Source: NORTH CAROLINA A&T STATE UNIV submitted to
A REACTIVE DISTILLATION PROCESS FOR UPGRADING BIO-OIL TO TRANSPORTATION FUELS AND BIOPLASTICS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
TERMINATED
Funding Source
OTHER GRANTS
Reporting Frequency
Annual
Accession No.
0223024
Grant No.
2010-38821-21512
Project No.
NCE-2010-02372
Proposal No.
2010-02372
Multistate No.
(N/A)
Program Code
EQ
Project Start Date
Sep 1, 2010
Project End Date
Aug 31, 2014
Grant Year
2010
Project Director
Wang, L.
Recipient Organization
NORTH CAROLINA A&T STATE UNIV
1601 EAST MARKET STREET
GREENSBORO,NC 27411
Performing Department
Natural Resources and Environmental Design
Non Technical Summary
This research project is to investigate a novel reactive distillation process for upgrading crude bio-oils into transportation fuels and biodegradable plastics. The crude bio-oil produced by liquefying animal wastes and pyrolyzing agricultural residues will be fed into a reactive distillation unit. The by-product gas from the crude bio-oil production will be upgraded to increase its hydrogen content via a water-gas shift reaction and used to catalytically upgrade the hot gaseous distillate fraction moving up through the reactive and rectifying zone of the distillation unit to decrease the water content, oxygen content, unsaturated bonds, viscosity and acidity while increasing the heating value and stability of the distillate via cracking, hydrogenation and esterification reactions. Proper multi-functional catalyst complexes will be developed to enhance four groups of upgrading reactions. The non-volatile bio-oil residue moving down through the striping zone will be extruded into biodegradable plastics. A mathematical model will be developed to qualify the process and the model will be used to optimize, scale-up and economically analyze the process at different scales. Introduction of the well developed process by this project into rural areas will be able to produce transportation fuels and biodegradable plastics from animal wastes and agricultural residues, and thereby enhance the rural economy, reduce US dependence on imported petroleum and reduce the pollution from animal wastes. The proposed project, with collaboration with two major universities, will significantly strengthen the increasing research capacity of NC A&T and provide training opportunities to underrepresented students at NC A&T in bioenergy and bioproducts.
Animal Health Component
(N/A)
Research Effort Categories
Basic
(N/A)
Applied
100%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5112499202050%
5113999202050%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
3999 - Animal research, general; 2499 - Plant research, general;

Field Of Science
2020 - Engineering;
Goals / Objectives
This proposed research is to develop a novel reactive distillation system to efficiently and economically fractionate and upgrade crude bio-oil derived from animal wastes and agricultural residues into transportation fuels and biodegradable plastics. We intend to reach our goal by realizing the following specific objectives: Objective 1: Produce bio-oil via hydrothermal liquefaction of wet animal wastes and pyrolysis of dry agricultural residues, and characterize the properties and distillation curves of crude bio-oil; Objective 2: Catalytically upgrade bio-oil distillate with the by-product gas, which will be collected from the bio-oil production process into transportation fuels; Objective 3: Extrude the non-volatile bio-oil residue into biodegradable plastics; and Objective 4: Integrate, design and analyze a reaction distillation process. A robust bio-oil characterization technique and protocol will be developed and integrated into the refinery processes for optimizing process efficiency and yields. A well-understood reactive distillation process will be developed to maximize the recovery of transportation fuels from the crude bio-oil and to ensure the quality of the final fuel product. An extrusion technique will be developed to convert no-volatile distillation oil residues into biodegradable plastics. A lab-scale reactive distillation unit will be ready for demonstration and training students. A mathematical tool will become available to optimize the design and operations, and analyze the economics of the reactive distillation process. Upon completion of the project, the capacity of our minority university to conduct research on bioenergy and bio-based products will be substantially enhanced. We also will provide training opportunities to graduate and undergraduate students who will have more chances to be hired in the bio-based industry. By replacing petroleum fuels with biofuels, the harmful air emissions from automobiles can be significantly reduced. The use of bioplastics could significantly reduce the use of petroleum-based plastics. Introduction of a well-understood process developed by this proposed project into rural areas will improve the economics of farming by reducing waste treatment costs and generating additional revenues from animal wastes and agricultural residues.
Project Methods
Study (1) Bio-oil production, characterization and distillation: Bio-oil will be produced from swine manure and chicken manure via hydrothermal liquefaction and from corn stover and wheat straw via thermal pyrolysis. The physical and chemical properties of biomass materials and bio-oil will be characterized using standard methods reported in the literature. A distillation curve is a graphical depiction of the boiling temperature of a fluid or fluid mixture plotted against the volume fraction distilled. The distillation curves of bio-oil will be obtained using the method developed by the U.S. National Institute of Standards and Technology. Study (2) Catalytic upgrading of distillate fraction into transportation fuels: The crude bio-oil will be fractionated into a light distillate fraction to the top and heavy oil residues to the bottom. The light distillate fraction will be catalytically upgraded into transportation fuels by reducing the viscosity, oxygen content and acidity and increasing heating value and stability via gas-solid cracking and hydrogenolysis reactions. The by-product gas collected from the bio-oil production process will be upgraded via a water-gas shift reaction to supply hydrogen for the hydrogenation reaction. Heterogeneous multifunction catalysts will be developed to enhance a group of reactions that occur during the upgrading of bio-oil distillate. These catalyst complexes will be used as packing for the rectifying zone of the distillation column. The changes in chemical components, thermal properties and physical properties of bio-oil before and after upgrading will be analyzed and compared to elucidate the effectiveness of the proposed novel refinery process. Petroleum diesel also will be analyzed for comparison. Study (3) Extrude non-volatile residual bio-oil into biodegradable plastics: The heavy oil residue from the distillations at different temperatures will be co-extruded with a small-amount of nano-clay/starch/polylactic acid to produce biodegradable plastics. Experiments will be conducted to analyze the effects of the mass ratio of nano-clay/starch/PLA to oil residue, the composition of the bio-oil residue, and extrusion operating conditions on the mechanical strength, physical properties and biodegradability of the bioplastics. Study (4) Design, testing and mathematical modeling of an integrated reactive distillation process: A bench-scale distillation processing unit will be designed and constructed. Crude bio-oil and by-product gas, collected from the crude bio-oil production process, will be tested in the system. The chemical and physical properties of the upgraded distillate fuels will be measured and compared with those of crude bio-oil and traditional diesel and biodiesel fuels. A multi-scale mathematical model will be developed on the ASPEN plus software platform to quantify the relationship between yields and quality of fuel product, and unit design and operating parameters and the properties of the crude bio-oil. An economic model will be developed to determine the profitability of the reactive distillation process at different scales.

