Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.; Behl, Mayank; Gjersing, Erica; Griffin, Michael; Zhu, Hongda; Subramaniam, Bala; Schaidle, Joshua A.; Hensley, Jesse E.

doi:10.1016/j.apcata.2015.11.019

Title: Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

Journal Article · Tue Dec 01 00:00:00 EST 2015 · Applied Catalysis. A, General

DOI:https://doi.org/10.1016/j.apcata.2015.11.019· OSTI ID:1235230

Nash, Connor P. ^[1]; Ramanathan, Anand ^[2]; Ruddy, Daniel A. ^[3]; Behl, Mayank ^[1]; Gjersing, Erica ^[1]; Griffin, Michael ^[1]; Zhu, Hongda ^[2]; Subramaniam, Bala ^[2]; Schaidle, Joshua A. ^[1]; Hensley, Jesse E. ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
Univ. of Kansas, Lawrence, KS (United States). Center for Environmentally Beneficial Catalysis
National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C₂–C₄ alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporous silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C₃₊-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office (BETO)

Grant/Contract Number:: AC36-08GO28308; AC36-080GO28308

OSTI ID:: 1235230

Alternate ID(s):: OSTI ID: 1400013

Report Number(s):: NREL/JA-5100-65042

Journal Information:: Applied Catalysis. A, General, Vol. 510; ISSN 0926-860X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 55 works

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References (55)

