The Properties of Bicyclic and Multicyclic Hydrocarbons as Bio-derived Compression Ignition Fuels That Can Be Prepared via Efficient and Scalable Routes from Biomass

Cosimbescu, Lelia; Campbell, Kristen B.; Subramaniam, Senthil; Swita, Marie S.; Hao, Naijia; Moore, Cameron M.; Kallupalayam Ramasamy, Karthikeyan; Sutton, Andrew D.; Mcenally, Charles S.; Pfefferle, Lisa D.; Zhu, Junqing

doi:10.1039/d0se01742f

The Properties of Bicyclic and Multicyclic Hydrocarbons as Bio-derived Compression Ignition Fuels That Can Be Prepared via Efficient and Scalable Routes from Biomass

Journal Article · Tue Apr 27 00:00:00 EDT 2021 · Sustainable Energy & Fuels

DOI:https://doi.org/10.1039/d0se01742f· OSTI ID:1813570

Cosimbescu, Lelia ^[1]; Campbell, Kristen B. ^[1]; Subramaniam, Senthil ^[1]; Swita, Marie S. ^[1]; Hao, Naijia ^[2]; Moore, Cameron M. ^[3]; Kallupalayam Ramasamy, Karthikeyan ^[1]; Sutton, Andrew D. ^[4]; Mcenally, Charles S. ^[5]; Pfefferle, Lisa D. ^[5]; Zhu, Junqing ^[5]

BATTELLE (PACIFIC NW LAB)
University of Tennessee
scientist
Los Alamos National Laboratory
Yale University

A series of multicyclic hydrocarbons were synthesized in high yield and under mild conditions from 2,5-hexanedione, cyclohexanone and cyclopentanone, at scales of 200 g. Aldol products were obtained with conversions of 97%, 80-90% and 70% respectively, based on the consumption of starting materials. Cyclopentanone and cyclohexanone aldol condensations resulted in mixtures containing mainly the bicyclic products (90%) as well as tricyclic analogs (10%). The 2,5-hexanedione aldol condensation produced 50% methylcyclopentenone (MCP) as expected and about 50% oligomers. Surprisingly, the complex heavy fraction after removal of MCP contained mainly products of Michael addition of MCP and not self-aldol condensation products of MCP or MCP and 2,5-hexanedione. The hydrogenation-hydrodeoxygenation (HYD-HDO) of cyclohexanone- and cyclopentanone-derived reactants under nickel on alumina (Ni-Al2O3) catalyst at 250 °C and pressures between 800 to 1200 psig produced the expected saturated hydrocarbons with good recovery (80% and 76% respectively), with only small amounts of oxygenated residual starting materials remaining (<2%). However, the HYD-HDO of the 2,5-hexanedione aldol mixture produced an equally complex mixture compared to its respective aldol/Michael addition products which contained a large amount of hydroxy compounds (most likely cyclic alcohols). All crude mixtures, only treated to remove water after HYD-HDO, were evaluated for their properties as potential compression-ignition fuels: distillation curve, derived cetane number, sooting tendency, lower heating value and density. The results show the utility of these hydrocarbons as viable compression-ignition fuels or blendstocks, particularly the cyclopentanone- or cyclohexanone-derived products, or as components of the same.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Colorado State University

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830; EE0008726

OSTI ID:: 1813570

Report Number(s):: PNNL-SA-156518

Journal Information:: Sustainable Energy & Fuels, Journal Name: Sustainable Energy & Fuels Journal Issue: 12 Vol. 5

Country of Publication:: United States

Language:: English

References (41)

