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ACCESSION NO: 0418201 SUBFILE: CRIS 

PROJ NO: 6435-41000-089-00D AGENCY: ARS 6435 

PROJ TYPE: USDA INHOUSE PROJ STATUS: TERMINATED 

START: 29 OCT 2009 TERM: 28 OCT 2014 FY: 2013

INVESTIGATOR: KLASSON K T; UCHIMIYA S M; LIMA I M

PERFORMING INSTITUTION:

Agricultural Research Service, Southern Regional Research Ctr 

1100 Robert E. Lee Blvd. 

New Orleans, LOUISIANA 70124-4305

THERMOCHEMICAL PROCESSING OF AGRICULTURAL WASTES TO VALUE-ADDED

PRODUCTS AND BIOENERGY

OBJECTIVES: The research objectives are to develop slow pyrolysis (or torrefaction) and activation

processes to convert agricultural feedstock (crop residues, manures, processing wastes, and

biorefinery by-products) into: (1) chars that can be used as industrial adsorbents; (2) chars that can be

used as soil amendments which improve soil quality, water quality, and sequester carbon; (3) chars

that can be used as energy sources (in combustion or gasification); and (4) bio-gas and bio-oil coproducts that provide some of the heat and power requirements of the pyrolysis/torrefaction/activation

operations and possibly excess heat/power for sale.

APPROACH: The approach will be to take agricultural feedstocks (crop residues, animal manure, and

biorefinery waste) and heat them under different gas atmospheres to a set temperature. In order to

create chars for target applications, the temperature, heating time, and gas atmosphere will be varied,

as well as performing pretreatment (before heating) or post treatment of the chars to obtain desired

properties. The products will be tested for target applications in our laboratories and also with

collaborators with expertise in ammonia adsorption, soil amendments, bio-oil production, and largescale pyrolysis.

PROGRESS: 2009/10 TO 2014/10

Progress Report Objectives (from AD-416): The research objectives are to develop slow pyrolysis (or

torrefaction) and activation processes to convert agricultural feedstock (crop residues, manures,

processing wastes, and biorefinery by-products) into: (1) chars that can be used as industrial

adsorbents; (2) chars that can be used as soil amendments which improve soil quality, water quality,

and sequester carbon; (3) chars that can be used as energy sources (in combustion or gasification);

and (4) bio-gas and bio-oil co-products that provide some of the heat and power requirements of the

pyrolysis/torrefaction/activation operations and possibly excess heat/power for sale. Approach (from

AD-416): The approach will be to take agricultural feedstocks (crop residues, animal manure, and

biorefinery waste) and heat them under different gas atmospheres to a set temperature. In order to

create chars for target applications, the temperature, heating time, and gas atmosphere will be varied,

as well as performing pretreatment (before heating) or post treatment of the chars to obtain desired

properties. The products will be tested for target applications in our laboratories and also with

collaborators with expertise in ammonia adsorption, soil amendments, bio- oil production, and largescale pyrolysis. This is the final report for the project 6435-41000-089-00D that terminated in

September 2013. Objectives were transferred to project 6435- 41000-103-00D and will continue until a

new project plan can be developed. The project began in October 2009 and significant progress has

been made in the last four years, addressing goals of National Program 213 and 306 action plans.
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Under Objective 1, we made significant progress in designing biochars for adsorption applications.

Unactivated and steam-activated biochars (charcoal created by pyrolysis of biomass) from poultry

(chicken or turkey) manure were shown to remove elemental mercury from air and flue- gas streams.

It was shown that post-treatment washing sometimes resulted in an improvement in performance but

sometimes it was not advantageous to wash the activated chars. We also created activated biochar

from almond shells. In a pilot-scale study, this material was used to remove a chlorinated organic

contaminant from well water in San Joaquin Valley, CA. We compared collaborators biochars created

in a fast pyrolysis with our slow pyrolysis. Fast pyrolysis did not result in any significant development

of surface area. Slow pyrolysis, on the other hand, produced a noticeable surface area. Activation of

the slow pyrolysis biochars resulted in an increase in the surface area. Activated biochars performed

better than slow-pyrolysis biochars which in turn performed better than fast-pyrolysis biochars when

