Source: UNIVERSITY OF KANSAS CENTER FOR RESEARCH, INC. submitted to NRP
GREEN TECHNOLOGIES FOR PRODUCT DIVERSIFICATION IN AN INTEGRATED BIOREFINERY
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
OTHER GRANTS
Reporting Frequency
Annual
Accession No.
0225077
Grant No.
2011-10006-30362
Cumulative Award Amt.
$5,635,858.00
Proposal No.
2010-05327
Multistate No.
(N/A)
Project Start Date
Jun 1, 2011
Project End Date
May 31, 2016
Grant Year
2011
Program Code
[BRDI]- Biomass R&D Initiative FY2009 Forward
Recipient Organization
UNIVERSITY OF KANSAS CENTER FOR RESEARCH, INC.
2385 IRVING HILL RD
LAWRENCE,KS 66045-7563
Performing Department
(N/A)
Non Technical Summary
The products for everyday life such as plastics, packaging materials, synthetic fibers and personal care products are currently derived almost entirely from petroleum. In the coming decades, the declining availability of petroleum and its increasing cost will require the chemical industry to transition to renewable feedstocks. The only sustainable option in this regard is non-food biomass. Following the paradigm of a profitable petrochemical refinery that produces a portfolio of liquid fuels and chemicals, it is envisioned that the integrated biorefinery of the future will convert a variety of biomass feedstocks into a balanced portfolio of bio-derived chemicals and advanced biofuels (beyond ethanol and biodiesel). Fortunately, the production of chemicals delivers ten times or greater value relative to fuels, which can make the advanced biorefinery profitable without subsidies, and will drive rural economic development. The challenge is to develop enabling catalytic technologies to make these conversion processes economically viable and environmentally sustainable. Specifically, this project seeks to accelerate the development and commercialization of a portfolio of green technologies to convert biomass-derived feedstocks into value-added products that are currently produced from petroleum on the order of millions of tons per year. The project will capitalize on the strengths of The University of Kansas Center for Environmentally Beneficial Catalysis (CEBC) in developing green catalytic processes and on Archer Daniel Midland Company's (ADM) expertise in the sustainable collection, storage, transportation, and processing of biomass such as corn stover and oil seeds. The outcome will be a demonstration of novel green pilot-ready technologies that diversify the product portfolio from these biomass sources beyond the traditional outputs (ethanol, methanol, biodiesel, sugars, starch and lignin). The spectrum of products includes advanced fuels (such as higher alcohols), high volume industrial chemicals (such as plasticizer alcohols, carboxylic acids and aromatic compounds), and chemical intermediates (such as terephthalic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and methacrylic acid used in the manufacture of plastics). ADM and its partners will test product samples from bench-scale processes to ensure their quality and performance. Techno-economic and life cycle assessments (TE/LCA) will continually guide research towards commercial viability. Successful implementation of sustainable biorefineries will have a lasting impact on future generations of our planet. Commercialization of the bio-products targeted in this project has a potential global market value of $127 billion/year. Assuming that one third of the global capacity is located in the USA, approximately 40,000 jobs in direct biorefinery employment and an additional 120,000 indirectly via supporting industries will be necessarily shifted to domestic rural areas, thereby curtailing overseas outsourcing of the chemicals industry.
Animal Health Component
50%
Research Effort Categories
Basic
20%
Applied
50%
Developmental
30%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5111510200010%
5111510202030%
5111820200010%
5111820202020%
5116110200015%
5116110202015%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
6110 - Economy of the United States and sectors thereof; 1510 - Corn; 1820 - Soybean;

Field Of Science
2020 - Engineering; 2000 - Chemistry;
Goals / Objectives
The overarching goal is to develop novel green technologies for producing an economically viable spectrum of targeted high-volume industrial chemicals, chemical intermediates and fuels from bio-based feedstocks in an integrated biorefinery. Specific objectives are as follows: (1) Develop appropriate feedstocks from a biorefinery that processes lignocellulosics and vegetable oils to yield sugars, lignin, biodiesel and fatty acid methyl esters (FAMEs) such that these refinery streams are effectively integrated and utilized to produce the targeted fuels, chemicals and chemical intermediates. (2) Demonstrate novel bench-scale and pilot-ready process concepts for transforming a variety of biomass feedstocks to targeted fuels and chemicals, employing CEBC's multiscale approach that involves exploiting/developing appropriate chemistries, novel catalysts, green solvents and multiphase reactors. Specific processes to be developed include: (a) Clean ozonolysis in liquid CO2 to convert (i) oils and fatty acid methyl esters (FAMEs) to acids and aldehydes in one step, and (ii) lignin, either neat or appropriately pretreated, to valuable aromatic compounds, including benzene, toluene and xylenes (BTX); (b) Facile hydroformylation of glycerol-derived allyl alcohol to produce 1,4-butanediol or methacrolein/methacrylic acid using gas-expanded liquids (GXLs) as reaction media to reduce solvent usage and enhance regioselectivity; (c) Selective oxidations of renewable p-xylene and hydroxymethylfurfural (HMF) in a spray reactor to produce plastic intermediates such as polymer-grade terephthalic acid (PTA) and 2,5-furan dicarboxylic acid (FDCA) in one step, obviating the need for the hydrogenation and the solvent intensive purification steps; (d) Synthesis of higher alcohols (C3+) from methanol and ethanol, derived from cellulosic sources, as a means of further upgrading these abundantly available feedstocks to produce chemicals and fuel alternatives. The spectrum of products includes advanced fuels (such as higher alcohols), high volume industrial chemicals (such as plasticizer alcohols, carboxylic acids and aromatic compounds), and chemical intermediates (such as terephthalic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and methacrylic acid used in the manufacture of plastics). The biobased fuels and chemicals targeted in this project will potentially displace the equivalent of 600 million barrels of oil equivalence (BOE) per year, with commensurate decreases in greenhouse gas emissions. Diversifying the product portfolio of the integrated biorefinery will insulate it from market fluctuations, and will revitalize the sagging chemical and manufacturing sectors in the US. Successes in the proposed R&D effort will eventually revolutionize rural development in agro-based economies. Commercialization of the bio-products targeted in this project has a potential global market value of $127 billion/year. Assuming that one third of the global capacity is located in rural US communities, the projected number of jobs injected into the rural economy will be 40,000 in direct biorefinery employment and an additional 120,000 indirectly via supporting industries.
Project Methods
This project will address the technical barriers/challenges for the sustainable manufacture of bio-based products including: (a) development of feedstock that is competitive with fossil-based feedstock in terms of transformability, purity and cost; (b) development of novel green catalytic systems (i.e., novel catalysts, solvents, reactors and separations) that convert the feedstock to desired product while maximizing carbon atom economy and minimizing waste and pollution; (c) quantitative sustainability assessment (techno-economic analysis and Life Cycle Analysis) at various R&D stages to ensure the development of practically viable catalytic technologies. The partnership between the University of Kansas Center for Environmentally Beneficial Catalysis (CEBC) and Archer Daniels Midland (ADM) Company will effectively integrate the essential upstream (feedstocks), downstream (conversion technologies) and sustainability aspects to successfully develop and demonstrate viable technologies. A multi-disciplinary R&D team involving scientists and engineers from the CEBC will exploit/develop appropriate chemistries, novel catalysts, green solvents and multiphase reactors to demonstrate the targeted conversion technologies. A rational design approach for catalyst development, one that takes into account such factors as mechanism-based molecular catalyst selection and design, nano-scale materials, and benign media, will yield novel and redesigned synthetic catalysts for the deconstruction/conversion of lignocellulosic biomass and oils. New operando and in situ high-pressure spectroscopic tools (such as ReactIR and UV-Vis) for probing catalytic reactions will be used, and complemented by computational chemistry models to greatly expand the fundamental understanding of metal catalyzed C-O, C-H and C-C bond activation mechanisms, including those involving CO, H2 and O3. The many synergies between catalysis and neoteric solvent media (such as gas-expanded liquids) will be exploited to develop sustainable continuous process concepts for selective oxidations, ozonolysis and hydroformylations with the following attributes: process intensification at mild conditions, minimization of waste and adverse environmental footprints, and enhanced inherent safety. The research program will leverage the ongoing biomass to fuels and chemicals program at ADM, and develop techno-economic (TE) and LCA models based on data obtained from commercial scale feedstock harvesting and processing. These assessments will conform to ISO 14040 and 14044 standards, and serve as decision-oriented tools. ADM and its partners will test product samples from bench-scale processes to ensure their quality and performance. Process-related economic and environmental impact assessments will be employed to benchmark the novel technology concepts against conventional processes. The results from such comprehensive analyses will guide R&D efforts toward rapid commercialization.