Progress 09/01/10 to 08/31/14

Outputs
Target Audience: 1.This project supported four graduate students including one Ph.D. in energy and environmental systems (NCA&T), one Ph.D. student in material science and engineering (Stony Brook University), two M.S. students in chemical engineering (NCA&T). These students were educated through formal classroom instruction, and practicum experiences with the financial support provided by this project. Three graduate students at NCA&Thave successfully graduated in the past academic year. 2. Two undergraduate students in biological engineering: weprovided training and research opportunities to two undergraduate students in biological engineering, who were hired to work on this project. 3. This projectsupported PI (Lijun Wang), and Co-PI (Abolghasem Shahbazi) to attend two professional conferences (2014 ASABE Annual Meetingand the TCS2014: symposium on thermal and catalytic sciences for biofuels and biobased products). The PI presented the research results generated by this project at these two conferences. 4. A field trip was supported by this project for the PI (Lijun Wang), Co-PI (Abolghasem Shahbazi), and five graduate students to visited the pilot-scale pyrolysis facility at the RTI International in Durham, NC. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? At NCA&T, three graduate students, including one Ph.D. student in energy and environmental systems, and two M.S. students in chemical engineering, have graduated with the support of this grant in the academic year 2013-2014. They have successfully completed the following dissertation and theses: Cheng, D., Ph.D. in energy and environmental systems, dissertation topic: Characterization and catalytic upgrading of crude bio-oil produced by hydrothermal liquefaction of swine manure and pyrolysis of biomass, published in the June of 2014. Ansah, E., M.S. in chemical engineering, thesis topic: Experimental investigation and ASPEN Plus simulation of the MSW pyrolysis process, published in the December of 2013. Md Arif Khan, M.S. in chemical engineering, thesis topic: Chemical reactive separation in energy and environmental processes, published in the May of 2014. Two undergraduate students (Justin Able and Bilal Riddick) in biological engineering received undergraduate research experience training in bio-oil characterization and biocomposite materials supported by this project. The grant was also used to train one postdoc (Dr. Hui Wang) who was hired to work on life cycle assessment of fast pyrolysis of municipal solid waste in North Carolina of USA, which has been published in Journal of Cleaner Production. The Co-PI at University of Nebraska-Lincoln, Dr. Milford Hanna, visited NCA&T in the January of 2014. During this visit, Dr. Hanna discussed this project with the PI and provided advice to graduate students and postdoc associate who worked on this project at NCA&T. At Stony Brook University, the grant from this project was used to support a Ph.D. student, Wei Nan to work on multifunctional catalysts for catalytic upgrading of bio-oil distillate fraction into transportation fuels with a focus on bio-oil upgrading using catalytic hydrodeoxygenation (HDO) approach. This grant provided travel funds to two graduate students (Md Arif Khan at NCA&T and Wei Nan at Stony Brook University) topresent their research results at the 2013 American Institute of Chemical Engineers (AIChE) in San Francisco, CA in the November of 2013. This grant also provided travel funds to the PI, Lijun Wang, to present the research results of this project at the 2014 ASABE Annual Meeting in Montreal, Canadain the July of 2014. How have the results been disseminated to communities of interest? During this report period, the PI, Co-PIs and graduate students who worked on this project published 1 book, 5 book chapters, 4 peer-reviewed journal articles and gave 5 presentations at notational and international conferences. The graduate students who worked on this project have completed and published 3 theses and dissertation during this report period. The PIs and five graduate students at NCA&T visited the pilot-scale pyrolysis facility at RTI International and discussed the research activities of this project and potential collaboration with the biofuels research group at RTI International. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? (1) Characterization and catalytic upgrading of bio-oil. The distillation curve of crude bio-oil from glycerol-assisted hydrothermal liquefaction of swine manure was measured using an advanced distillation apparatus. The crude bio-oil had much higher distillation temperatures than diesel and gasoline and was more distillable than the bio-oil produced by the traditional liquefaction of swine manure and the pyrolysis of corn stover. The appearance of hydrocarbons in the distillates collected the temperature of 410.9°C above indicated that the thermal cracking at a temperature from 410°C to 500°C may be a proper approach to upgrade the crude bio-oil produced from the glycerol-assisted liquefaction of swine manure. The effects of thermal cracking conditions including reaction temperature (350-425°C), retention time (15-60 min) and zeolite-based catalyst loadings (0-10 wt%) on the yield and quality of the upgraded oil were analyzed. Under the optimum thermal cracking conditions at 400°C, a catalyst loading of 5% by mass and the reaction time of 30 min, the yield of bio-oil was 46.14% of the mass of the crude bio-oil and 62.5% of the energy stored in the crude bio-oil was recovered in the upgraded bio-oil. The upgraded bio-oil with a heating value of 41.4 MJ/kg and viscosity of 3.6 cP was comparable to commercial diesel. In upgrading crude bio-oil from fast pyrolysis, converting organic acids into neutral esters is significant. Activated carbon and bio-char were prepared from fermentation residues and then sulfonated with concentrated sulfuric acid at 150oC for 18 h. The sulfonated activated carbon with BET surface area of 349.8 m2/g and 5% loading, was effective to catalyze the esterification of acetic acid