pyrolysis of biosolids to biochar -...
TRANSCRIPT
Pyrolysis of Biosolids to Biochar
Dr. Patrick McNamara
Assistant ProfessorDept. of Civil, Construction & Environmental Engineering
Marquette University
Resource Recovery SeminarWednesday, November 14, 2018
Biomass• Wood
• Switchgrass
• Biosolids
Py-gas (5-30%)
Bio-oil (20-50%)
Biochar (~50%)
H2, CO, CH4
Pyrolysis: Heating Without Oxygen
~500°C
Benefits of Biosolids Pyrolysis
Micropollutant Removal
Micropollutant
Adsorption
Nutrient Adsorption
Agricultural Application
Energy Recovery
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Why Pyrolysis for Milwaukee
Metropolitan Sewerage District
(MMSD)?
From MMSD’s 2035 vision
•Meet a net 100% of MMSD's energy needs with renewable energy sources
•Meet 80% of MMSD's energy needs with internal, renewable sources
•Reduce MMSD's carbon footprint by 90% from its 2005 baseline
MMSD Solids Flow Process
Anaerobic Digested
Primary Solids
Drying,
Pelletizing
Soil
Amendment
Land
Application
Waste Activated
Sludge
MMSD Solids Flow Process
Anaerobic Digested
Primary Solids
Drying,
Pelletizing
Soil
Amendment
Land
Application
Waste Activated
Sludge
Pyrolysis
Biochar
Py-Gas (CH4, CO, H2)
Bio-OilEnergy Recovery
Benefits of Biosolids Pyrolysis
Biosolids
Pyrolysis
Energy Recovery
Research Questions
1. What are product yields for pyrolysis of Milorganite?
2. Can this process recover energy for your water resource recovery facility?
Lab-Scale Pyrolysis
Biosolids
(~100 g)
Furnace
Pyrolysis Reactor
(1.6 L)
Gas Sampling Bag
(Py-gas)
Bio-Oil in Ice Bath
(Condensate)
Char and Bio-Oil Yields by Weight
Gas Analysis by GC-TCD
Identify the major (>1%) py-gas products
• Hydrogen [H2]
• Methane [CH4]
• Carbon Monoxide [CO]
• Ethane [C2H4]
• Propane [C3H8]
• Isobutane [C4H10]
• N-butane [C4H10]
• Carbon Dioxide [CO2]
Impact of Temperature on Yields
0
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300 400 500 600 700 800 900
Mass Y
ield
Fra
cti
on
Temp (°C)
Char
Py-Oil
Py-Gas
Impact of Temp on Product Yields
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
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300 400 500 600 700 800 900
Mass Y
ield
Fra
cti
on
Temp (°C)
Char
Impact of Temp on Product Yields
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H.., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
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300 400 500 600 700 800 900
Mass Y
ield
Fra
cti
on
Temp (°C)
Char
Py-Oil
Impact of Temp on Product Yields
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H.., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
Bio-Oil
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300 400 500 600 700 800 900
Mass Y
ield
Fra
cti
on
Temp (°C)
Char
Py-Oil
Py-Gas
↑ Temperature : ↑ Py-gas, ↑ Bio-oil, ↓Char
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H.., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
Bio-Oil
Energy Balance Results:
Pyrolysis Recovers Energy from
Milorganite
Energy in Products (assuming 100% energy recovery) > Energy Required for Pyrolysis
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
Pyrolyzing dewatered biosolids at 95% solids
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
Energy Required Energy Content
kJ/k
g-b
iosolid
s
Pyrolysis Drying Py-gas Bio-Oil
What if you have wet biosolids?
Drying is Energy IntensiveDewatered Biosolids at 20% Solids
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H.., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
Energy Required Energy Content
kJ/k
g-b
iosolid
s
Pyrolysis Drying Py-gas Bio-Oil
Drying is Energy IntensiveDewatered Biosolids at 20% Solids
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H.., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
Energy Required Energy Content
kJ/k
g-b
iosolid
s
Pyrolysis Drying Py-gas Bio-Oil
Energy in Products (assuming 70% energy recovery) < Energy Required for Pyrolysis & Drying
McNamara, P.J., Koch, J.D., Liu, Z., Zitomer, D.H.., 2016. Pyrolysis of Dried Biosolids Can Be Energy Positive.