Progress 06/01/11 to 05/31/16

Outputs
Target Audience:The primary audience for this work includes agricultural processors, chemical manufacturers, and entrepreneurs seeking to adopt new technologies for producing value-added chemicals from biomass-derived feedstocks, as well as product manufacturers or agricultural producers who would benefit from such bio-derived chemicals. One such company, Archer Daniels Midland (ADM), is already a key partner on this project. Via the University of Kansas Center for Environmentally Beneficial Catalysis (CEBC), some of the results are being discussed with representatives from other companies to gage interest and obtain feedback on potential commercial opportunities. Additionally, the discoveries made in this work are being shared with broader audiences to share lessons about developing and evaluating more environmentally benign chemical technologies. Researchers on this project are active in making conference presentations and writing technical journal articles to disseminate the findings. Researchers have also presented this work to area high school science teachers and to government (State and Federal) representatives. Changes/Problems:There were some technical challenges that had to be overcome, resulting in minor delays in progress. In particular, the development of the continuous ozonolysis reactor and the continuous spray reactor posed several unexpected challenges. The use of ozone required gasket materials that are inert to ozone and the compressors required adequate cooling to prevent ozone decomposition. In the continuous spray process, the titanium metering valve at the reactor exit plugged from premature crystallization of the dicarboxylic acid product. This problem was successfully overcome by operating at T & P conditions where product precipitation was avoided. The most significant change in scope is perhaps a focus in the development of novel catalysts. Based on parallel developments in chemocatalytic conversion of biomass feedstocks, our team recognized early on during the project that we should also focus on the development of novel multifunctional solid mesoporous catalysts that can accommodate large biomass-based molecules without causing steric hindrance (as conventional catalysts do). Accordingly, we also devoted effort towards development of such catalysts aimed at understanding C-C cleavage, C-O cleavage and C-C coupling that are applicable to dehydration, depolymerization, increasing chain length, etc. Such catalysts were deemed to be clearly relevant to the various chemistries investigated in the USDA proposal including lignin dehydration, hydroformylation, development of higher alcohols and selective oxidations. Indeed, in addition to successfully developing the pre-pilot ready technologies envisioned in our original proposal, our team has also developed a family of novel catalysts that have led to several inventions and new process concepts for the effective utilization of sugar streams, lignin depolymerization, and the dehydration of ethanol and higher alcohols to olefins. The development of new catalysts for biomass conversion has also helped in developing new fundamental insights into the underlying reaction mechanisms and paved the way for new federal grants aimed at lignin depolymerization. The fundamental studies were particularly well suited for training graduate students and were also supplemented with other sources of funding. These technical challenges and additional complementary tasks resulted in the request for a one year, no-cost extension. What opportunities for training and professional development has the project provided?Students and postdoctoral researchers (collectively referred to below as students) on this project worked closely with highly respected faculty mentors in weekly multi-disciplinary research meetings. Intellectual Property (IP) training was provided annually to aid students in identifying and protecting potentially patentable information. Students are encouraged to draft journal papers and present their work at professional society meetings. Students on this project also worked regularly with ADM scientists, through regular videoconferenced group meetings, quarterly site-visits, and secure shared data server space. Students interacted directly with CEBC's Industrial Advisory Board (IAB), which is comprised of leading chemical and energy companies, such as ADM, Evonik, INVISTA, SABIC, Solvay and UOP/Honeywell, among others. Students had opportunities to make oral and poster presentations at semi-annual IAB meetings and receive project evaluations conducted by IAB members. CEBC's IAB members bring unique perspectives on the commercial potential of early stage research projects, complementing the academic perspective. Students also met with speakers in CEBC's Industrial Colloquia Program, which features prominent industrial researchers on a variety of topics, and provide a glimpse into how R&D in industry differs from academia. The CEBC Education Director organized professional development workshops for students, addressing topics such as technical presentation skills, communication to general audiences, career guidance, intellectual property and commercialization issues, laboratory safety, and "lunch-and-learn" peer-to-peer skill development sessions. Students also served on the CEBC Laboratory Safety Committee, which coordinates and enforces good laboratory practices for the Center. Several of these professional development activities were leveraged by CEBC's NSF Research Experience for Teachers program, to provide hands-on research and professional development for regional high-school science teachers. How have the results been disseminated to communities of interest?The project has contributed significant fundamental science and technology advances for producing bio-derived chemicals, as documented in the 51 publications and new intellectual property being licensed. The cross-fertilization of ideas has led to additional research opportunities (based on both bio-based and other feedstocks) and provided direct training for more than 26 young scientists and engineers. Technology transfer occurred throughout the project by virtue of the close collaboration between KU and ADM. Furthermore, KU has granted ADM a non-exclusive, royalty-free license to the four patents/applications. ADM is currently sponsoring additional proprietary research through KU to continue development of these technologies. The ongoing development of these bench-scale technologies, in collaboration with industry, continues to hold promise for one or more commercially viable processes to emerge. The ultimate development and commercialization of these technologies will represent a significant transformation for the biorefinery industry as envisioned by the BRDI program. The research progress and potential of biorefining technologies, including results from this grant, were presented to several federal and state government officials and their staff members, highlighting the success of public/private partnerships such as this project. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Feedstock Development: ADM completed work on the DOE integrated biorefinery project to produce ethanol, propylene glycol, and ethyl acrylate from corn stover. The first step separates the stover into cellulose, hemicellulose, and lignin streams. The lignin is suitable for further reaction to chemicals and intermediates, and the streams have been sampled to various industrial and academic partners for evaluation. From the cellulose, dextrose was produced for conversion to sorbitol, which underwent subsequent hydrogenolysis to glycerol and glycols. The glycerol could be recovered for production of chemicals such as allyl alcohol. The dextrose may also be converted to fructose, the precursor molecule to HMF, as well. HMF, lignin, allyl alcohol, fatty acid methyl ester feedstocks were characterized and supplied to KU researchers for evaluation in the bench-scale processes below. FAME Ozonolysis: A continuous bench-scale process for the ozonolysis of fatty acid methyl esters (FAMEs) in liquid CO2 was successfully built and demonstrated. Carbon dioxide was used because it is inert to ozone (no oxidation byproducts from a solvent), shrinks the flammability envelope, and dissolves higher O3 concentrations than common solvents. The Henry's Law constant for O3/CO2 was measured for the first time. Using FAME feed stock provided by ADM, complete conversion was observed at mild conditions, with high selectivity to the secondary ozonides (SOZ). The SOZ generated are stable at ambient conditions. Hence, a subsequent stirred reactor was used to demonstrate the safe thermal decomposition of the SOZ into the desired organic acids and aldehydes. The kinetics for the thermal decomposition were determined to aid in future process scale-up. Complementary DFT calculations based on the Criegee intermediate shed valuable insight into the underlying reaction mechanism and product distribution based on activation energy barriers. Lignin Ozonolysis: Several novel oxidative pathways for the controlled deconstruction of lignin to aromatic monomers were explored, including acidic, basic, and aerobic treatments. To date, the most promising approach combines the use of an organic acid and ozone in a continuous reactor. Significant yields of vanillin and 4-hydroxybenzaldehyde have been achieved using this relatively simple process at ambient conditions, using both ADM-supplied lignin as well as an organosolv corn stover lignin prepared in-house. Spray Oxidation: The single-step oxidation to produce 2,5-furandicarboxylic acid (FDCA) from 4-HMF and purified terephthalic acid from p-xylene (pX) has been successfully demonstrated in a 4L continuous spray reactor. Both systems employ the well-known Co/Mn/Br catalytic system to oxidize the substrate to the corresponding dicarboxylic acid. The oxidation spray reactor process concept was first developed using the pX oxidation. The spray reactor was successfully scaled up to 4 L. At typical reaction conditions, the solid product from the spray process contains < 25 ppm of impurities. During semi-batch spray reactor operation, a post-reaction oxidation step with continuous air addition while maintaining a constant reactor pressure is essential to obtain polymer grade product. The use of air as the oxidant and higher pX concentrations were also successfully demonstrated in order to reduce operating costs. Guided by results from the pX reaction, the optimization of reaction conditions for maximizing the FDCA yield in the spray reactor was carried out, resulting in the reduction of the burning reactions. At optimized conditions, we achieved 95% yield of FDCA product, the highest reported with the Co/Mn/Br system. Kinetic data were obtained using a sophisticated sampling system designed for use with a stirred reactor to rapidly capture and quench samples. The kinetic parameters were validated and used by ADM engineers to carry out a technoeconomic analysis. Allyl Alcohol Hydroformylation: We have optimized a carbon dioxide-expanded liquid (CXL)-based process for converting allyl alcohol to 1,4-butanediol with high activity and regio-selectivity with a Rh/TPP homogeneous catalyst. A maximum regio-selectivity of nearly 7 was obtained at mild operating conditions. By extracting the hydroformylation products with water and hydrogenating them on Raney Ni, quantitative yield of 1,4 BDO has been demonstrated. In parallel work, we have shown that by attaching the Rh to a phosphine-functionalized polydimethylsiloxane (PDMS) ligand, continuous hydroformylation of linear olefins can be achieved in a stirred membrane reactor containing the soluble Rh/PDMS catalyst complex. Further, the dissolved bulky Rh complex is effectively retained by the nanofiltration membrane. Complementary DFT studies of ligand effects are guiding the design of regioselective hydroformylation catalysts. Additionally, the rhodium-catalyzed hydroformylation of acrolein diethyl acetal was shown to be a highly efficient reaction, with linear/branched product ratios around 9. Guerbet Alcohol Synthesis: We have discovered alkali promoted Cu-containing mixed metal oxide catalysts that convert methanol and ethanol mixtures to products of higher value and energy content, which can be used as chemical intermediates and/or fuel additives. These products are produced at yields higher than those of previously reported catalysts. Alkali metal-promoted Cu17MgAlOx mixed metal oxide catalysts are highly active for MeOH+EtOH coupling reactions because addition of promoter increases medium strength basicity. Alkali metals also free active sites for C-C coupling reactions by minimizing surface population of unreactive formate species. Mesoporous Catalyst Development: A variety of multifunctional metal-incorporated (such as Zr, Nb, Ce, W) mesoporous catalysts that can accommodate large bio-based molecules without causing steric hindrance have been developed. These catalysts are thus relevant to the various chemistries including lignin dehydration, hydroformylation, development of higher alcohols and selective oxidation. As one example, a mesoporous Zr-KIT-5 was found to give better catalytic performance than commercial zeolites for the acid-catalyzed decomposition of lignin, with 97% lignin conversion, yielding 65% of THF soluble products containing 5.5% identified monomers. Utilization of Sugar Streams: A new catalyst was developed for converting various biopolyols to lactic acid with glycols and linear alcohols as co-products at mild temperatures without external addition of either hydrogen or oxygen. Among various catalysts evaluated, Pt/C catalyst gives the highest selectivity (>95%) for lactic acid, glycols, and linear alcohols. Importantly, two-thirds of the hydrogen generated in situ via dehydrogenation of polyols over Pt/C catalyst is efficiently utilized for the conversion of the remaining polyols and intermediates to glycols and linear alcohols. The remaining hydrogen would be available for use elsewhere in a biorefinery. Furthermore, it is observed that Ba2+ alkali ion promotes the activity of the Pt/C catalyst by almost 12-fold compared to other alkali promoters. In addition to being the first reported study on the conversion of C5∼C6 polyols to lactic acid at relatively low temperatures, the results also provide new insights into the mechanism of tandem catalysis of biopolyols conversion to value-added commodity chemicals. Catalytic synthesis of glucaric acid by oxidation of gluconic acid/glucose using novel TiO2-supported bimetallic PtCu catalysts and O2 as oxidant exhibited significantly enhanced activity and selectivity compared to those in previous work. Bimetallic alloy Pt1Cu3 catalysts supported on TiO2 display unusual synergy and exceptional oxidation activity compared with monometallic Pt and Cu catalysts, with 46% glucaric acid selectivity. Further, it is shown with the Pt1Cu3 alloy catalyst that glucose may also be directly oxidized to glucaric acid and co-products.

