Research in the catalytic conversion of lignocellulose and sugars targets large-volume specialty and commodity chemicals common to everyday materials. Glucose conversion to p-xylene yields renewable PET plastic (#1 recycling logo), while biomass-sourced toluene permits renewable polyurethane. Conversion of sugars to butadiene and isoprene enable renewable rubbers and elastomers including automobile tires, rubber gloves, and hard plastics such as ABS pipes and toy bricks. Catalytic carbon-coupling reactions combine sugar- and oil-derived chemicals to form oleo-furan sulfonate (OFS) surfactants, a renewable surfactant with novel properties for detergent applications.
Sugars derived from lignocellulosic biomass can be converted to monomer chemicals including butadiene, isoprene, and hexadiene which form many common types of rubbery materials. Dehydration of sugars forms furans, a five-atom ring containing one oxygen, which can be further reduced to THF (or tetrahydrofuran). In the last step, THF and its sister chemicals methyl-THF undergo a new reaction called "dehydra-decyclization" to simultaneously ring open and dehydrate to form dienes. This chemistry occurs on solid acid catalysts including aluminum-containing zeolites and all-silica phosphorous-containing zeolites.
- "Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran," Omar Abdelrahman, D.S. Park, K. Vinter, C.Spanjers, L. Ren, H.J. Cho, D.G. Vlachos, W. Fan, M. Tsapatsis, P.J. Dauenhauer, ACS Sustainable Chemistry and Engineering. 2017. LINK
- "Renewable Isoprene by Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3-Methyl-Tetrahydrofuran," Omar A. Abdelrahman, Dae Sung Park, Katherine P Vinter, Charles S. Spanjers, Limin Ren, Hong Je Cho, Kechun Zhang, Wei Fan, Michael Tsapatsis, Paul J. Dauenhauer, ACS Catalysis 2017, 7(2), 1428-1431. DOI: 10.1021/acscatal.6b03335. LINK
Preparation of soaps and detergents (amphiphiles) from renewable feedstocks is challenged by the need to invent efficient synthesis methods using sustainable materials. Additionally, sustainable surfactants must achieve comparable or better performance than existing petroleum-derived molecules. In this work, we have invented a new class of "oleo-furan sulfonates" (OFS) which are synthesized entirely from bio-derived resources. Furan from sugar and fatty acids from natural oils are combined with a sulfonate head group to form linear (unbranched) surfactants with exception proclivity to form stable micelles at low temperature. Moreover, OFS surfactants exhibit stability in hard water with high concentrations of magnesium or calcium. Their tunable synthesis method allows for modification to achieve performance needs in varying applications.
- "Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans," Dae Sung Park, Kristeen E. Joesph, Maura Koehle, Christoph Krumm, Limin Ren, Jonathan N. Damen, Meera H. Shete, Han Seung Lee, Xiaobing Zuo, Byeongdu Lee, Wei Fan, Dionisios G. Vlachos, Raul F. Lobo, Michael Tsapatsis, Paul Dauenhauer, ACS Central Science 2016, 2(11), 820-824. DOI: 10.1021/acscentsci.6b00208. LINK
Renewable Aromatic Chemicals
The use of petroleum for chemicals and materials has led to the utilization of six-carbon aromatic rings as the bases for much of the modern chemical industry. Aromatics are ubiquitous including: (i) phenol for polycarbonate, (ii) toluene for polyurethanes, (iii) styrene for polystyrene, (iv) xylene for PET plastic and (v) phthalic anhydride as a plasticizer, with many other examples. However, research to produce six-carbon aromatics renewably has been challenged by natural sugars tendency to form five-atom furans as low energy products. In this work, we demonstrate the use of tandem Diels-Alder cycloaddition of biomass-derived furans and subsequent dehydration to convert bio-derived furans into six-carbon aromatic rings. By this method, the functional groups on the parent furan can be transferred to the aromatic ring product, allowing for numerous different aromatic products to be produced renewably.
- "Renewable p-Xylene from 2,5-dimethylfuran and ethylene using phosphorous-containing zeolite catalysts,," Wei Fan, Hong Je Cho, L. Ren, V. Vattipailli, Y.H. Yeh, N. Gould, B. Xu, R.J. Gorte, R. Lobo, P.J. Dauenhauer, M. Tsapatsis, ChemCatChem2017, 9(3), 398-402. DOI: 10.1002/cctc.201601294. LINK
- "Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products," R.E. Patet, N. Nikbin, C.L. Williams, S.K. Green, C.C. Chang, W. Fan, S. Caratzoulas, P.J. Dauenhauer, D.G. Vlachos, ACS Catalysis 2015, 5(4), 2367-2375. DOI: 10.1021/cs5020783. LINK
- "Cycloaddition of Biomass-Derived Furans for Catalytic Production of p-Xylene," C.Luke Williams, Chun-Chih Chang, Phuong Do, Nima Nikbin, Stavros Caratzoulas, Dionisios G. Vlachos, Raul F. Lobo, Wei Fan, Paul J. Dauenhauer, ACS Catalysis2012, 2(6), 935-93. LINK