Progress 01/01/11 to 12/31/15
Outputs
Target Audience: Clifford Walton , Calgoncarbon (US) Research Leader, CWalton@calgoncarbon-us.com Calgoncarbon Inc. Sustainable activated carbon for supercapacitors, water purification and chemical separation (Non disclose and Materials Transfer documents already signed, collaboration is going on) Michael Everett Chief Technical Officer Meverett@maxwell.com Maxwell Inc Sustainable super activated carbon and bio-renewable graphene for supercapacitors Albert.Bennett, Technology Manager Albert.Bennett@ICMINC.com ICM. Inc Upgrading bio-char to activated carbon Steven C. Peterson, Senior Scientist Steve.Peterson@ARS.USDA.GOV Plant Polymer Research Unit, USDA - ARS - NCAUR Activation of biochar to enhance properties as filler of polymers Jonathan Trent, Ph.D. OMEGA Project Scientist Jonathan.D.Trent@nasa.gov Bioengineering Branch NASA Ames Research Center Activated carbon from biochar of algae for water treatment (CEC removal) Wang, Yuguo, Senior Scientist yuguo.wang@aramco.com Saudi Aramco Carbon for natural gas storage and petroleum coke/pitch based advanced carbon materials Ali Manesh, Ph.D., P.E. am@amsnt.com American Science and Technology Upgrading bio-char to activated carbon Toshinori Kato R&D Manager, toshinori.kato@kuraray.com Kuraray Research & Technical Center Kuraray America, Inc. Biochar based super-AC and C-Si composite for supercapacitor and lithium batteries. Joseph Kimetu jmkimetu@ucalgary.ca University of Calgary Institute for Sustainable Energy, Environment and Economy Activated carbon from biochar for oil-sands processing water treatment Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Graduate students: Jing, H. (PhD graduated in 2014); Polin, J (MS graduated in 2013). Li, S.H. (MS graduated in 2014); Qu, W.D. (MS graduated in 2014); Wang, K.L. (PhD candidate); Cao, Y.H.(PhD candidate); Cai J.J. (PhD candidate transferred); Cheng Q.H. (PhD candidate transferred). Undergraduates: Name Training dates & Research project Current position Ms. Tatiana Rosser (African American) 2011Summer (May to July) The Adsorption and Photocatalytic Activity of Enhanced Titanium Dioxide Nanoparticles Medical school student in South Carolina Mr. David Moore 2012 Summer (May to July) Photocatalysis as remediation method to degrade antibiotics in water Research Aide at Argonne National Lab, Chicago Mr. Jacob Bassett 2013 Summer (May to July) Desorption Thermodynamics of Volatile Organic Compounds from Activated Carbon Graduate School in Fred Hutchinson Cancer Research Center Ms. Vu Han (American born Vietnamese) 2014 Summer (May to July) Recovery of Butanol from Fermentation Using Chemically Modified Activated Carbon Adsorbent Department of Chemistry, Amherst College, Amherst, MA Mr. Tyler Ambrico 2015 summer (May to July) Adsorption of creatinine on biorenewable porous carbon adsorbents Department of Chemistry, UNY (Buffalo NY) Ms. Maria Andrea Castro (Hispanic American) 2015 summer (May to July) Lignin based porous carbon materials for supercapacitor Department of Chemistry, Univ. of Iowa How have the results been disseminated to communities of interest?The results obtained in this NIFA project has been disseminated through academic conference to academica and industrial collaborators. Dr. Robert Brown (Iowa State University); Dr. Liu Jun (North Pacific National Lab.) Dr. Semual Darko (Benedict College, an HBCU). Industrial collaborators have been reported in audience section. Undergraduates students (funded through NSF-REU and other funding cources) In addition theresults has been reported by news media: http://www.azom.com/news.aspx?newsID=43241; http://newswise.com/articles/transforming-biochar-into-activated-carbon; https://landgrantimpacts.tamu.edu/impacts/article/1306 What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Overview: multiple innovative processes for upgrading biochar to advanced biorenewable carbpn materials, such as activated carbon, and grapgene, were developed. Simultaneously, applications of these advanced carbon materials in energy storage, biofuel recovery and separation and catalysts were evaluated and demonstrated. Biochar upgrading technologies: 1 Physical activation The physical activation process, using CO2, H2O, spiked bio-syngas, i.e. mixture of CO2/ CO, and spiked flue gas i.e. mixture of CO2/H2O/N2 as the activating agents, has been successfully developed for upgrading biochar (of pine wood chips, pine bark and beetle killed trees) to activated carbon. Physical activation experiments were conducted using a fixed bed reactor (FBR) and a plug flow reactor (PFR) coupled with a gas flow system for metering the activating agent. We have quantified the influence of process parameters such as temperature, reaction time, flow rates, and gas composition on yield, and properties of generated activated carbons. The response variables include burn off %, BET surface area, total pore volume, and measurements of methylene blue adsorption capacity and iodine number. The biochar based physical activated carbon materials have yield, pore characteristics, surface area, methylene blue adsorption capacity, and iodine number that are better than current commercial activated carbon materials and previously reported results. These value added carbon materials can be produced more economically using a synergistic combination of thermochemical, physical activation, and heat recovery processes. 2 Chemical Activation Several high ash biochar (15~50% ash) biocahr from different biomass (corn stover, switch grass, prairie cordgrass, big bluestem, craft lignin, DDGS, wheat straw and rice husk) after fast pyrolysis, have been converted to super-activated carbon with base (KOH, NaOH and carbonates of sodium or potassium) catalytic activation. Activation mechanism (base catalytic activation) of high ash bio-char was comprehensively investigated and understood. The activation of high ash bio-char with alkaline hydroxide and carbonates includes multiple processes: dehydration and dehydroge-nation of non-carbonized components; gasification of carbon with catalysts and derivative product; intercalation of metallic species as well as generating soluble compounds, which are templates for forming porous structure after dissolving in washing steps, through reaction among ash components with catalysts. As a result, the development of porosity in bio-char by chemical activation using alkali hydroxides and carbonates depends on several interrelated parameters: ash compositions and distribution in bio-char; initial porous structure of bio-char; type and dosage of activation catalysts; activation temperature; time; atmosphere conditions. 