ATA)

Determines substrate inhibition on CH4 production

Semi-Continuous Bench-scale Digesters

30 L bench-scale digesters (20 L operating volume) Intermittent mixing Housed in heat room (35 2oC) Biogas volume measured using wet tip meters CH4 and CO2 composition determined using gas chromatograph Typically run for several months

Characteristics of Cellulosic Substrates

Parameter pH Alkalinity, mg CaCO3/kg TS, g/kg VS, g/kg VS/TS, % tCOD, g/kg sCOD, g/kg C:N TN, g/kg TP, g/kg Liquid Dairy Manure 7.35 (0.17) 7564 (223) 78 (20) 57 (19) 73 74.6 (14.1) 8.9 (3.5) 22:1 (3) 4.1 (0.7) 0.6 (0.1) Corn Silage 7.22 111 900 851 95 ----27:1 11.9 1.7 Switchgrass 6.99 130 922 869 94 ----24:1 9.8 1.2 Woodchips 7.73 120 470 450 96 ----500:1 2.1 0.4

Corn Silage

Switchgrass

Woodchips

Co-digestion of Dairy Manure with Switchgrass or Corn Silage

Manure Co-digestion with Switchgrass and Corn Silage (Co-substrates contribute 20% (w/w) of feed VS)
0.60
30 days of Digestion

Cumulative Biogas Yield (L biogas/g VS)

0.50

0.40

0.30

0.20

0.10

0.00 0 200 400 600 800 1000 1200 1400

Duration of Digestion (hours)

Dairy Manure + Switchgrass

Dairy Manure + Corn Silage

Dairy Manure

Substrates Manure + Switchgrass Manure + Corn Silage Dairy Manure

Biogas Production (L biogas/g feed) 0.06 0.05 0.04

Biogas Yield (L biogas/g VS) 0.49 0.45 0.38

Co-digestion of Dairy Manure with Switchgrass or Corn Silage

Manure Co-digestion with Switchgrass and Corn Silage (Co-substrates contribute 40% (w/w) of feed VS)
0.60
30 days of Digestion Cumulative Biogas Yield (L biogas/g VS)

0.50

0.40

0.30

0.20

0.10

0.00 0 200 400 600 800 1000 1200 1400

Duration of Digestion (hours)

Dairy Manure + Switchgrass

Dairy Manure + Corn Silage

Dairy Manure (12% TS)

Substrates Manure + Switchgrass Manure + Corn Silage Dairy Manure

Biogas Production (L biogas/g feed) 0.07 0.06 0.04

Biogas Yield (L biogas/g VS) 0.52 0.51 0.38

Co-digestion of Horse Manure with Woodchips

Co-digestion of Horse Manure with Woodchips
0.70 Cumulative Biogas Yield (L biogas/g VS)
30 days of Digestion

0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 500 1000 1500 Duration of Digestion (hours) 2000 2500 3000

Woodchips - 25% of Feed VS Woodchips - 75% of Feed VS

Woodchips - 50% of Feed VS Horse Manure - 100% of Feed VS

Substrates Woodchips 25% of Feed VS Woodchips 50% of Feed VS Woodchips 75% of Feed VS Horse Manure

Biogas Production (L biogas/g feed) 0.14 0.13 0.10 0.15

Biogas Yield (L biogas/g VS) 0.51 0.39 0.23 0.64

Study in Collaboration with H. H. Angus & Associates Ltd.