Publications

  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Bala Subramaniam. Novel sustainable technologies for emerging feedstocks, 6th International Conference on Green and Sustainable Chemistry. Aug. 4-7, 2013, Nottingham England.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Bala Subramaniam. Sustainable catalytic technologies for biomass-based feedstocks, Green Chemistry Gordon Research Conference, July27-Aug 1, 2014, Hong Kong, China.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Bala Subramaniam. Ad Astra, Per Renewables KU Elevate: Innovation in Action. Oct. 16, 2015, Overland Park KS.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: R.V. Chaudhari. Advances in Catalysis and Reaction Engineering Toward Green Process Engineering Green Chemistry Gordon Conference, July 31-Aug. 5, 2016, Stowe VT.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Banning, J. Strain-Release Activation of alpha, beta-Unsaturated Amides Towards Conjugate Addition of Nitrogen, Oxygen and Sulfur Nucleophiles, Ph.D. Dissertation, University of Kansas, 2013.
  • Type: Book Chapters Status: Published Year Published: 2013 Citation: Bravo-Suarez, J.J.; Chaudhari, R.V.; Subramaniam, B. "Design of Heterogeneous Catalysis for Fuels and Chemicals Processing: An Overview," in Novel Materials for Catalysis and Fuels Processing; ACS Symposium Series 1132; J. J. Bravo-Su�rez, M. Kidder, V. Schwartz, Eds.; American Chemical Society: Washington, D.C., 3-68, 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Ghanta, M. Development of an Economically Viable H2O2-based, Liquid-Phase Ethylene Oxide Technology: Reactor Engineering and Catalyst Development Studies, Ph.D. Dissertation, University of Kansas 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Jin, X. Catalytic Conversion of Biomass-Derived Polyols to Value-Added Chemicals: Catalysis and Kinetics, Ph.D. Dissertation, University of Kansas 2014.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Li, M. A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid, Ph.D. Dissertation, University of Kansas 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Pan, Q. Intrinsic Kinetics of Lower Alcohols: C2, C3 Dehydration over Lewis Acidic Ordered Mesoporous Silicate: Zr-KIT-6, M.S. Thesis, University of Kansas, 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Ryabchuk, P. Synthesis of Densely Functionalized Cyclopropanes via Diastereoselective Nucleophilic Additions to in Situ Generated Cyclopropenes Ph.D. Dissertation, University of Kansas 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Torres, A. Hydrogenation of Biomass-Derived Feedstocks: Catalyst, Kinetics, And Reaction Engineering Studies PhD Dissertation, University of Kansas, 2014.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Xie, Z. "Greener Hydroformylation with Nanofilterable Rhodium Catalysts in A Stirred Membrane Reactor," Ph.D. Dissertation, University of Kansas 2013.
  • Type: Theses/Dissertations Status: Published Year Published: 2016 Citation: Yan, W. Novel Metal-Incorporated Mesoporous Catalysts for Liquid Phase Ethylene Epoxidation with H2O2 Oxidant, PhD. Dissertation, University of Kansas 2016.
  • Type: Other Status: Published Year Published: 2014 Citation: "Single Solvent Gas Expanded Hydroformylation Process", B. Subramaniam, R. V. Chaudhari, B. Sarkar. U.S. Patent 8,822,734 Sept. 2 2014. (U.S. Patent Application Publication No. 20140081050, filed 2/14/2012)
  • Type: Other Status: Under Review Year Published: 2012 Citation: "Spray Oxidation Process for Producing 2,5-Furandicarboxylic Acid from Hydroxymethylfurfural," B. Subramaniam, X. Zuo, D. H. Busch, P. Venkitasubramanian. (U.S. Patent Application Publication No. 20150183755, filed 4/28/2012)
  • Type: Other Status: Under Review Year Published: 2012 Citation: "Process for Producing Both Biobased Succinic Acid and 2,5-Furandicarboxylic Acid", B. Subramaniam, D. Busch, X. Zuo, P. Venkitasubranian. (U.S. Patent Application Publication No. 20140343305, filed 8/28/2012)?
  • Type: Other Status: Published Year Published: 2014 Citation: "Ozonolysis Reactions in Liquid CO2 and CO2-Expanded Solvents", B. Subramaniam, D. Busch, A. Danby, T. Binder. U.S. Patent 8,801,939 Aug. 12, 2014. (U.S. Patent Application Publication No. 20130240781, filed 4/1/2013)
  • Type: Other Status: Published Year Published: 2016 Citation: Alkylene epoxidation with mesoporous catalysts, B. Subramaniam, A. Ramanathan, M. Ghanta, W. Yan. U.S. Patent 9,233,944 Jan. 12, 2016. (U.S. Patent Application Publication No. 20150191442, filed 6/27/2013)
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Bravo-Suarez, J. J., Subramaniam, B., Chaudhari, R. V. "Ultraviolet-Visible Spectroscopy and Temperature Programmed Techniques as Tools for Structural Characterization of Cu in CuMgAlOX Mixed Metal Oxides," J. Phys. Chem. C 2012 116:34 18207-18221.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Ramanathan, A.; Subramaniam, B.; Badloe, D.; Hanefeld, U.; Maheswari, R. "Direct incorporation of tungsten into ultra-large-pore three-dimensional mesoporous silicate framework: W-KIT-6" J. Porous. Mater. 2012 19:6 961-968.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Ryabchuk, P.; Rubina, M.; Xu, J.; Rubin, M. "Formal Nucleophilic Substitution of Bromocyclopropanes with Azoles," Org. Lett. 2012 14:7 1752-1755.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Subramaniam, B., Akien, G.R. "Sustainable Catalytic Reaction Engineering with Gas-Expanded Liquids," Curr. Op. in Chem. Engg. 2012 1:3 336-341.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Wan, H.; Chaudhari, R. V.; Subramaniam, B. "Catalytic Hydroprocessing of p-Cresol: Metal, Solvent, and Mass-Transfer Effects," Topics in Catal. 2012 55:3-4 129-139.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Ye, K.; Freund, H.; Xie, Z. Subramaniam, B.; Sundmacher, K. "Prediction of Multicomponent Phase Behavior of CO2-Expanded Liquids using CEoS/GE Models and Comparison with Experimental Data," J. Sup. Fluids 2012 67 41-52.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Banning, J.E.; Gentillon, J.; Ryabchuk, P.G.; Prosser, A.R.; Rogers, A.; Edwards, A.; Holtzen, A.; Babkov, I.A.; Rubina, M.; Rubin, M. "Formal Substitution of Bromocyclopropanes with Nitrogen Nucleophiles," J. Org. Chem. 2013 78:15 7601-7616.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Bravo-Su�rez, J.J.; Subramaniam, B.; Chaudhari, R.V. "Vapor-Phase Methanol and Ethanol Coupling Reactions on CuMgAl Mixed Metal Oxides," App. Catal. A 2013 455 234-246.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Chaudhari, R.V.; Torres, A.; Jin, X.; Subramaniam, B. "Multiphase Catalytic Hydrogenolysis/Hydrodeoxygenation Processes for Chemicals from Renewable Feedstocks: Kinetics, Mechanism, and Reaction Engineering," Ind. Eng. Chem. Res. 2013 52:44 15226-15243.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ghanta, M.; Fahey, D.; Subramaniam, B. "Environmental impacts of ethylene production from diverse feedstocks and energy sources," Appl. Petrochem. Res. 2013 4:2 167-179.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Jin, X.; Dang, L.; Lohrman, J.; Subramaniam, B.; Ren, S.; Chaudhari, R.V. "Lattice-Matched Bimetallic CuPd-Graphene Nanocatalysts for Facile Conversion of Biomass-Derived Polyols to Chemicals," ACS Nano 2013 7:2 1309-1316.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Jin, X.; Roy, D.; Thapa, P.S.; Subramaniam, B.; Chaudhari, R.V. "Atom Economical Aqueous-Phase Conversion (APC) of Biopolyols to Lactic Acid, Glycols, and Linear Alcohols Using Supported Metal Catalysts," ACS Sus. Chem. Eng. 2013 1:11 1453-1462.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Li, M.; Niu, F.; Zuo, X.; Metelski, P.D.; Busch, D.H.; Subramaniam, B. "A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid," Chem. Eng. Sci. 2013 104 93-102.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Pan, Q.; Ramanathan, A.; Snavely, W.K.; Chaudhari, R.V.; Subramaniam, B. "Synthesis and Dehydration Activity of Novel Lewis Acidic Ordered Mesoporous Silicate: Zr-KIT-6," Ind. Eng. Chem. Res. 2013 52:44 15481-15487.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ramanathan, A., Subramaniam, B., Maheswari, R., Hanefeld, U. "Synthesis, and characterization of Zirconium incorporated ultra large pore mesoporous silicate, Zr-KIT-6," Micropor. Mesopor. Mat. 2013 167 207-212.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Ghanta, M.; Fahey, D.; Subramaniam, B. "Environmental impacts of ethylene production from diverse feedstocks and energy sources," Appl. Petrochem. Res. 2014 4:2 167-179.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Wan, H.; Chaudhari, R. V.; Subramaniam, B. "Aqueous Phase Hydrogenation of Acetic Acid and Its Promotional Effect on p-Cresol Hydrodeoxygenation," Energy & Fuels 2013 27:1 487-493.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Xie, Z.; Fang, J.; Subramaniam, B.; Maiti, S.K.; Snavely, W.; Tunge, J. A. "Enhanced hydroformylation by carbon dioxide-expanded media with soluble Rh complexes in nanofiltration membrane reactors," AIChE J. 2013 59:11 4287-4296.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Edwards, A.; Ryabchuk, P.; Barkov, A.; Rubina, M.; Rubin, M. "Preparative resolution of bromocyclopropylcarboxylic acids," Tetrahedron: Assym. 2014 25:23 1537-1549.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Hong, C.; Jin, X.; Totleben, J.; Lohrman, J.; Harak, E.; Subramaniam, B.; Chaudhari, R. V.; Ren, S. "Graphine oxide stabilized Cu2O for shape selective nanocatalysis," J. Mat. Chem. A 2014 2:20 7147-7151.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Barrierless tautomerization of Criegee intermediates via acid catalysis," Phys. Chem. Chem. Phys. 2014 16:42 22968-22973.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ramanathan, A.; R. Maheswari; Grady, B. P.; Moore, D. S.; Barich, D. H.; Subramaniam, Bala. "Tungsten-incorporated cage-type mesoporous silicate: W-KIT-5" Micro. Meso. Mat. 2013 175 43-49.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Role of Tunable Acid Catalysis in Decomposition of a-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry," J. Phys. Chem. A 2014 118:41 9701-9711.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ryabchuk, P.; Edwards, A.; Gerasimchuk, N.; Rubina, M.; Rubin, M. "Dual Control of the Selectivity in the Formal Nucleophilic Subsittution of Bromocyclopropanes en Route to Densely Functionalized, Chirally Rich Cyclopropyl Derivatives," Org. Lett. 2013 15:23 6010-6013.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Criegee Intermediate Reaction with CO: Mechanism, Barriers, Conformer-Dependence, and Implications for Ozonolysis Chemistry," J. Phys. Chem. A 2014 118:10 1887-1894.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Organic Acids Tunably Catalyze Carbonic Acid Decomposition," J. Phys. Chem. A 2014 118:27 5020-5028.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, Manoj; Chaudhari, Raghunath V.; Subramaniam, B.; Jackson, T.A. "Ligand Effects on the Regioselectivity of Rhodium-Catalyzed Hydroformylation: Density Functional Calculations Illuminate the Role of Long-Range Noncovalent Interactions," Organometallics 2014 33:16 4183-4191.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Li, M.; Niu, F.; Busch, D. H.; Subramaniam, B. "Kinetic Investigations of p-Xylene Oxidation to Terephthalic Acid with a Co/Mn/Br Catalyst in a Homogeneous Liquid Phase," Ind. Eng. Chem. Res. 2014 53:22 9017-9026.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Li, M.; Ruddy, T.; Fahey, D.; Busch, D. H.; Subramaniam, B. "Terephthalic Acid Production via Greener Spray Process: Comparative Economic and Environmental Impact Assessments with Mid-Century Process," ACS Sus. Chem. Eng. 2014 2(4) 823-835.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Maheswari, R.; Pachamuthu, M. P.; Ramanathan, A.; Subramaniam, B. "Synthesis, Characterization, and Epoxidation Activity of Tungsten-Incorporated SBA-16 (W-SBA-16)," Ind. Eng. Chem. Res. 2014 53:49 18833-18839.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Pan, Q.; Ramanathan, A.; Snavely, W. K.; Chaudhari, R. V.; Subramaniam, B. "Intrinsic Kinetics of Ethanol Dehydration Over Lewis Acidic Ordered Mesoporous Silicate, Zr-KIT-6," Top. Catal. 2014 57:17-20 1407-1411.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Ramanathan, A.; Maheswari, R.; Barich, D. H.; Subramaniam, B. "Niobium incorporated mesoporous silicate, Nb-KIT-6: Synthesis and characterization," Micro. Meso. Mat. 2014 190 240-247.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Jin, X.; Zhao, M.; Shen, J.; Yan, W.; He, L.; Thapa, P. S.; Ren, S.; Subramaniam, B.; Chaudhari, R. V. "Exceptional performance of bimetallic Pt1Cu3/TiO2 nanocatalysts for oxidation of gluconic acid and glucose with O2 to glucaric acid," J. Catal. 2015 330 323-329.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Kumar, M.; Chaudhari, R.V.; Subramaniam, B.; Jackson, T.A. "Importance of Long-Range Noncovalent Interactions in the Regioselectivity of Rhodium-Xantphos-Catalyzed Hydroformylation," Organometallics 2015 34:6 1062-1073.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Lundin, M. D.; Danby, A. M.; Akien, G. R.; Binder, T. P.; Busch, D. H.; Subramaniam, B. "Liquid CO2 as a Safe and Benign Solvent for the Ozonolysis of Fatty Acid Methyl Esters," ACS Sus. Chem. Eng. 2015 3:12 3307-3314.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ramanathan, A.; Maheswari, R.; Subramaniam, B. "Facile Styrene Epoxidation with H2O2 over Novel Niobium Containing Cage Type Mesoporous Silicate, Nb-KIT-5," Top. Catal. 2015 58:4-6 314-324.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ramanathan, A.; Zhu, H.; Maheswari, R.; Subramaniam, B. "Novel zirconium containing cage type silicate (Zr-KIT-5): An efficient Friedel-Crafts alkylation catalyst," Chem. Eng. J. 2015 278 113-121.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ramanathan, A.; Zhu, H.; Maheswari, R.; Thapa, P. S.; Subramaniam, B. "Comparative Study of Nb-Incorporated Cubic Mesoporous Silicates as Epoxidation Catalysts," Ind. Eng. Chem. Res. 2015 54:16 4236-4242.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Subramaniam, B. "Perspectives on exploiting near-critical fluids for energy-efficient catalytic conversation of emerging feedstocks," J. Supercrit. Fluids 2015 96 96-102.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Subramaniam, B.; Chaudhari, R. V.; Chaudhari, A. S.; Akien, G. R.; Xie, Z. "Supercritical fluids and gas-expanded liquids as tunable media for multiphase catalytic reactions," Chem. Eng. Sci. 2014 115 3-18.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Wan, H.; Vitter, A.; Chaudhari, R. V.; Subramaniam, B. "Kinetic investigations of unusual solvent effects during Ru/C catalyzed hydrogenation of model oxygenates," J. Catal. 2014 309 174-184.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Xie, Z.; Subramaniam, B. "Development of a Greener Hydroformylation Process Guided by Quantitative Sustainability Assessments," ACS Sus. Chem. Eng. 2014 2:12 2748-2757.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Jin, X.; Shen, J.; Yan, W.; Zhao, M.; Thapa, P. S.; Subramaniam, B.; Chaudhari, R. V. "Sorbitol Hydrogenolysis over Hybrid Cu/CaO-Al2O3 Catalysts: Tunable Activity and Selectivity with Solid Base Incorporation," ACS Catal. 2015 5:11 6545-6558.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Zhu, H.; Maheswari, R.; Ramanathan, A.; Subramaniam, B. "Evaporation-induced self-assembly of mesoporous zirconium silicates with tunable acidity and facile catalytic dehydration activity," Micro. Meso. Mat. 2016 223 46-52.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Xie, Z.; Akien, G. R.; Sarkar, B. R.; Subramaniam, B.; Chaudhari, R. V. "Continuous Hydroformylation with Phosphine-Functionalized Polydimethylsiloxane Rhodium Complexes as Nanofilterable Homogeneous Catalysts," Ind. Eng. Chem. Res. 2015 54:43 10656-10660.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Jin, X.; Subramaniam, B.; Chaudhari, R. V.; Thapa, P. S. "Kinetic modeling of Pt/C catalyzed aqueous phase glycerol conversion with in situ formed hydrogen," AIChE J. 2016 62:4 1162-1173.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Srinivasan, V. V.; Ranoux, A.; Maheswari, R.; Hanefeld, U.; Ramanathan, A.; Subramaniam, B. "Potential applications of Zr-KIT-5: Hantzsch reaction, Meerwein-Ponndorf-Verley (MPV) reduction of 4-tert-butylcyclohexanone, and Prins reaction of citronellal," Res. Chem. Intermed. 2016 42:3 2399-2408.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Zuo, X.; Venkitasubramanian, P.; Busch, D. H.; Subramaniam, B. Optimization of Co/Mn/Br-catalyzed oxidation of 5-hydroxymethylfurfural to enhance 2,5-furandicarboxylic acid yield and minimize substrate burning, ACS Sus. Chem. Eng. 2016 4:7 3659-3668.
  • Type: Book Chapters Status: Published Year Published: 2013 Citation: Jin, Xin; Bala Subramaniam, Raghunath V. Chaudhari, Activity and Selectivity of Bimetallic Catalysts for Polyols Hydrogenolysis. Novel Materials for Catalysis and Fuels Processing ACS Symposium Book Series, Vol. 1132, Chapter 12, pp 273285. Washington, D. C. 2013.
  • Type: Book Chapters Status: Published Year Published: 2013 Citation: Ramanathan, A.; Maheswari, R.; P. S. Thapa; Subramaniam, B. "Rapid room temperature synthesis of Ce-MCM-48: an active catalyst for trans-stilbene epoxidation with tert-butyl hydroperoxide," in Novel Materials for Catalysis and Fuels Processing ACS Symposium Series 1132, Bravo-Suarez, Kidder, and Schwartz, Eds. 2013 213-228.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: R.V. Chaudhari. Homogeneous Catalysis in Synthesis of Chemicals & Industrial Applications, 24th Organic Reactions Catalysis Society Meeting. March 15-19, 2012, Annapolis MD.