3 Hydrothermal activation with HNO3 or H2O2: After the hydrothermal treatment, the micropore volume increased more than 15%, which could be verified with increases in specific surface area. Compared to the original hierarchical activated carbon sample, the mesopore volume and total pore volume also increased after hydrothermal oxidization. Furthermore, after hydrothermal activation, oxygen content in the activated carbon increased significantly and most oxygen groups were allocated on the surface of activated carbon. As the result, surface hydrophilicity and wetting ability of hydrothermal activated carbon increased significantly. 4 Low temperature plasma activation of biochar: The biochar of yellow pine was successfully activated with an innovative oxygen plasma at 100~150 °C. After only 5 minutes plasma activation, surface area, pore volume and electrical conductivity of the activated biochar increased significantly. Compared to tradition high temperature activation techniques, such as physical activation, which generates activated carbon at 700~1000 °C after 1~6 hours activation, the low temperature plasma process is an innovative fast, low energy consumption biochar activation technique, which will enable activated carbon manufacturers achieve much higher productivity (90% carbon yield) with significant lower cost. This new technique will enhance competiveness of American's activated carbon producers in global market as well as significantly increase the value of biochar. 5 High value bio-renewable graphene from biochar through catalytic processes: multiple biochar, obtained from pyrolysis of different biomass, such as lignin, big-blue stem, dried distilled grain and soluble (DDGS), have been successfully converted into advanced carbon materials containing graphene-like structure. The biochar of DDGS was successfully converted to 3D nitrogen doped porous graphene with a facile catalytic thermochemical process. According to the patent pending preparation process, the cost of bio-renewable graphene (including cost of feedstock, catalysts, labor, capital, transportation and management) is expected to be less than $60/lb with wholesale price at $400/lb. The bio-renewable graphene, developed in this project will benefits current bio-renewable energy and biofuel producers with high value co-products, as well as enable development of domestic advanced energy storage device industries. Application of biochar based advanced carbon materials: 1 Electrochemical super-capacitors based on advanced bio-renewable carbon materials Biochar based advanced carbon materials, including both different activated carbons and bio-renewable graphene, can be used in place of expensive, activated graphene to coat the electrodes of energy storage devices - supercapacitors. Bio-renewable carbon materials based supercapacitors have achieved energy storage capacity comparable (e.g. with energy and power density at 80 Wh/kg and 110 KW/kg respectively) to current Li-ion batteries, also tolerate charge/discharge cycles (currently being tested to 50,000 cycles with fully charging/discharging and still maintained over 95% of the original energy storage capacity), while a typical Li ion battery would be down to 80% capacity after only 500 charge/discharge cycles. Furthermore, unlike conventional batteries, supercapacitors can withstand low temperatures. The bio-renewable advanced carbon materials preparation technology developed in this NIFA project will not only bring addition profits/incomes for biofuel producers, but also benefits "made in USA" electrical automobiles producers and domestic renewable electricity producers. Bio-renewable advanced carbon materials enable development of domestic advanced technology industries for producing next generation energy storage systems and devices, such as supercapacitors, Li-ion batteries and etc. These advanced energy storage devices will significantly promote application of hybrid-automobile, electrical-automobile, and enable integrating more renewable electricity (solar and wind power) generation systems into current and future smart grids. 2 Biochar based activated carbon as biofuel separation media in gas-stripping adsorption /desorption processes: Different activated carbon materials were developed and compared to optimize the adsorption dynamic and equilibrium for individual model chemical products (such as butanol).The thermodynamic adsorption characteristics of each activated carbon are influenced by the method of activation. Surface oxygen functional groups demonstrated significant impact on reducing butanol dynamic adsorption capacity and increased the desorption energy consumption due to formation of chemical bonds during adsorption /desorption cycles. The advanced carbon adsorbents have been developed for selectively separating biofuel, such as butanol from water. These new carbon adsorbents will also benefits current corn ethanol plants as a low energy ethanol recovery unit for reducing ethanol loss in fermentation processes.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Cao Y, Han V (undergraduate), Wang X, Gu ZR, Gibbons W, 2015, Adsorption of butanol vapor on active carbons with nitric acid hydrothermal modification, accepted by Bioresource Technology, 196, 525-532.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Cao Y, Han V (undergraduate), Wang X, Gu ZR, Gibbons W, 2015, Butanol vapor adsorption behavior on active carbons and ZSM-5 zeolite crystal, J. Applied Surface Science 349, 1-7.