Biofuels, biodiversity, and people: Understanding the conflicts and finding opportunities Koh, Lian Pin; Ghazoul, Jaboury Biological Conservation, Vol. 141, Issue 10 https://doi.org/10.1016/j.biocon.2008.08.005	journal	October 2008
The Path Forward for Biofuels and Biomaterials Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H. Science, Vol. 311, Issue 5760, p. 484-489 https://doi.org/10.1126/science.1114736	journal	January 2006
A techno-economic review of thermochemical cellulosic biofuel pathways Brown, Tristan R. Bioresource Technology, Vol. 178 https://doi.org/10.1016/j.biortech.2014.09.053	journal	February 2015
An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery Huber, George W.; Dumesic, James A. Catalysis Today, Vol. 111, Issue 1-2 https://doi.org/10.1016/j.cattod.2005.10.010	journal	January 2006
Compositional Analysis and Advanced Distillation Curve for Mixed Alcohols Produced via Syngas on a K-CoMoS _x Catalyst Hensley, Jesse E.; Lovestead, Tara M.; Christensen, Earl Energy & Fuels, Vol. 27, Issue 6 https://doi.org/10.1021/ef400252x	journal	May 2013
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
Recent advancements in ethylene and propylene production using the UOP/Hydro MTO process Chen, John Q.; Bozzano, Andrea; Glover, Bryan Catalysis Today, Vol. 106, Issue 1-4 https://doi.org/10.1016/j.cattod.2005.07.178	journal	October 2005
The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction Chen, De; Moljord, Kjell; Fuglerud, Terje Microporous and Mesoporous Materials, Vol. 29, Issue 1-2 https://doi.org/10.1016/S1387-1811(98)00331-X	journal	June 1999
Synthesis of SAPO-34 with small and tunable crystallite size by two-step hydrothermal crystallization and its catalytic performance for MTO reaction Wang, Pengfei; Yang, Dexing; Hu, Jie Catalysis Today, Vol. 212 https://doi.org/10.1016/j.cattod.2012.08.027	journal	September 2013
Synthesis of Mesoporous SAPO-34 Molecular Sieves and Their Applications in Dehydration of Butanols and Ethanol Jun, Jong Won; Jeon, Jaewoo; Kim, Chul-Ung Journal of Nanoscience and Nanotechnology, Vol. 13, Issue 4 https://doi.org/10.1166/jnn.2013.7387	journal	April 2013
Dehydration reaction of bio-ethanol to ethylene over modified SAPO catalysts Chen, Yu; Wu, Yulong; Tao, Ling Journal of Industrial and Engineering Chemistry, Vol. 16, Issue 5 https://doi.org/10.1016/j.jiec.2010.07.013	journal	September 2010
Dehydration of Ethanol into Ethylene over Solid Acid Catalysts Takahara, Isao; Saito, Masahiro; Inaba, Megumu Catalysis Letters, Vol. 105, Issue 3-4 https://doi.org/10.1007/s10562-005-8698-1	journal	December 2005
Comparison of four catalysts in the catalytic dehydration of ethanol to ethylene Zhang, Xian; Wang, Rijie; Yang, Xiaoxia Microporous and Mesoporous Materials, Vol. 116, Issue 1-3 https://doi.org/10.1016/j.micromeso.2008.04.004	journal	December 2008
Dehydration of Ethanol to Ethylene Zhang, Minhua; Yu, Yingzhe Industrial & Engineering Chemistry Research, Vol. 52, Issue 28 https://doi.org/10.1021/ie401157c	journal	July 2013
Catalytic Conversion of Bio-ethanol to Ethylene over La-Modified HZSM-5 Catalysts in a Bioreactor Ouyang, Jia; Kong, Fengxia; Su, Guodong Catalysis Letters, Vol. 132, Issue 1-2 https://doi.org/10.1007/s10562-009-0047-3	journal	June 2009
Conversion of lower alcohols into C2–C4 olefins over acid-base catalysts Ermakov, R. V.; Plakhotnik, V. A. Petroleum Chemistry, Vol. 48, Issue 1 https://doi.org/10.1134/S0965544108010015	journal	January 2008
Catalyst activity comparison of alcohols over zeolites Ramasamy, Karthikeyan K.; Wang, Yong Journal of Energy Chemistry, Vol. 22, Issue 1 https://doi.org/10.1016/S2095-4956(13)60008-X	journal	January 2013
Conversion of Ethanol into Polyolefin Building Blocks: Reaction Pathways on Nickel Ion-loaded Mesoporous Silica Iwamoto, Masakazu; Kasai, Kouji; Haishi, Teruki ChemSusChem, Vol. 4, Issue 8 https://doi.org/10.1002/cssc.201100168	journal	June 2011
Fast and Quantitative Dehydration of Lower Alcohols to Corresponding Olefins on Mesoporous Silica Catalyst Haishi, Teruki; Kasai, Kouji; Iwamoto, Masakazu Chemistry Letters, Vol. 40, Issue 6 https://doi.org/10.1246/cl.2011.614	journal	June 2011
Intrinsic Kinetics of Ethanol Dehydration Over Lewis Acidic Ordered Mesoporous Silicate, Zr-KIT-6 Pan, Qing; Ramanathan, Anand; Kirk Snavely, W. Topics in Catalysis, Vol. 57, Issue 17-20 https://doi.org/10.1007/s11244-014-0311-7	journal	September 2014
