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Processes, Biofuels, and Bioproducts Dr. Hanwu Lei's Group Bioproducts, Science, and Engineering Laboratory Department of Biological Systems Engineering, Washington State University

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Processes, Biofuels, and Bioproducts. Dr. Hanwu Lei's Group Bioproducts, Science, and Engineering Laboratory Department of Biological Systems Engineering, Washington State University. Outline. Dr. Hanwu Lei’s research group - PowerPoint PPT Presentation

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Page 1: Processes, Biofuels, and Bioproducts

Processes, Biofuels, and Bioproducts

Dr. Hanwu Lei's GroupBioproducts, Science, and Engineering Laboratory

Department of Biological Systems Engineering, Washington State University

Page 2: Processes, Biofuels, and Bioproducts

Outline

Dr. Hanwu Lei’s research group

Processes: torrefaction, pyrolysis, catalysis, liquid-liquid extraction, organosolv liquefaction, hot-water pretreatment, organosolv fractionation, CO2 removal and absorption, and fuel process kinetics

Biofuels: bio-oil, hydrocarbons, aromatics, hydrogen, bio-jet fuel, bio-gasoline, biodiesel, fuel ethanol

Chemicals: bio-phenols, bio-aromatics, bio-polyols

Bioproducts: biochar, carbon catalyst, activated carbon, carbon catalyst, carbon absorber, polyurethane foam

(PUF), water resistant wood adhesive

Page 3: Processes, Biofuels, and Bioproducts

Dr. Hanwu Lei’s Group

Post-Doc Research Associate:

Lu Wang, PhD. Working on catalysis for jet fuels

Post-MS Research Associate:

Di Yan, MS. Working on microwave pyrolysis

Gayatri Yadavalli, MS. Working on microwave pyrolysis, CO2 removal, protein extraction

 Current Graduate Students:

Lei Zhu, PhD Research Assistant, Department of Biological Systems Engineering, WSU; PhD dissertation: Development of processes and catalysts for aviation biofuels production (in progress)

Xuesong Zhang, PhD Research Assistant, Department of Biological Systems Engineering, WSU; PhD dissertation: Upgrading bio-oils from Douglas fir pellets with packed-bed catalysis over catalysts coupled with microwave-assisted pyrolysis (in progress)

Charles Shaw, PhD Research Assistant, Environmental Science, WSU, PhD thesis: Life-cycle-analysis of microwave pyrolysis of hybrid poplar for the production of biofuels and biochar (in progress)

Yupeng Liu, MS Research Assistant, Department of Biological Systems Engineering, WSU; MS thesis: Torrefaction of Douglas fir pellets and its upgrading (in progress)

Page 4: Processes, Biofuels, and Bioproducts

Graduated PhD Students (6): Yi Wei, PhD, Department of Biological Systems Engineering, WSU (Research Assistant

from Aug. 2011-Aug. 2015); PhD dissertation: Advanced upgrading of pyrolysis oil via liquid-liquid extraction and catalytically upgrading (Graduated Spring 2015)

Quan Bu, PhD, Department of Biological Systems Engineering, WSU (Research Assistant from Aug. 2010-Aug. 2013; Now Associate Professor at Jiangsu University); PhD dissertation: Catalytic microwave pyrolysis of biomass for renewable phenols and fuels (Graduated Summer 2013).

Lu Wang, PhD, Department of Biological Systems Engineering, WSU (Research Assistant from Aug. 2010-Aug. 2013; Now post-doc at Washington State University); PhD dissertation: Aromatic hydrocarbons production from catalyst assisted microwave pyrolysis of Douglas fir sawdust pellet (Graduated Summer 2013).

Shoujie Ren, PhD, Department of Biological Systems Engineering, WSU (Research Assistant from Jan. 2010-Dec. 2012; Now post-doc at University of Tennessee); PhD dissertation: Catalytic microwave torrefaction and pyrolysis of Douglas fir pellet to improve biofuel quality (Graduated Fall 2012).

Iwona Cybulska, PhD, Department of Biological and Agricultural Engineering, SDSU (Research Assistant from Jan. 2008-May. 2012; Now post-doc at Masdar Institute of Science and Technology); PhD dissertation: Pretreatment methods for lignocellulosic materials employed to produce fuel ethanol and value-added products (Graduated Spring 2012).

