Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis
Abstract
Biofuels production from lignocellulosic biomass is hindered by high conversion costs in the generation of high-quality fuels, driving research towards the development of new pathways with less severe conditions, higher yields and higher-quality products. In this report, we present a market-responsive biorefinery concept based on methanol as the key intermediate, which generates high-octane gasoline (HOG) and jet fuel blendstocks from biomass. Process models and techno-economic analysis are linked with both fundamental and applied catalyst development research to quantify the impact of catalyst advancements on process economics. By facilitating reincorporation of C4 by-products during dimethyl ether homologation, a Cu-modified beta zeolite catalyst enabled a 38% increase in yield of the HOG product and a 35% reduction in conversion cost compared to the benchmark beta zeolite catalyst. Alternatively, C4 by-products were directed to a synthetic kerosene that met five specifications for a typical jet fuel, with a small increase in the fuel synthesis cost versus the HOG-only case.
- Authors:
-
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
- OSTI Identifier:
- 1544996
- Report Number(s):
- NREL/JA-5100-72206
Journal ID: ISSN 2520-1158
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Nature Catalysis
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 7; Journal ID: ISSN 2520-1158
- Publisher:
- Springer Nature
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; high octane gasoline; alkane dehydrogenation; market responsive biorefinery
Citation Formats
Ruddy, Daniel A., Hensley, Jesse E., Nash, Connor P., Tan, Eric C. D., Christensen, Earl, Farberow, Carrie A., Baddour, Frederick G., Van Allsburg, Kurt M., and Schaidle, Joshua A. Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis. United States: N. p., 2019.
Web. doi:10.1038/s41929-019-0319-2.
Ruddy, Daniel A., Hensley, Jesse E., Nash, Connor P., Tan, Eric C. D., Christensen, Earl, Farberow, Carrie A., Baddour, Frederick G., Van Allsburg, Kurt M., & Schaidle, Joshua A. Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis. United States. https://doi.org/10.1038/s41929-019-0319-2
Ruddy, Daniel A., Hensley, Jesse E., Nash, Connor P., Tan, Eric C. D., Christensen, Earl, Farberow, Carrie A., Baddour, Frederick G., Van Allsburg, Kurt M., and Schaidle, Joshua A. 2019.
"Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis". United States. https://doi.org/10.1038/s41929-019-0319-2. https://www.osti.gov/servlets/purl/1544996.
@article{osti_1544996,
title = {Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis},
author = {Ruddy, Daniel A. and Hensley, Jesse E. and Nash, Connor P. and Tan, Eric C. D. and Christensen, Earl and Farberow, Carrie A. and Baddour, Frederick G. and Van Allsburg, Kurt M. and Schaidle, Joshua A.},
abstractNote = {Biofuels production from lignocellulosic biomass is hindered by high conversion costs in the generation of high-quality fuels, driving research towards the development of new pathways with less severe conditions, higher yields and higher-quality products. In this report, we present a market-responsive biorefinery concept based on methanol as the key intermediate, which generates high-octane gasoline (HOG) and jet fuel blendstocks from biomass. Process models and techno-economic analysis are linked with both fundamental and applied catalyst development research to quantify the impact of catalyst advancements on process economics. By facilitating reincorporation of C4 by-products during dimethyl ether homologation, a Cu-modified beta zeolite catalyst enabled a 38% increase in yield of the HOG product and a 35% reduction in conversion cost compared to the benchmark beta zeolite catalyst. Alternatively, C4 by-products were directed to a synthetic kerosene that met five specifications for a typical jet fuel, with a small increase in the fuel synthesis cost versus the HOG-only case.},
doi = {10.1038/s41929-019-0319-2},
url = {https://www.osti.gov/biblio/1544996},
journal = {Nature Catalysis},
issn = {2520-1158},
number = 7,
volume = 2,
place = {United States},
year = {Mon Jul 08 00:00:00 EDT 2019},
month = {Mon Jul 08 00:00:00 EDT 2019}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Kinetic studies of zeolite-catalyzed methylation reactions. Part 2. Co-reaction of [12C]propene or [12C]n-butene and [13C]methanol
journal, September 2005
- Svelle, S.; Ronning, P.; Olsbye, U.
- Journal of Catalysis, Vol. 234, Issue 2
Recent advances in heterogeneous catalysts for bio-oil upgrading via “ex situ catalytic fast pyrolysis”: catalyst development through the study of model compounds
journal, January 2014
- Ruddy, Daniel A.; Schaidle, Joshua A.; Ferrell III, Jack R.
- Green Chem., Vol. 16, Issue 2
Beyond Oil and Gas: The Methanol Economy
journal, April 2005
- Olah, George A.
- Angewandte Chemie International Edition, Vol. 44, Issue 18
Evidence for a “Carbene-like” Intermediate during the Reaction of Methoxy Species with Light Alkenes on H-ZSM-5
journal, January 2011
- Yamazaki, Hiroshi; Shima, Hisashi; Imai, Hiroyuki
- Angewandte Chemie International Edition, Vol. 50, Issue 8
Conversion of Dimethyl Ether to 2,2,3-Trimethylbutane over a Cu/BEA Catalyst: Role of Cu Sites in Hydrogen Incorporation
journal, February 2015
- Schaidle, Joshua A.; Ruddy, Daniel A.; Habas, Susan E.
