Hydrophobic mesoporous acidic resin for hydroxyalkylation/alkylation of 2‐methylfuran and ketone to high‐density biofuel

Abstract

Hydroxyalkylation/alkylation of biomass‐derived 2‐methylfuran with cyclic ketones (cyclopentanone and cyclohexanone) has great potential in synthesizing high‐density biofuel. But the conversion and selectivity are still unsatisfactory because the in‐situ formed water decreases the acidity of catalyst and induces side reaction. Herein, hydrophobic mesoporous resins with sulfonic acid group (PS) and fluoride sulfonic acid group (PCS) were synthesized by a simple solvothermal reaction and ion exchange treatment, which have good mesoporous structure with surface area of 300–700 m2/g. Notably, PS and PCS have better hydrophobicity and oleophilicity as compared to widely used sulfonic acid functional amberlyst‐15 and fluoride sulfonic acid functional nafion‐212. In the hydroxyalkylation/alkylation reaction, PS shows higher activity and selectivity than amberlyst‐15 while PCS surpasses nafion‐212. Furthermore, both PS and PCS have good recycling stability in consecutive 5 runs. After hydrodeoxygenation, two high‐density biofuels with density of 0.819 and 0.825 g/mL were obtained. © 2016 American Institute of Chemical Engineers AIChE J, 63: 680–688, 2017

Synthesis of C15 and C10 fuel precursors with cyclopentanone and furfural derived from hemicellulose

“…31 Cyclopentanone can undergo condensation with valeraldehyde, 32 furfural 33,34 or itself. [35][36][37][38] It can also react with 2-methyl furan through hydroxyalkylation/alkylation, 9,39,40 generating C 10 -C 15 oxygen-containing compounds, and then the C 10 -C 15 oxygencontaining compounds can be converted into high-density diesel or jet fuel by hydrodeoxygenation. Aldol condensation of cyclopentanone and furfural by sodium hydroxide in solution free system achieved 2,5-bis(2-furylmethylidene)cyclopentanone yield of 96.0%.…”

Bio‐Based Cycloalkanes: The Missing Link to High‐Performance Sustainable Jet Fuels

“…[181,183] High thermal stability is critical for the prevention of deposits generated by high temperature pyrolysis. [184] Cold jet fuel flows through heat exchangers to transfer heat from the aircraft parts to the hydrocarbon fuel. The heated fuel can then be combusted to provide thrust.…”

“…Studies of the HAA reaction of 2-MF with cyclic ketones, suggested that water produced from the reaction had a negative effect on conversion and selectivity. [184] Water is a common product generated during deoxygenation of biomass derivatives that can reduce the activity of traditional acid catalysts. [236][237][238][239][240][241][242][243] To address this issue, Zou and coworkers synthesized a sulfonic acid functionalized resin (PS) and an ionic sulfonic acid-functionalized resin (PCS) by a solvothermal process (Scheme 25).…”

“…The resins exhibited excellent hydrophobicity/oleophilicity as well as high surface area (300-700 m 2 g À 1 ). [184] The electron-withdrawing effect of the cationsincreased the acidity of the sulfonic acids in PCS. [244] Due to its hydrophobicity and greater access to acid sites, 2.34 % PCS showed the highest conversion of 2-MF (81.2 %) and selectivity to DPC (84.4 %).…”

“…[244] Due to its hydrophobicity and greater access to acid sites, 2.34 % PCS showed the highest conversion of 2-MF (81.2 %) and selectivity to DPC (84.4 %). [184] Recently, Zhong et al studied hydrophobic acid-functionalized biochar as a catalyst for the HAA reaction of 2-MF and cyclic ketones. [245] Biochar, a carbonaceous material readily obtained through pyrolysis of biomass, [246][247][248][249] can be acidified with H 2 SO 4 (B-PhSO 3 H).…”