and ethanol at a mass ratio of 1:3, 78°C for 60 min. Crude pyrolytic oil obtained from RTI International had distillation temperatures from 164.8°C to 365.5°C and 50% volumetric fraction of the crude bio-oil was distillable. Esterified pyrolytic bio-oil had an increased distillability up to 55% volumetric fraction. The esterified pyrolytic bio-oil had an increased pH of 6.12. Diesel range pyrolytic bio-oil distilled from esterified pyrolytic bio-oil had comparable properties with commercial diesel, with an energy content of 41.41 MJ/kg, water content of 0.58 wt%, and viscosity of 7.45 cP. (2) Catalytic upgrading of bio-oil produced by fast pyrolysis of switchgrass. Upgrading of fast pyrolysis oils produced from swtichgrass was carried out using 5 wt % Ru and 5 wt % Rh on a carbon support as catalysts slurried in a polyethylene glycol solvent in a 300 mL Parr batch reactor in the presence of hydrogen. A hydrodeoxygenation (HDO) reaction was evaluated in the temperature range of 200−280 °C under hydrogen pressure of 300−1000 psig. The raw pyrolysis oil and the upgraded products were characterized by gas chromatography (GC), gas chromatography/mass spectrometry (GC/MS), and Fourier transform infrared spectroscopy (FTIR) techniques to establish the effectiveness of the hydrogenation process. With Ru/C at 280 °C and 1000 psig, the GC/MS data showed the absence of acetic acid and the principal liquid product slate included alcohols, hydrocarbons, cyclic compounds, and phenolics at a relative concentration of 5.2, 21.2, 3.8, and 35.7%, respectively. (3) Experiments and computer simulation of biomass pyrolysis. The maximum bio-oil yields for the pyrolysis of paper, wood and textile in the MSW in a 100 ml tubular reactor were 57, 64.9 and 52.8 wt.%, respectively. The yield of biochar from the pyrolysis of different MSW components was found to decrease with increasing temperature. The heating value of the biochar increased with the pyrolysis temperature for all MSW components. The heating values of biochar obtained from different MSW components at a high temperature were close. The moisture content of the bio-oil was very high in the range of 68-72% at a low pyrolysis temperature (e.g., 300oC) and then decreased with increasing temperature to between 40 and 50% at 700oC. The TGA profiles showed that the yields of the evolved volatile gases for paper, wood, textile and plastic at a heating rate of 20oC/min were 69.5, 67.9, 75.3 and 83.7 wt.%, respectively. The yields of the volatile gases were found to decrease to 63.4, 63.6 and 64.3 wt% for paper, wood and textile respectively when the heating rate was increased to 60oC/min. The yield of the volatile gases generated from plastic, however, increased from 83.7 wt% obtained at 20oC/min to 89 wt% at 60oC/min. The DSC curves revealed that the caloric requirement for MSW components increased with increasing temperature and became almost constant at the charring stage. The mass spectra profiles obtained from the pyrolysis of MSW components showed that CO2, H2O, CH4 and H2 formed the main components in the non-condensable gas stream. An ASPEN plus simulation model could be used to predict the variations in pyrolysis products with increasing pyrolysis temperature when correlation equations from experimental results were modeled in the ASPEN RYIELD reactor block and the char obtained from the pyrolysis could be combusted to supply the energy for drying of the MSW feed. The economic analysis shows that for a pyrolysis plant at a scale of 100 MT/day, it costs $0.10 to process 1 kg of raw MSW and the corresponding production cost of the bio-oil is $0.36/l bio-oil. The production cost decreases with the increase of production size and at a plant capacity of 300 MT/day the unit cost of bio-oil is $ 0.26/l. (4) Simulation of bio-oil upgrading process. ASPEN simulation of the reactive distillation of pyrolysis bio-oil with n-butanol was carried out using RADFRAC module and UNIQUAC property method by minimizing Gibbs free energy. The binary and ternary interaction and chemical and phase equilibrium (CPE) between the components were studied to determine the azeotropes and homogeneous region of mixture. The conversions for the esterification reactions were found to be 70-90% for various simulated bio-oils, and water was separated from the ester products. All the distillation column parameters such as condenser and reboiler heat duty, number of stages, reflux ratio with different inlet conditions etc., were studied to develop a completely energy cost minimized RD unit. (5) Life cycle assessment of pyrolysis-based biorefinery. Based on the analysis of primary landfills and wasteflow across North Carolina, five pyrolysis plants were assumed to be built to utilize MSW. Life cycle assessment results indicate that global warming potential (GWP), acidification potential (AP), human toxicity potential (HTP) and photochem ozone creation potential (POCP) are mainly from bio-oil production, which accounts for 32.8%, 59.4%, 98.2% and 99.8% of the total potentials generated by the whole process, respectively. Besides, the main source of ozone depletion potential (ODP) and terrestric ecotoxicity potential (TETP) is electricity for bio-oil production. Eutrophication potential (EP) emission is mainly from the exhaust of diesel vehicle operation. Hydrogen and char are produced in production and upgrading of bio-oil as co-products, which generate 5.5 MJ and 2.7 MJ energy credits per kg MSW, respectively. Sensitivity analysis indicates that the yield of bio-oil is the most sensitive parameter in determining GWP and the electricity consumption also plays a significant role on GWP. The impact potentials of MSW pyrolysis were compared with those of other three alternatives of anaerobic digestion, incineration and landfill for treating MSW. Results show fast pyrolysis for bio-oil causes the least impact, while the disposal of the MSW in landfills causes the worst impact on the environment. Based on above results, pyrolysis of MSW for transportation fuels is an environment-friendly way to utilize the MSW.