Synthesis and Dehydration Activity of Novel Lewis Acidic Ordered Mesoporous Silicate: Zr-KIT-6 Pan, Qing; Ramanathan, Anand; Snavely, W. Kirk Industrial & Engineering Chemistry Research, Vol. 52, Issue 44 https://doi.org/10.1021/ie4019484	journal	September 2013
Ethylene and Acetaldehyde Production by Selective Oxidation of Ethanol Using Mesoporous V−MCM-41 Catalysts Gucbilmez, Yesim; Dogu, Timur; Balci, Suna Industrial & Engineering Chemistry Research, Vol. 45, Issue 10 https://doi.org/10.1021/ie050952j	journal	May 2006
Study of operating variables in the transformation of aqueous ethanol into hydrocarbons on an HZSM-5 zeolite: Transformation of aqueous ethanol into hydrocarbons Aguayo, Andres T.; Gayubo, Ana G.; Tarrío, Ana M. Journal of Chemical Technology & Biotechnology, Vol. 77, Issue 2 https://doi.org/10.1002/jctb.540	journal	January 2002
Increase in the number of acid sites of a H-ZSM5 zeolite during the dehydration of ethanol Takahara, Isao; Saito, Masahiro; Matsuhashi, Hiromi Catalysis Letters, Vol. 113, Issue 3-4 https://doi.org/10.1007/s10562-007-9025-9	journal	March 2007
The transformation of ethanol over AlPO₄ and SAPO molecular sieves with AEL and AFI topology. Kinetic and thermodynamic approach Arias, D.; Colmenares, A.; Cubeiro, M. L. Catalysis Letters, Vol. 45, Issue 1/2, p. 51-58 https://doi.org/10.1023/A:1019055309967	journal	January 1997
Highly selective conversion of ethene to propene over SAPO-34 as a solid acid catalyst Oikawa, H.; Shibata, Y.; Inazu, K. Applied Catalysis A: General, Vol. 312 https://doi.org/10.1016/j.apcata.2006.06.045	journal	September 2006
Solid-state dealumination of zeolites for use as catalysts in alcohol dehydration Müller, Júlia M.; Mesquita, Gustavo C.; Franco, Sheila M. Microporous and Mesoporous Materials, Vol. 204 https://doi.org/10.1016/j.micromeso.2014.11.002	journal	March 2015
Relationship between acid amount and framework aluminum content in mordenite Sawa, Masahiko; Niwa, Miki; Murakami, Yuichi Zeolites, Vol. 10, Issue 6 https://doi.org/10.1016/S0144-2449(05)80308-2	journal	July 1990
Determination of the Acidic Properties of Zeolite by Theoretical Analysis of Temperature-Programmed Desorption of Ammonia Based on Adsorption Equilibrium Katada, Naonobu; Igi, Hirofumi; Kim, Jong-Ho The Journal of Physical Chemistry B, Vol. 101, Issue 31 https://doi.org/10.1021/jp9639152	journal	July 1997
Steaming of Zeolite BEA and Its Effect on Acidity: A Comparative NMR and IR Spectroscopic Study Maier, Sarah M.; Jentys, Andreas; Lercher, Johannes A. The Journal of Physical Chemistry C, Vol. 115, Issue 16 https://doi.org/10.1021/jp108338g	journal	April 2011
Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts Emeis, C. A. Journal of Catalysis, Vol. 141, Issue 2 https://doi.org/10.1006/jcat.1993.1145	journal	June 1993
Synthesis and characterization of Zirconium incorporated ultra large pore mesoporous silicate, Zr–KIT-6 Ramanathan, Anand; Subramaniam, Bala; Maheswari, Rajamanickam Microporous and Mesoporous Materials, Vol. 167 https://doi.org/10.1016/j.micromeso.2012.09.008	journal	February 2013
Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism Kresge, C. T.; Leonowicz, M. E.; Roth, W. J. Nature, Vol. 359, Issue 6397, p. 710-712 https://doi.org/10.1038/359710a0	journal	October 1992
Investigation into the shape selectivity of zeolite catalysts for biomass conversion Jae, Jungho; Tompsett, Geoffrey A.; Foster, Andrew J. Journal of Catalysis, Vol. 279, Issue 2, p. 257-268 https://doi.org/10.1016/j.jcat.2011.01.019	journal	April 2011
Small-Pore Molecular Sieves SAPO-34 and SAPO-44 with Chabazite Structure: A Study of Silicon Incorporation Ashtekar, Sunil; Chilukuri, Satyanarayana V. V.; Chakrabarty, Dipak K. The Journal of Physical Chemistry, Vol. 98, Issue 18 https://doi.org/10.1021/j100069a018	journal	May 1994
On the interpretation of the NH3-TPD patterns of H-ZSM-5 and H-mordenite Lónyi, Ferenc; Valyon, József Microporous and Mesoporous Materials, Vol. 47, Issue 2-3 https://doi.org/10.1016/S1387-1811(01)00389-4	journal	October 2001
Surface Reactions of Acetone on Al ₂ O ₃ , TiO ₂ , ZrO ₂ , and CeO ₂ : IR Spectroscopic Assessment of Impacts of the Surface Acid−Base Properties Zaki, M. I.; Hasan, M. A.; Pasupulety, L. Langmuir, Vol. 17, Issue 3 https://doi.org/10.1021/la000976p	journal	February 2001