Rui Zhou, PhD, Department of Biological and Agricultural Engineering, SDSU (Research Assistant from Jan. 2008-Dec. 2014); PhD dissertation: Microwave pyrolysis of biomass and kinetics (Graduated Spring 2015).

Dr. Hanwu Lei’s Group

Page 5: Processes, Biofuels, and Bioproducts

Graduated MS Students (2): Gayatri Yadavalli, MS student, Environmental Engineering, WSU (Aug. 2013-Dec. 2014);

MS dissertation: activated carbon surface modification for carbon dioxide adsorption (Graduated Fall 2014)

Jing Liang, MS, Department of Biological Systems Engineering, WSU (Research Assistant from Aug. 2011-Aug. 2013; Now PhD student at University of California, Riverside); MS project title: Tech-economic analysis of microwave pyrolysis of Douglas fir pellet (Graduated Summer 2013)

Dr. Hanwu Lei’s Group

Page 6: Processes, Biofuels, and Bioproducts

Biomass Pyrolysis

Conventional Pyrolysis:

Microwave Pyrolysis:

BiomassBiomass

Size reductionrequired <1mmSize reductionrequired <1mm Drying Fast/Flash Pyrolysis Bio-oilBio-oil

Bio-gasBio-gas

Bio-charBio-char

BiomassBiomass

Size reductionNot RequiredSize reductionNot Required

Microwave Pyrolysis Bio-oilBio-oil

Bio-gasBio-gas

Bio-charBio-char

Biomass has to be driedbefore fast/flash pyrolysis

Wet biomass can be used

Page 7: Processes, Biofuels, and Bioproducts

Energy Consumed in Size Reduction

Microwave: No energy required as size not important.

Demonstrated on 4 mm pellets, 7x15mm2 wood blocks, and 1x0.6x0.6m3 stover bales (Lei et al, 2009; Moen et al., 2009; Zhao et al., 2011)

Conventional: > 1600 kJ/kg biomass for <1mm particles

Demonstrated on fluidized bed pyrolysis on particles <0.5 mm (Yi et al., 2008; Boateng et al., 2007; Luo et al., 2005)

Miao et al., 2011

Page 8: Processes, Biofuels, and Bioproducts

Microwave: No energy required before pyrolysis!

Do NOT require biomass (8-20%MC) drying before pyrolysis stage

Conventional: 2940 to 5538 kJ/kg of water

Requires biomass (8-20% MC) drying before pyrolysis Energy required to evaporate water and increase temperature of both water and biomass.

• Moreno et al., 2007; Hailer 1993; Snezhkin et al., 1997; Vanecek et al 1996; Moreno and Rios 2002; Renstrom and Berghel 2002

Energy Consumed in Drying

Page 9: Processes, Biofuels, and Bioproducts

Biomass size reduction (1mm)

1600 kJ/kg

Drying required to provide energy at 80% efficiency raising to 140°C

561.53 kJ/kg (wet)

Raising temp of dry biomass to 500°C at 90% efficiency

1116.78 kJ/ 0.92 kg (dry)

Maintaining temp and pyrolysis

Up to 3064 kJ/kg (literature)

kJ/ 0.92 kg (dry)

Total (1 kg wet biomass with 8% water content)

3278.31 kJ/kg (wet)

Biomass size reduction

0 kJ/kg

Drying and raising temp to 177°C

55.56+666.67=722.23

kJ/kg (wet)

Raising temp of dried biomass to 500°C

777.78 kJ/ 0.92 kg (dry)

Maintaining temp and pyrolysis

311.11 kJ/ 0.92 kg (dry)

Total (1 kg wet biomass with 8% water content)

1811.11 kJ/kg (wet)

Microwave pyrolysis Conventional pyrolysis

Microwave vs Conventional: Energy Comparison

Conclusion:1.Microwave pyrolysis consumes 504 kwh per ton of wet biomass2.Conventional pyrolysis estimated to consume >910 kwh per ton of wet biomass

Microwave pyrolysis does not require energy for size reduction and uses less in pyrolysis.

***Larger scale microwave pyrolysis requires less energy: University of Nottingham microwave pyrolysis pilot scale (250kg/hr) energy requirement: 230 kWh per tonne.