Characteristics of Fat Based Substrates

Parameter pH Alkalinity, mg CaCO3/kg TS, g/kg VS, g/kg VS/TS, % tCOD, g/kg sCOD, g/kg C:N TKN, g/kg Ammonium (NH4+-N), g/kg TP, g/kg Horse & Giraffe Manure Liquid Dairy Manure 7.35 (0.17) 7564 (223) 78 (20) 57 (19) 73 74.6 (14.1) 8.9 (3.5) 22:1 (3) 3.9 (0.9) 1.9 (0.7) 0.6 (0.1) DAF Horse & Giraffe Manure 8.33 5489 408 263 65 ----32:1 3.3 --0.6 DAF 5.87 7073 172 147 85 102.1 38.3 37:1 2.7 0.8 0.3 Grease Waste Grease Waste 3.99 0 468 461 99 207 74.5 34:1 6.1 0.9 0.4

Co-digestion of Dairy and Poultry Manure Mix with DAF

Co-digestion of Dairy and Poultry Manure Mix (14%TS) with DAF
1.20 30 days of Digestion

Cumulative Biogas Yield (L biogas/g VS)

1.00

0.80

0.60

0.40

0.20

0.00 0 200 400 600 800 1000 1200 1400 1600

Duration of Digestion (hours) DAF - 20% of Feed VS DAF - 48% of Feed VS DAF - 30% of Feed VS Manure (Dairy + Poultry)

Substrates DAF 20% of Feed VS DAF 30% of Feed VS DAF 48% of Feed VS Dairy & Poultry Manure Mix

Biogas Production (L biogas/g feed) 0.08 0.10 0.10 0.09

Biogas Yield (L biogas/g VS) 0.74 0.83 0.98 0.62

Co-digestion of Horse and Giraffe Manure Mix with Waste Grease

Co-digestion of Horse & Giraffe Manure Mixture with Waste Grease
1.20
30 days of Digestion

1.00

Biogas Yield (L biogas/g VS)

0.80

0.60

0.40

0.20

0.00 0 200 400 600 800 1000 1200 1400 1600 1800

Duration of Digestion (hours)

Grease - 30% of Feed VS Grease - 80% of Feed VS Grease - 58% of Feed VS Manure - 100% of Feed VS

Waste grease as 70% of feed VS may be more realistic

Substrates Grease 30% of Feed VS Grease 58% of Feed VS Grease 80% of Feed VS Horse & Giraffe Manure Mix

Biogas Production (L biogas/g feed) 0.28 0.37 0.41 0.16

Biogas Yield (L biogas/g VS) 0.92 1.07 1.03 0.61

Study in Collaboration with H. H. Angus & Associates Ltd.

Characteristics of Food Wastes

Parameter pH Alkalinity, mg CaCO3/kg TS, g/kg VS, g/kg VS/TS, % tCOD, g/kg sCOD, g/kg C:N TKN, g/kg Ammonium (NH4+-N), g/kg TP, g/kg Horse & Giraffe Manure Liquid Dairy Manure 7.35 (0.17) 7564 (223) 78 (20) 57 (19) 73 74.6 (14.1) 8.9 (3.5) 22:1 (3) 3.9 (0.9) 1.9 (0.7) 0.6 (0.1) Horse & Giraffe Manure 8.33 5489 408 263 65 ----32:1 3.3 --0.6 Food Waste (ORRS) 5.69 5942 196 191 97 95.3 27.1 36:1 2.6 1.2 0.4 Fish Offal 6.86 7620 349 300 86 218 46 19:1 12.1 5.9 1.0

ORRS Organic Resources Recovery System (form Organic Resource Management Inc.)

Food Waste

Fish Offal

Co-digestion of Dairy Manure and Food Waste

Co-digestion of Dairy Manure with Food Waste (ORRS)
0.60

Cumulative Biogas (L biogas/g VS)

0.50

0.40

0.30

0.20

0.10

0.00 0 100 200 300 400 500 600 700 800 900

Duration of Digestion (hours)

Food Waste - 35% of Feed VS Food Waste - 55% of Feed VS

Food Waste - 45% of Feed VS Dairy Manure - 100% of Feed VS

Substrates Food Waste 35% of Feed VS Food Waste 45% of Feed VS Food Waste 55% of Feed VS Dairy Manure

Biogas Production (L biogas/g feed) 0.02 0.03 0.03 0.01

Biogas Yield (L biogas/g VS) 0.41 0.45 0.49 0.26

Study in Collaboration with Organic Resources Management Inc.