- Type:
Journal Articles
Status:
Accepted
Year Published:
2015
Citation:
Wang K, Wang XM, Cao YH, Gu ZR, Q Fan; W Gibbons; T Johnson; B Luo; 2015 Pyrolytic cyanobacteria derived activated carbon as high performance electrode in symmetric supercapacitor, Energy (accepted)
|
Progress 01/01/14 to 12/31/14
Outputs
Target Audience: Industrial collaborators have been attracted by Dr. Gu’s presentation in international conferences. Name/Title Company or Institute Interests Clifford Walton , Calgoncarbon (US) Research Leader, CWalton@calgoncarbon-us.com Calgoncarbon Inc. Sustainable activated carbon for supercapacitors, water purification and chemical separation (Non disclose and Materials Transfer documents already signed, collaboration is going on) Michael Everett Chief Technical Officer Meverett@maxwell.com Maxwell Inc Sustainable super activated carbon for supercapacitors Nate Anderson, Research Forester nathanielmanderson@fs.fed.us Rocky Mountain Research Station USDA Forest Service Upgrading bio-char to activated carbon Albert.Bennett, Technology Manager Albert.Bennett@ICMINC.com ICM. Inc Upgrading bio-char to activated carbon 1. R. Gupta, H. Jin, Q.Fan, Z. Gu, Biochar Nanomaterials Activated by Oxygen Plasma for Energy Storage, Proc. 5th International Conference on Advanced Nanomaterials, 2-4 July,2014 , Aveiro, Portugal (with peer reviewed proceeding full article) 2. H. Jin, X. Wang, Z. Gu, porous carbon and its electrochemical properties as anode materials for lithium-ion batteries, 2014 ASABE and CSBE SCGAB Annual International Meeting, July 13-16, 2014, Montreal, Quebec Canada 3. J. Cai, Z. Gu, Silicon and Carbon Nanomaterials Application in Anode for Li?ion batteries. 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 4. H. Jin, Z. Gu, Graphitized Activated Carbon Based on Big Bluestem as Electrodes for Supercapacitors. 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 5. J. Polin, X. Wang, J. Bassett, Z. Gu, K. Muthukumarappan, and W. Gibbons, Recovery of Butanol and Ethanol From a Photobioreactor Using Bio-Char Based Activated Carbon As Adsorbent, 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 6. R. Gupta, H. Jin, Q.Fan, Z. Gu, High performance plasma treated biochar for supercapacitor. 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 7. Hong Jin, Zhengrong Gu and Xiaomin Wang, 2014, A Facile Method for N-Doped Graphitized Activated Carbon and the Application in Supercapacitors, AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. 8. Zhengrong Gu; Xiaomin Wang, 2014, Silicon@Carbon Nanomaterials Application in Anode for Li-Ion Batteries ? AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. 9. Rakesh Gupta, Zhengrong Gu, Qihua Fan, 2014, Comparison of Argon and Oxygen Plasma Activation of Biochar for Supercapacitors, AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. 10. ? Xiaomin Wang, Qinghui Cheng, Zhengrong Gu, 2014, Porous Graphitized Carbon Supported Catalysts for Lignin Depolymerization in Hydrothermal Conditions, AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? Ms. Vu Han (ABV)d 2014 Summer (June to Aug) Recovery of Butanol from Fermentation Using Chemically Modified Activated Carbon Adsorbent Department of Chemistry, Amherst College, Amherst, MA Mr Hong Jin PhD Biological science (2011 Aug-2014) Bio-renewable carbon materials for electrical energy storage. Received SDSU Nelson Graduate Award 2013; 6 first author journal articles, Waterloo University, Chemical Engineering, Postdcotor Mr. Ryan Bouza MS Agricultural Engineering (2012 Aug-) “Pretreatment Processes for Cellulosic Ethanol and Generation of Nano-Crystal Cellulose” Mr. Cao Yuhe PhD Biology (2013 Aug-) ”Bioseparation platform for value added products from biorefinery processes” Mr. Keliang Wang PhD Agricultural and Mechanic Engineering (2014 July-) “Bioinspired nanostructured carbon and silicon materials for advanced Li batteries” Mr. Qinghui Cheng PhD Agricultural and Mechanic Engineering (2014 Aug-) “Carbon supported Transition Metal Catalysts for lignin Hydrothermal Depolymerization” How have the results been disseminated to communities of interest? 1. R. Gupta, H. Jin, Q.Fan, Z. Gu, Biochar Nanomaterials Activated by Oxygen Plasma for Energy Storage, Proc. 5th International Conference on Advanced Nanomaterials, 2-4 July,2014 , Aveiro, Portugal (with peer reviewed proceeding full article) 2. H. Jin, X. Wang, Z. Gu, porous carbon and its electrochemical properties as anode materials for lithium-ion batteries, 2014 ASABE and CSBE SCGAB Annual International Meeting, July 13-16, 2014, Montreal, Quebec Canada 3. J. Cai, Z. Gu, Silicon and Carbon Nanomaterials Application in Anode for Li?ion batteries. 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 4. H. Jin, Z. Gu, Graphitized Activated Carbon Based on Big Bluestem as Electrodes for Supercapacitors. 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 5. J. Polin, X. Wang, J. Bassett, Z. Gu, K. Muthukumarappan, and W. Gibbons, Recovery of Butanol and Ethanol From a Photobioreactor Using Bio-Char Based Activated Carbon As Adsorbent, 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 6. R. Gupta, H. Jin, Q.Fan, Z. Gu, High performance plasma treated biochar for supercapacitor. 2014 ASABE Intersectional Meeting, Mar 28-29, 2014, Brookings SD. 7. Hong Jin, Zhengrong Gu and Xiaomin Wang, 2014, A Facile Method for N-Doped Graphitized Activated Carbon and the Application in Supercapacitors, AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. 8. Zhengrong Gu; Xiaomin Wang, 2014, Silicon@Carbon Nanomaterials Application in Anode for Li-Ion Batteries ? AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. 9. Rakesh Gupta, Zhengrong Gu, Qihua Fan, 2014, Comparison of Argon and Oxygen Plasma Activation of Biochar for Supercapacitors, AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. 10. ? Xiaomin Wang, Qinghui Cheng, Zhengrong Gu, 2014, Porous Graphitized Carbon Supported Catalysts for Lignin Depolymerization in Hydrothermal Conditions, AICHE 2014 annual meeting Nov 16-21, 2014, Atlanta GA. What do you plan to do during the next reporting period to accomplish the goals? 1) Economic evaluation of the process for producting biorenewable graphene 2) Plasma low temperature process for preparing activated graphene from biochar
Impacts
What was accomplished under these goals?