- ACS Catalysis, Vol. 5, Issue 3
Selective Homogeneous and Heterogeneous Catalytic Conversion of Methanol/Dimethyl Ether to Triptane
journal, December 2011
- Hazari, Nilay; Iglesia, Enrique; Labinger, Jay A.
- Accounts of Chemical Research, Vol. 45, Issue 4, p. 653-662
Kinetics of Butene Isomer Methylation with Dimethyl Ether over Zeolite Catalysts
journal, July 2012
- Hill, Ian M.; Ng, Yong Sam; Bhan, Aditya
- ACS Catalysis, Vol. 2, Issue 8
Lignocellulose conversion: an introduction to chemistry, process and economics
journal, January 2007
- Lange, Jean-Paul
- Biofuels, Bioproducts and Biorefining, Vol. 1, Issue 1, p. 39-48
Mechanism of the Catalytic Conversion of Methanol to Hydrocarbons
journal, December 2012
- Ilias, Samia; Bhan, Aditya
- ACS Catalysis, Vol. 3, Issue 1, p. 18-31
Kinetic studies of zeolite-catalyzed methylation reactions1. Coreaction of [12C]ethene and [13C]methanol
journal, May 2004
- Svelle, Stian; Rønning, Per Ola; Kolboe, Stein
- Journal of Catalysis, Vol. 224, Issue 1
Shape Selectivity in the Conversion of Methanol to Hydrocarbons: The Catalytic Performance of One-Dimensional 10-Ring Zeolites: ZSM-22, ZSM-23, ZSM-48, and EU-1
journal, November 2011
- Teketel, Shewangizaw; Skistad, Wegard; Benard, Sandrine
- ACS Catalysis, Vol. 2, Issue 1
Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process
journal, June 2018
- Yarulina, Irina; De Wispelaere, Kristof; Bailleul, Simon
- Nature Chemistry, Vol. 10, Issue 8
Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite To Enable Alkane Recycle in Dimethyl Ether Homologation
journal, April 2017
- Farberow, Carrie A.; Cheah, Singfoong; Kim, Seonah
- ACS Catalysis, Vol. 7, Issue 5
Estimating Precommercial Heterogeneous Catalyst Price: A Simple Step-Based Method
journal, September 2018
- Baddour, Frederick G.; Snowden-Swan, Lesley; Super, John D.
- Organic Process Research & Development, Vol. 22, Issue 12
Shape-Selective Conversion of Methanol to Hydrocarbons Over 10-Ring Unidirectional-Channel Acidic H-ZSM-22
journal, August 2009
- Teketel, Shewangizaw; Svelle, Stian; Lillerud, Karl-Petter
- ChemCatChem, Vol. 1, Issue 1
Reactivity of Surface Alkoxy Species on Acidic Zeolite Catalysts
journal, August 2008
- Wang, Wei; Hunger, Michael
- Accounts of Chemical Research, Vol. 41, Issue 8
Methanol-to-hydrocarbons: catalytic materials and their behavior
journal, June 1999
- Stöcker, Michael
- Microporous and Mesoporous Materials, Vol. 29, Issue 1-2
Recent trends and fundamental insights in the methanol-to-hydrocarbons process
journal, June 2018
- Yarulina, Irina; Chowdhury, Abhishek Dutta; Meirer, Florian
- Nature Catalysis, Vol. 1, Issue 6
Mechanistic details of acid-catalyzed reactions and their role in the selective synthesis of triptane and isobutane from dimethyl ether
journal, January 2011
- Simonetti, Dante A.; Ahn, John H.; Iglesia, Enrique
- Journal of Catalysis, Vol. 277, Issue 2, p. 173-195
A descriptor for the relative propagation of the aromatic- and olefin-based cycles in methanol-to-hydrocarbons conversion on H-ZSM-5
journal, July 2013
- Ilias, Samia; Khare, Rachit; Malek, Andre
- Journal of Catalysis, Vol. 303
Techno-economics for conversion of lignocellulosic biomass to ethanol by indirect gasification and mixed alcohol synthesis
journal, March 2012
- Dutta, Abhijit; Talmadge, Michael; Hensley, Jesse
- Environmental Progress & Sustainable Energy, Vol. 31, Issue 2
Lifetime improvement in methanol-to-olefins catalysis over chabazite materials by high-pressure H2 co-feeds
journal, August 2018
- Arora, Sukaran S.; Nieskens, Davy L. S.; Malek, Andrzej
- Nature Catalysis, Vol. 1, Issue 9
Mechanistic Aspects of the Zeolite Catalyzed Methylation of Alkenes and Aromatics with Methanol: A Review
journal, August 2011
- Svelle, Stian; Visur, Melina; Olsbye, Unni
- Topics in Catalysis, Vol. 54, Issue 13-15
A mechanistic basis for the effect of aluminum content on ethene selectivity in methanol-to-hydrocarbons conversion on HZSM-5
journal, April 2017
- Khare, Rachit; Liu, Zhaohui; Han, Yu
- Journal of Catalysis, Vol. 348
Methanol to Olefins (MTO): From Fundamentals to Commercialization
journal, February 2015
- Tian, Peng; Wei, Yingxu; Ye, Mao
- ACS Catalysis, Vol. 5, Issue 3
Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates
journal, October 2015
- Tan, Eric CD; Talmadge, Michael; Dutta, Abhijit
- Biofuels, Bioproducts and Biorefining, Vol. 10, Issue 1
Comparative techno‐economic analysis and process design for indirect liquefaction pathways to distillate‐range fuels via biomass‐derived oxygenated intermediates upgrading
journal, September 2016
- Tan, Eric C. D.; Snowden‐Swan, Lesley J.; Talmadge, Michael
- Biofuels, Bioproducts and Biorefining, Vol. 11, Issue 1
Catalytic Co-Homologation of Alkanes and Dimethyl Ether and Promotion by Adamantane as a Hydride Transfer Co-Catalyst
journal, February 2011
- Simonetti, Dante A.; Ahn, John H.; Iglesia, Enrique
- ChemCatChem, Vol. 3, Issue 4, p. 704-718
The Mechanism of Methanol to Hydrocarbon Catalysis
journal, May 2003
- Haw, James F.; Song, Weiguo; Marcus, David M.