Wat. Env. Res. 88 (9), 804-810
Pyrolyzing dewatered biosolids at 20% solids
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
Energy Required Energy Content
kJ/k
g-b
iosolid
s
Pyrolysis Drying Py-gas Bio-Oil
Pyrolysis could be used to offset some drying energy costs
Benefits of Biosolids Pyrolysis
Biosolids
Pyrolysis
Energy Recovery
Benefits of Biosolids Pyrolysis
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Bio-oil is difficult to handle
Properties of bio-oil:
1. Acidic
2. High oxygen content
3. Corrosive
4. Thermally unstable
Oil is corrosive & py-gas more readily used…
Can we convert bio-oil to py-gas?
?
Lab-scale Catalytic Pyrolysis SystemCatalytic Tubular Reactor
Pyrolysis Reactor
1. Reactor vessel
2. Radiative heater
3. Gas purge, release
and vacuum system
4. Thermocouple and
pressure gauge
5. Tubular reactor
6. Radiative heater
7. Condensers
8. Chiller and ice bath
9. Connector for Tedlar®
bag
10. PID controller
11. Flowmeter
12. Gas tank
Mobile Lab-scale
Pyrolysis System
Metals in biochar will provide catalytic activity to crack bio-oil into py-gas
Hypothesis
•Determine the catalytic impact on the product yield distribution
(i.e. mass fraction)
•Determine the catalytic impact on the product properties
(e.g. composition, optical property)
•Determine the catalytic impact on the product energy distribution
Research Objectives
No Major Catalytic Impacts at 500 or 600ºC
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
No Major Catalytic Impacts at 500 or 600ºC
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Major Catalytic Impacts at 700 and 800ºC
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Major Catalytic Impacts at 700 and 800ºC
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Py-Gas Increased, Bio-oil Decreases:
Does Bio-oil quality improve?
Optical Property Change of Bio-oil Product
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Catalyst
No Catalyst
Product energy distribution per mass of biosolids pyrolyzed
Product energy = Yield × Higher Heating ValueLiu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Product energy distribution per mass of biosolids pyrolyzed
Product energy = Yield × Higher Heating ValueLiu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
What is the mechanism for biosolids as a catalyst?
Prominent Metal Content in Biosolids
0
2
4
6
8
10
12
Ca Fe Mg P
Meta
l C
onte
nt
(% D
ry W
eig
ht)
Biosolids
Grains
Calcium and Iron Improve Catalysis
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Calcium and Iron Improve Catalysis
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
Calcium and Iron Improve Catalysis
Liu, Z., McNamara, P., Zitomer, D. 2017. Autocatalytic pyrolysis of wastewater biosolids for product upgrading. Environmental
Science & Technology, 51 (17), 9808–9816.
What about other biomass sources for catalysts?
How do wastewater biosolids compare?
A: Corn stover
B: Dried distillers grains
with solubles
F: Pinewood residue
L: Cow manure
P: Paper mill sludge
W: Wastewater biosolids
Most of these industrial
wastes have annual
production of millions
dry tons in the United
States
Industrial Waste Candidates for Biochar Catalyst Precursors
Product Distribution
0Q: Control test
A: Corn stover
B: Dried distillers grains with solubles
F: Pinewood residue
L: Cow manure
P: Paper mill sludge
W: Wastewater biosolids
0Q: Control test
A: Corn stover
B: Dried distillers grains
with solubles
F: Pinewood residue
L: Cow manure
P: Paper mill sludge
W: Wastewater biosolids
Optical Property Change of Bio-oil Products (800℃)
0Q: Control test A: Corn stover
B: Dried distillers grains with solubles F: Pinewood residue
L: Cow manure P: Paper mill sludge W: Wastewater biosolids
How does this process scale up?