we studied removal of metals from water. This pattern was also true when the adsorption of phenol

was studied. Activated biochars also helps fermentation of bioethanol. We showed that fermentation

inhibitors created by weak acid pretreatment of plant materials could be removed with activated

biochar made from flax shive. Under Objective 2, we made significant progress stabilizing

contaminants found in soil and groundwater. Both un-activated and steam-activated biochars from

chicken litter significantly helped the soil stabilize toxic metals. The poultry based chars were found to

serve as an excellent source for phosphorous. Work with collaborators investigated the metal uptake

abilities of biochars made from dairy cows, swine, chicken, and turkey manure. In all biochar

amendment cases, metal concentrations were lower than in control experiments. In another study, we

investigated how the soil type impacted the sorption of several pesticides to the soil. Biochars with

greater surface area were better sorbents of the pesticides. In collaboration with Army Research

Laboratory and U.S. Department of Defense partners, we demonstrated specific bindings of lead,

copper, and zinc by carboxyl surface functional groups of biochar. Under Objective 3, we made

progress on investigating the fuel value of biochar. A literature review was conducted to determine the

up-to-date knowledge of biochar made from sugarcane bagasse for the use of fuel or co-products.

The heating value was calculated for many biochars created by slow pyrolysis at different

temperatures, from different raw materials, and for different pyrolysis times. Accomplishments 01

Activated biochars helps fermentation of bioethanol. Fermentation inhibitors created by weak acid

pretreatment of plant materials negatively affects bioethanol fermentation. ARS scientists at the

Southern Regional Research Laboratory in New Orleans, LA, and at the National Center for

Agricultural Utilization Research in Peoria, IL, showed that activated biochars made from agricultural

plant waste could be used to either remove fermentation inhibitors or reduce them to the levels that

allowed rapid fermentation. It was also shown that the biochars could be left in during fermentation

without negative effects. The benefit from this approach is reduced neutralization and separations cost

in biofuel-from-biomass approaches that involves acid pretreatment.

PUBLICATIONS (not previously reported): 2009/10 TO 2014/10

1. He, Z., Wang, J.J. 2012. Characterization of plant nutrients and traceable marker components in

dairy manure for organic dairy farming management evaluation. In: He, Z., editor. Applied Research of

Animal Manure: Challenges and Opportunities beyond the Adverse Environmental Concerns. New

York, NY:Nova Science. p. 3-19.

2. Guo, M., Shen, Y., He, Z. 2012. Poultry litter-based biochar: preparation, characterization, and

utilization. In: He, Z., editor. Applied Research of Animal Manure: Challenges and Opportunities

beyond the Adverse Environmental Concerns. New York, NY:Nova Science. p. 169-202.

3. Uchimiya, S.M., He, Z. 2012. Calorific values and combustion chemistry of animal manure. In: He,

Z., editor. Applied Research of Animal Manure: Challenges and Opportunities beyond the Adverse

Environmental Concerns. New York, NY:Nova Science. p. 45-62.

4. Miyagi, A., Uchimiya, M., Kawai-Yamada, M., Uchimiya, H. 2013. Impact of aluminum stress on

oxalate and other metabolites in Rumex obtusifolius. Weed Research. 53:(1)30-41.

5. Han, Y., Boateng, A.A., Qi, P.X., Lima, I.M., Jainmin, C. 2013. Heavy metal and phenol adsorption

properties of biochars from pyrolyzed switchgrass and woody biomass in correlation with surface

properties. Environmental Management. 118:196-204.

6. Klasson, K.T., Dien, B.S., Hector, R.E. 2013. Simultaneous detoxification, saccharification, and
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ethanol fermentation of weak-acid hydrolyzates. Industrial Crops and Products. 49:292-298.

7. Uchimiya, M., Orlov, A., Ramakrishnan, G., Sistani, K. 2013. In situ and ex situ spectroscopic

monitoring of biochar's surface functional groups. Journal of Analytical & Applied Pyrolysis. 102:53-59.

8. Uchimiya, M., Cantrell, K.B., Hunt, P.G., Novak, J.M., Chang, S. 2012. Retention of heavy metals in

a Typic Kandiudult amended with different manure-based biochars. Journal of Environmental Quality.

41:1138-1149.