Publications

  • Type: Books Status: Published Year Published: 2014 Citation: Wang, L. J. (editor). 2014. Sustainable Bioenergy Production. Boca Raton, FL: CRC Press, Taylor & Francis (600 pages, ISBN: 9781466505520).
  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Wang, L.J., Agyemang, S.A. and Shahbazi, A. 2014. Chapter 3 Mathematical modeling in biomass and bioenergy systems in: Wang, L.J. (editor), Sustainable Bioenergy Production, Boca Raton, FL: CRC Press, Taylor & Francis, pp.67-97.
  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Wang, H. and Wang, L.J. 2014. Chapter 12(April). Animal Wastes as an Energy Feedstock: Availability and Sustainability in: Wang, L.J. (editor), Sustainable Bioenergy Production, Boca Raton, FL: CRC Press, Taylor & Francis, pp.247-263.
  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Wang, L.J. 2014 (April). Chapter 14 Food Processing Wastes as an Energy Feedstock: Availability and Sustainability. in: Wang, L.J. (editor), Sustainable Bioenergy Production, Boca Raton, FL: CRC Press, Taylor & Francis, pp.285-309.
  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Wang, L.J. and Cheng, D. 2014 (April). Chapter 18 Biomass Pyrolysis and Bio-oil Utilization.in: Wang, L.J. (editor), Sustainable Bioenergy Production, Boca Raton, FL: CRC Press, Taylor & Francis, pp.367-387.
  • Type: Book Chapters Status: Published Year Published: 2013 Citation: Wang, H., Wang, L.J. and Shahbazi, A. 2013 (Oct.). Chapter 7 Biomass pyrolysis for bio-oil, In: Zhang, B. and Wang, Y. (editors), Biomass Processing, Conversion and Biorefinery, New York: Nova Publishers, pp. 139-153.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Wang, H., Wang, L.J., and Shahbazi, A. 2014. Life cycle assessment of fast pyrolysis of municipal solid waste. Journal of Cleaner Production, in press, online: http://dx.doi.org/10.1016/j.jclepro.2014.09.011.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Nan, W., Krishna, C.R., Kim, T.J., Wang, L.J., and Mahajan, D. 2014. Catalytic upgrading of switchgrass-derived pyrolysis oil using supported ruthenium and rhodium catalysts. Energy & Fuels, 28: 4588-4595.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Cheng, D., Wang, L.J., Shahbazi, A., Xiu, S. and Zhang, B. 2014. Catalytic cracking of crude bio-oil from glycerol-assisted liquefaction of swine manure. Energy Conversion and Management, 87: 378-384.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Cheng, D., Wang, L.J., Shahbazi, A., Xiu, S. and Zhang, B. 2014. Characterization of the physical and chemical properties of the distillate fractions of crude bio-oil produced by the glycerol-assisted liquefaction of swine manure. Fuel, 130: 241-256.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Wang, H., Wang, L.J. and Shahbazi, A. 2014. Life cycle assessment of fast pyrolysis of municipal solid waste in North Carolina of USA. ASABE Annual Meeting, Montreal, Quebec Canada, July 13-16.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Wang, H., Wang, L.J. and Shahbazi, A. 2014. Experimental investigation of pyrolysis oil based natural biocomposite materials. ASABE Annual Meeting, Montreal, Quebec Canada, July 13-16.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Wang, L.J., Cheng, D., Shahbazi, A. 2014. CFD modeling of flow and heat transfer in a reactive distillation column for upgrading bio-oil. ASABE Annual Meeting, Montreal, Quebec Canada, July 13-16.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Nan,W., Krishna,C.R.,Kim, T.J., and Mahajan, D. 2014. Bio-oil Production and Catalytic Upgrading to Transportation Fuels. Advanced Energy Research and Technology Center (AERTC) Conference, Hilton, Albany, New York. April 28 & 29.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Nan, W., Kim, T.J., Krishna, C.R., and Mahajan, D. 2013. Bio-oil Production and Catalytic Upgrading to Transportation Fuels American Institute of Chemical Engineers (AIChE) Annual Meeting, Hilton, San Francisco, California. November 3-8.
  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Cheng, D., 2014. Characterization and catalytic upgrading of crude bio-oil produced by hydrothermal liquefaction of swine manure and pyrolysis of biomass. Dissertation, North Carolina Agricultural and Technical State University.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Ansah, E., 2013. Experimental investigation and ASPEN Plus simulation of the MSW pyrolysis process. Thesis, North Carolina Agricultural and Technical State University.
  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Khan, M.A., 2014. Chemical reactive separation in energy and environmental processes. Thesis, North Carolina Agricultural and Technical State University.