Bench Scale, Sub-Pilot Scale, Pilot Scale
0.1 kg (per batch test)
Bench Scale, Sub-Pilot Scale, Pilot Scale
0.5 kg/hr
Sub-Pilot > Bench
Liu, Z., Singer, S., Zitomer, D., McNamara, P. 2018. Sub-pilot-scale autocatalytic pyrolysis of wastewater biosolids for enhanced
energy recovery. Catalysts, 8 (11), pp. 11.
Bench Scale, Sub-Pilot Scale, Pilot Scale
68 kg/hr
Catalysis works in pilot-scale too
Benefits of Biosolids Pyrolysis
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Benefits of Biosolids Pyrolysis
Nutrient Adsorption
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Benefits of Biosolids Pyrolysis
Nutrient Adsorption
Agricultural Application
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Biochar as a Beneficial Soil Amendment
• Improved moisture holding capacity
•Carbon sequestration
•Adsorb ammonia from belt filter press filtrate
$13 a jar
Biochar as a Beneficial Soil Amendment
Carey D.E., McNamara, P.J., Zitomer, D.H. 2015. Biochar from Pyrolysis of Biosolids for Nutrient
Adsorption and Turfgrass Cultivation. Wat. Env. Res. 87 (12), 2098-2105.
Biochar as a Beneficial Soil Amendment
Benefits of Biosolids Pyrolysis
Nutrient Adsorption
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Benefits of Biosolids Pyrolysis
Nutrient Adsorption
Agricultural Application
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Benefits of Biosolids Pyrolysis
Micropollutant Removal Nutrient Adsorption
Agricultural Application
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Pyrolysis removes micropollutants from biosolids
BD: Below Detection Limit
Pyrolysis removes micropollutants from biosolids
Ross J.J., Zitomer, D.H., Miller, T.R., Weirich, C.A., McNamara, P.J. 2016. Emerging investigators series: pyrolysis
removes common microconstituents triclocarban, triclosan, and nonylphenol from biosolids. Environ. Sci.: Water
Res. Technol (2) 282-289.
BD: Below Detection Limit
Pyrolysis removes micropollutants from biosolids
Hoffman TC., Zitomer, D.J. McNamara, P.J. 2016. Pyrolysis of wastewater biosolids significantly reduces
estrogenicity. J. Haz. Mat. 317, 579-584
Ross J.J., Zitomer, D.H., Miller, T.R., Weirich, C.A., McNamara, P.J. 2016. Emerging investigators series: pyrolysis
removes common microconstituents triclocarban, triclosan, and nonylphenol from biosolids. Environ. Sci.: Water
Res. Technol (2) 282-289.
Pyrolysis removes micropollutants from biosolids
Kimbell, L., Kappell, A., McNamara, P. 2018. Effect of pyrolysis on the removal of antibiotic
resistance genes and class 1 integrons from municipal biosolids. Environmental Science: Water
Research & Technology, 4, 1807-1818.
Stripes indicate below detection limit
Benefits of Biosolids Pyrolysis
Micropollutant Removal Nutrient Adsorption
Agricultural Application
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Benefits of Biosolids Pyrolysis
Micropollutant Removal
Micropollutant
Adsorption
Nutrient Adsorption
Agricultural Application
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Removal of Micropollutants from Wastewater Using Biochar as an Adsorbent
Removal of Micropollutants from Wastewater Using Biochar as an Adsorbent
Tong YT, Mayer, BK., McNamara, PJ. 2016. Triclosan adsorption using wastewater biosolids-derived biochar.
Environ. Sci.: Water Res. Technol 2 (4), 761-768
Benefits of Biosolids Pyrolysis
Micropollutant Removal
Micropollutant
Adsorption
Nutrient Adsorption
Agricultural Application
Enhanced energy
recovery via catalysis
Biosolids
Pyrolysis
Energy Recovery
Big Picture
Conventional Solids Treatment System
NEWAGE System
(Nutrient, Energy, Water for Agriculture and Green Environment)
NEWAGE System
(Nutrient, Energy, Water for Agriculture and Green Environment)
Marquette pilot-scale
pyrolysis system
Interested in Collaborations?