Outputs: 1 High value bio-renewable graphene from biochar through catalytic processes: After pyrolysis, the bio-oil is further processed for biofuel; biochar is generally considered a byproduct. With the current USDA funded project “2011-67009-20030” through NIFA “Value-added co-product of biofuel and bioenergy” program, an innovative process for upgrading biochar to biorenewable grapgene, was developed. Through the process developed in this project, the biochar, a charcoal like material obtained from pyrolysis of dried distilled grain and soluble (DDGS), has been successfully converted into graphene which can be used in place of expensive, activated graphene to coat the electrodes of energy storage devices – supercapacitors. The biorenewable graphene based supercapacitors has achieved energy storage capacity comparable (e.g. with energy and power density at 80 Wh/kg and 110 KW/kg respectively) to current Li-ion batteries, also tolerate charge/discharge cycles (currently being tested to 50,000 cycles with fully charging/discharging and still maintained over 95% of the original energy storage capacity), while a typical Li ion battery would be down to 80% capacity after only 500 charge/discharge cycles. Furthermore, unlike conventional batteries, supercapacitors can withstand low temperatures. When biochar of DDGS is transformed into graphene, the yield is from 70 to 90% (based on biochar, e.g. 20%~36% based on DDGS), depending on the amount of catalysts used, the temperature and the nitrogen gas flow. In the other word, a pound of DDGS costs 7.5 to 9 cents and converts to approximately 3~5.7 ounces of graphene, which currently worth at least $75 ($400/lb according to the lowest price of current industrial manufactured graphene) with processing cost (cost of catalysts, labor, capital, transportation and management) less than $10. This process can convert biochar of not only DDGS but also other biomass, such as big bluestem, into porous graphene. The process developed in this USDA funded project enable us convert agricultural and/or biofuel residue to a high-value advanced material that is easy to ship. In summary, the biorenewable graphene preparation technique will not only benefits farmers and biofuel producers with additional income, but also benefits USA’s advanced carbon materials and advanced energy storage device industries. Currently, the largest activated carbon producer, Calgon Carbon Inc and the largest supercapacitor producer, Maxwell Inc. are collaborating with Dr. Gu and SDSU’s technology transfer office for further validating this innovative technique in industrial environment. 2 Low temperature plasma activation of biochar: In the current USDA funded project “2011-67009-20030” through NIFA “Value-added co-product of biofuel and bioenergy” program, besides high temperature process, the biochar of yellow pine was successfully activated with an innovative technology, e.g. oxygen plasma at 100~150 °C. After only 5 minutes plasma activation, surface area, pore volume and electrical conductivity of the activated biochar increased significantly. Compared to tradition high temperature activation techniques, such as physical activation, which generates activated carbon at 700~1000 °C after 1~6 hours activation, plasma activation is able to generate advanced carbon materials from biochar at low temperature, with significant less energy consumption and less time (5 minutes). Therefore, the low temperature plasma process is an innovative fast, low energy consumption biochar activation technique, which will enable activated carbon manufacturers achieve much higher productivity with significant lower cost. This new technique will enhance competiveness of American’s activated carbon producers in global market as well as significantly increase the value of biochar. As a result, through combining activation methods with suitable pyrolysis processes, porous carbon materials, with tunneling structure (derivate from capillary tubes for delivering water in biomass), can be prepared from corn stover, which provide the pathways for easy accessibility of electrolytes and fast transportation of ions beyond the benefits of better sustainability and lower cost. 3 Advanced carbon adsorbents in biofuel recovery: Traditional energy intensive biofuel recovery methods, such as distillation, significantly bother development of next generation biofuel, such as cellulosic ethanol or butanol. In Dr. Gu’s laboratory, a new energy efficient biofuel recovery and purification technique, gas-stripping and adsorption/desorption is being developed in the current USDA funded project “2011-67009-20030” through NIFA “Value-added co-product of biofuel and bioenergy” program,. The advanced carbon adsorbents have been developed for selectively separating biofuel, such as butanol from water. These new carbon adsorbents will also benefits current corn ethanol plants as a low energy ethanol recovery unit for reducing ethanol loss in fermentation processes. Outcomes/Impact: Collaboration: Dr. Gu also established collaboration with Dr. Nate Anderson ( in Rocky Mountain Research Station USDA Forest Service) on “Activating biochar of beetle killed trees after fast pyrolysis” which will occur to enhance sustainability of activated carbon and improve economic viability of applying beetle killed trees. Based on research progress, new research projects was funded: Related projects: J Rice, W Gibbons, Zhengrong Gu, D Raynie, C Zhang, NSF-EPSCor $ 3,000,000 09/2013-08/2016 $340,000 awarded to Dr. Gu’s group Collaborative Research: Dakota Bioprocessing Consortium (DakotaBioCon). Biochar based graphene as catalysts’ support for improving hydrothermal converting lignin to aromatics and monomers of polymers. To establish separation platforms to generate and purify renewable aromatics from lignin with gas-stripping and adsorption/desorption (based on renewable carbon adsorbents) techniques Zhengrong Gu (PI) Q. Fan H. Bucking RB. Zhou C. Zhang NSF-MRI, $775,155; SDSU matching, $341,300; 08/2014-07/2017 MRI: Acquisition of a Transmission Electron Microscope. To establish the 1st high resolution TEM facility in eastern SD and SDSU. This instrument will be used to characterize biorenewable carbon materials and investigated the mechanism of generating 3D graphene from biochar. Sandeep Kumar, Lin Wei, K. Muthu , Zhengrong Gu (Co-PI) Sun-Grant (North Central), DOT; $ 300,000; 09/2014-08/2015 $30,000 to Dr. Gu’s group Evaluation of biomass and bioenergy production, environmental performance and life cycle analysis of Prairie Cordgrass. To develop innovative renewable carbon materials supported catalysts for producing biofuel from native grass