Co-digestion of Horse and Giraffe Manure Mix with Food Waste

Co-digestion of Horse & Giraffe Manure Mixture with Food Waste
1.00
30 days of Digestion

Cumulative Biogas Yield (L biogas/g VS)

0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 200 400 600 800 1000 1200 1400 1600 1800

Duration of Digestion

Food Waste - 35% of Feed VS Food Waste - 82% of Feed VS

Food Waste - 62% of Feed VS Manure - 100% of Feed VS

Substrates Food Waste 35% of Feed VS Food Waste 62% of Feed VS Food Waste 82% of Feed VS Horse & Giraffe Manure

Biogas Production (L biogas/g feed) 0.18 0.19 0.18 0.16

Biogas Yield (L biogas/g VS) 0.77 0.90 0.91 0.61

Study in Collaboration with H. H. Angus & Associates Ltd.

Co-digestion of Fish Offal with Sawdust

Co-digestion of Fish Offal with Sawdust
1.00

Cumulative Biogas Yield (L biogas/g VS)

30 days of Digestion

0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 200 400 600 800 1000 1200 1400 1600 1800

Duration of Digestion (hours) Fish Offal - 25% of Feed VS Fish Offal - 88% of Feed VS Fish Offal - 50% of Feed VS Fish Offal - 100% of Feed VS Fish Offal - 75% of Feed VS

Substrates Fish Offal 25% of Feed VS Fish Offal 50% of Feed VS Fish Offal 75% of Feed VS Fish Offal 88% of Feed VS Fish Offal

Biogas Production (L biogas/g feed) 0.10 0.20 0.30 0.29 0.35

Biogas Yield (L biogas/g VS) 0.36 0.57 0.71 0.76 0.89

Study in Collaboration with Meeker Aquaculture Inc.

Industrial Wastes
Characteristics of Thin Stillage
Parameter pH Alkalinity, mg CaCO3/kg TS, g/kg VS, g/kg VS/TS, % tCOD, g/kg sCOD, g/kg C:N TKN, g/kg Ammonium (NH4+-N), g/kg Total Phosphorus, g/kg Liquid Dairy Manure Liquid Dairy Manure 7.35 (0.17) 7564 (223) 78 (20) 57 (19) 73 74.6 (14.1) 8.9 (3.5) 22:1 (3) 3.9 (0.9) 1.9 (0.7) 0.6 (0.1) Corn Thin Stillage Thin Stillage 3.64 0 85 67 79 141.4 63.6 39:1 2.1 0.8 1.1

Co-digestion of Dairy Manure with Corn Thin Stillage

Co-digestion of Dairy Manure with Thin Stillage
0.6

Cumulative Biogas Yield (L biogas/g VS)

0.5

0.4

0.3

0.2

0.1

0 0 100 200 300 400 500 600 700 800 900 1000

Duration of Digestion (hours) Stillage - 20% of Feed VS Stillage - 60% of Feed VS Stillage - 40% of Feed VS Dairy Manure - 100% of Feed VS

Substrates Thin Stillage 20% of Feed VS Thin Stillage 40% of Feed VS Thin Stillage 60% of Feed VS Dairy Manure

Biogas Production (L biogas/g feed) 0.02 0.03

Biogas Yield (L biogas/g VS) 0.43 0.56

Complete Inhibition 0.02 0.32

Biogas

Co-digestion of Dairy Manure with Corn Thin Stillage (Two-Stage Digestion System)
2.5

Single Stage
2.0

Two-Stage

Biogas Acid Production

Biogas Production, m 3/m 3/day

1.5

1.0

0.5

0.0 0 500 1000 1500 2000 2500 3000 3500 4000 4500 Duration of Digestion, hours

Two Phase Digestion (Dairy Manure & Stillage) Single Phase Digestion (Dairy Manure & Stillage)

Methane Production

Thin stillage is 50% of feed VS Two stage system will be used to push digestion to 70% stillage as feed VS

