Catalytic Upgrading of Biomass-Derived Compounds via C–C Coupling Reactions: Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

Liu, Cong; Evans, Tabitha J.; Cheng, Lei; Nimlos, Mark R.; Mukarakate, Calvin; Robichaud, David J.; Assary, Rajeev S.; Curtiss, Larry A.

doi:10.1021/acs.jpcc.5b08141

Cited by 19 publications

(46 citation statements)

References 54 publications

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“…This keto-enol coupling has also been predicted for acetaldehyde coupling to form crotonaldehyde. 59 However, in that case cyclization is not possible due to the location of the oxygen functionalities. After the cyclization reaction, tetrahydro-2,3,4-furantriol, 2, is formed, which is the key intermediate for the following dehydration reactions (see Scheme 2-4 for structure).…”

Section: Theoretical Investigationmentioning

confidence: 99%

Furan Production from Glycoaldehyde over HZSM-5

Kim

Evans

Mukarakate

et al. 2016

ACS Sustainable Chem. Eng.

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Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300°C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalytic fast pyrolysis conditions (>400°C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts. TOC Graphic Synopsis Identifying potential thermochemical pathways of biomass to furan, which can help biomass displace petroleum for fuels and chemicals. While strongly acidic zeolites have been used to completely deoxygenate bio-oils and pyrolysis vapors, other less reactive and/or partially deactivated zeolites have been shown to partially deoxygenate pyrolysis vapors to form furan and alkyl furans. 16-20 French and Czernik evaluated 40 selected catalysts (including HZSM-5) for their hydrocarbon production performance on aspen wood, cellulose, and straw lignin and demonstrated formation of partially dehydrated oxygenates, such as furan, methyl furan, furfural, and methyl furfural in the products. 17 Mukarakate et al. studied the conversion of pine pyrolysis vapors over fixed beds of β-zeolite and HZSM-5 and found the formation of several furan derivatives (furan, methyl furan, dimethyl furan, and trimethyl furan). 19,20 Jae et al. identified 4-methyl-2,3-dihydrofuran, furfural, 5-methyl furfural, 2-furanmethanol, and 5-methyl-2(5H)-furanone in the products during CFP of glucose over 13 zeolites with a variety of pore size and shape. 18 Carlson et al. identified furan, 2-methyl furan, 4-methyl-furfural, furan-2-methanol as the thermally stable oxygenated intermediates in the production of aromatics from

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Section: Theoretical Investigationmentioning

confidence: 99%

Furan Production from Glycoaldehyde over HZSM-5

Kim

Evans

Mukarakate

et al. 2016

ACS Sustainable Chem. Eng.

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“…At temperatures above 370 °C, the reaction of acetic acid over HZSM-5 showed a high selectivity to iso-butene and acetone, which further react towards aromatics. Aldehydes show a low reactivity to hydrocarbons over HZSM-5, with a noticeable deactivation caused by coke deposition [32,[34][35][36].…”

Section: Introductionmentioning

confidence: 99%

Catalytic conversion of acetol over HZSM-5 catalysts – influence of Si/Al ratio and introduction of mesoporosity

2021

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“…The hydrogen‐bonded complexes (RC=O⋅⋅⋅H + ) are in chemical equilibrium with their protonated forms (RC + −O−H), because of small differences in their heats of adsorption. For example, the energy difference between chemisorbed and physisorbed acetaldehyde on H‐ZSM‐5 is approximately 6 kJ mol −1 . Replacing the Brønsted acid sites with alkali cations leads to aldehyde or ketone adsorption on these cations as cationic bonded complexes (RC=O⋅⋅⋅M n + ), as evidenced from the detection of C=O vibrational bands at approximately 1715 cm −1 with IR spectroscopy during acetaldehyde adsorption on Li + , Na + , K + , Ca 2+ , Ni 2+ , or Al 3+ cation‐exchanged montmorillonites .…”

Section: Introductionmentioning

confidence: 99%