Progress 06/01/14 to 05/31/15

Outputs
Target Audience:The primary audience for this work includes agricultural processors, chemical manufacturers, and entrepreneurs seeking to adopt new technologies for producing value-added chemicals from biomass-derived feedstocks, as well as product manufacturers or agricultural producers who would benefit from such bio-derived chemicals. One such company, Archer Daniels Midland (ADM), is already a key partner on this project. Via the University of Kansas Center for Environmentally Beneficial Catalysis (CEBC), some of the results are being discussed with representatives from other companies to gage interest and obtain feedback on potential commercial opportunities. Additionally, the discoveries made in this work are being shared with broader audiences to share lessons about developing and evaluating more environmentally benign chemical technologies. Researchers on this project are active in making conference presentations and writing technical journal articles to disseminate the findings. Researchers have also presented this work to area high school science teachers and to government (State and Federal) representatives. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Technical Mentoring Students and postdoctoral researchers (collectively referred to below as students) on this project work closely with highly-respected faculty mentors in weekly multi-disciplinary research meetings. In keeping with the multi-disciplinary nature of the project, these meetings typically feature chemists and chemical engineers at the faculty, postdoctoral, and graduate levels, and occasionally involve team members from other science or engineering disciplines. Intellectual Property (IP) training is provided annually to aid students in identifying and protecting potentially patentable information. Students are encouraged to draft journal papers and present their work at professional society meetings. Industrial Mentoring Students interact directly with CEBC's Industrial Advisory Board (IAB), which is comprised of leading chemical and energy companies, such as ADM, Evonik, Invista, SABIC, Solvay and UOP/Honeywell, among others. Students have opportunities to make oral and poster presentations at semi-annual IAB meetings and receive project evaluations conducted by IAB members. In addition, CEBC and ADM hold weekly teleconferences to collaborate on various aspects of the project. CEBC's IAB members bring unique perspectives on the commercial potential of early stage research projects, complementing the academic perspective. Students also meet with speakers in CEBC's Industrial Colloquia Program, which features prominent industrial researchers on a variety of topics, and provide a glimpse into how R&D in industry differs from academia. Professional Development The CEBC Education Director organizes professional development workshops for students, addressing topics such as technical presentation skills, communication to general audiences, career guidance, intellectual property and commercialization issues, laboratory safety, and "lunch-and-learn" peer-to-peer skill development sessions. Students also play an important role on the CEBC Laboratory Safety Committee, which coordinates and enforces good laboratory practices for the Center. The students often act as co-mentors for summer REU students in order to develop research training and management skills. Campus Networking Students may participate in Students for Green Chemistry, a campus organization formed by CEBC students to stimulate interest in sustainable chemical technologies among non-scientists. Students for Green Chemistry participate in K-12 and community outreach programs. The University of Kansas Postdoctoral Association supports postdoctoral scholars by improving their training in all aspects of professional research and career development. Additionally, the group promotes a sense of community for postdoctoral scholars in diverse academic fields with opportunities to share research and interact socially. How have the results been disseminated to communities of interest?After taking appropriate measures to protect intellectual property, researchers have disseminated the results widely through peer-reviewed publications and national/international symposia presentations as listed below in the Products section. ADM, as a core partner on the project, has actively participated in all aspects of this project, through weekly teleconferences, quarterly on-site meetings. Selected results have also been shared with other third-party companies to gage interest and identify potential collaborations, including Chevron Phillips Chemical, DuPont, Evonik, Invista, Reliance Industries, SABIC, UOP/Honeywell. What do you plan to do during the next reporting period to accomplish the goals?Goal 1: ADM will continue to provide feedstocks for evaluation in the processes. These will be derived from current and potential product streams within ADM. ADM will provide intellectual property and economic model assistance, and continue to engage potential commercial partners with selected results. Goal 2a: In the upcoming period, the conversion of aldehydes to acids from the secondary ozonide decomposition mixture will be completed. CEBC and ADM researchers are working closely on thorough technology transfer of the ozonolysis and thermal decomposition processes so that scale-up will continue within ADM beyond this project. Work on optimizing oxidative and acid-catalyzed lignin depolymerization including demonstration of a continuous process for at least one of the more promising routes will be completed. Goal 2b: We will demonstrate continuous hydroformylation of allyl alcohol to 1,4 BDO over Rh/PDMS catalyst in a CXL-based membrane reactor under the optimized conditions. Goal 2c: Completion of intrinsic kinetics for HMF to FDCA will enable reactor design for scale-up. CEBC and ADM researchers are working closely on thorough technology transfer of the FDCA process so that scale-up can continue within ADM beyond this project. The continued optimization of spray reactor reaction conditions (especially spray rate, gas flow rate, temperature and feed composition) for polymer grade TPA product will provide a third-party investor additional information whether to pursue scale-up. Refinement of the mathematical model of spray reactor and comparison with experiments will further move the project toward pilot plant studies.