Impact of Rumensin on Biogas Production

Impact of Rumensin in Biogas Production
Cumulative Biogas Yield (L biogas/g VS) 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0 500 1000 Duration of Digestion, hours
Dairy Manure (No Rumensin) Beef Manure (With Rumensin) Dairy Manure (No Rumensin) + Beef Manure (With Rumensin) [50% w/w]

Rumensin fed at 29 ppm

1500 2000

Substrates Dairy Manure (No Rumensin) Beef Manure (With Rumensin) Dairy Manure (No Rumensin) + Beef Manure (with Rumensin)

Biogas Production (L biogas/g feed) 0.02 0.02 0.02

Biogas Yield (L biogas/g VS) 0.30 0.38 0.28

Toxicity assays (ATA) are currently being conducted

Summary
Good co-substrates available Need to characterize co-substrates to evaluate potential in digester performance Batch lab studies are useful to determine optimum addition of co-substrates to digestion Need to monitor digester performance to detect for possible digester upset

Managing and Diagnosing Digester Start Up

Digester start-up phase is critical and can take 2 to 10 months
Increasing temperature takes external heat Incoming substrates are cold Biology ecology not developed Gas quality is normally better than quantity Very unstable, low gas production means limited heat, slow digestion Biological consumption Heat requirements Gas yield Parameters : temperature, gas quality, gas quantity, pH, FOS/TAC, C:N, TS, VS, VFA, eyes Variables : heat demand, mixing schedule, feeding schedule, substrates

Substrate feeding rate optimises:

Substrate feeding recipe evolves, requires management

Engine commissioning requires substantial biogas production to enable extended run-time Delayed start up delays revenue
500 kW ~ $1800/day 100 kW ~ $400/day

FOS/TAC
Acid concentration and the buffer capacity in the digester substrate: pH - measure of a liquid's acidity - neutral is 7, FOS stands for Flchtige Organische Suren (volatile organic acids) TAC stands for Totales Anorganisches Carbonat (total inorganic carbonate (alkaline buffer capacity) The FOS/TAC ratio is a guide value for assessing digestion processes. It enables detecting imminent digester biology disruptions at an early stage so that corrective actions can be taken

Example start-up
Liquid dairy, off-farm substrates are grease trap liquids 1500 m3, continuous stirred, mesophilic, heating started in September No gas flow meter Farmer working with digester firm, seeking assistance, conducting daily measurements
CH4 Concentration % 80 70 60 50 40 04-Oct 40 35 30 25 20 12-Mar Temp C

24-Oct

13-Nov

03-Dec

23-Dec Date CH4%

12-Jan

01-Feb

21-Feb

Gas analyser not calibrated

Digester T

120 Substrates m3 100 80 60 40 20 0 04-Oct 24-Oct 13-Nov 03-Dec 23-Dec Date Manure Input [m3] Off-farm Input [m3] Digester T 12-Jan 01-Feb 21-Feb

40 35 30 25 20 12-Mar Temp C

12 10 pH 8 6 4 2 0 04-Oct 24-Oct 13-Nov 03-Dec 23-Dec Date Digester pH FOS TAC FOS/TAC 12-Jan 01-Feb 21-Feb

0.8 0.6 0.4 0.2 0 12-Mar

FOS, TAC, FOS/TAC

14

Important Lessons
Digester acidification was narrowly avoided but start-up is still slow and ongoing Daily+ measurement Digestate and gas measurement equipment on-site is very useful Recipe development for start-up phase and normal Consult with biogas system firm, consultants Substrates having different digestion rates and gas yields manage accordingly Fats, high sugar substrates cause rapid responses and increase in acid levels Substrates may have inhibition effects (i.e. Rumensin) Heat demand is critical Delayed start-up means thousands of dollars delayed revenue

Acknowledgments
Funding for these projects was provided by:
OMAFRA Organic Resources Management Inc. (ORMI) H. H. Angus & Associates Ltd. Meeker Aquaculture Inc. Fisheries and Oceans Canada Iogen Corporation