Page 10: Processes, Biofuels, and Bioproducts

Mass In Mass Out

Douglas fir pellets (kg)

Syngas (scf) Bio oil (kg) Bio Char (kg)

1,000 4,073 550 300

Energy In Energy Out

Douglas fir pellets

Electricity Syngas Bio oil Bio Char

Unit Btu17,621

(Btu/kg)3340

(Btu/kwh)335 (Btu/scf)

17,061 (Btu/kg)

28,435 (Btu/kg)

Sub-total Btu

17,621,000540*3340kwh=1,804,012

1,364,589 9,383,388 8,530,353

Mass / energy balances of microwave pyrolysis for Douglas fir pellets

Supply biochar for a coal-firing plant: 35% efficiency to electricity and 90% transmission efficiency to microwave pyrolysis plant =8,530,353*35%*90%=2,687,061 BTU

More than 150% electricity can be supplied from biochar firing

Bio-oil yield is about 60% based on dry Douglas fir pellets

Page 11: Processes, Biofuels, and Bioproducts

Microwave Pyrolysis

S. Ren, H. Lei*, L. Wang, Q. Bu, S. Chen, J. Wu, J. Julson, and R. Ruan. 2012. Biofuel production and kinetics analysis of microwave pyrolysis for Douglas fir sawdust pellet. Journal of Analytic and Applied Pyrolysis, 94: 163-169. doi: 10.1016/j.jaap.2011.12.004.

H. Lei*, S. Ren, L. Wang, Q. Bu, J. Julson, J. Holladay, and R. Ruan. 2011. Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production. Bioresource Technology, 102 (10) 6208-6213, doi:10.1016/j.biortech.2011.02.050

H. Lei*, S. Ren, and J. Julson. 2009. The effects of reaction temperature and time and particle size of corn stover on microwave pyrolysis. Energy and Fuels, 23, 3254-3261.

Page 12: Processes, Biofuels, and Bioproducts

Biomass Torrefaction to Torrefied Biomass

Torrefaction: 200–300 in absence of ℃

oxygen

70-90% yield torrefied biomass

Water is reduced

Hemicellulose is decomposed, cellulose

and lignin are partial decomposed

O/C ratio is decreased

Heating value is increased

Yang H. et al., Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel, 2007, 86: 1781–1788

Tumuluru J.S. et al., A review on biomass torrefaction process and product properties for energy applications. Industrial Biotechnology, 2011, 7: 384-401.

Page 13: Processes, Biofuels, and Bioproducts

Microwave Torrefaction

H. Lei* and S. Ren. 2010. Filed patent (US 61404560), Method and apparatus for biomass torrefaction and pyrolysis.

S. Ren, H. Lei*, L. Wang, Q. Bu, S. Chen, J. Wu. 2013. Thermal behavior and kinetic study for woody biomass torrefaction and torrefied biomass pyrolysis by TGA. Biosystems Engineering, 116, 4, 420-426. doi: 10.1016/j.biosystemseng.2013.10.003.

S. Ren, H. Lei*, L. Wang, Q. Bu, S. Chen, J. Wu, J. Julson, and R. Ruan. 2013. The effects of torrefaction on compositions of bio-oil and syngas from biomass pyrolysis by microwave heating. Bioresource Technology, 135, 659-994. doi: 10.1016/j.biortech.2012.06.091.

S. Ren, H. Lei*, L. Wang, Q. Bu, Y. Wei, J. Liang, Y. Liu, J. Julson, S. Chen, J. Wu, and R. Ruan. 2012. Microwave torrefaction of Douglas fir sawdust pellet. Energy & Fuels, 26, 5936-5943. doi: 10.1021/ef300633c.

shoulder

Page 14: Processes, Biofuels, and Bioproducts

Torrefied Biomass Pyrolysis

Cellulose

Lignin

Torrefied biomass

furans

Enhanced

Char + gases

+ CH4

catalysis

O-CH3 homolysis hydrogenation

+ gases + char

Phenol, 2-methoxy-4-methyl- 1,2-Benzenediol

Page 15: Processes, Biofuels, and Bioproducts

Overview Processes in Dr. Lei’s Group

Lignocellulosic biomass

Microwave pyrolysis

Torrefaction

Pyrolysis bio-oil

Char

Syngas

Activated carbon

Biofuels (i.e. gasoline, jet fuel)

Substitute of petroleum-based phenols as for chemical industry

(i.e. phenol formaldehyde resin, bio-plastics)

Catalysis/Catalytic upgradingPurification/separation

Chemical feedstocks (i.e. aromatics, phenols)