Sooting tendencies of co-optima test gasolines and their surrogates McEnally, Charles S.; Xuan, Yuan; St. John, Peter C. Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.05.071	journal	January 2019
Synthesis of High-Density Aviation Fuel with Cyclopentanol Chen, Fang; Li, Ning; Yang, Xiaofeng ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 11 https://doi.org/10.1021/acssuschemeng.6b01678	journal	July 2016
Hydrodeoxygenation of 2,5-Hexanedione and 2,5-Dimethylfuran by Water-, Air-, and Acid-Stable Homogeneous Ruthenium and Iridium Catalysts Sullivan, Ryan J.; Latifi, Elnaz; Chung, Benjamin K. -M. ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs501202t	journal	October 2014
Synthesis of Diesel and Jet Fuel Range Cycloalkanes with Cyclopentanone and Furfural Wang, Wei; Sun, Shaoying; Han, Fengan Catalysts, Vol. 9, Issue 11 https://doi.org/10.3390/catal9110886	journal	October 2019
Integrated Conversion of Cellulose to High-Density Aviation Fuel Liu, Yanting; Li, Guangyi; Hu, Yancheng Joule, Vol. 3, Issue 4 https://doi.org/10.1016/j.joule.2019.02.005	journal	April 2019
Sulfamic acid: An efficient, cost-effective and green catalyst for crossed-aldol condensation of ketones with aromatic aldehydes under solvent-free Rostami, Amin; Ahmad-Jangi, Firoz Chinese Chemical Letters, Vol. 22, Issue 9 https://doi.org/10.1016/j.cclet.2011.03.015	journal	September 2011
High-Density Renewable Diesel and Jet Fuels Prepared from Multicyclic Sesquiterpanes and a 1-Hexene-Derived Synthetic Paraffinic Kerosene Harvey, Benjamin G.; Merriman, Walter W.; Koontz, Thomas A. Energy & Fuels, Vol. 29, Issue 4 https://doi.org/10.1021/ef5027746	journal	March 2015
RuCl3 catalyses aldol condensations of aldehydes and ketones Iranpoor, Nasser; Kazemi, Foad Tetrahedron, Vol. 54, Issue 32 https://doi.org/10.1016/S0040-4020(98)00575-4	journal	August 1998
High-Density Renewable Fuels Based on the Selective Dimerization of Pinenes Harvey, Benjamin G.; Wright, Michael E.; Quintana, Roxanne L. Energy & Fuels, Vol. 24, Issue 1 https://doi.org/10.1021/ef900799c	journal	January 2010
Aldol Condensations Catalyzed by PEG400 and Anhydrous K ₂ CO ₃ Without Solvent Cao, Yu‐Qing; Dai, Zhi; Zhang, Rui Synthetic Communications, Vol. 35, Issue 8 https://doi.org/10.1081/SCC-200054198	journal	April 2005
Improved sooting tendency measurements for aromatic hydrocarbons and their implications for naphthalene formation pathways Mcenally, C.; Pfefferle, L. Combustion and Flame, Vol. 148, Issue 4 https://doi.org/10.1016/j.combustflame.2006.11.003	journal	March 2007
Producing methylcyclopentadiene dimer and trimer based high-performance jet fuels using 5-methyl furfural Nie, Genkuo; Shi, Chengxiang; Dai, Yiying Green Chemistry, Vol. 22, Issue 22 https://doi.org/10.1039/D0GC02361B	journal	January 2020
Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates Román-Leshkov, Yuriy; Barrett, Christopher J.; Liu, Zhen Y. Nature, Vol. 447, Issue 7147, p. 982-985 https://doi.org/10.1038/nature05923	journal	June 2007
Highly Selective Upgrading of Biomass-Derived Alcohol Mixtures for Jet/Diesel-Fuel Components Liu, Qiang; Xu, Guoqiang; Wang, Xicheng ChemSusChem, Vol. 9, Issue 24 https://doi.org/10.1002/cssc.201601152	journal	November 2016
Synthesis of biomass-derived methylcyclopentane as a gasoline additive via aldol condensation/hydrodeoxygenation of 2,5-hexanedione Sacia, Eric R.; Deaner, Matthew H.; Louie, Ying “Lin” Green Chemistry, Vol. 17, Issue 4 https://doi.org/10.1039/C4GC02292K	journal	January 2015