Progress 09/01/12 to 08/31/13

Outputs
Target Audience: During this report period, the PI, Co-PIs and graduate students who worked on this project gave eight presentations based on the research results from this project at difference professional conferences. A Ph.D. student (Dan Cheng) who is working on this project gave a seminar about reactive distillation of bio-oil to the interdisciplinary Ph.D. program of Energy and Environmental Systems at NC A&T. The PI, Lijun Wang, offered a special topic course of advanced reactive distillation to Ph.D. students in the interdisciplinary Ph.D. program of Energy and Environmental Systems at NC A&T. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? At NCAT, the grant from this project was used to directly support three graduate students, one undergraduate student and one postdoc research associates who were hired to work on this project. This grant provided travel funds to two graduate students who presented their research results at the 2013 American Society of Agricultural and Biological Engineers (ASABE), and the 2013 American Institute of Chemical Engineers (AIChE). This grant also provided travel funds to the PI, Lijun Want, to present the research results of this project at the 2013 ASABE Annual Meeting and the 17th ARD Biennial Research Symposium. With the support of this project, the PI, Lijun Wang, offered a special PI, Lijun Wang, offered a special topic course of advanced reactive distillation to Ph.D. students in the interdisciplinary Ph.D. program of Energy and Environmental Systems at NC A&T. At Stony Brook University, the grant from this project was used to support a Ph.D. student, Wei Nanto work on multi-functional catalysts for catalytic upgrading of bio-oil distillate fraction into transportation fuels with a focus on bio-oil upgrading using catalytic hydrodeoxygenation (HDO) approach. The Co-PI at University of Nebraska-Lincoln, Dr. Milford Hanna, visited North Carolina &T State University in the January of 2013. During this visit, Dr. Hanna discussed this project with faculty, students and postdoc associate at NC A&T. How have the results been disseminated to communities of interest? During this report period, the PI, Co-PIs and graduate students who worked on this project gave eight presentations based on the research results from this project at difference professional conferences. The PI, students and postdoc visited 3 MSW transfer stations and 2 landfills in NC to discuss the technology of MSW pyrolysis and bio-oil upgrading for the management of MSW. The PI gave one seminar at the School of Agriculture and Environmental Science, NC A&T. The communication office at NC A&T has written an article to report this research in its Research Magazine. What do you plan to do during the next reporting period to accomplish the goals? Future work will be focused on developing a continuous system that integrates fast pyrolysis and reactive distillation. There will be three major research activities including: Multifunctional catalysts for upgrading reactions (hydrocracking, esterification and steam reforming) Reactive distillation column design and analysis ASPEN Plus simulations of the reactive distillation process: A simulation will be carried out including 10% hydroxyl-acetaldehyde with all other compounds already included in the simulation. Life cycle assessment and economic analysis of the reactive distillation process Experimental investigation of pyrolysis oil based biocomposites and biofertilizer

Impacts
What was accomplished under these goals? At NCAT, three graduate students have been recruited to work on this project, which include: Ph.D. student, Dan Cheng, Energy and Environmental Systems, Dissertation topic: Investigation of a reactive distillation process for upgrading bio-oil into transportation fuels, expected graduation date: July 2014 M.S. student, Md Arif Khan, Chemical Engineering, Thesis topic: Simulation of Reactive Distillation for Esterification of Pyrolysis Bio-oil, expected graduation date: May 2014. M.S., Emmanuel Ansah, Chemical Engineering, Thesis title: Experimental investigation and ASPEN Plus simulation of the MSW pyrolysis process, Graduation date: December 2013. Below were the major accomplishments from the above three thesis/dissertation research activities during this report period: A laboratory screw-auger, fluidized bed reactor and fixed bed reactor were designed and constructed to investigate the biomass pyrolysis process and supply bio-oil samples for this project. A laboratory reactive distillation column was designed and constructed to upgrade bio-oil for this project. Experiments have been started on those units and results will be reported during next report period. The thermal degradation characteristics (TGA curves), differential scanning calorimetry (DSC) and mass spectrometry (MS) curves of biomass and MSW samples, eleven simulated MSW components, biomass constituent components of cellulose, hemicellulose and lignin during pyrolysis in nitrogen were measured by a TGA/DSC/MS analyzer. The TGA, DSC and MS curves were used to develop kinetic models of biomass and MSW pyrolysis, determine reaction heat and analyze the evolving gas profile during pyrolysis, respectively. Advanced distillation unit that was purchased from Nation Institution of Science and Technology was used to generate a distillation curve of crude bio-oil that was produced from glycerol-assisted hydrothermal liquefaction of swine manure in a high-pressure and high-temperature Parr reactor. Each 10% volumetric fraction collected from the distillation unit was analyzed to determine their chemical compositions, water content, and energy content. Volumetric fractions with higher distillation temperature showed lower water content and higher energy density. GC-MS shows that crude bio-oil produced from the glycerol-assisted hydrothermal liquefaction of swine manure mainly consisted of long-chain acid esters. Catalytic cracking was chosen as the main method to upgrade crude bio-oil produced from glycerol-assisted hydrothermal liquefaction of swine manure because this kind of bio-oil had much higher distillation temperatures and long chain acid esters were detected by GC-MS. Carbon based catalysts was made by wet impregnation methods. Physical properties of crude bio-oil and upgraded bio-oil including water content, heating value and viscosity were measured by Karl Fish Titration Unit, Calorie Bomb and Brookfield Viscometer (25°C), respectively. Chemical compositions of crude bio-oil and upgraded bio-oil were analyzed by GC-MS. For comparison, No.2 diesel and No.87 gasoline that were purchased from a gas station were also analyzed. The research showed that crude bio-oil from glycerol assisted liquefaction of swine manure was highly distillable with 90% volume distilled at 499°C. However, it had very high distillation temperatures and large temperature range compared to those of gasoline and diesel. An ASPEN Plus model was developed to simulate the reactive distillation of bio-oil via the esterification with n-butanol and about 90% conversions were found for some compositions of bio-oil. Design specification and sensitivity analysis were also performed to optimize the reactive distillation process and establish the effect of various parameters on others. Phenols and other high carbon alcohols present in bio-oil were incorporated in the simulation and the butanol feed reduced accordingly. Three manuscripts based on the above resarch results are under review. At Stony Brook University, a Ph.D. student, Wei Nan has been recruited to work on multi-functional catalysts for catalytic upgrading of bio-oil distillate fraction into transportation fuels with a focus on bio-oil upgrading using catalytic hydrodeoxygenation (HDO) approach. The bio-oil samples: corn stover and soybean straw, were obtained from Dr. Boteng’s group at the USDA-ARS facility in Wyndmoor, Pennsylvania.The bio-oil samples were characterized and then subjected to upgrading in a Parr 300 mL batch reactor. A series of catalysts were screened for HDO in batch mode under T < 300oC and P < 500 psig. Results for corn stover derived bio-oil were reported previously in the August 2012 Annual Project Report. Between September 2012 and March 2013, the Biofuels Group at Stony Brook University (SBU) received a major internal grant to purchase instrumentation for Fuels R&D. The group was renamed Low-Carbon Energy Management (L-CEM) and it is now housed in two state-of-the-art laboratories in the newly opened Advanced Energy Research & Technology Center (www.aertc.org). The instrumentation includes both batch and continuous units for catalyst evaluation and a number of materials characterization equipment (FTIR, UV-VIS, GC-MS). These facilities allow us to characterize bio-oils and their processed products. A series of runs are now underway with bio-oil derived from switch grass. We are following the set procedure for batch screening: 10% bio-oil/90% PEG-400; 0.6 g catalyst. Again the temperature and pressure are being kept at < 300oC and < 500 psig, respectively. In parallel, we are characterizing bio-oil products from the HDO reaction using CG-MS. The catalyst is selected from Ru and Rh supported on carbon or alumina. We also plan to design a scheme that would integrate these results in to the Reactive Distillation system being developed in the primary PI’S group. These results will be the subject of the next annual report. The results have been disseminated at various conferences.