Patrick McNamara, PhD
Assistant Professor
Civil, Construction & Environmental
Engineering
Marquette University | P.O. Box 1881
Milwaukee, Wisconsin 53201-1881
Phone: 414-288-2188
Acknowledgements
Faculty
Dr. Daniel Zitomer
Dr. Zhongzhe Liu
Dr. Simcha Singer
Dr. Jon Koch
Collaborators
Mr. Matt Magruder(Milwaukee Metropolitan Sewerage District)
Mike Dollopf & other WQC
colleagues
Graduate Students
John Ross
Thomas Hoffman
Yiran Tong
Erik Anderson
Daniel Carey
Lee Kimbell
Undergraduate Students
John Kissel
Mark Wendtland
Hui Liu
Matthew Hughes
Questions?
0%
20%
40%
60%
80%
100%
Triclosan Triclocarban Nonylphenol Estradiol
Recovery
Sand
Tubing
Impingers
Greater Triclosan and Nonylphenol Recovery
Triclocarban Products
Dechlorinated Triclocarban Found
Standard
Impinger
Dechlorinated Triclocarban Found
Standard
Impinger
Ross et al., 2016. Emerging investigators series: pyrolysis removes common microconstituents triclocarban,
triclosan, and nonylphenol from biosolids. Environ. Sci.: Water Res. Technol (2) 282-289.
Dechlorinated Triclocarban Found
Standard
Impinger
Pyrolysis can transform micropollutants
Ross et al., 2016. Emerging investigators series: pyrolysis removes common microconstituents triclocarban,
triclosan, and nonylphenol from biosolids. Environ. Sci.: Water Res. Technol (2) 282-289.
Impact of Temperature on Gas Composition and Energy Content
↑ Temperature : ↑ HHV
y = 33.418x - 7815.2R² = 0.8145
0
2,000
4,000
6,000
8,000
10,000
0
5,000
10,000
15,000
20,000
25,000
300 400 500 600 700 800 900
BT
U/l
b g
as
HH
V (
KJ
/kg
-gas)
Temperature (°C)
Biogas
Impact of T on Gas Energy Content
Energy Costs of Pyrolysis
Energy
In
800°C 40C/min ramp
Energy lost during pyrolysis
(sensible, latent heat loss)
Energy Cost
(Heat of
Pyrolysis)
Energy
Out Py-Oil, HV
Py-Gas, HV
Heat of Pyrolysis
Energy
In
Energy
Out
10C/min ramp 40C/min ramp
Heat of Pyrolysis
Energy
In
Energy
Out
Energy
Cost
Surface Area and Ultimate Analysis
Milorganite Biochar ActivatedBiochar
Zeolite Peat
Surface Area (m2/g)
- 10 19 15 -
C (%) 36.0 31.6 30.5 - 44.4
H (%) 5.6 2.1 2.7 - 5.9
N (%) 6.3 5.2 4.9 - 0.9
S (%) 0.8 0.9 0.7 - 0.1
SolubleSample Salts NH4-N NO3-N Total C Total N
ID pH dS/m (ppm) (ppm) (%) (%) C/N
1. Millorginite 6.3 3.2 590 2.1 34 7.0 5
2. Millorginite Biochar 6.8 0.47 33 0.78 32 6.4 5
3. Millorginite Activated Biochar 8.0 0.92 13 0.70 33 6.4 5
5. Peat 5.3 0.06 11 19 44 0.8 55
Sample P K Ca Mg Fe NaID ppm ppm ppm ppm ppm ppm
1. Milorganite 200 800 470 240 52 4002. Milorganite Biochar 6.1 640 460 22 37 160
3. Milorganite Activated Biochar 8.9 600 34 27 5.3 9705. Peat 1.6 3.5 46 19 16 10.00
Nutrient Value