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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.

M. Toufiq Reza, Mi Lu, Tianlin Song, Keenan Conrad, Sage Hiibel, Hongfei Lin ACS meeting, August

Traditional practices of manure

management need updating for contemporary dairies

of manure management need updating for contemporary dairies • Sustainable practices suitable for large, modern
of manure management need updating for contemporary dairies • Sustainable practices suitable for large, modern

Sustainable practices suitable for large, modern dairies are needed

Average dairy has herd of 100 cows (up from 20 in

• Average dairy has herd of 100 cows (up from 20 in 1970) • Numerous dairies

1970)

Numerous dairies have > 1000 cows

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)

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 distances- high costs

Over application Eutrophication

• “Nutrient management” is a headache for many dairymen

“Nutrient management” is a headache for many dairymen − Associated regulatory and compliance issues − Lagoon

Associated regulatory and compliance issues

Lagoon management is especially unwelcome

Capturing the value of manure

Fuel Manure Nutrients
Fuel
Manure
Nutrients
Capturing the value of manure Fuel Manure Nutrients Chuck Coronella Hydrothermal Carbonization of Cow Manure 5

Hydrothermal conditions

Properties of liquid water:

Hydrothermal conditions Properties of liquid water: Biomass undergoes chemical reactions: Hydrolysis Decarboxylation

Biomass undergoes chemical

reactions:

Hydrolysis

Decarboxylation

Dehydration

Deammination

etc.

Decarboxylation Dehydration Deammination etc. Figure taken from Peterson et al. Energy Environ. Sci. ,

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

Hydrothermal carbonization

Hydrothermal carbonization CO 2 High pressure reactor Heat Water, solubles Dairy manure and water Carbonized fuel
CO 2 High pressure reactor
CO 2
High pressure
reactor

Heat

Hydrothermal carbonization CO 2 High pressure reactor Heat Water, solubles Dairy manure and water Carbonized fuel

Water, solubles

CO 2 High pressure reactor Heat Water, solubles Dairy manure and water Carbonized fuel (for power
CO 2 High pressure reactor Heat Water, solubles Dairy manure and water Carbonized fuel (for power

Dairy manure and water

reactor Heat Water, solubles Dairy manure and water Carbonized fuel (for power generation or carbon

Carbonized fuel (for

power generation or

carbon sequestration)

Reaction conditions:

180 – 280 ˚C

P > P sat

(10 64 bar)

Manure products

Manure  products Dried manure  + Solid “ hydrochar ” Very hydrophobic Solid fuel for
Manure  products Dried manure  + Solid “ hydrochar ” Very hydrophobic Solid fuel for

Dried manure

Manure  products Dried manure  + Solid “ hydrochar ” Very hydrophobic Solid fuel for

+

Solid “hydrochar

Very hydrophobic

Solid fuel for on-farm power generation

” Very hydrophobic Solid fuel for on-farm power generation Water and soluble chemicals Chuck Coronella Hydrothermal

Water and soluble chemicals

Experimental methods

• T is between 180 and 260 ˚C

Reaction time 5 or 30 min

Biomass : water = 1:5

• Reaction time 5 or 30 min • Biomass : water = 1:5 100 mL Parr
• Reaction time 5 or 30 min • Biomass : water = 1:5 100 mL Parr

100 mL Parr reactor

Yield of solid char (dry basis)

100% 75% 50% 180 °C 220 °C 260 °C 25% 0% 0 10 20 30
100%
75%
50%
180
°C
220
°C
260
°C
25%
0%
0
10
20
30
40
180 °C 220 °C 260 °C 25% 0% 0 10 20 30 40 Time (min) Chuck

Time (min)

Elemental analysis of chars

100% 80% 60% 40% 20% 0% Raw 180 °C 180 °C 220 °C 220 °C
100%
80%
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
°C 260 °C 5 min 30 min 5 min 30 min 5 min 30 min S

S°C 260 °C 5 min 30 min 5 min 30 min 5 min 30 min N

N°C 260 °C 5 min 30 min 5 min 30 min 5 min 30 min S

O260 °C 5 min 30 min 5 min 30 min 5 min 30 min S N

H260 °C 5 min 30 min 5 min 30 min 5 min 30 min S N

C260 °C 5 min 30 min 5 min 30 min 5 min 30 min S N

Carbon partitioning

50% 40% 30% Gas 20% Liquid Solid 10% 0% Raw 180 °C 180 °C 220
50%
40%
30%
Gas
20%
Liquid
Solid
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
°C 260 °C 5 min 30 min 5 min 30 min 5 min 30 min Note:

Note: Carbon in gas calculated by balance

Nitrogen distribution

2.5% 2.0% 1.5% 1.0% 0.5% 0.0%
2.5%
2.0%
1.5%
1.0%
0.5%
0.0%
Nitrogen distribution 2.5% 2.0% 1.5% 1.0% 0.5% 0.0% Raw 180 °C 180 °C 220 °C 220

Raw

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

30 min

5 min

30 min

5 min

30 min

5 min

N/A°C 260 °C 260 °C 30 min 5 min 30 min 5 min 30 min 5

Liquid260 °C 260 °C 30 min 5 min 30 min 5 min 30 min 5 min

Solid260 °C 30 min 5 min 30 min 5 min 30 min 5 min N/A Liquid

Hydrochar as fertilizer

30 25 20 15 10 5 0 Raw 180 °C 180 °C 220 °C 220
30
25
20
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
kg/ton
manure 5 min 30 min 5 min 30 min 5 min 30 min kg/ton P is

P is expressed as P 2 O 5 , and K as K 2 O.

NP is expressed as P 2 O 5 , and K as K 2 O. P

PP is expressed as P 2 O 5 , and K as K 2 O. N

KP is expressed as P 2 O 5 , and K as K 2 O. N

Ash in char

30 20 180 °C 220 °C 10 260 °C 0 0 20 40 Ash content
30
20
180
°C
220 °C
10
260
°C
0
0
20
40
Ash content of hydrochar (%)

Time (min)

20 15 10 180 °C 5 220 °C 260 °C 0 0 20 40 g
20
15
10
180
°C
5
220
°C
260
°C
0
0
20
40
g ash in char per 100 g manure

Time (min)

Ash content of manure is 16.4%

per 100 g manure Time (min) Ash content of manure is 16.4% Chuck Coronella Hydrothermal Carbonization

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.

with time at all temperatures studied between 5 and 30 min. Chuck Coronella Hydrothermal Carbonization of

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

compounds Ammonia, acetamide, etc. 4. Sugars and derivatives 5. Unidentified Chuck Coronella Hydrothermal Carbonization

5. Unidentified

Aqueous product characterization

HTC Time \

Temperature

180 °C

220 °C

260 °C

Legend

5 min.

30 min.

 
 
 
 

Organic  acids Amino acids Other amines Sugars and derivatives Unidentified

acids

Amino acids  Organic acids Other amines Sugars and derivatives Unidentified

Other  Organic acids Amino acids amines Sugars and derivatives Unidentified

amines
amines
amines

amines

Sugars and  Organic acids Amino acids Other amines derivatives Unidentified

derivatives

Unidentified  Organic acids Amino acids Other amines Sugars and derivatives

amines Sugars and derivatives Unidentified Chuck Coronella Hydrothermal Carbonization of Cow Manure
Discussion • Very high production of carboxylic acids • Fewer sugars than expected • Deammination

Discussion

Very high production of carboxylic acids

Fewer sugars than expected

Deammination is taking place when T > 220 °C

Membrane distillation

MD can be used to concentrate the aqueous

products

• Produce a relatively clean “gray water” byproduct

• Produce a relatively clean “gray water” byproduct  + Chuck Coronella Hydrothermal Carbonization of Cow
• Produce a relatively clean “gray water” byproduct  + Chuck Coronella Hydrothermal Carbonization of Cow

Produce a relatively clean “gray water” byproduct  + Chuck Coronella Hydrothermal Carbonization of Cow Manure

+

Produce a relatively clean “gray water” byproduct  + Chuck Coronella Hydrothermal Carbonization of Cow Manure

Direct contact membrane

distillation

Warmer Feed Stream

(Low temperature heat)

distillation Warmer Feed Stream (Low temperature heat) Cooler Distillate Stream Hydrophobic, Microporous Membrane

Cooler Distillate Stream

Hydrophobic, Microporous Membrane (PTFE)

Distillate Stream Hydrophobic, Microporous Membrane (PTFE) Chuck Coronella Hydrothermal Carbonization of Cow Manure

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

of feed ≈ 5.9 Distillate pH decreased from 7.03 to 5.7   TOC (mg/L) TN (mg/L)
 

TOC (mg/L)

TN (mg/L)

Distillate Initial

0.05

0

Distillate Final

265.70

15.01

Feed Initial

9345

903

Feed Final

31590

3024

Rejection

99.16%

99.50%

Yield

98.92%

99.36%

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

solutions − Expect first tests with manure ~ September 1 Chuck Coronella Hydrothermal Carbonization of Cow
Acknowledgements Collaborators at UNR : Chemical engineering: Dr. Toufiq Reza, Dr. Hongfei Lin, Mi Lu,

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

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