Impacts
What was accomplished under these goals? Impact This project is largely on track toward demonstrating pre-pilot ready concepts for viable manufacturing technologies for renewable chemicals--produced from biomass, not petroleum--which can be used in plastics, fibers, personal care products and other everyday goods. As described below, several technical challenges have been overcome and at least three of the targeted technologies are on pace to meet the criteria for pre-pilot testing readiness. Feedstock Development ADM completed work on the integrated biorefinery project undertaken with funding assistance from the DOE. The final products of ethanol, propylene glycol, and ethyl acrylate were produced from corn stover. The first step in this process separates the stover into cellulose, hemicellulose, and lignin streams. The lignin is suitable for further reaction to chemicals and intermediates, and the streams have been sampled to various industrial and academic partners for evaluation. From the cellulose, dextrose was produced for conversion to sorbitol, which underwent subsequent hydrogenolysis to glycerol and glycols. The glycerol could be recovered for production of chemicals such as allyl alcohol. The dextrose could have been converted to fructose, the precursor molecule to HMF, as well. Hemicellulose made up part of the feed to the fermenters and alcohol production. Ozonolysis Having previously demonstrated the clean and efficient ozonolysis of methyl oleate to the secondary ozonide, the subsequent thermal decomposition of neat secondary ozonides and gem-diperoxides was thoroughly explored in a CSTR over a temperature range of 80°C to 150°C. This investigation enabled the regression of kinetic parameters for both types of species individually. The heat of combustion for the secondary ozonide mixture obtained from the ozonolysis of FAMEs was determined using a high precision bomb calorimeter, which was in turn used to determine the heat released from the thermal decomposition of said product mixture. Additionally, Henry's law data were obtained for ozone in carbon dioxide and sulfur hexafluoride at temperatures ranging from -10°C to 10°C. Based on these data, ADM engineers are completing their economic evaluation. Several approaches to oxidatively pretreat/depolymerize lignin have been explored. The aerobic catalytic oxidation of the supplied lignin in basic aqueous solution (KOH, NaOH) with (Mn(Et2EBC)Cl2) catalyst at 150°C has been shown to yield formic and acetic acid as products. Similar catalysts were examined and found to be less effective than the Mn(Et2EBC)Cl2 catalyst. Higher hydroxide concentrations gave higher yields of acid product, however hydroxide is consumed during this process resulting in a pH drop. Higher temperatures (200 - 250 °C) resulted in lower yields of the simple carboxylic acids and an increase in both insoluble char and recombination products of higher polymer weight than the starting material. Model compound studies suggested that the presence of a phenolic moiety in the substrate promoted oxidation and that recombination only occurred in the presence of the catalyst. The production of recombination products could be reduced by separating the base catalyzed depolymerization reaction and the Mn(Et2EBC)Cl2 catalyzed oxidation and performing them sequentially with the base catalyzed depolymerization first. This approach also reduced the degree of complete oxidation to H2O and CO2. However, high temperature base catalyzed depolymerization followed by low temperature Mn(Et2EBC)Cl2 catalyzed oxidation did not yield monomeric carboxylic acid products. The formic acid catalyzed depolymerization of lignin was examined. Literature reports suggested that lignin oxidized at the a-carbon on b-O-4 linkages should be particularly susceptible to this type of depolymerization. Several methods of oxidizing the supplied lignin were examined and enhancement of the formic acid catalyzed depolymerization, which proceeds via the formylation of a primary alcohol followed by a stepwise cleavage initiated by a base catalyzed proton abstraction, was attempted by examining methods of formylation and base treatment of the resulting formate. Mixed results were obtained and studies are continuing. Hydroformylation We have optimized a carbon dioxide-expanded liquid (CXL)-based process for converting allyl alcohol to 1,4-butanediol with high activity and regio-selectivity with a Rh/TPP homogeneous catalyst. A maximum regio-selectivity of nearly 7 was obtained at mild operating conditions. By extracting the hydroformylation products with water and hydrogenating them on Raney Ni, quantitative yield of 1,4 BDO has been demonstrated. In parallel work, we have shown that by attaching the Rh to a phosphine-functionalized polydimethylsiloxane (PDMS) ligand, continuous hydroformylation of linear olefins can be achieved in a stirred membrane reactor containing the soluble Rh/PDMS catalyst complex. Further, the dissolved bulky Rh complex is almost quantitatively retained in the reactor by the nanofiltration membrane. We are currently applying the Rh/PDMS concept to demonstrate continuous hydroformylation of allyl alcohol to 1,4 BDO in a CXL-based membrane reactor. The rhodium catalyzed hydroformylation of acrolein diethyl acetal has been extensively shown to be a highly efficient route to access both linear and branched aldehyde containing acetal products. This type of conversion was found to be highly efficient and reproducible utilizing very low catalyst loadings and mild reaction conditions on small scales. Upon conducting initial scalability evaluations, it was discovered that this reaction experiences an extensive induction period, during which very little to no effective conversion of the starting material occurs. This period lasts approximately one hour and appears to be independent of reaction scale. Following the induction period, the reaction proceeds to completion rather quickly, in most situations in under one hour. Two possible explanations for this observation are 1) a starting material inhibition or 2) product assisted initiation. To evaluate this hypothesis, a series of experiments were conducted which were either diluted to study the possibility of starting material inhibition or doped with a natural ratio of purified product to determine the possibility of product initiation. Reaction parameterization initially began with the intention of fully mapping the following: temperature, stirring rate, pressure, catalyst:ligand ratio, substrate:catalyst ratio, syngas composition, reaction concentration, and product doped reactions. Mapping these parameters would allow for proper understanding of the reaction mechanism and provide a rational to optimize the ratio of two possible hydroformylation products under the mildest possible reaction conditions. Spray Oxidation The optimization of reaction conditions for maximizing the FDCA yield was carried out, resulting in the reduction of the burning reactions (i.e. reducing formation of CO/CO2). Under these optimized conditions (temperature, pressure and HMF solution feed rate), we achieved 95% yield of FDCA product. In order to scale up the process, kinetic rate data are needed; to accomplish this, a sophisticated sampling system was designed to rapidly capture and quench samples during the start of this very fast reaction. The preliminary kinetic parameters are being validated and used by ADM engineers to carry out a techno-economic analysis. In parallel, the development of the oxidation spray reactor process continued, with emphasis on the PTA reaction. The spray reactor was successfully scaled up from 700 ml to 4000 ml in both semi-batch and continuous operating modes. To further explore operating conditions to enhance commercial viability, the use of air as the oxidant was successfully demonstrated to reduce operating costs. Likewise, the p-xylene substrate concentration was increased from 1.3 to 5.1 wt%.

Publications

  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Jin, X. Catalytic Conversion of Biomass-Derived Polyols to Value-Added Chemicals: Catalysis and Kinetics PhD Dissertation, University of Kansas, 2014.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Edwards, A.; Ryabchuk, P.; Barkov, A.; Rubina, M.; Rubin, M. "Preparative resolution of bromocyclopropylcarboxylic acids," Tetrahedron: Assym. 2014 25:23 1537-1549.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Hong, C.; Jin, X.; Totleben, J.; Lohrman, J.; Harak, E.; Subramaniam, B.; Chaudhari, R. V.; Ren, S. "Graphine oxide stabilized Cu2O for shape selective nanocatalysis," J. Mat. Chem. A 2014 2:20 7147-7151.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Organic Acids Tunably Catalyze Carbonic Acid Decomposition," J. Phys. Chem. A 2014 118:27 5020-5028.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, Manoj; Chaudhari, Raghunath V.; Subramaniam, B.; Jackson, T.A. "Ligand Effects on the Regioselectivity of Rhodium-Catalyzed Hydroformylation: Density Functional Calculations Illuminate the Role of Long-Range Noncovalent Interactions," Organometallics 2014 33:16 4183-4191.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Role of Tunable Acid Catalysis in Decomposition of ?-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry," J. Phys. Chem. A 2014 118:41 9701-9711.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Barrierless tautomerization of Criegee intermediates via acid catalysis," Phys. Chem. Chem. Phys. 2014 16:42 22968-22973.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Kumar, M.; Chaudhari, R.V.; Subramaniam, B.; Jackson, T.A. "Importance of Long-Range Noncovalent Interactions in the Regioselectivity of Rhodium-Xantphos-Catalyzed Hydroformylation," Organometallics 2015 34:6 1062-1073.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Maheswari, R.; Pachamuthu, M. P.; Ramanathan, A.; Subramaniam, B. "Synthesis, Characterization, and Epoxidation Activity of Tungsten-Incorporated SBA-16 (W-SBA-16)," Ind. Eng. Chem. Res. 2014 53:49 18833-18839.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Pan, Q.; Ramanathan, A.; Snavely, W. K.; Chaudhari, R. V.; Subramaniam, B. "Intrinsic Kinetics of Ethanol Dehydration Over Lewis Acidic Ordered Mesoporous Silicate, Zr-KIT-6," Top. Catal. 2014 57:17-20 1407-1411.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ramanathan, A.; Maheswari, R.; Subramaniam, B. "Facile Styrene Epoxidation with H2O2 over Novel Niobium Containing Cage Type Mesoporous Silicate, Nb-KIT-5," Top. Catal. 2015 58:4-6 314-324.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ramanathan, A.; Zhu, H.; Maheswari, R.; Subramaniam, B. "Novel zirconium containing cage type silicate (Zr-KIT-5): An efficient Friedel-Crafts alkylation catalyst," Chem. Eng. J. 2015 278 113-121.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ramanathan, A.; Zhu, H.; Maheswari, R.; Thapa, P. S.; Subramaniam, B. "Comparative Study of Nb-Incorporated Cubic Mesoporous Silicates as Epoxidation Catalysts," Ind. Eng. Chem. Res. 2015 54:16 4236-4242.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Subramaniam, B.; Chaudhari, R. V.; Chaudhari, A. S.; Akien, G. R.; Xie, Z. "Supercritical fluids and gas-expanded liquids as tunable media for multiphase catalytic reactions," Chem. Eng. Sci. 2014 115 3-18.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Subramaniam, B. "Perspectives on exploiting near-critical fluids for energy-efficient catalytic conversation of emerging feedstocks," J. Supercrit. Fluids 2015 96 96-102.
  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Torres, A. Hydrogenation Of Biomass-Derived Feedstocks: Catalyst, Kinetics, And Reaction Engineering Studies PhD Dissertation, University of Kansas, 2014.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Xie, Z.; Subramaniam, B. "Development of a Greener Hydroformylation Process Guided by Quantitative Sustainability Assessments," ACS Sus. Chem. Eng. 2014 2:12 2748-2757.