Carbon catalysts

Organosolv fractionation Hydrothermal/hot water pretreatment

Page 16: Processes, Biofuels, and Bioproducts

Aromatics

CelluloseHemicelluloses

Lignin

DF

Zeolite CatalysisZeolite assisted

demethoxylation

DehydrationDepolymerization

Catalyst assisted dehydration

Depolymerization

Fragmentation

Ethers, Alcohols, Ketones, Aldehydes

DecarboxylationDecarbonylationOligimerization

Page 17: Processes, Biofuels, and Bioproducts

Aromatics from Biomass

H. Lei* and L. Wang. 2014. Filed patent (USPTO 61938416). Aromatic hydrocarbons from lignocellulose biomass.

L. Wang, H. Lei*, Q. Bu, L. Zhu, Y. Wei, X. Zhang, Y. Liu, G. Yadavalli, J. Lee, S. Chen, and J. Tang. 2014. Aromatic hydrocarbons production from ex-situ catalysis of pyrolysis vapor over Zinc modified ZSM-5 in a packed-bed catalysis coupled with microwave pyrolysis reactor. Fuel. Under review.

L. Wang, H. Lei*, J. Lee, S. Chen, J. Tang, B. Ahring. 2013. Aromatic hydrocarbons from packed-bed catalysis coupled with microwave pyrolysis of Douglas fir sawdust pellets. RSC Advances, 34, 3, 14609 – 14615. doi: 10.1039/C3RA23104F.

Z. Du, X. Ma, Y. Li, P. Chen, Y. Liu, X. Lin, H. Lei, R. Ruan. 2013. Production of aromatic hydrocarbons by catalytic pyrolysis of microalgae with zeolites: Catalyst screening in a pyroprobe. Bioresource Technology, 139, 397-401 doi: 10.1016/j.biortech.2013.04.053

L. Wang, H. Lei*, S. Ren, Q. Bu, J. Liang, Y. Wei, Y. Liu, G. J. Lee, S. Chen, J. Tang, Q. Zhang, and R. Ruan. 2012. Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst. Journal of Analytic and Applied Pyrolysis, 98, 194-200. doi: 10.1016/j.jaap.2012.08.002.

Page 18: Processes, Biofuels, and Bioproducts

Aromatics from Waste Plastics

H2C CH A CH2

R1

H2C CH CH CH2

R1

H2C CH CH CH2

R2R2

HC CH2 n

R

HC CH2n

R

n

H2

+

n n

R2R1 +

LDPE H2C CH R

R R

H2C CH CH CH2

RR

H2

n

X. Zhang, H. Lei**, G. Yadavalli, L. Zhu, Y. Wei, Y. Liu. 2015. Gasoline-range Hydrocarbons produced from Microwave-induced Pyrolysis of Low-Density Polyethylene over ZSM-5. Fuel, 144: 33-42. doi: 10.1016/j.fuel.2014.12.013.

Page 19: Processes, Biofuels, and Bioproducts

Aromatics Aromatic hydrocarbons are the most desired products

to increase fuel octane number and decrease the tendency of engine knock and damage.

Aromatics cause elastomeric seals swell and increase the fuel density to meet the minimum requirement in jet fuels.

Jet fuels without aromatics will cause some of these elastomers to shrink, which may lead to fuel leaks.

Component (v %)

Crude oil

Fuel Oil #6

Diesel Fuel Marine (DFM)

Jet fuelsNaval

Distillate Fuels, F-76

US Gasoline

Brazil Gasoline

Kuwait Gasoline

Russia Gasoline

Saturates 58-61 21.1 12 75% 45.8-69.0 38 28.7 14.4 34.5Aromatics 33-36 78.9 88 25% 29.0-53.8 62 71.3 85.6 65.5

Data derived from NIPER Report 1989 by National Institute for Petroleum and Energy Research (NIPER-428); DFM and F-76 data derived from National Academy of Sciences.

US gas data from CA based Guided Wave, Inc.; other countries' data from Faruq et al., 2012.