Publications
- Type:
Journal Articles
Status:
Accepted
Year Published:
2014
Citation:
1. H. Jin; X. Wang; Z. Gu; Q. Fan; B. Luo; 2014, A facile method for preparing Nitrogen-doped graphene and its application in supercapacitors, J. Power Source; Volume 273, 1 January 2015, Pages 11561162
- Type:
Journal Articles
Status:
Accepted
Year Published:
2014
Citation:
2. H. Jin; X. Wang; Y. Shen; Z. Gu, 2014, A high-performance carbon derived from slow pyrolysis for supercapacitors, J. Analy. Appl. Pyrolysis; Volume 110, November 2014, Pages 1823
- Type:
Journal Articles
Status:
Accepted
Year Published:
2014
Citation:
3. H. Jin; X, Wang; Z. Gu; G. Anderson; K. Muthukumarappan; 2014: Distillers Dried Grains with Soluble (DDGS) Bio-char Based Activated Carbon for Supercapacitors with Organic Electrolyte Tetraethylammonium Tetrafluoroborate, Journal of Environmental Chemical Engineering Volume 2, Issue 3, September 2014, Pages 14041409
- Type:
Journal Articles
Status:
Accepted
Year Published:
2014
Citation:
4. H. Jin; X. Wang; Z. Gu; J. Hoefelmeyer; K. Muthukumarappan; J. Julson; 2014, Graphitized activated carbon based on big bluestem as electrodes for supercapacitors, RSC Adv, 4, 14136-14142
- Type:
Journal Articles
Status:
Accepted
Year Published:
2014
Citation:
5. R. Chintala, T.E. Schumacher, S. Kumar, D.D. Malo, J. Rice, B. Bleakley, G. Chilom, S. Papiernik, J.L. Julson, D. Clay, and Z.R. Gu. 2014. Molecular characterization of biochar materials and their influence on microbiological properties of soil. Journal of Hazardous Materials 279, 244-256
- Type:
Journal Articles
Status:
Accepted
Year Published:
2014
Citation:
6. M. Dubey, G. Rakesh, Z. Gu, Q. Fan, 2014 Biochar Nanomaterials Activated by Oxygen Plasma for Supercapacitors , J. Power Source; Volume 274, 15 January 2015, Pages 13001305
|
Progress 01/01/13 to 12/31/13
Outputs
Target Audience: Target Audiences: Industrial collaborators have been attracted by Dr. Gu’s presentation in international conferences. Name/Title Company or Institute Interests Clifford Walton , Calgoncarbon (US) Research Leader, CWalton@calgoncarbon-us.com Calgoncarbon Inc. Sustainable activated carbon for supercapacitors, water purification and chemical separation (Non disclose and Materials Transfer documents already signed, collaboration is going on) Michael Everett Chief Technical Officer Meverett@maxwell.com Maxwell Inc Sustainable super activated carbon for supercapacitors Nate Anderson, Research Forester nathanielmanderson@fs.fed.us Rocky Mountain Research Station USDA Forest Service Upgrading bio-char to activated carbon Albert.Bennett, Technology Manager Albert.Bennett@ICMINC.com ICM. Inc Upgrading bio-char to activated carbon Related projects: Zhengrong Gu, K. Muthukumarappan, W. Gibbons Sungrant (DOE) $ 37,923 03/2013-01/14 Developing Gas Stripping - Adsorption/Desorption Separation Processes based on Porous Carbon Adsorbents for Biofuel Purification from Bioreactors Q. Fan, Zhengrong Gu, Sungrant (DOE) $ 31,509 03/2013-01/14 Electrophoretic Deposition of Biochar Nanoparticle based Films for Energy Storage J Rice, W Gibbons, Zhengrong Gu, D Raynie, C Zhang, NSF-EPSCor $ 3,000,000 09/2013-08/2016 Collaborative Research: Dakota Bioprocessing Consortium (DakotaBioCon). Biochar based graphene similar structure as catalysts’ support for improving hydrothermal converting lignin to aromatics and monomers of polymers. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? 1, Mr. Polin Joseph already completed his MS degree in ABE in this project and went to Iowa State University for continuing his PhD in biorefinery. 2, Mr. Hong Jin is pursuing his PhD degree, which focusing on developing biochar based advanced carbon materials for energy storagein ABE at SDSU. 3, Mr. Sihan Li is pursuing his MS degree andfocusing on uaing biochar based activated carbon as separation media inbiofuel recoveryprocess and catalyst in biorefinery. 4, Mr. Cao Yuhe just started his PhD study (in Sep 2013) for developing gas-stripping adsorption/desorption separation methods to recover and purify biofuels from bio-reactors. 5, Mr. Cai Junjie just started his PhD study (in Sep 2013) for developing innovative nanostructured carbon-silicon materials for energy storage from high silica biomass/biochar How have the results been disseminated to communities of interest? Name/Title Company or Institute Interests Clifford Walton , Calgoncarbon (US) Research Leader, CWalton@calgoncarbon-us.com Calgoncarbon Inc. Sustainable activated carbon for supercapacitors, water purification and chemical separation (Non disclose and Materials Transfer documents already signed, collaboration is going on) Michael Everett Chief Technical Officer Meverett@maxwell.com Maxwell Inc Sustainable super activated carbon for supercapacitors Nate Anderson, Research Forester nathanielmanderson@fs.fed.us Rocky Mountain Research Station USDA Forest Service Upgrading bio-char to activated carbon Albert.Bennett, Technology Manager Albert.Bennett@ICMINC.com ICM. Inc Upgrading bio-char to activated carbon What do you plan to do during the next reporting period to accomplish the goals? 1, Complete economic and energy evaluation of different activation methods based on laboratory results and scale up simulation 2, Complete test of microwave, ultrasound, ozone activation methods 3, Complete thermodynamic evaluation of activation processes using auto chemical adsorption analyzer and GC-MS system
Impacts
What was accomplished under these goals?