- Accounts of Chemical Research, Vol. 36, Issue 5
A mechanistic basis for the effects of crystallite size on light olefin selectivity in methanol-to-hydrocarbons conversion on MFI
journal, January 2015
- Khare, Rachit; Millar, Dean; Bhan, Aditya
- Journal of Catalysis, Vol. 321
Methanol-to-hydrocarbons: process technology
journal, June 1999
- Keil, Frerich J.
- Microporous and Mesoporous Materials, Vol. 29, Issue 1-2
Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration
journal, January 2018
- Griffin, Michael B.; Iisa, Kristiina; Wang, Huamin
- Energy & Environmental Science, Vol. 11, Issue 10
Synthetic Middle-Distillate-Range Hydrocarbons via Catalytic Dimerization of Branched C6–C8 Olefins Derived from Renewable Dimethyl Ether
journal, August 2015
- Behl, Mayank; Schaidle, Joshua A.; Christensen, Earl
- Energy & Fuels, Vol. 29, Issue 9, p. 6078-6087
Gas Conversion to Liquid Fuels and Chemicals: The Methanol Route‐Catalysis and Processes Development
journal, January 2009
- Mokrani, Touhami; Scurrell, Mike
- Catalysis Reviews, Vol. 51, Issue 1, p. 1-145
Selective Homologation Routes to 2,2,3-Trimethylbutane on Solid Acids
journal, May 2009
- Ahn, John H.; Temel, Burcin; Iglesia, Enrique
- Angewandte Chemie International Edition, Vol. 48, Issue 21, p. 3814-3816
Isotopic tracer studies of methanol-to-olefins conversion over HSAPO-34: The role of the olefins-based catalytic cycle
journal, May 2016
- Hwang, Andrew; Prieto-Centurion, Dario; Bhan, Aditya
- Journal of Catalysis, Vol. 337
The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts
journal, May 1977
- Chang, C.
- Journal of Catalysis, Vol. 47, Issue 2
27 Al MAS NMR Studies of HBEA Zeolite at Low to High Magnetic Fields
journal, June 2017
- Hu, Jian Zhi; Wan, Chuan; Vjunov, Aleksei
- The Journal of Physical Chemistry C, Vol. 121, Issue 23
Growing the Bioeconomy through Catalysis: A Review of Recent Advancements in the Production of Fuels and Chemicals from Syngas-Derived Oxygenates
journal, April 2019
- Grim, R. Gary; To, Anh T.; Farberow, Carrie A.
- ACS Catalysis, Vol. 9, Issue 5
Selective Homologation Routes to 2,2,3-Trimethylbutane on Solid Acids
journal, May 2009
- Ahn, John H.; Temel, Burcin; Iglesia, Enrique
- Angewandte Chemie, Vol. 121, Issue 21
Evidence for a “Carbene-like” Intermediate during the Reaction of Methoxy Species with Light Alkenes on H-ZSM-5
journal, January 2011
- Yamazaki, Hiroshi; Shima, Hisashi; Imai, Hiroyuki
- Angewandte Chemie, Vol. 123, Issue 8
The Mechanism of Methanol to Hydrocarbon Catalysis
journal, July 2003
- Haw, James F.; Song, Weiguo; Marcus, David M.
- ChemInform, Vol. 34, Issue 30
Beyond Oil and Gas: The Methanol Economy
journal, April 2011
- Prakash, G. K. Surya; Olah, George; Goeppert, Alain
- ECS Transactions, Vol. 35, Issue 11
Beyond Oil and Gas: The Methanol Economy
journal, July 2005
- Olah, George A.
- ChemInform, Vol. 36, Issue 29
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