Aromatics in chemical refined petroleum fuels

Page 20: Processes, Biofuels, and Bioproducts

Jet fuels

X. Zhang, H. Lei**, L. Wang, L. Zhu, Y. Wei, Y. Liu, G. Yadavalli, D Yan, J. Wu, S. Chen. 2015. Insight in the integrated catalytic processes of intact biomass for production of renewable jet fuel range paraffins and aromatics. Bioresource Technology. Under review

Project: Hydrogen saving process for cycloalkanes (naphthenes) in jet fuels from diverse Washington state forest biomasses. Joint Center for Aerospace Technology and Innovation, Joint Industry-University Research Program. (awarded 07/01/2014-06/30/2015)

Page 21: Processes, Biofuels, and Bioproducts

General near-term opportunities (power, fuel and syngas) Generally medium-term opportunities (macromolecules such as phenols (more than 95% of phenol used is derived from petroleum based benzene by cumene process)) Long-term opportunities (aromatics and other monomers)

Opportunity for Utilizing Lignin

Holladay et al., 2007

Possible lignin transformation technologies

Page 22: Processes, Biofuels, and Bioproducts

The high concentrations of bio-phenols were probably generated by the free radical reaction of O–CH homolysis where cellulose-derived volatiles and lignin-derived products function as H-donations and H acceptors, respectively.

Lignin-to-phenols Mechanism

CH3

H3C SH

CH3lignin

OHH3C

H (or lignin)

OH

OH3C

1

2

43 5

6

α

β

γ

Low temperatureIntermediate(Polyaromatics)

β-O-4 ,C-C cleavage

>400°CVolatile + Char

C + H2O CH4 + H2O CO + H2O

CO + H2

Hydrogenolysis,HDODecarboxylation, DME, DMO

Page 23: Processes, Biofuels, and Bioproducts

0

10

20

30

40

50

60

70

80

90

100

MRX DARCO-830

1240PLUS GAC830PLUS

No AC

Ch

emic

al c

om

po

siti

on

by

GC

/MS

an

alys

is(%

)

Acids

Sugars

Ketones/aldehydesGuaiacols

Phenols

Hydrocarbons

Alcohols

Furans

Ester

Others

GC/MS Analysis of Phenols Enriched Bio-oils

The phenols content of bio-oils was 74.61%, 73.88% for MRX and DARCO 830, respectively vs. 2.5% of control.

The guaiacols content was 1.5% and 0% for MRX and DARCO 830, respectively vs. 52% of control.

Page 24: Processes, Biofuels, and Bioproducts

Bio-phenols

H. Lei*, Q. Bu, S. Ren, and L. Wang. 2011. Filed patent (USPTO 61483132). Microwave Assisted Pyrolysis and Phenol Recovery.

Q. Bu, H. Lei*, L. Wang, Y. Wei, L. Zhu, L. Zhu, X. Zhang, Y. Liu, G. Yadavalli and J. Tang. 2014. Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons. Bioresource Technology. Under review

Q. Bu, H. Lei*, L. Wang, Y. Liu, J. Liang, Y. Wei, L. Zhu, and J. Tang. 2013. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts. Bioresource Technology, 142: 546-552. doi: 10.1016/j.biortech.2013.05.073.

Q. Bu, H. Lei*, A. H. Zacher, L. Wang, S. Ren, J. Liang, Y. Wei, Y. Liu, J. Tang, Q. Zhang, and R. Ruan. 2012. A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis. Bioresource Technology, 124, 470-477. doi: 10.1016/j.biortech.2012.08.089. 07.10.12

Q. Bu, H. Lei*, S. Ren, L. Wang, Q. Zhang, J. Tang, and R. Ruan. 2012. Production of phenols and biofuels by catalytic microwave pyrolysis of lignocellulosic biomass. Bioresource Technology, 108: 274-279. doi: 10.1016/j.biortech.2011.12.125.

Q. Bu, H. Lei*, S. Ren, L. Wang, J. Holladay, Q. Zhang, J. Tang, and R. Ruan. 2011. Phenol and phenolics from lignocellulosic biomass by catalytic microwave pyrolysis. Bioresource Technology, 102: 7004-7007. doi:10.1016/j.biortech.2011.04.025

OH

OCH3

R

decarbonylation

dealkylation

OH

OCH3

DMEDMOalkylation

OH OH OH OH OHR: H, CH3, CHO, C2H5

Page 25: Processes, Biofuels, and Bioproducts

Phenols

• Phenol and its derivatives are vital industrial chemical compounds found in myriad industrial products mainly produced from petroleum.

• The phenol price is $1,609-1,649/ton CFR (cost and freight) according to ICIS Pricing Report (Feb. 2014).

