Hydrothermal carbonization (HTC) of

cow manure: carbon and nitrogen

distribution in HTC products
Presented by Chuck Coronella, Ph.D., P.E.
With coauthors:
M. Toufiq Reza, Mi Lu, Tianlin Song, Keenan Conrad,
Sage Hiibel, Hongfei Lin

ACS meeting, August 15, 2015

Boston, Mass.

Traditional practices of manure

management need updating for
contemporary dairies

Sustainable practices suitable for large, modern

dairies are needed
Average dairy has herd of 100 cows (up from 20 in
1970)
Numerous dairies have > 1000 cows
Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Beneficial uses of manure

Cow pies have been used for fuel for centuries
Intrinsic fuel value

Macronutrients (especially nitrogen and

phosphorous)
Valuable fertilizer (when applied in the right
quantities)

Chuck Coronella

Hydrothermal Carbonization of Cow Manure

The challenge:
Modern dairies produce a lot of manure (up to 50
kg per cow per day)
More than 160 million ton/yr (dry basis) in the U.S.
Moisture > 90%

Traditional methods of spreading on fields

Large amounts must be spread over large distanceshigh costs
Over application Eutrophication

Nutrient management is a headache for many

dairymen
Associated regulatory and compliance issues
Lagoon management is especially unwelcome
Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Capturing the value of

manure
Fuel

Manure

Nutrients

Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Hydrothermal conditions
Properties of liquid water:

Biomass undergoes chemical

reactions:
Hydrolysis
Decarboxylation
Dehydration
Deammination
etc.

Figure taken from Peterson et al. Energy Environ. Sci., 2008, 1, 3265

Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Hydrothermal carbonization
CO2

Heat
Water, solubles

Dairy manure
and water

High pressure
reactor
Carbonized fuel (for
power generation or
carbon sequestration)

Reaction conditions:
180 280 C
P > Psat (10 64 bar)
Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Manure products

Dried manure

+
Solid hydrochar

Water and soluble

chemicals

Very hydrophobic
Solid fuel for on-farm
power generation
Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Experimental methods
T is between 180 and 260 C
Reaction time 5 or 30 min
Biomass : water = 1:5

100 mL Parr reactor

Chuck Coronella

Hydrothermal Carbonization of Cow Manure

Yield of solid char (dry basis)

100%

75%

180 C
220 C
260 C

50%

25%

0%
0

Chuck Coronella

10

20
Time (min)

30

40

Hydrothermal Carbonization of Cow Manure

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Elemental analysis of chars

100%
80%
S
N
O
H
C

60%
40%
20%
0%
Raw

180 C 180 C 220 C 220 C 260 C 260 C

5 min 30 min 5 min 30 min 5 min 30 min

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Hydrothermal Carbonization of Cow Manure

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Carbon partitioning
50%
40%
30%

Gas
Liquid
Solid

20%
10%
0%
Raw

180 C 180 C 220 C 220 C 260 C 260 C

5 min 30 min 5 min 30 min 5 min 30 min

Note: Carbon in gas calculated by balance

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Hydrothermal Carbonization of Cow Manure

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Nitrogen distribution
2.5%

2.0%
1.5%
N/A
Liquid
Solid

1.0%
0.5%
0.0%
Raw 180 C 180 C 220 C 220 C 260 C 260 C
5 min 30 min 5 min 30 min 5 min 30 min

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Hydrothermal Carbonization of Cow Manure

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Hydrochar as fertilizer
30

25
kg/ton

20
N
P
K

15
10
5
0
Raw 180 C 180 C 220 C 220 C 260 C 260 C
manure 5 min 30 min 5 min 30 min 5 min 30 min
P is expressed as P2O5, and K as K2O.
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Hydrothermal Carbonization of Cow Manure

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30

20

180 C
220 C
260 C

10

0
0

20
Time (min)

40

g ash in char per 100 g manure

Ash content of hydrochar (%)

Ash in char
20
15
10
180 C
220 C
260 C

5
0

20
Time (min)

40

Ash content of manure is 16.4%

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Hydrothermal Carbonization of Cow Manure

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During HTC
Organic mass is decreasing (hydrolysis,
dehydration, etc.)
Monovalent cations (e.g., K) dissolve

Polyvalent cations (e.g., P) are apparently sorbing

Mass of inorganic ash in solid char actually
increases with time at all temperatures studied
between 5 and 30 min.