1 Physical activation: It was found that upgrading bio-char using physical activation with mixed reagents, flue gas and syngas, further improved the development of BET specific surface area (SSA) compared to single reagents, CO2 and H2O, previously evaluated. The bio-char’s initial surface area, 245 m2 g-1, increased using flue gas (mixture of CO2 and H2O) and syngas (mixture of CO2 and CO) activation to produce activated carbon samples with normalized BET SSA values in the range of 733 ~ 1088 m2 g-1 and 868 ~ 1122 m2 g-1 for CO2 and H2O activation respectively. An equi-molar flue gas developed the best normalized BET SSA based on AC yield % for optimization purposes. For these conditions, the maximum surface area development is achieved before excessive bio-char burn off limits the activated carbon yield. A proposed method of process integration was introduced to generate the flue gas for physical activation as well as additional process heat. Syngas physical activation also improved the surface area of the initial bio-char, and a proposed method of process integration is introduced for the co-production of bio-oil and activated carbon. This should allow for greater process efficiency by further converting the carbon in bio-char into additional CO which in turn could be further combusted for additional process heat. 2 Hydrothermal Activation with Nitric acid: After the treatment of HNO3, the micropore volume increased more than 15%, which could be verified with increases in specific surface area. Compared to the original hierarchical activated carbon sample, the mesopore volume and total pore volume also increased for the HNO3 wet chemical oxidization. Furthermore, after HNO3 treatment, oxygen content in the activated carbon increased significantly and most oxygen groups were allocated on the surface of activated carbon after HNO3 hydrothermal oxidization, because HNO3 treatment is a surface oxidization methods. As a result of the mentioned reason, the nitric acid modified activated carbon presented 30% higher specific capacitance than the hierarchical activated carbon. And the supercapacitor made by the nitric acid modified activated carbon showed a extremely small inner resistance of 0.4 ?, which is competitive to graphene. 3 Biochar based activated carbon as biofuel separation media in gas-stripping adsorption/desorption processes: Developing an integrated, recirculating adsorption recovery system, which harvests volatile products with lower energy consumption by gas stripping the bioreactor’s exhaust, will be critical for expanding novel biorefinery technologies. Different activated carbon materials were developed and compared to optimize the adsorption dynamic and equilibrium for individual model chemical products.The enthalpy of solvents desorption from activated carbon samples (1.0- 2.0 kJ*g-1 for Water, 0.4- 1.2 kJ*g-1 for Ethanol, and 0.2- 1.0 kJ*g-1 for n-Butanol) are evaluated to better understand the relationship between solvent loading percent and the energy of desorption. over the range of 5 to 30% solvent loading (g solvent/ g carbon). This data was then reinterpreted with the incorporation of the activated carbon’s BET surface areas. These results provide two interpretations of the enthalpy of desorption over both a range of solvent loading percentages and solvent loading per unit area (mm solvent/ M2 carbon). The thermodynamic characteristics of each activated carbon is influenced by the method of activation. Second, a general trend was observed with more energy required to desorb water, ethanol, and butanol in that respective order. Third, the energy of desorption decreased as the solvent loading percent increased. Fourth, the rate of this decrease in energy of desorption become more pronounced with an increase in the activated carbons surface area.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
H Jin, X Wang, Z Gu, 2013, Hierarchical Carbon Materials from High Ash Bio-char of Distiller's Dried Grain with Solubles for Supercapacitor, Materials Focus 2, 105-112 (http://www.aspbs.com/mat.htm#v2n2)
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
H Jin, X Wang, Z Gu, J. Polin, 2013, Carbon Materials from High Ash Bio-char for Supercapacitor and Improvement of Capacitance with HNO3 Surface Oxidation, J. Power Sources 236, 285-292 (http://dx.doi.org/10.1016/j.jpowsour.2013.02.088)
- Type:
Journal Articles
Status:
Accepted
Year Published:
2013
Citation:
Sihan Li, Zhengrong Gu, Evan Brady Bjornson, Arthy Muthukumarappan, Biochar Based Solid Acid Catalyst Hydrolyze Biomass, Journal of Environmental Chemical Engineering (in press http://www.sciencedirect.com/science/article/pii/S2213343713001693)
- Type:
Journal Articles
Status:
Accepted
Year Published:
2013
Citation:
H Jin, X Wang, Z Gu, 2013, Porous Activated Carbon Derived from DDGS as Lithium ion Battery Anode Material, Materials Focus (in press http://mstracker.com/reviews.php?id=38422&aid=62943)
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Progress 01/01/12 to 12/31/12
Outputs
OUTPUTS: 1 Physical activation: The biochar based physical activated carbon materials have pore characteristics, surface area, methylene blue adsorption capacity, and iodine number that are comparable to conventional activated carbon materials and previously reported results. These value added carbon materials can be produced more economically using a synergistic combination of thermochemical, physical activation, and heat recovery processes. 2 Chemical Activation: In the present work, several high ash biochar (15~50% ash) biocahr from different biomass (corn stover, switch grass, prairie cordgrass, big bluestem, craft lignin, DDGS, wheat straw and rice husk) after fast pyrolysis, have been converted to super-activated carbon with base catalytic activation. The activation of high ash bio-char with alkaline hydroxide and carbonates includes multiple processes: dehydration and dehydroge-nation of non-carbonized components; gasification of carbon with catalysts and derivative product; intercalation of metallic species as well as generating soluble compounds, which are templates for forming porous structure after dissolving in washing steps, through reaction among ash components with catalysts. As a result, the development of porosity in bio-char by chemical activation using alkali hydroxides and carbonates depends on several interrelated parameters: ash compositions and distribution in bio-char; initial porous structure of bio-char; type and dosage of activation catalysts; activation temperature; time; atmosphere conditions. It is noteworthy that super activated carbon based on biochar from protein and mineral rich feedstock shown nanostructure similar to activated graphene. Protein rich precursors and the high ash content are possible major factors in forming a nanostructure similar to that of activated graphene. Although the roles of mineral templates, as a space constraint and substrate for carbon nano-sheet growth in forming a graphene like structure is well understood, the mechanism to form carbon nano-sheets from protein rich precursors is still not clear and needs to be further investigated in the future. 