• Current phenol production volumes amount to 8 million tonnes per year and the phenol market is expected to grow at a compound annual growth rate of 3.9% over the next 10 years.

• The phenol and its derivatives are currently used for chemical industry, and its main applications—phenolic resins, plastics, and caprolactam—achieve costs in the region of $1,870 to $3,120 per tonne. N. Smolarski. 2012

Phenolic Resins

Page 26: Processes, Biofuels, and Bioproducts

Hydrogen and High Quality Syngas

Y. Wei, H. Lei*, Y. Liu, L. Wang, L. Zhu, X. Zhang, G. Yadavalli, B. Ahring, S. Chen. 2014. Renewable hydrogen produced from different renewable feedstocks by aqueous-phase reforming process. Journal of Sustainable Bioenergy Systems. In press.

S. Ren, H. Lei*, L. Wang, Q. Bu, S. Chen, J. Wu. 2014. Hydrocarbons and hydrogen-rich syngas production by biomass catalytic pyrolysis and bio-oil upgrading over biochar catalysts. RSC Advances, 4 (21), 10731 – 10737. doi: 10.1039/c4ra00122b.

Page 27: Processes, Biofuels, and Bioproducts

Catalysis: Zeolite Catalysts

L. Wang, H. Lei*, Q. Bu, L. Zhu, Y. Wei, X. Zhang, Y. Liu, G. Yadavalli, J. Lee, S. Chen, and J. Tang. 2014. Aromatic hydrocarbons production from ex-situ catalysis of pyrolysis vapor over Zinc modified ZSM-5 in a packed-bed catalysis coupled with microwave pyrolysis reactor. Fuel. Under review.

L. Wang, H. Lei*, J. Lee, S. Chen, J. Tang, B. Ahring. 2013. Aromatic hydrocarbons from packed-bed catalysis coupled with microwave pyrolysis of Douglas fir sawdust pellets. RSC Advances, 34, 3, 14609 – 14615. doi: 10.1039/C3RA23104F.

Z. Du, X. Ma, Y. Li, P. Chen, Y. Liu, X. Lin, H. Lei, R. Ruan. 2013. Production of aromatic hydrocarbons by catalytic pyrolysis of microalgae with zeolites: Catalyst screening in a pyroprobe. Bioresource Technology, 139, 397-401 doi: 10.1016/j.biortech.2013.04.053

L. Wang, H. Lei*, S. Ren, Q. Bu, J. Liang, Y. Wei, Y. Liu, G. J. Lee, S. Chen, J. Tang, Q. Zhang, and R. Ruan. 2012. Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst. Journal of Analytic and Applied Pyrolysis, 98, 194-200. doi: 10.1016/j.jaap.2012.08.002.

Z. Du, B. Hu, X. Ma, Y. Cheng, Y. Liu, X. Lin, Y. Wan, H. Lei, P. Chen, and R. Ruan*. 2013. Catalytic pyrolysis of microalgae and their three major components: carbohydrates, proteins, and lipids. Bioresource Technology, 130: 777–782. doi: 10.1016/j.biortech.2012.12.115

Page 28: Processes, Biofuels, and Bioproducts

Catalysis: Biochar Catalysts and Biomass Derived Carbon Catalysts

S. Ren, H. Lei**, L. Wang, Q. Bu, S. Chen, J. Wu. 2014. Hydrocarbons and hydrogen-rich syngas production by biomass catalytic pyrolysis and bio-oil upgrading over biochar catalysts. RSC Advances, 4 (21), 10731 – 10737. doi: 10.1039/c4ra00122b.

L. Zhu, H. Lei*, L. Wang, X. Zhang, Y. Wei, Y Liu, G. Yadavalli. Characterization of surface functional groups in corn stover biochar derived from microwave-assisted pyrolysis. 2014 ASABE International Meeting, Jul 13-16, 2014, Montreal, QC, Canada.

L. Zhu, H. Lei*, L. Wang, Q. Bu, Y. Wei, Y. Liu, and J. Liang. 2013. Carbon catalyst from corn stover and its application to catalytic microwave pyrolysis. American Society of Agricultural and Biological Engineers (ASABE) 2013 Annual International Meeting, 2013(3): 1854-1860. doi: http://dx.doi.org/10.13031/aim.20131594788.

L. Zhu, H. Lei*, L. Wang, Q. Bu, J. Liang, Y. Wei, Y. Liu. Catalytic Microwave Pyrolysis of Douglas Fir Pellets With Carbon Catalysts Derived From Corn Stover. 2013 AIChE Annual Meeting, San Francisco, California, November 3 – 8, 2013.