Publications

  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Wang, L.J., Cheng, D., Xiu, S., Wang, H. and Shahbazi, A. 2013. Hydrotreatment of bio-oil in a reactive distillation column. ASABE Annual Meeting, Kansas City, Missouri, July 21-24.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Cheng, D., Wang, L.J., Shahbazi, A. and Xiu, S. 2013. Reactive distillation of crude bio-oil from fast pyrolysis of bagasse. ASABE Annual Meeting, Kansas City, Missouri, July 21-24.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Md Arif Khan and Yusuf G. Adewuyi. 2013. Simulation of Reactive Distillation for Esterification of Pyrolysis Bio-oil. The AIChE Annual Meeting, San Francisco, CA, November 3-8, 2013.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Wang, L.J., Ansah, E., Wang, H., Shahbazi, A. and Reddy, G.B. 2013. Pyrolysis of municipal solid waste into bio-oil. 17th ARD Biennial Research Symposium, Jacksonville, FL., April 7-10, 2013.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Wei Nan, CR Krishna and D. Mahajan. Bio-oil Production and Catalytic Upgrading to Transportation Fuels. 6th Advanced Energy Conference (AEC), Jacob K. Javits Convention Center, New York. April 30- May 1, 2013.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Wei Nan, Debayon Dutta, CR Krishna and D. Mahajan. Bio-oil Production and Catalytic Upgrading to Transportation Fuels. Earthstock 2013, Poster Exhibition, Stony Brook University, Long Island, New York. April 19, 2013.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Wei Nan, CR Krishna and D. Mahajan. Bio-oil Production and Catalytic Upgrading to Transportation Fuels. International Energy and Sustainability Conference (IESC), Farmingdale State College, Long Island, New York. March 19, 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Emmanuel Ansah, M.S. thesis: Experimental investigation and ASPEN Plus simulation of the MSW pyrolysis process, Department of Chemical, Biological and BioEngineering, North Carolina A&T State University, Graduation date: December 2013.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Debayon Dutta, Wei Nan, CR Krishna and D. Mahajan. Bio-oil Production and Catalytic Upgrading to Transportation Fuels. Undergraduate Research & Creative Activities (URECA), Stony Brook University, Long Island, New York. April 24, 2013.