Acid strength and solvation effects on methylation, hydride transfer, and isomerization rates during catalytic homologation of C₁ species Simonetti, Dante A.; Carr, Robert T.; Iglesia, Enrique Journal of Catalysis, Vol. 285, Issue 1, p. 19-30 https://doi.org/10.1016/j.jcat.2011.09.007	journal	January 2012
Mechanism of the Catalytic Conversion of Methanol to Hydrocarbons Ilias, Samia; Bhan, Aditya ACS Catalysis, Vol. 3, Issue 1, p. 18-31 https://doi.org/10.1021/cs3006583	journal	December 2012
Tuning the selectivity of methanol-to-hydrocarbons conversion on H-ZSM-5 by co-processing olefin or aromatic compounds Ilias, Samia; Bhan, Aditya Journal of Catalysis, Vol. 290 https://doi.org/10.1016/j.jcat.2012.03.016	journal	June 2012
The Mechanism of Methanol to Hydrocarbon Catalysis Haw, James F.; Song, Weiguo; Marcus, David M. Accounts of Chemical Research, Vol. 36, Issue 5 https://doi.org/10.1021/ar020006o	journal	May 2003
Selective Homologation Routes to 2,2,3-Trimethylbutane on Solid Acids Ahn, John H.; Temel, Burcin; Iglesia, Enrique Angewandte Chemie International Edition, Vol. 48, Issue 21, p. 3814-3816 https://doi.org/10.1002/anie.200900541	journal	May 2009
Zeolite acid strength and reaction mechanisms in catalysis Haw, James F. Phys. Chem. Chem. Phys., Vol. 4, Issue 22 https://doi.org/10.1039/B206483A	journal	January 2002
Alcohol Dehydration: Mechanism of Ether Formation Using an Alumina Catalyst Shi, B. C.; Davis, B. H. Journal of Catalysis, Vol. 157, Issue 2 https://doi.org/10.1006/jcat.1995.1301	journal	December 1995
An Ethoxy Intermediate in Ethanol Dehydration on Brønsted Acid Sites in Zeolite Kondo, Junko N.; Ito, Keiichi; Yoda, Eisuke The Journal of Physical Chemistry B, Vol. 109, Issue 21 https://doi.org/10.1021/jp050721q	journal	June 2005
Alcohol Reactivity on Zeolites and Molecular Sieves Bezoukhanova, Cvetana P.; Kalvachev, Yuri A. Catalysis Reviews, Vol. 36, Issue 1 https://doi.org/10.1080/01614949408013922	journal	February 1994
The characteristics of SAPO-34 which influence the conversion of methanol to light olefins Wilson, Stephen; Barger, Paul Microporous and Mesoporous Materials, Vol. 29, Issue 1-2 https://doi.org/10.1016/S1387-1811(98)00325-4	journal	June 1999
Methanol Conversion to Light Olefins Chang, Clarence D. Catalysis Reviews, Vol. 26, Issue 3-4 https://doi.org/10.1080/01614948408064716	journal	August 1984
Gas Conversion to Liquid Fuels and Chemicals: The Methanol Route‐Catalysis and Processes Development Mokrani, Touhami; Scurrell, Mike Catalysis Reviews, Vol. 51, Issue 1, p. 1-145 https://doi.org/10.1080/01614940802477524	journal	January 2009
The effect of crystallite size on the activity and selectivity of the reaction of ethanol and 2-propanol over SAPO-34 Dahl, Ivar M.; Wendelbo, Rune; Andersen, Anne Microporous and Mesoporous Materials, Vol. 29, Issue 1-2 https://doi.org/10.1016/S1387-1811(98)00328-X	journal	June 1999
Insights into the reaction mechanism of methanol-to-olefins conversion in HSAPO-34 from first principles: Are olefins themselves the dominating hydrocarbon pool species? Wang, Chuan-Ming; Wang, Yang-Dong; Xie, Zai-Ku Journal of Catalysis, Vol. 301 https://doi.org/10.1016/j.jcat.2013.01.024	journal	May 2013
Coke precursor formation and zeolite deactivation: mechanistic insights from hexamethylbenzene conversion Bjørgen, M. Journal of Catalysis, Vol. 215, Issue 1 https://doi.org/10.1016/S0021-9517(02)00050-7	journal	April 2003
In situ solid-state NMR study of methanol-to-gasoline chemistry in zeolite HZSM-5 Munson, Eric J.; Kheir, Ali A.; Lazo, Noel D. The Journal of Physical Chemistry, Vol. 96, Issue 19 https://doi.org/10.1021/j100198a046	journal	September 1992
Mechanisms of the Deactivation of SAPO-34 Materials with Different Crystal Sizes Applied as MTO Catalysts Dai, Weili; Wu, Guangjun; Li, Landong ACS Catalysis, Vol. 3, Issue 4 https://doi.org/10.1021/cs400007v	journal	February 2013
Influence of Coke Deposition on Selectivity in Zeolite Catalysis Chen, D.; Rebo, H. P.; Moljord, K. Industrial & Engineering Chemistry Research, Vol. 36, Issue 9 https://doi.org/10.1021/ie9700223	journal	September 1997

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Title: Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

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