Page 29: Processes, Biofuels, and Bioproducts

Catalysis: Activated Carbon Catalysts

Q. Bu, H. Lei**, L. Wang, Y. Liu, J. Liang, Y. Wei, L. Zhu, and J. Tang. 2013. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts. Bioresource Technology, 142: 546-552. doi: 10.1016/j.biortech.2013.05.073.

Q. Bu, H. Lei**, L. Wang, Y. Liu, J. Liang, Y. Wei, L. Zhu, and J. Tang. 2013. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts. Bioresource Technology, 142: 546-552. doi: 10.1016/j.biortech.2013.05.073.

Q. Bu, H. Lei**, L. Wang, Y. Wei, L. Zhu, L. Zhu, X. Zhang, Y. Liu, G. Yadavalli and J. Tang. 2014. Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons. Bioresource Technology. Under review.

Page 30: Processes, Biofuels, and Bioproducts

CO2 Removal

Dr. Lei’s group developed a carbon which selectively removed >97 % carbon dioxide from a mixed gas stream containing methane, carbon

dioxide, carbon monoxide, nitrogen and hydrogen.

Page 31: Processes, Biofuels, and Bioproducts

Biochar for Crop Management, Herbicide Absorbents, and Control of Weeds

D. D. Malo, S. A. Clay*, T.E. Schumacher, H. J. Woodard, D. E. Clay, R. H. Gelderman, H. Lei and J. L. Julson. Interactions of biochar source/properties impacts on soil properties, c sequestration potential, and crop management. In 2010 SunGrant Annual Meeting, Reno, NV.

Dr. Lei's biochar was used by Drs. Clay and Malo for herbicide sorption studies: Clay, S.A. and D.D. Malo. 2012. The Influence of Biochar Production on Herbicide Sorption Characteristics, Herbicides - Properties, Synthesis and Control of Weeds, M. N. A. E. Hasaneen (Ed.), InTech, ISBN: 978-953-307-803-8. http://www.intechopen.com/articles/show/title/the-influence-of-biochar-production-on-herbicide-sorption-characteristics.

Page 32: Processes, Biofuels, and Bioproducts

Liquid-Liquid Extraction

Y. Wei, H. Lei*, L. Wang, L. Zhu, X. Zhang, Y. Liu, S. Chen, B. Ahring. 2014. Liquid-liquid extraction of biomass pyrolysis bio-oil. Energy and Fuels, 28(2), 1207-1212. doi: 10.1021/ef402490s.

C. Yang, B. Zhang, J. Moen, K. Hennessy, Y. Liu, X. Lin, Y. Wan, H. Lei*, P. Chen, and R. Ruan*. 2010. Fractionation and characterization of bio-oil from microwave-assisted pyrolysis of corn stover. International Journal of Agricultural and Biological Engineering, 3(3): 54-61.

Liquid-liquid extraction was used to extract the phenols and guaiacols from water phase:

Chloroform solvent has a better results than the other two solvents on liquid-liquid extraction for selecting phenols and guaiacols.

When under 1:1 solvent to water-phase ratio, using chloroform as extraction solvent, the organic concentration reached to 85% of total phenol and guaiacols compounds in water-phase of bio-oil.

Through liquid-liquid extraction, sugar and acid can be completely removed from mixture and stayed in the water phase.

Page 33: Processes, Biofuels, and Bioproducts

Organosolv Liquefaction

Bio-Polyurethane Foam (PUF) and Bio-Adhesives

L. Gao, Y. Liu, H. Lei*, H. Peng, R. Ruan*. 2010. Preparation of semirigid polyurethane foam with liquefied bamboo residues. Journal of Applied Polymer Science, 116, 1694-1699.

Y. Wang, J. Wu, Y. Wan, H. Lei*, F. Yu, P. Chen, X. Lin, and R. Ruan*. 2009. Liquefaction of corn stover using industrial biodiesel glycerol. International Journal of Agricultural and Biological Engineering, 2(2): 32-40. 

Polyurethane foam Adhesive

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Hydrothermal/Hot Water Pretreatment

I. Cybulska, G. Brudecki, H. Lei*. 2013. Hydrothermal pretreatment of lignocellulosic biomass. In Green Biomass Pretreatment and Processing Methods for Bioenergy Production. Ed. T. Gu. Springer. ISBN: 978-94-007-6052-3. pp 87-106. doi: 10.1007/978-94-007-6052-3_4.