Progress 06/01/13 to 05/31/14

Outputs
Target Audience: The primary audience for this work includes agricultural processors, chemical manufacturers, and entrepreneurs seeking to adopt new technologies for producing value-added chemicals from biomass-derived feedstocks, as well as product manufacturers or agricultural producers who would benefit from such bio-derived chemicals. One such company, Archer Daniels Midland (ADM), is already a key partner on this project. Via the University of Kansas Center for Environmentally Beneficial Catalysis (CEBC), some of the results are being discussed with representatives from other companies to gage interest and to obtain feedback on potential commercial opportunities. Additionally, the discoveries made in this work are being shared with broader audiences to share lessons about developing and evaluating more environmentally benign chemical technologies. Researchers on this project are active in making conference presentations and writing technical journal articles to disseminate the findings. Researchers have also presented this work to area high school science teachers and to government (State and Federal) representatives. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Technical Mentoring Students and postdoctoral researchers (collectively referred to below as students) on this project work closely with highly-respected faculty mentors in weekly multi-disciplinary research meetings. In keeping with the multi-disciplinary nature of the project, these meetings typically feature chemists and chemical engineers at the faculty, postdoctoral, and graduate levels, and occasionally involve team members from other science or engineering disciplines. Intellectual Property (IP) training is provided annually to aid students in identifying and protecting potentially patentable information. Students are encouraged to draft journal papers and present their work at professional society meetings. Industrial Mentoring Students interact directly with CEBC’s Industrial Advisory Board (IAB), which is comprised of leading chemical and energy companies, such as ADM, Chevron Phillips Chemical, Evonik, Invista, SABIC and UOP/Honeywell, among others. Students have opportunities to make oral and poster presentations at semi-annual IAB meetings and receive project evaluations conducted by IAB members. In addition, CEBC and ADM hold weekly teleconferences to collaborate on various aspects of the project. CEBC’s IAB members bring unique perspectives on the commercial potential of early stage research projects, complementing the academic perspective. Students also meet with speakers in CEBC’s Industrial Colloquia Program, which features prominent industrial researchers on a variety of topics, and provide a glimpse into how R&D in industry differs from academia. Professional Development The CEBC Education Director organizes professional development workshops for students, addressing topics such as technical presentation skills, communication to general audiences, career guidance, intellectual property and commercialization issues, laboratory safety, and “lunch-and-learn” peer-to-peer skill development sessions. Students also play an important role on the CEBC Laboratory Safety Committee, which coordinates and enforces good laboratory practices for the Center. The students often act as co-mentors for summer REU students in order to develop research training and management skills. Campus Networking Students may participate in Students for Green Chemistry, a campus organization formed by CEBC students to stimulate interest in sustainable chemical technologies among non-scientists. Students for Green Chemistry participate in K-12 and community outreach programs. The University of Kansas Postdoctoral Association supports postdoctoral scholars by improving their training in all aspects of professional research and career development. Additionally, the group promotes a sense of community for postdoctoral scholars in diverse academic fields with opportunities to share research and interact socially. How have the results been disseminated to communities of interest? After taking appropriate measures to protect intellectual property, researchers have disseminated the results widely through peer-reviewed publications and national/international symposia presentations as listed below in the Products section. ADM, as a core partner on the project, has actively participated in all aspects of this project, through weekly teleconferences, quarterly on-site meetings. Selected results have also been shared with other third-party companies to gage interest and identify potential collaborations, including Chevron Phillips Chemical, DuPont, Evonik, Invista, Reliance Industries, SABIC, UOP/Honeywell. What do you plan to do during the next reporting period to accomplish the goals? Goal 1: ADM will provide feedstocks for evaluation in the processes. These will be derived from current and potential product streams within ADM. ADM will provide intellectual property and economic model assistance, and continue to engage potential commercial partners with selected results. Goal 2A: In the upcoming year, the conversion of aldehydes to acids from the secondary ozonide decomposition mixture will be investigated. The entire process (ozonolysis, thermal decomposition, aldehyde conversion) will be attempted with FAMEs from soybean oil as the feedstock. Further process modeling and economic impact analysis will be conducted. Goal 2B: Optimizationstudies (varying temperature, pressure and syngascomposition) are underway to maximize activity and selectivity. In parallel, construction of acontinuous reactor with a nano-filtration membrane was completed. Followingoptimization studies, this continuous reactor will be used to demonstrate a pre-pilot ready technology concept for the hydroformylation of allyl alcohol in propane-expanded liquids. Goal 2C: Development of intrinsic kinetics for HMF to FDCA for reactor design purposes will be carried out. Optimization of spray reactor reaction conditions (viz. spray rate, gas flow rate, temperature and feed composition) for polymer grade TPA product will be based on experiments in 4L spray reactor. Development of a refined mathematical model of spray reactor and comparison with experiments will further optimization to move towards the pilot plant studies. Further optimization of the production of polymer grade FDCA will help establish commercial potential of the spray oxidation process through extended runs. Goal 2D: Steps are being taken to (i) improve catalyst selectivity to C-C coupling products and stability by addition of other transition or noble metals such as Fe, Cr, or Pd, and (ii) improve catalyst activity by optimizing catalyst preparation (i.e., nature of metal precursors), composition, and reaction conditions.

Impacts
What was accomplished under these goals? Impact: This project is largely on track toward demonstrating pre-pilot ready concepts for viable manufacturing technologies for renewable chemicals—produced from biomass, not petroleum—which can be used in plastics, fibers, personal care products and other everyday goods. In the coming decades, declining availability of petroleum and its increasing cost will require the the chemical industry to gradually transition to renewable feedstocks, and the only sustainable option in this regard is non-food biomass. As described below, several technical challenges have been overcome and at least three of the targeted chemical technologies are on pace to meet the criteria for pre-pilot testing readiness. Goal 1: ADM completed work on the integrated biorefinery project undertaken with funding assistance from the DOE. The final products of ethanol, propylene glycol, and ethyl acrylate were produced from corn stover. The first step in this process separates the stover into cellulose, hemicellulose, and lignin streams. The lignin would be suitable for further reaction to chemicals and intermediates, and the streams have been sampled to various industrial and academic partners for evaluation. From the cellulose, dextrose was produced for conversion to sorbitol, which underwent subsequent hydrogenolysis to glycerol and glycols. The glycerol could be recovered for production of chemicals such as allyl alcohol. The dextrose could have been converted to fructose, the precursor molecule to HMF, as well. Hemicellulose made up part of the feed to the fermenters and alcohol production. Goal 2A: Various reactor configurations were investigated for controlled and safe thermal decomposition of secondary ozonides generated from the ozonolysis of methyl oleate and similar model compounds, encompassing batch and continuous reaction modes. A suitable reaction scheme was developed (IP submission in progress) which allowed for safe decomposition of the intermediates to aldehyde and acid products. Kinetic data were obtained in the developed process at various temperatures allowing for the regression of both the pre-exponential factor and activation energy for the Arrhenius equation. These results will allow for safer design of commercial processes going forward. Goal 2B: Using NMR and GC techniques, a reliable analytical method was developed for identifying the aldehydeisomers of allyl alcohol hydroformylation products. The regioselectivity (n/iratio) in propane-expanded liquids wassignificantly enhancedwhen using 1,4-bis(diphenylphosphino)butane ligand with Rh and triphenylphosphine. Optimizationstudies (varying temperature, pressure and syngascomposition) are underway to maximize activity and selectivity. In parallel, construction of acontinuous reactor with a nano-filtration membrane was completed. Followingoptimization studies, this continuous reactor will be used to demonstrate a pre-pilot ready technology concept for the hydroformylation of allyl alcohol in propane-expanded liquids. Goal 2C: The spray oxidation process was successfully demonstrated in a larger 4L spray reactor for liquid phase catalytic oxidation of p-Xylene (pX) to Terephthalic acid (TPA) and 5-(Hydroxymethyl) furfural (HMF) to 2, 5-furandicarboxylic acid (FDCA). Technical challenges to continuous operation in the small lab-scale reactor (liquid level control, solids formation) were overcome, leading to extended runs of more than 45 minutes (based on discussions with industry, such issues are not anticipated at larger scales). To aid the rational design of a scaled-up spray reactor, a basic mathematical model using a mixing cell approach was developed; while this model provided a useful qualitative interpretation, a more refined model is being developed based on momentum, mass and energy balance analyses as well reliable kinetic data. Optimization of reaction conditions (temperature, pressure and HMF solution feed rate) that maximize the FDCA yield (>90%) with reducing the burning reactions (i.e. reducing formation of CO/CO2) was achieved. Kinetic studies are underway. Goal 2D: We previously demonstrated alkali-promoted copper-containing oxide catalysts provide the highest reported yields of methanol-ethanol coupling. Clues to the role of the alkali metal were obtained through a suite of studies using FT-IR, UV-Vis, and temperature programmed methods. Alkali metal-promoted Cu17MgAlOx mixed metal oxide (MMO) catalysts are highly active for MeOH + EtOH coupling reactions because addition of promoter increases medium strength basicity. Alkali metals also free active sites for C-C coupling reactions by minimizing surface population of unreactive formate species. The post-doctoral researcher working on this project was hired away during the past year, causing an interruption in progress on this project. A replacement has been hired for year 4, and progress is expected to resume.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Banning, J.E.; Gentillon, J.; Ryabchuk, P.G.; Prosser, A.R.; Rogers, A.; Edwards, A.; Holtzen, A.; Babkov, I.A.; Rubina, M.; Rubin, M. "Formal Substitution of Bromocyclopropanes with Nitrogen Nucleophiles," J. Org. Chem. 2013 78:15 7601-7616.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Chaudhari, R.V.; Torres, A.; Jin, X.; Subramaniam, B. "Multiphase Catalytic Hydrogenolysis/Hydrodeoxygenation Processes for Chemicals from Renewable Feedstocks: Kinetics, Mechanism, and Reaction Engineering," Ind. Eng. Chem. Res. 2013 52:44 15226-15243.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Jin, X.; Roy, D.; Thapa, P.S.; Subramaniam, B.; Chaudhari, R.V. "Atom Economical Aqueous-Phase Conversion (APC) of Biopolyols to Lactic Acid, Glycols, and Linear Alcohols Using Supported Metal Catalysts," ACS Sus. Chem. Eng. 2013 1:11 1453-1462.
  • Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Jin, X. Catalytic Conversion of Biomass-Derived Polyols to Value-Added Chemicals: Catalysis and Kinetics, Ph.D. Dissertation, University of Kansas 2014.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. "Criegee Intermediate Reaction with CO: Mechanism, Barriers, Conformer-Dependence, and Implications for Ozonolysis Chemistry," J. Phys. Chem. A 2014 118:10 1887-1894.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Li, M.; Niu, F.; Zuo, X.; Metelski, P.D.; Busch, D.H.; Subramaniam, B. "A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid," Chem. Eng. Sci. 2013 104 93-102.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Li, M.; Ruddy, T.; Fahey, D.; Busch, D. H.; Subramaniam, B. "Terephthalic Acid Production via Greener Spray Process: Comparative Economic and Environmental Impact Assessments with Mid-Century Process," ACS Sus. Chem. Eng. 2014 2(4) 823-835.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Li, M. A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid, Ph.D. Dissertation, University of Kansas 2013.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Ramanathan, A.; Maheswari, R.; Barich, D. H.; Subramaniam, B. "Niobium incorporated mesoporous silicate, Nb-KIT-6: Synthesis and characterization," Micro. Meso. Mat. 2014 190 240-247.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ryabchuk, P.; Edwards, A.; Gerasimchuk, N.; Rubina, M.; Rubin, M. "Dual Control of the Selectivity in the Formal Nucleophilic Subsittution of Bromocyclopropanes en Route to Densely Functionalized, Chirally Rich Cyclopropyl Derivatives," Org. Lett. 2013 15:23 6010-6013.
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Ryabchuk, P. Synthesis of Densely Functionalized Cyclopropanes via Diastereoselective Nucleophilic Additions to in Situ Generated Cyclopropenes Ph.D. Dissertation, University of Kansas 2013.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Wan, H.; Vitter, A.; Chaudhari, R. V.; Subramaniam, B. "Kinetic investigations of unusual solvent effects during Ru/C catalyzed hydrogenation of model oxygenates," J. Catal. 2014 309 174-184.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Xie, Z.; Fang, J.; Subramaniam, B.; Maiti, S.K.; Snavely, W.; Tunge, J. A. "Enhanced hydroformylation by carbon dioxide-expanded media with soluble Rh complexes in nanofiltration membrane reactors," AIChE J. 2013 59:11 4287-4296.