3 Supercapacitors: For two different super activated carbon samples, according to galvanostatic charge-discharge curves in 6 mol/L KOH, a specific capacitance of 270~325 F g-1 was obtained at the current density of 100mA g-1, while the current density increased up to 1000 mA g-1, the specific capacitance of the supercapacitor dropped down to 200 and 293 F g-1 respectively. In addition, high ash biochar derivate hierarchical carbon exhibited excellent capacitance performance and high energy efficient in inorganic electrolyte, i.e. 6 mol L-1 KOH. In organic electrolytes, one super activated carbon shown 150 F g-1 at the current density of 500mA g-1. The specific capacitance of our biochar based super activated carbon was significantly higher than most bio-inspired activated carbon, metal carbides derivate carbon (CDC), organized mesoporous carbon (OMC), some academic laboratory graphene materials and commercial graphene (Grade C from XGScience Inc) at similar or comparable current density. PARTICIPANTS: Participants: (1) principal investigator(s)/project director(s) (PIs/PDs): Gu, Z.R.; (2) Co-PI Muthukumarappan, K.; Wei, L.; Julson, J. (3) Other persons: Wang, X.M.; Li, S.H.; Qu, W.D.; Jing, H.; Polin, J. (4) Collaborators (non funded): Brown R. (Iowa State University); Nate Anderson (USDA-FS Mountain Station) ICM.Inc; Chippewa Valley Ethanol Inc. David Moore (NSF-REU student) TARGET AUDIENCES: industrial/academic partners. 1) Michael Everett, Chief Technical Officer,Maxwell Technology Inc, Meverett@maxwell.com; Research topic: Sustainable super activated carbon for supercapacitors 2) Steven C. Peterson, Senior Scientist, Plant Polymer Research Unit, USDA - ARS - NCAUR; Steve.Peterson@ARS.USDA.GOV; Research topic: Activation of biochar to enhance properties as filler of polymers 3) Jonathan Trent, Ph.D., OMEGA Project Scientist, Bioengineering Branch NASA Ames Research Center; Jonathan.D.Trent@nasa.gov; Research topic: Activated carbon from biochar of algae for water treatment (CEC removal) 4) Wang, Yuguo, Senior Scientist, Saudi Aramco, yuguo.wang@aramco.com, Research topic: Carbon for natural gas storage and petroleum coke/pitch based advanced carbon materials 5) Nate Anderson, Research Forester, Rocky Mountain Research Station USDA Forest Service ; nathanielmanderson@fs.fed.us; Research topic: Upgrading bio-char to activated carbon 6) Ali Manesh,American Science and Technology; Ph.D., P.E. am@amsnt.com Research topic: Upgrading bio-char to activated carbon 7)Toshinori Kato,Kuraray Research & Technical Center; Kuraray America, Inc. R&D Manager, toshinori.kato@kuraray.com; Research topic: Biochar/biomass based super-AC and C-Si composite for supercapacitor and lithium batteries. 8) Albert.Bennett, Technology Manager, ICM. Inc; Albert.Bennett@ICMINC.com Research topic: Upgrading bio-char to activated carbon 9) Joseph Kimetu, University of Calgary; Institute for Sustainable Energy, Environment and Economy, jmkimetu@ucalgary.ca; Research topic: Activated carbon from biochar for oil-sands processing water treatment 10)Roger S. Williams, Technical Director, Carbon Technologies, MWV Specialty Chemicals Inc., roger.williams@mwv.com, Research topic: Sustainable Biofuel and advanced carbon materials integrated processes. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
Collaboration: Dr. Gu also established collaboration with Dr. Nate Anderson ( in Rocky Mountain Research Station USDA Forest Service) on "Activating biochar of beetle killed trees after fast pyrolysis" which will occur to enhance sustainability of activated carbon and improve economic viability of applying beetle killed trees. Target Audiences: Industrial collaborators have been attracted by Dr. Gus presentation in international conferences. Collaboration has been established with several industrial/academic partners. 1) Michael Everett, Chief Technical Officer,Maxwell Technology Inc, Meverett@maxwell.com; Research topic: Sustainable super activated carbon for supercapacitors 2) Steven C. Peterson, Senior Scientist, Plant Polymer Research Unit, USDA - ARS - NCAUR; Steve.Peterson@ARS.USDA.GOV; Research topic: Activation of biochar to enhance properties as filler of polymers 3) Jonathan Trent, Ph.D., OMEGA Project Scientist, Bioengineering Branch NASA Ames Research Center; Jonathan.D.Trent@nasa.gov; Research topic: Activated carbon from biochar of algae for water treatment (CEC removal) 4) Wang, Yuguo, Senior Scientist, Saudi Aramco, yuguo.wang@aramco.com, Research topic: Carbon for natural gas storage and petroleum coke/pitch based advanced carbon materials 5) Nate Anderson, Research Forester, Rocky Mountain Research Station USDA Forest Service ; nathanielmanderson@fs.fed.us; Research topic: Upgrading bio-char to activated carbon 6) Ali Manesh,American Science and Technology; Ph.D., P.E. am@amsnt.com Research topic: Upgrading bio-char to activated carbon 7)Toshinori Kato,Kuraray Research & Technical Center; Kuraray America, Inc. R&D Manager, toshinori.kato@kuraray.com; Research topic: Biochar/biomass based super-AC and C-Si composite for supercapacitor and lithium batteries. 8) Albert.Bennett, Technology Manager, ICM. Inc; Albert.Bennett@ICMINC.com Research topic: Upgrading bio-char to activated carbon 9) Joseph Kimetu, University of Calgary; Institute for Sustainable Energy, Environment and Economy, jmkimetu@ucalgary.ca; Research topic: Activated carbon from biochar for oil-sands processing water treatment 10)Roger S. Williams, Technical Director, Carbon Technologies, MWV Specialty Chemicals Inc., roger.williams@mwv.com, Research topic: Sustainable Biofuel and advanced carbon materials integrated processes.
Publications
- J Polin, Z Gu, X Wang. 2012, Upgrading biochar into activated carbon materials through physical activation using flue gas atmospheres, in the session Carbonized Biomass Utilization and Application. (in ASABE 2012 July 29 Dallas TX)
- Gu, Zhengrong; Wang, Xiaomin; 2012, Carbon Materials from High Ash Bio-char: A Nanostructure Similar to Activated Graphene, accepted by American Transactions on Engineering and Applied Sciences (Online http://tuengr.com/ATEAS/V02/015-034.pdf).