I. Cybulska, G. Brudecki, H. Lei*, J. Julson. 2012. Optimization of combined clean fractionation and hydrothermal post-treatment of prairie cord grass. Energy & Fuels, 26(4): 2303-2309. doi: 10.1021/ef300249m

I. Cybulska, H. Lei*, J. Julson. 2010. Hydrothermal pretreatment and enzymatic hydrolysis of prairie cord grass. Energy & Fuels, 24 (1): 718-727.

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Organosolv Fractionation/Separation of Biomass:

I. Cybulska*, G. P. Brudecki, B. R. Hankerson, J. L. Julson, H. Lei. 2013. Catalyzed modified clean fractionation of switchgrass. Bioresource Technology, 127, 92-99. doi: 10.1016/j.biortech.2012.09.131. 03.08.12

I. Cybulska*, G. Brudecki, K. Rosentrater, J. Julson, H. Lei. 2012. Comparative study of organosolv lignins extracted from prairie cordgrass, switchgrass and corn stover. Bioresource Technology, 118C: 30-36. doi: 10.1016/j.biortech.2012.05.073.

I. Cybulska*, G. Brudecki, K. Rosentrater, H. Lei, J. Julson. 2012. Catalyzed modified clean fractionation of prairie cordgrass integrated with hydrothermal post-treatment. Biomass and Bioenergy, 46, 389-401. doi: 10.1016/j.biombioe.2012.08.002.

I. Cybulska, H. Lei*, J. Julson, G. Brudecki. 2012. Optimization of Modified Clean Fractionation of Prairie Cord Grass. International Journal of Agricultural and Biological Engineering, 5(2): 42-51. doi: 10.3965/j.ijabe.20120502.00?

Organic phase

Aqueous phase

Lignin precipitated

Organic phase

Aqueous phase

Cellulose after clean fractionation

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Canola Oil/Protein Extraction

Pressing

Solvent extraction/

Expeller pressing

K. Zhong (PI), H. Lei (Co-PI), L. Scudiero, T. Marsh, P. Tozer, Applying Abundant Plants to Develop Battery Materials and Study the Benefits on Agricultural Economy. USDA,

$494,805, 12/11/2014-12/31/2017

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Fuel Process Kinetics

S. Ren, H. Lei*, L. Wang, Q. Bu, S. Chen, J. Wu. 2013. Thermal behavior and kinetic study for woody biomass torrefaction and torrefied biomass pyrolysis by TGA. Biosystems Engineering, 116, 4, 420-426. doi: 10.1016/j.biosystemseng.2013.10.003.

H. Lei*, I. Cybulska, J. Julson. 2013. Hydrothermal pretreatment of lignocellulosic biomass and kinetics. Journal of Sustainable Bioenergy Systems, 3(4): 250-259. doi: 10.4236/jsbs.2013.34034.

R. Zhou, H. Lei*, J. Julson. 2013. Reaction temperature and time and particle size on switchgrass microwave pyrolysis and reaction kinetics. International Journal of Agricultural and Biological Engineering, 6(1): 53-61. dio: 10.3965/j.ijabe.20130601.005.

R. Zhou, H. Lei*, J. Julson. 2013. The Effects of pyrolytic conditions on microwave pyrolysis of prairie cordgrass and kinetics. Journal of Analytic and Applied Pyrolysis, 101, 172-176. doi: 10.1016/j.jaap.2013.01.013.

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Acknowledgements My research group members: Dr. Quan Bu, Dr. Iwona Cybulska, Dr. Shoujie Ren, Dr.

Lu Wang, Dr. Yi Wei, Dr. Rui Zhou, and Ms. Jing Liang, Mr. Yupeng Liu, Ms. Gayatri Yadavalli, Ms. Di Yan, Mr. Xuesong Zhang, Mr. Lei Zhu, Mr. Charles Shaw

Collaborators: Dr. John Holladay, Dr. Rick Orth, Mr. Doug Elliott, Mr. Alan Zacher, Dr. Ayman Karim, Dr. John Lee, Dr. James Julson, Dr. Katie Zhong, Dr. Roger Ruan, Dr. Gary Fulcher, and many others.

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Thank you!

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