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Hydrothermal Carbonization of Cow Manure

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Aqueous product characterization

GC/MS analysis: 5 broad groups.
Semi-quantitative analysis

1. Organic Acids
Propanoic acid, butanoic acid, acetic acid, etc.

2. Amino acids
l-alanine, diethylamine, leucine

3. Other nitrogen-containing compounds

Ammonia, acetamide, etc.

4. Sugars and derivatives

5. Unidentified
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Hydrothermal Carbonization of Cow Manure

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Chart Title

Aqueous product characterization

HTC Time \
Temperature

180 C 17%

220 C

260 C

Legend

1%

5 min.

Organic
acids
Amino acids

8%
0%
Organic acids

Amino acids

Sugars and derivatives Unidentified

Other amines Organic acids

Amino acids

Sugars and derivatives Unidentified

Other amines Organic acids

Amino acids

Other amines

Sugars and derivatives Unidentified

74%

30 min.

Organic acids

Amino acids

Sugars and derivatives Unidentified

Chuck Coronella

Amino acids
Other amines Organic acids
Sugars and derivatives Unidentified

Other aminesOrganic acids

Amino acids

Other
amines
Sugars and
derivatives
Unidentified

Other amines

Sugars and derivatives Unidentified

Hydrothermal Carbonization of Cow Manure

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Discussion
Very high production of carboxylic acids
Fewer sugars than expected
Deammination is taking place when T > 220 C

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Hydrothermal Carbonization of Cow Manure

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Membrane distillation
MD can be used to concentrate the aqueous
products
Produce a relatively clean gray water byproduct

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Hydrothermal Carbonization of Cow Manure

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Direct contact membrane

distillation

Warmer Feed Stream

Cooler Distillate Stream

(Low temperature heat)

Hydrophobic, Microporous Membrane (PTFE)

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MD: representative results

Sample: liquor produced at 260 C, 5 min
Feed volume reduced from 650 mL to 178 mL
pH of feed 5.9
Distillate pH decreased from 7.03 to 5.7
TOC (mg/L)
Distillate Initial

TN (mg/L)

0.05

265.70

15.01

Feed Initial

9345

903

Feed Final

31590

3024

Rejection

99.16%

99.50%

Yield

98.92%

99.36%

Distillate Final

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Remaining steps
Optimize conditions for nutrient recovery and
concentration
Couple HTC with membrane distillation
Demonstrate gasification of hydrochar pellets
Life cycle analysis
Construction of a continuous reactor

Nominal capacity of 5 gal/h ~ 0.3 lpm

Design and fabrication are complete
Currently undergoing testing with sugar solutions
Expect first tests with manure ~ September 1

Chuck Coronella

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Acknowledgements
Collaborators at UNR:
Chemical engineering:
Dr. Toufiq Reza, Dr.
Hongfei Lin, Mi Lu, Tianlin
Song, Dr. Victor Vasquez
CEE: Dr. Sage Hiibel
Cooperative extension: Jay
Davison
Undergraduate students:
Sean Sullivan, Akbar Saba,
Keenan Conrad-Williams,
Brandon Lopez

Chuck Coronella

Hydrotorr, LLC:
Dr. Reza Shekarriz

Desert Research Institute:

Dr. S. Kent Hoekman, Curt
Robbins, Dr. Vivian Liu

APL, Bear Kaufmann

Financial support from the

USDA through the
Western Sun Grant
Initiative, grant number
2010-38502-21839

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