Progress 06/01/12 to 05/31/13

Outputs
Target Audience: The primary audience for this work includes agricultural processors, chemical manufacturers, and entrepreneurs seeking to adopt new technologies for producing value-added chemicals from biomass-derived feedstocks, as well as product manufacturers or agricultural producers who would benefit from such bio-derived chemicals. One such company, Archer Daniels Midland (ADM), is already a key partner on this project. Via the University of Kansas Center for Environmentally Beneficial Catalysis (CEBC), technical results are being discussed with representatives from other companies to gage interest and obtain feedback on potential commercial opportunities. Equally important, the discoveries made in this work are being disseminated to broader audiences to share lessons about developing and evaluating more environmentally benign chemical technologies. Researchers on this project are active in making conference presentations and writing technical journal articles to disseminate the findings. Researchers have also presented this work in a less technical form to area high school science teachers and to government representatives from the State of Kansas. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Technical Mentoring Students and postdoctoral researchers on this project (collectively referred to below as students) work closely with highly-respected faculty mentors in weekly multi-disciplinary research meetings. In keeping with the multi-disciplinary nature of the project, these meetings typically feature chemists and chemical engineers at the faculty, postdoctoral, and graduate levels, and occasionally involve team members from other science or engineering disciplines. Intellectual Property (IP) training is provided annually to aid students in identifying and protecting potentially patentable information. Students are encouraged to draft journal papers and present their work at professional society meetings. Industrial Mentoring Students interact directly with CEBC’s Industrial Advisory Board (IAB), which is comprised of twelve leading chemical and energy companies, such as ADM, Chevron Phillips, Evonik, Invista, UOP/Honeywell, among others. Students have opportunities to make oral and poster presentations at semi-annual IAB meetings and receive project evaluations conducted by IAB members. CEBC’s IAB members bring unique perspectives on the commercial potential of early stage research projects, complementing the academic perspective. Students also meet with speakers in CEBC’s Industrial Colloquia Program, which features prominent industrial researchers on a variety of topics, and provide a glimpse into how R&D in industry differs from academia. Professional Development The CEBC Education Director organizes professional development workshops for students, addressing topics such as technical presentation skills, communication to general audiences, career guidance, intellectual property and commercialization issues, laboratory safety, and “lunch-and-learn” peer-to-peer skill development sessions. Students also play an important role on the CEBC Laboratory Safety Committee, which coordinates and enforces good laboratory practices for the Center. The students often act as co-mentors for summer REU students in order to develop research training and management skills. Campus Networking Students may participate in Students for Green Chemistry, a campus organization formed by CEBC students to stimulate interest in sustainable chemical technologies among non-scientists. Students for Green Chemistry participate in K-12 and community outreach programs. In addition, a University of Kansas Postdoctoral Association was formed in 2012 with financial assistance from the Office of Research and Graduate Studies. The purpose of this group is twofold. First, it supports postdoctoral scholars by improving their training in all aspects of professional research and career development. Second, the group promotes a sense of community for postdoctoral scholars in diverse academic fields with opportunities to share research and interact socially. KU supports this group financially by paying for travel scholarships, invited speakers, lunches, and a yearly symposium. The group meets twice a month and uses social media to promote interactions. How have the results been disseminated to communities of interest? Input from Industry ADM, as a core partner on the project, has actively participated in all aspects of this project, through weekly teleconferences, quarterly on-site meetings. Selected results have also been shared with other companies to gage interest and identify potential collaborations, including ChevronPhillips Chemical, Evonik, First Green Partners, Invista, UOP, and ZeaChem. Publications and Conference Presentations The publications and presentations are described in the "Outputs" section of this report. What do you plan to do during the next reporting period to accomplish the goals? As reported in the accomplishments section, the technical progress has met or exceeded expectations, and work will continue as originally proposed. We expect by the end of the next reporting period, each of the sub-projects will be on a trajectory toward pre-pilot scale testing. The following tasks are planned for the upcoming year: Feedstocks and Pretreatment (a) Continued feedstock refinement to meet process requirements; (b) Continued production of feedstocks for bench-scale and pre-pilot testing. Ozonolysis (a) Continuous reactor operation with mixed oil feeds; (b) Demonstration of ozonolysis with real feed oils; (c) Solvent screening for lignin depolymerization by ctalytic oxidation. Allyl Alcohol Hydroformylation (a) Kinetic studies on immobilized rhodium catalyst; (b) Demonstrate continuous hydroformylation; (c) Membrane reactor modeling p-Xylene/HMF Oxidation (a) Extended continuous production of PTA; (b) Continuous FDCA production at optimized conditions; (c) Modeling of spray reactor. Guerbet Alcohol Synthesis (a) Mechanistic and theoretical modeling studies; (b) Reaction kinetics on leading metal oxide catalysts. Product and Process Assessment (a) Refinement of process concept designs; (b) revised techno-economic and LCA projections; (c) performance testing of products made at lab scale.

Impacts
What was accomplished under these goals? Feedstock development ADM has further developed its proprietary processes for producing biorefinery feedstocks, and has supplied these to CEBC researchers for use in these studies, including fatty acid methyl esters (FAMES), vegetable oils, isolated lignin, 5-hydroxymethylfurfural (HMF), and allyl alcohol. ADM research have developed a process for economically producing HMF and are in the process of building a pilot reactor for producing HMF (kg scale) that would be subsequently converted to FDCA. Development of New Conversion Technologies/Catalysts: FAMEs Ozonolysis: The conversion of FAME model compounds, most notably methyl oleate, by ozonolysis in liquid CO2 medium to a mixture of stable secondary ozonides along with desirable acids and aldehydes has been achieved in a continuous bench-scale bubble column reactor. Complete conversion of the FAME model compound methyl oleate in the initial ozonolysis step has been observed at high production rates. A tubular reactor has been constructed and tested for safe decomposition of secondary ozonide solutions with promising preliminary results. This technology continues to progress toward pre-pilot testing. Lignin depolymerizaiton: In a parallel effort, untreated lignin was aerobically oxidized with a proprietary catalyst to yield significant quantities of depolymerized lignin without char formation. Allyl alcohol hydroformylation: 1,4-Butanediol (BDO) is an important industrial compound that is used to make organic solvents. In this work, BDO is made from bio-derived allyl alcohol through hydroformylation and hydrogenation reactions. Our work demonstrated that several advantages were obtained when performing the hydroformylation reaction in propane-expanded liquids (PXL). Under PXL conditions, the reaction is fast and has little unwanted products. The results show nearly 100% allyl alcohol conversions with ~94% chemoselectivity to aldehydes. The precious rhodium (Rh) catalysts can be separated out from the hydroformylation products by extraction using water and recycled for more reactions. An alternative recyclable Rh catalyst was also developed. This catalyst shows good activity and selectivity compared to conventional Rh catalyst. A new lab-scale nanofiltration reactor has been constructed to demonstrate the continuous operation with good Rh retention. This is aimed at demonstrating a pilot-ready version of the technology. Also of commercial interest as an alternative, hydroformylation of acrolein diethyl acetal in the presence of a soluble polymer-supported phosphite ligand has been optimized to produce 4,4-diethoxybutanal with >9:1 n/iso selectivity and >99% chemoselectivity, using lower ligand loadings p-Xylene/HMF oxidation: Intrinsic kinetic studies of p-xylene oxidation to terephthalic acid (TPA) under homogeneous conditions confirm that it is not possible to completely overcome the gas-liquid mass transfer limitations in a conventional stirred reactor. Any further increase in the overall reaction rate must involve another reactor configuration—such as spray reactor type. Several engineering challenges were resolved in the development of a laboratory spray reactor capable of fully-continuous operation with reliable process control and no fouling/plugging by the solid TPA product. Comparative economic analyses and life cycle assessments of the spray process and the conventional Mid-Century (MC) process for TPA production show that the spray process significantly reduces capital and operating costs by 55% and 16% respectively, and also imposes less adverse environmental impacts than the MC process. These developments above also enabled continuous conversion of HMF to FDCA at yields in excess of 80%. The reaction/reactor conditions are being optimized to further increase the yield via minimization of side reactions e.g. substrate decomposition. A few hundred grams of FDCA have already been produced in the continuous reactor for product testing. A mathematical model of the spray reactor that incorporates reliable kinetic data is being developed for rational process optimization and scale-up. Guerbet alcohol synthesis: We have discovered alkali promoted Cu containing mixed metal oxide catalysts that convert methanol and ethanol mixtures to products of higher value and energy content, which can be used as chemical intermediates and/or fuel additives. These products are produced at yields higher than those of previously reported state-of-the-art catalysts. The design of these catalysts was enabled by a better understanding of the variables that affect the reaction productivity and the interactions between reactants and products on the surface of the catalyst as provided by systematic parametric and advanced spectroscopic characterization studies. Development of a cradle-to-grave LCA methodology: One of the important USDA project deliverables is LCA analyses of all process concepts developed. We developed the LCA framework based on GaBi® software by performing an analysis of the CEBC-EO process with data from published literature.This methodology has been successfully applied for the LCA of the TPA and hydroformylation processes as well as energy production from various sources such as coal, natural gas and crude oil.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Jin, X.; Dang, L.; Lohrman, J.; Subramaniam, B.; Ren, S.; Chaudhari, R.V. "Lattice-Matched Bimetallic CuPd-Graphene Nanocatalysts for Facile Conversion of Biomass-Derived Polyols to Chemicals," ACS Nano 2013 7:2 1309-1316.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Bravo-Suarez, J. J., Subramaniam, B., Chaudhari, R. V. "Ultraviolet-Visible Spectroscopy and Temperature Programmed Techniques as Tools for Structural Characterization of Cu in CuMgAlOX Mixed Metal Oxides," J. Phys. Chem. C 2012 116:34 18207-18221.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Bravo-Su�rez, J.J.; Subramaniam, B.; Chaudhari, R.V. "Vapor-Phase Methanol and Ethanol Coupling Reactions on CuMgAl Mixed Metal Oxides," App. Catal. A 2013 455 234-246.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ramanathan, A., Subramaniam, B., Maheswari, R., Hanefeld, U. "Synthesis, and characterization of Zirconium incorporated ultra large pore mesoporous silicate, Zr-KIT-6," Micropor. Mesopor. Mat. 2013 167 207-212.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ramanathan, A.; R. Maheswari; Grady, B. P.; Moore, D. S.; Barich, D. H.; Subramaniam, Bala. "Tungsten-incorporated cage-type mesoporous silicate: W-KIT-5" Micro. Meso. Mat. 2013 175 43-49.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Ryabchuk, P.; Rubina, M.; Xu, J.; Rubin, M. "Formal Nucleophilic Substitution of Bromocyclopropanes with Azoles," Org. Lett. 2012 14:7 1752-1755.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Wan, H.; Chaudhari, R. V.; Subramaniam, B. "Aqueous Phase Hydrogenation of Acetic Acid and Its Promotional Effect on p-Cresol Hydrodeoxygenation," Energy & Fuels 2013 27:1 487-493.
  • Type: Book Chapters Status: Awaiting Publication Year Published: 2013 Citation: Bravo-Suarez, J.J.; Chaudhari, R.V.; Subramaniam, B. "Design of Heterogeneous Catalysis for Fuels and Chemicals Processing: An Overview," in Novel Materials for Catalysis and Fuels Processing; ACS Symposium Series 1132; J. J. Bravo-Su�rez, M. Kidder, V. Schwartz, Eds.; American Chemical Society: Washington, D.C., 3-68, 2013
  • Type: Book Chapters Status: Awaiting Publication Year Published: 2013 Citation: Ramanathan, A.; Maheswari, R.; Subramaniam, B. "Rapid room temperature synthesis of Ce-MCM-48: an active catalyst for trans-stilbene epoxidation with tert-butyl hydroperoxide," ACS Symposium Series 2013 in press
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Xie, Z. "Greener Hydroformylation with Nanofilterable Rhodium Catalysts in A Stirred Membrane Reactor," Ph.D. Dissertation, University of Kansas 2013.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: Meng Li, Fenghui Niu, Xiaobin Zuo, Daryle Busch & Bala Subramaniam, "A one-step spray reactor for production of polymer-grade terephthalic acid," ISCRE 22 (International Symposia on Chemical Reaction Engineering), Maastricht, the Netherlands, September 4, 2012
  • Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Meng Li, A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid, PhD Dissertation, University of Kansas, 2013
  • Type: Book Chapters Status: Published Year Published: 2013 Citation: Xin Jin, Bala Subramaniam, Raghunath V. Chaudhari*, Activity and Selectivity of Bimetallic Catalysts for Polyols Hydrogenolysis. Novel Materials for Catalysis and Fuels Processing (ACS Symposium Book Series, Vol. 1132) Chapter 12, pp 273285. Washington, D. C. 2013.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2013 Citation: Raghunath V. Chaudhari*, Arely Torres, Xin Jin, Bala Subramaniam. Multiphase Catalytic Hydrogenolysis/Hydrodeoxygenation Processes for Chemicals from Renewable Feedstocks: Kinetics, Mechanism & Reaction Engineering. Ind. & Eng. Chem. Res., 2013 DOI: 10.1021/ie400709d.
  • Type: Journal Articles Status: Submitted Year Published: 2013 Citation: Xin Jin, Debdut Roy, Prem Thapa, Bala Subramaniam, Raghunath V. Chaudhari, Atom Economical, Aqueous Phase Conversion (APC) of Biopolyols to Lactic Acid, Glycols and Linear Alcohols. ACS Sustainable Chemistry & Engineering (submitted)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Qing Pan, Anand Ramanathan and Bala Subramaniam, "Intrinsic kinetics of isopropanol dehydration to propene on acidic mesoporous Zr-KIT-6 catalyst," NASCRE-3, 2013, Houston TX.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Qing Pan, Anand Ramanathan and Bala Subramaniam, "Tungsten oxide supported cage-type mesoporous silicate: W-KIT-5," 23rd North American Catalysis Society Meeting in Louisville, KY, June 2-7, 2013
  • Type: Conference Papers and Presentations Status: Published Year Published: 2012 Citation: Xin Jin, Bala Subramaniam, Raghunath V. Chaudhari*. One Pot Conversion of Bio-derived Polyols to Lactic Acid. AIChE Annual Meeting Oct. 2012 in Pittsburgh, PA.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: R. V. Chaudhari*, Arely Torres, Xin Jin, Bala Subramaniam. Multiphase Catalytic Processes for Renewable Feedstocks to Chemical Intermediates: Kinetics, Mechanism and Reaction Engineering. 3rd North American Symposium on Chemical Reaction Engineering, Mar. 2013 in Houston, TX.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Xin Jin, Bala Subramaniam, Raghunath V. Chaudhari*. Kinetic Modelling of Hydrogenolysis of Sugar Based Polyols using a Bimetallic Ru-Re/C Catalyst in a Slurry Reactor. 3rd North American Symposium on Chemical Reaction Engineering, Mar. 2013 in Houston, TX.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: J. J. Bravo-Su�rez, B. Subramaniam, R. V. Chaudhari Reactivity and Spectroscopic Studies of Cu Containing Mixed Metal Oxides for Vapor-Phase Methanol and Ethanol Coupling Reactions, 23rd North American Catalysis Society Meeting, Louisville, Kentucky, June 27, 2013
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Xin Jin, Lianna Dang, Jessica Lohrman, Bala Subramaniam, Shenqiang Ren*, Raghunath V. Chaudhari*. Graphene Supported Cu Nanocatalysts for Conversion of Bio-mass Derived Polyols to Chemicals. 23rd North American Catalysis Society Meeting, Jun. 2013 in Louisville, KY.
  • Type: Journal Articles Status: Submitted Year Published: 2013 Citation: Meng Li, Fenghui Niu, Xiaobin Zuo, Peter D. Metelski, Daryle H. Busch, Bala Subramaniam, A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid, submitted to Chemical Engineering Science, 2013
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2013 Citation: Ghanta, M.; Fahey, D.; Subramaniam, B. "Environmental impacts of ethylene production from diverse feedstocks and energy sources," Appl. Petrochem. Res. 2013 in press. doi:10.1007/s13203-013-0029-7