Efficient Production of the Liquid Fuel 2,5-Dimethylfuran from Fructose Using Formic Acid as a Reagent Thananatthanachon, Todsapon; Rauchfuss, Thomas B. Angewandte Chemie International Edition, Vol. 49, Issue 37 https://doi.org/10.1002/anie.201002267	journal	August 2010
Synthesis of 2,5-Hexanedione from Biomass Resources Using a Highly Efficient Biphasic System Li , Yueqin; Lv , Guangqiang; Wang , Yuqi ChemistrySelect, Vol. 1, Issue 6 https://doi.org/10.1002/slct.201600280	journal	May 2016
Highly selective self-condensation of cyclic ketones using MOF-encapsulating phosphotungstic acid for renewable high-density fuel Deng, Qiang; Nie, Genkuo; Pan, Lun Green Chemistry, Vol. 17, Issue 8 https://doi.org/10.1039/C5GC01287B	journal	January 2015
Elastomer Swell Behavior in 1-Propanol, Diisobutylene, Cyclopentanone, and a Furan Mixture Blended in E10 and a Blendstock for Oxygenate Blending (BOB) Kass, Michael D.; Janke, Christopher J.; Connatser, Raynella M. SAE International Journal of Fuels and Lubricants, Vol. 12, Issue 3 https://doi.org/10.4271/04-12-03-0011	journal	February 2019
Aqueous-phase selective hydrogenation of phenol to cyclohexanone over soluble Pd nanoparticles Zhu, Jing-Fang; Tao, Guo-Hong; Liu, Hang-Yu Green Chem., Vol. 16, Issue 5 https://doi.org/10.1039/C3GC42408A	journal	January 2014
Diesel Surrogate Fuels for Engine Testing and Chemical-Kinetic Modeling: Compositions and Properties Mueller, Charles J.; Cannella, William J.; Bays, J. Timothy Energy & Fuels, Vol. 30, Issue 2 https://doi.org/10.1021/acs.energyfuels.5b02879	journal	February 2016
Improved Pd/Ru metal supported graphene oxide nano-catalysts for hydrodeoxygenation (HDO) of vanillyl alcohol, vanillin and lignin Arora, Shalini; Gupta, Neeraj; Singh, Vasundhara Green Chemistry, Vol. 22, Issue 6 https://doi.org/10.1039/D0GC00052C	journal	January 2020
Production of 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one from 5-hydroxymethylfurfural Ren, Dezhang; Song, Zhiyuan; Li, Lu Green Chemistry, Vol. 18, Issue 10 https://doi.org/10.1039/C5GC02493E	journal	January 2016
Selective Phenol Hydrogenation to Cyclohexanone Over a Dual Supported Pd–Lewis Acid Catalyst Liu, Huizhen; Jiang, Tao; Han, Buxing Science, Vol. 326, Issue 5957 https://doi.org/10.1126/science.1179713	journal	November 2009
Renewable high-density spiro-fuels from lignocellulose-derived cyclic ketones Xie, Junjian; Zhang, Xiangwen; Pan, Lun Chemical Communications, Vol. 53, Issue 74 https://doi.org/10.1039/C7CC05101H	journal	January 2017
Efficient synthesis of high-density aviation biofuel via solvent-free aldol condensation of cyclic ketones and furanic aldehydes Deng, Qiang; Xu, Jisheng; Han, Peijuan Fuel Processing Technology, Vol. 148 https://doi.org/10.1016/j.fuproc.2016.03.016	journal	July 2016
Bio‐Based Cycloalkanes: The Missing Link to High‐Performance Sustainable Jet Fuels Muldoon, Jake A.; Harvey, Benjamin G. ChemSusChem, Vol. 13, Issue 22 https://doi.org/10.1002/cssc.202002326	journal	November 2020
A facile synthesis of α,α′-bis(substituted benzylidene) cycloalkanones catalyzed by p -TSA under solvent-free conditions Karimi-Jaberi, Zahed; Pooladian, Baharak Green Chemistry Letters and Reviews, Vol. 5, Issue 2 https://doi.org/10.1080/17518253.2011.611478	journal	June 2012
Chemical Processing in High-Pressure Aqueous Environments. 8. Improved Catalysts for Hydrothermal Gasification Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G. Industrial & Engineering Chemistry Research, Vol. 45, Issue 11 https://doi.org/10.1021/ie060031o	journal	May 2006
Direct aldol reactions catalyzed by 1,1,3,3-tetramethylguanidine lactate without solvent Zhu, Anlian; Jiang, Tao; Wang, Dong Green Chemistry, Vol. 7, Issue 7 https://doi.org/10.1039/b501925g	journal	January 2005