- Z Gu, 2012, Provisional patent: Materials and Methods for Production of Activated Carbons, has been filed to USPTO on July 11 2012
- Z Gu, X Wang. 2012, Soluble Inert Template for Preparing Nanostructured Carbon Materials From Forest and Plant Bioproducts, (AICHE 2012 Annual Meeting in Pittsburgh, PA October 28, 2012 to Friday, November 2, 2012)
- Joe Polin, Z Gu, X Wang. 2012, Utilizing Thermochemical Process Streams to Upgrade Bio-Char Into Value Added Activated Carbon Through Physical Activation, (AICHE 2012 Annual Meeting in Pittsburgh, PA October 28, 2012 to Friday, November 2, 2012)
- J Polin, Z Gu, M Ramanathan, X Wang and K Muthukumarappan. 2012, Biochar Based Activated Carbon As Adsorbent to Recover Volatile Chemicals From Photobioreactor, (AICHE 2012 Annual Meeting in Pittsburgh, PA October 28, 2012 to Friday, November 2, 2012)
- Z Gu, H Jin, X Wang. 2012, Synthesis of Biorenewable C/Si/SiO2 As the Li-Ion Battery Anode Material, (AICHE 2012 Annual Meeting in Pittsburgh, PA October 28, 2012 to Friday, November 2, 2012)
- Z Gu, G Anderson, X Wang and D Moore, 2012, Coupling of a Photocatalysis Reactor with a Photobioreactor, (AICHE 2012 Annual Meeting in Pittsburgh, PA October 28, 2012 to Friday, November 2, 2012)
- Z Gu, G Anderson, X Wang and D Moore, 2012, Photocatalysis as a pretreatment of wastewater to produce nutrients to grow microalgae for bioenergy in a photobioreactor, (in Eastern South Dakota Water Conference, Brookings SD Oct 30 2012).
- Zhengrong Gu, Hong Jin, Xiaomin Wang, Muthukumarappan, K.; Julson, J. ; High Ash Biochar Based Mesoporous Superactivated Carbon and Application in Supercapacitor,
NIFA PI meeting DC NIFA center 2012 Dec 4.
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Progress 01/01/11 to 12/31/11
Outputs
OUTPUTS: Bio-char samples have been collected through collaboration with Dr Muthu and Dr. Julson's group at SDSU and Dr. Brown's group at Iowa State University. The biochars was produced from corn stover, switch grass, and sawdust for developing drop-in biofuels in other projects. Industrial biochar from gasification and fast pyrolysis platform have been obtained from ICM Inc and Chippewa Valley Ethanol Inc. All those processes are designed and optimized to maximize bioenergy or biofuel recovery. All biochars samples have been characterized, most biochar samples generated from microwave pyrolysis and fast pyrolysis have higher ash content than charcoal, but wood chip based biochar generated in microwave pyrolysis has lower ash content. In addition, all biochars contains significant volatile, which is residue of biooil. Specific surface area of all biochar samples were much lower than activated carbon. ZnCl2 and H3PO4 cannot effectively activate biochar, while NaOH or KOH can effectively activate most biochar samples. Adsorption capacity, specific surface area and pore distribution depends on base/biochar ratio, type of base, biomass feedstock and pyrolysis conditions. Adsorption capacity increased with base/biochar ratio, KOH is better than NaOH for higher adsorption capacity, mesoporous volume and surface area. Big bluestem and Prairie cordgrass based biochar can be activated to high quality activated carbon with highest adsorption capacity and specific surface area. Physical activation methods with steam have been tested for woody and herbaceous biomass based biochar generated in fast pyrolysis processes supplied by industrial partners. Biochar generated from fast pyrolysis of pine bark can be effectively activated with steam at temperature higher than 800 C. However, physical activation with water steam can only active wheat bran fast pyrolysis biochar or gasification biochar partially to achieve MB value around 45~75 mg MB/g as well as specific surface area around 300~450 m2/g. In the first year, Dr. Gu obtained two automatic BET systems from DOE-ERLE program. One is ASAP2010 Micropore Analyzer with Krypton function for physical gases adsorption and analysis. The other one is ASAP2000 Micropore Analyzer with Krypton and Chemical adsorption function. In the first year, PIs of this project also established a Biorenewable Energy Central Analysis Laboratory through collaboration with Mechanic Engineering Department in SDSU. Two graduate students have been recruited in Dr. Gu's group for developing further activation methods and investigate mechanisms behind impact of activation parameters and properties of biochar feedstock. PARTICIPANTS: (1) principal investigator(s)/project director(s) (PIs/PDs): Gu, Z.R.; Muthukumarappan, K.; Wei, L.; Julson, J. (2) Other persons: Wang, X.M.; Li, S.H.; Qu, W.D.; Jing, H.; Polin, J. (3) Collaborators (non funded): Brown R. (Iowa State University); ICM.Inc; Chippewa Valley Ethanol Inc. Tatiana Rosser (Benedict College) TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
Collaboration: Dr. Gu also established collaboration with Dr. Darko in Benedict College (an HBCU) on photocatalys research, which will occur to enhance sustainability of activated carbon developed in this project by supplying an environmentally friendly regeneration method. In addition, characterization and understanding of those innovative activated carbons, obtained in this project, will be shared with Dr. Darko to help him select rational adsorbent support for TiO2 photocatalyst as well as enhance established collaboration between Dr. Gu and Dr. Darko on photocatalysis techniques. Ms. Tatiana Rosser is the first America African undergraduate involved in this collaboration, she worked in Dr. Gu's group (May 20 - July 15, 2011) to develop innovative technology for doping and immobilization of TiO2 photocatalyst on activated carbon in one step. Dr. Gu also start collaboration with Rocky Mountain Research Station of USDA Forest Service to activate woodybased biochar from forest residues.
Publications
- Gu,Z.R.2011.Development of high value carbon based adsorbents from thermochemically produced biochar. ASABE 2011 Annual International Meeting, Louisville, Kentucky, USA.
- Muthu, K. 2011. Physical and Chemical Characterization of Biochar from different Feedstocks. ASABE 2011 Annual International Meeting, Louisville, Kentucky, USA.
- Gu, Z.R. 2011. Adsorption properties of biochar-based activated carbon. ACS annual meeting, Denver, Colorado.
- Gu, Z.R. 2011. Innovative Nanostructured Activated Carbon - Silica Composite Adsorbent Based On High Ash Biochar. AICHE annual meeting, Minneapolis, Minneasota.
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