Progress 06/01/11 to 05/31/12

Outputs
OUTPUTS: [1] Intellectual Property: Two provisional patent applications (61/529,427 and 61/529,430) regarding a process for synthesis of carboxylic acids were filed with the USPTO, and an additional invention disclosure regarding novel catalysts for conversion of polyols was submitted to the University of Kansas (KU) technology commercialization office. A PhD student (M. Ghanta) who was partly funded with USDA funds to develop LCA methodology completed his dissertation in May 2012. [2] Technical Presentations: Several presentations were made at international research conferences, including the American Institute of Chemical Engineers Annual Meeting (Nov. 2011), the 10th International Symposium on Supercritical Fluids (May 2012), the American Chemical Society Meeting (Mar. 2012) and the 15th International Congress on Catalysis (July 2012). The USDA award has elevated renewable chemicals R&D at KU as a top priority. [3] Submitted Manuscripts that Describe USDA-funded Research: (A) J. J. Bravo-Suarez, B. Subramaniam, R. V. Chaudhari, "Ultraviolet-Visible Spectroscopy and Temperature Programmed Techniques as Tools for Structural Characterization of Cu in CuMgAlOx Mixed Metal Oxides," (B) X. Jin, D. Roy, B. Subramaniam and R. V. Chaudhari, "One Pot Conversion of Sugars and Polyols to Lactic Acid" (C) A. Ramanthan, B. Subramaniam, R. Maheswari and U. Hanefeld, "Synthesis, characterization and catalytic activity of Zirconium incorporated ultra large pore mesoporous silicate, Zr-KIT-6," (D) A. Ramanthan, R. Maheswari and B. Subramaniam, "Rapid room temperature synthesis of Ce-MCM-48: an active catalyst for trans-stilbene epoxidation with tert-butyl hydroperoxide,". (E) M. Ghanta, T. Ruddy, D. Fahey, D. Busch, B. Subramaniam, "Is the Liquid-Phase H2O2-based Ethylene Oxide Process More Economical and Greener Than the Gas-Phase O2-based Silver-Catalyzed Process," [4] New Biorefining Hub Initiative: KU is leading an effort to establish a Biorefining R&D Hub in Lawrence, KS. The major goal of the Hub is to bring together companies across the value chain to engage in pre-pilot testing of technology concepts that show promise at the lab-scale and thereby expedite their commercialization. A series of high-level presentations on renewable chemicals and their potential economic impact on Kansas were made between Oct. 2011 and May 2012 to members of the State of Kansas Executive Branch, including Governor Brownback. The goal was to inform state leaders about the progress and opportunities for a chemical biorefining industry, and to leverage USDA funds into a broader state-wide initiative that brings together stakeholders from industry, agriculture, academia and economic development to accelerate commercial development. ADM, the major industry collaborator in this initiative, has decided to locate a research operation in Lawrence, KS to work more closely with KU researchers to advance bench-scale biorefining concepts towards commercialization. Other industry partners of the Center for Environmentally Beneficial Catalysis (CEBC) [DuPont, P&G, ChevronPhillips, UOP, ConocoPhillips, ZeaChem] have also provided input on R&D and thus also become involved in the project. PARTICIPANTS: [A] Individuals: Prof. Bala Subramaniam, PI; Prof. Daryle Busch, Faculty Researcher; Prof. Raghunath V. Chaudhari, Faculty Researcher; Prof. Michael Rubin, Faculty Researcher; Dr. Christopher Lyon, Project Manager; Dr. Darryl Fahey, Industry Liaison; Dr. Feng Niu, Laboratory Director; Dr. Juan Bravo-Suarez, Postdoc; Dr. Haijun Wan, Postdoc; Dr. Andrew Danby, Postdoc; Dr. Michael Lundin, Postdoc; Dr. Bibhas Sarkar, Postdoc; Dr. Maheswari Rajamanickam, Postdoc; Dr. Anand Ramanathan, postdoc; Arely Torres, PhD Student; Xin Jin, PhD Student, Meng Li, PhD Student; Shirley Xie, PhD Student; Madhav Ghanta, PhD Student; Qing Pan, MS Student. [B] Partner Organizations: Archer Daniels Midland Company. [C] Collaborators and Contacts: Evonik Industries, Procter & Gamble, DuPont, River City Engineering [D] Life Cycle Assessment (LCA) methodology/software training. TARGET AUDIENCES: A formalized education/outreach program for K-12 science teachers (funded from another source) featured research and demonstrations from graduate students and postdocs working on this project. The six-week summer program targets teachers from across Kansas including both rural and inner-city school districts. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
R&D Progress: [1] Ozonolysis of fatty acid methyl esters: A continuous ozonolysis reactor capable of processing real feeds from a biorefinery (supplied by the industry partner) has been refined and tested. The primary products from the ozonolysis reactor have been identified using a complement of techniques including NMR, HPLC and GC-MS. Based on this analysis, post-ozonolysis workup strategies to produce acid and/or aldehyde products are being currently developed. Computational chemistry calculations are providing valuable insights into plausible ozonolysis reaction pathways that in turn are guiding experiments and rational process development. [2] Lignin valorization: Analytical techniques for analyzing lignin depolymerization products are being developed. These include (a) GPC and MALDI-TOF techniques to determine molecular weight distributions of neat and processed lignin; (b) Solid-state NMR techniques for determining aromatic and aliphatic contents; (c) IR techniques; (d) HPLC and GC-MS analysis of low molecular weight fractions (molecular weight < 1000). Depolymerization strategies are being developed with real lignin. [3] One-step production of renewable plastic intermediates: Based on reactor optimization studies, optimum residence times have been determined for converting p-Xylene to terephthalic acid with a 4-CBA content of lass than 25 ppm. A continuous 4 L spray reactor with excellent T and P control and equipped with continuous harvesting of solid TPA product from the reactor effluent has been constructed and demonstrated. Complementary reactor models are also being developed to aid in rational reactor optimization and design. This reactor has also been successfully tested with real feeds from a biorefinery to make plastic intermediates. [4] Hydroformylation of biomass-derived substrates: Novel catalysts and process concepts for hydroformylating biomass-derived substrates with unprecedented chemo- and region-selectivities have been developed. The processes use mild temperatures and pressures. The current focus is on developing efficient catalyst recovery and recycle techniques for continuous operation. [5] Guerbet alcohol synthesis: In the quest to design and develop active, selective, and stable catalysts for synthesis of fuels (higher alcohols) and chemicals (oxygenates) from methanol and ethanol mixtures, alkali modified zeolite catalysts and CuMgAOx mixed oxides have been developed. The performances of both these catalysts are superior to those reported to date in the literature. A new and simple methodology, based on UV-vis spectroscopy and temperature programmed reduction methods, has been developed to gain a better understanding on the effect of Cu on catalyst activity and selectivity. These results are paving the way for the rational development of highly active, selective and relatively inexpensive catalysts.

Publications

  • Ramanathan, A.; Subramaniam, B.; Badloe, D.; Hanefeld, U.; Maheswari, R. "Direct incorporation of tungsten into ultra-large-pore three-dimensional mesoporous silicate framework: W-KIT-6" J. Porous. Mater. 2012, In press. doi:10.1007/s10934-011-9553-y
  • Subramaniam, B.; Akien, G. R. "Sustainable catalytic reaction engineering with gas-expanded liquids," Curr. Op. Chem. Eng. 2012 In press. doi:10.1016/j.coche.2012.02.005
  • Wan, H.; Chaudhari, R. V.; Subramaniam, B. "Catalytic Hydroprocessing of p-Cresol: Metal, Solvent, and Mass-Transfer Effects," Topics in Catal. 2012 55:3-4 129-139. doi:10.1007/s11244-012-9782-6
  • Ye, K.; Freund, H.; Xie, Z. Subramaniam, B.; Sundmacher, K. "Prediction of Multicomponent Phase Behavior of CO2-Expanded Liquids using CEoS/GE Models and Comparison with Experimental Data," J. Sup. Fluids 2012 67 41-52. doi:10.1016/j.supflu.2012.03.007