Progress 09/01/11 to 08/31/12

Outputs
OUTPUTS: At NCAT, a lab-scale twin-screw auger reactor was designed and fabricated to supply bio-oil via pyrolysis of biomass. Bio-oil was also produced from hydrothermal liquefaction of swine manure in a 5-liter Parr Reactor. A distillation curve measured on crude bio-oil from swine manure shows that the yield of the distillate at 450C was 54% of the crude bio-oil by volume. The distillate had a much higher heating value and lower viscosity than crude bio-oil. Thermalgravimetric analysis shows over 70% distillate was burnt off at 300C compared to 30% for crude bio-oil at the same temperature. A lab-scale reactive distillation column was designed and fabricated, which consists of four sections for stripping/water-gas shift reaction, feeding, hydrocracking reaction and esterification. Carbon-based catalysts were investigated as the packing of the column. A solid carbon-based acid catalyst was prepared from lignocellulosic biomass using a carbonization-sulfonation process to catalyze the esterification reaction. Ni catalyst on the support of activated carbon was prepared to catalyze the hydrocracking reaction. A novel membrane reactor is currently investigated to catalytically enrich hydrogen in syngas via water-gas shift reaction to supply hydrogen for the hydrocracking reaction. The three plug-flow reactors with proper catalysts will then be integrated to form a reactive distillation column in 2012/2013. The RADFRAC module of the ASPEN Plus software was used to simulate the reactive distillation of simulated bio-oil. The esterification reaction of simulated bio-oil (70% acetic acid and 30% water) with n-butanol was successfully simulated using UNIQUAC property model for phase equilibrium and minimizing Gibbs free energy for chemical reaction. The simulation continues to be extended to a more complex simulated bio-oil (30% acetic acid, 20% formic acid, 20%propionic acid and 30% water). At Stony Brook U., a series of catalyst precursors including NiCl2, Al2O3, CoCl2, Ru/C and Rh/C, Ru(bipy)(CO)2Cl2, Ru/Al2O3 and Rh/Al2O3 were selected for the hydrodeoxygenation of bio-oil. Bio-oil samples were provided by the USDA-ARS in Wyndmoor, Pennsylvania. Polyethylene glycol and hexadecane were used as a solvent during hydrodeoxygenation. Ru/Al2O3 and Ru/C showed the highest H2 consumption in the operating temperature range of 150-200C. NiCl2/Al2O3 and CoCl2/Al2O3 had good effect on producing of C5 and C6 hydrocarbons at a low temperature <250C. No methane was detected in final gas samples. Research also showed that the reaction time at 4 hours was enough for Ru(bipy)(CO)2(Cl)2 with corn stover bio-oil at 150C. The crude and upgraded bio-oil were recently sent to the collaborators at NCAT for the measurement of distillation curves. The Co-PI at UNL, Dr. Milford A. Hanna, visited NCAT on 09/09/2011 and gave a seminar titled "Biofuels-Production and Research Opportunities" to the faculties and students. We will start to work on the conversion of bio-oil residue into biocomposites and biofertilizer in 2012/2013 ater the reactive distillation column at NCAT becomes ready to fractionate crude bio-oil into light fraction of fuels and heavy fraction of bio-oil residue. PARTICIPANTS: Partner Organizations: North Carolina Agricultural and Technical State University (NCAT) Stony Brook University (SBU) University of Nebraska-Lincoln (UNL) Senior personnel: Lijun Wang (PI, NCAT) Abolghasem Shahbazi (Co-PI, NCAT) Shuangning Xiu (Co-PI, NCAT) Yusuf G. Adewuyi, Y. (Co-PI, NCAT) Devinder Mahajan (Co-PI, SBU) Milford A. Hanna (Co-PI, UNL) Graduate students: At NCAT, one Ph.D. student in Energy and Environmental Systems and three M.S. students in Chemical Engineering have been hired to conduct their research supported by this project toward their dissertation/thesis. All of these four students who are supported by this project have completed their courses by the end of the fall semester of 2012. They have started to conduct research on the following research activities proposed by this project on a full time basis: (1) Investigation of a reactive distillation process for upgrading bio-oil into transportation fuels (Dan Cheng, Ph.D. candidate), (2) Simulation of reactive distillation for the esterification of bio-oil using Aspen-PLUS (Md Arif Khan, M.S. candidate), (3) investigation of a novel membrane reactor for the production of hydrogen from syngas via water-gas shift reaction (Kwabena Darkwah, M.S. candidate), and (4) Experimental investigation of pyrolysis oil based biocomposites and biofertilizer (Mansoor Pasha, MS). At Stony Brook University, a Ph.D. student, Wei Nan has been recruited to work on multi-functional catalysts for catalytic upgrading of bio-oil distillate fraction into transportation fuels. TARGET AUDIENCES: PI, Dr. Lijun Wang gave a presentation titled "Biorefineries for Sustainable Bioenergy Production" that included the research results from this project to the faculty, extension specialists and students at School of Agriculture and Environmental Sciences at NCAT on 10/20/2011. An article about the research of this project was published in the magazine, Research (Volume 9), published by School of Agriculture and Environmental Sciences at NCAT in 2012. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
This project has strengthened the capacity of our minority university, NCAT, to conduct research on bioenergy and bio-based products by establishing a platform for us to collaborate with major universities, Stony Brook University and University of Nebraska-Lincoln, and providing necessary instruments and lab supplies our research. In the past fiscal year, we have obtained significant amount of knowledge in the fields of catalysis for upgrading bio-oil, reactive distillation design, and mathematical modeling of reactive distillation. This knowledge will be essential for us to eventually develop a reactive distillation process for upgrading bio-oil into transportation fuels as proposed by this project. This project directly provided training opportunities to two Ph.D. students, three MS students and one undergraduate student in 2011/2012. At NCAT, this project provided support for three education programs, including Biological Engineering (undergraduate program), Chemical Engineering (M.S. program) and Energy and Environmental Systems (Ph.D. program). With the financial support from this grant, we built a laboratory-scale twin-screw auger reactor for the research on the production of bio-oil from biomass via pyrolysis and a laboratory-scale reactive distillation column for the catalytic upgrading of bio-oil. Collaboration with SBU and UNL on this project has further strengthened the linkages between NCAT, and major universities and national research labs.

Publications

  • In 2012/2013, we will start to prepare journal manuscripts based on our research on catalysis of water-gas shift reaction, hydrocracking reaction and esterification reaction.
  • 1. Wang, L.J. and Cheng, D. 2012. Chapter 3.4 Biomass pyrolysis and bio-oil utilization, In: Wang, L.J. (editor), Sustainable Bioenergy Production, Boca Raton, FL: CRC Press, Taylor and Francis, In press.
  • 2. Wang, L.J., Cheng, D., Xiu, S.N., Iyyamperumal, E. and Shahbazi, A. 2012. Multifunctional Catalysis For Bio-oil Upgrading. ASABE Annual Meeting, Dallas, TX, July 29-August 1.
  • 3. Cheng, D., Wang, L.J., and Shahbazi, A. 2012. Measurement of Reactive Distillation Curves of Bio-oil. ASABE Annual Meeting, Dallas, TX, July 29-August 1.