Solvent-Free Conversion of Linalool to Methylcyclopentadiene Dimers: A Route To Renewable High-Density Fuels Meylemans, Heather A.; Quintana, Roxanne L.; Goldsmith, Bryan R. ChemSusChem, Vol. 4, Issue 4 https://doi.org/10.1002/cssc.201100017	journal	February 2011
Synthesis of renewable high-density fuels using cyclopentanone derived from lignocellulose Yang, Jinfan; Li, Ning; Li, Guangyi Chemical Communications, Vol. 50, Issue 20 https://doi.org/10.1039/c3cc46588h	journal	January 2014
Photoinduced cycloaddition of biomass derivatives to obtain high-performance spiro-fuel Xie, Junjian; Pan, Lun; Nie, Genkuo Green Chemistry, Vol. 21, Issue 21 https://doi.org/10.1039/C9GC02790D	journal	January 2019
Selective Hydrogenation of Phenol to Cyclohexanone over Pd-HAP Catalyst in Aqueous Media Xu, Guangyue; Guo, Jianhua; Zhang, Ying ChemCatChem, Vol. 7, Issue 16 https://doi.org/10.1002/cctc.201500442	journal	July 2015
Zeolite catalytic synthesis of high‐performance jet‐fuel‐range spiro‐fuel by one‐pot Mannich–Diels–Alder reaction Pan, Lun; Xie, Junjian; Nie, Genkuo AIChE Journal, Vol. 66, Issue 1 https://doi.org/10.1002/aic.16789	journal	September 2019
Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose Sheng, Xueru; Li, Ning; Li, Guangyi Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep09565	journal	March 2015
LiOH·H2O as a novel dual activation catalyst for highly efficient and easy synthesis of 1,3-diaryl-2-propenones by Claisen–Schmidt condensation under mild conditions Bhagat, Srikant; Sharma, Ratnesh; Sawant, Devesh M. Journal of Molecular Catalysis A: Chemical, Vol. 244, Issue 1-2 https://doi.org/10.1016/j.molcata.2005.08.039	journal	February 2006
Enthalpies of combustion of toluene, benzene, cyclohexane, cyclohexene, methylcyclopentane, 1-methylcyclopentene, and n-hexane Good, William D.; Smith, Norris Kirk Journal of Chemical & Engineering Data, Vol. 14, Issue 1 https://doi.org/10.1021/je60040a036	journal	January 1969
Conversion of furfural into cyclopentanone over Ni–Cu bimetallic catalysts Yang, Yanliang; Du, Zhongtian; Huang, Yizheng Green Chemistry, Vol. 15, Issue 7 https://doi.org/10.1039/c3gc37133f	journal	January 2013
Heats of Combustion, Formation, and Isomerization of Nineteen Alkanols. Chao, Jing; Rossini, F. D. Journal of Chemical & Engineering Data, Vol. 10, Issue 4 https://doi.org/10.1021/je60027a022	journal	October 1965
Toward an optimal formulation of alternative jet fuels: Enhanced oxidation and thermal stability by the addition of cyclic molecules Ben Amara, Arij; Kaoubi, Skander; Starck, Laurie Fuel, Vol. 173 https://doi.org/10.1016/j.fuel.2016.01.040	journal	June 2016

Similar Records

The properties of bicyclic and multicyclic hydrocarbons as bio-derived compression ignition fuels that can be prepared via efficient and scalable routes from biomass

Journal Article · Tue Jun 15 00:00:00 EDT 2021 · Sustainable Energy & Fuels · OSTI ID:1784362

Synthesis of biomass-derived methylcyclopentane as a gasoline additive via aldol condensation/hydrodeoxygenation of 2,5-hexanedione

Journal Article · Thu Jan 22 23:00:00 EST 2015 · Green Chemistry · OSTI ID:1571040

Branched Bio-Lubricant Base Oil Production through Aldol Condensation

Journal Article · Mon Sep 30 00:00:00 EDT 2019 · ChemSusChem · OSTI ID:1767533

The Properties of Bicyclic and Multicyclic Hydrocarbons as Bio-derived Compression Ignition Fuels That Can Be Prepared via Efficient and Scalable Routes from Biomass

Citation Formats

References (41)

Similar Records

Related Subjects