Progress 09/01/10 to 08/31/11

Outputs
OUTPUTS: At NC A&T, one Ph.D. student in Energy & Environmental Systems and three M.S. students in Chemical Engineering have been hired to conduct the research supported by this project toward their dissertation/thesis. The tentative titles of their dissertation/thesis are: (1) Dan Cheng (Ph.D.)-Design and optimization of reactive distillation for refining bio-oil, (2) Jarret L. McClendon (M.S.)-Multifunctional catalysis for bio-oil upgrading, (3) Md. Arif Khan (M.S.)-Investigation of a reactive distillation column for bio-oil upgrading, (4) Mansoor Pasha (M.S.)-Screw extrusion of bio-oil/starch/nanoparticles into biodegradable plastics. These students have already started to conduct literature review on the topics assigned to them. Two undergraduate students have been paid on an hourly basis and trained on characterization of physical and chemical properties of bio-oil. With the support of this project, the PI has won another relevant projected titled "Assessment of municipal solid wastes into transportation fuels via pyrolysis" recently funded by the Biofuels Center of North Carolina. Both projects are enhancing our research capability to both produce and refine bio-oil. An advance distillation curves apparatus has been fabricated by National Institute of Standards and Technology (NIST). This instrument is used to measure the distillate fractions of crude bio-oil with and without the addition of catalysts and chemicals at different temperatures. Mr. Dan Cheng has completed two-day training on the use of the instrument by NIST. A viscometer has been purchased to measure the viscosity of bio-oil before and after upgrading. A screw-auger pyrolysis reactor has been fabricated to pyrolyze biomass for the supply of bio-oil for this project. Research has been conducted at Stony Brook University to evaluate catalysts for upgrading of bio-oil. At SBU, a graduate student, Wei Nan, was recruited to work on this project at SBU. A series of catalyst precursors including nickel, cobalt, ruthenium, and rhodium based: NiCl2, Al2O3, CoCl2, Ru/C and Rh/C, Ru(bipy)(CO)2Cl2, Ru/Al2O3, Rh/Al2O3 were selected and screened for upgrading bio-oil. Two bio-oil samples were obtained from the group of Dr. Akwasi Boateng at the Eastern Regional Research Center, USDA-ARS, Wyndmoor, Pennsylvania. Preliminary data showed that the catalytic treatment of bio-oil has successfully removed O from the bio-oil by 14.4%. The catalysts of Ru/Al2O3 and Ru/C showed the highest H2 consumption at the operating temperature of 150o - 200oC for the hydrogenation of bio-oil. Several runs showed that at T: < 230oC, no methane was detected in final gas samples. This was a very desirable result for bio-oil upgrading. Our collaborator at University of Nebraska-Lincoln, Dr. Milford A. Hanna, visited NC A&T on the September 9th of 2011 and gave a seminar titled "Biofuels-Production and Research Opportunities" to our faculties and students. We have discussed the collaboration on this project in details. Both sides agreed to arrange a trip for a graduate student from NC A&T to conduct summer research on screw extrusion of bio-oil based plastics at UNL in the summer of 2012. PARTICIPANTS: Partner Organizations: North Carolina Agricultural and Technical State University (NCAT) Stony Brook University (SBU) University of Nebraska-Lincoln (UNL) Senior personnel: Lijun Wang (PI, NCAT) Abolghasem Shahbazi (Co-PI, NCAT) Shuangning Xiu (Co-PI, NCAT) Yusuf G. Adewuyi, Y. (Co-PI, NCAT) Devinder Mahajan (Co-PI, SBU) Milford A. Hanna (Co-PI, UNL) Graduate students: Dan Cheng (Ph.D. student, NCAT) Jarret L. McClendon (M.S. student, NCAT) Mansoor Pasha (M.S. student, NCAT) Md. Arif Khan (M.S. student, NCAT) Wei Nan (Ph.D. student, SBU) Undergraduate student: Maria Hargis Carmen Young Five graduate and two undergraduate students have been trained by this project. A research senimar on the subject of biofuels has been given to relevant faculties and students at NC A&T by Co-PI, Dr. Milford Hanna. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
This project has already provided training opportunities to seven graduate and undergraduate students who will have more chances to be hired in the bio-based industry. This project has provided support for three education programs at NC A&T, including Biological Engineering (undergraduate program), Chemical Engineering (M.S. program) and Energy and Environmental Systems (Ph.D. program). Five graduate and two undergraduate students have been hired and supported to work on this project. Specific research topics have been assigned to these five graduate students. Most of the graduate students have already completed their courses and started to conduct literature review on the topics assigned to them. Equipment and instruments for this project have been purchased and they are ready to use. We have already started to work on (1) production and characterization of bio-oil, (2) selection and screening of multi-functional catalysts for upgrading bio-oil, and (3) measurement of reactive distillation curves of bio-oil. All these research activities will eventually enable us to develop a well-understood reactive distillation process to maximize the recovery of transportation fuels from the crude bio-oil, to ensure the quality of the final fuel product and to convert no-volatile distillation oil residues into biodegradable plastics. The grant from this project has strengthened the capacity of our minority university, NC A&T, to conduct research on bioenergy and bio-based products by enabling us to win another relevant project and providing necessary instruments and lab supplies. Collaboration with SBU and UNL on this project has further strengthened the linkages between NC A&T, and major universities and national research labs.

Publications

  • Two abstracts titled Multifunctional Catalysis For Bio-oil Upgrading, and Measurement of Reactive Distillation Curves of Bio-oil based on the research supported by this project have been submitted to the 2012 Annual Meeting of American Society of Agricultural and Biological Engineers. We will start to prepare journal manuscript in years 2 and 3 as proposed.