Green synthesis of cellulose formate and its efficient conversion into 5-hydroxymethylfurfural

Gong, Chunxiao; Meng, Xianzhi; Jin, Caidi; Yang, Ming; Liu, Jianglong; Sheng, Kuichuan; Pu, Yunqiao; Ragauskas, Arthur; Ji, Guanya; Zhang, Ximing

doi:10.1016/j.indcrop.2022.115985

Green synthesis of cellulose formate and its efficient conversion into 5-hydroxymethylfurfural

Journal Article · Tue Nov 29 00:00:00 EST 2022 · Industrial Crops and Products

DOI:https://doi.org/10.1016/j.indcrop.2022.115985· OSTI ID:1968672

Gong, Chunxiao ^[1]; Meng, Xianzhi ^[2]; Jin, Caidi ^[1]; Yang, Ming ^[1]; Liu, Jianglong ^[1]; Sheng, Kuichuan ^[3]; ^[4]; ^[5]; Ji, Guanya ^[6]; Zhang, Ximing ^[3]

Zhejiang University, Hangzhou (China)
University of Tennessee, Knoxville, TN (United States)
Zhejiang University, Hangzhou (China); Institute of Zhejiang University, Quzhou (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JIBS)
University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JIBS)
Jiangsu University, Zhejiang (China)

5-hydroxymethylfurfural (HMF) production from cellulose is a hot topic, while the rigidity of cellulose limits its efficient conversion into HMF. Cellulose formate has exhibited the great potential for HMF production but it’s synthesis via direct formylation of cellulose in formic acid is difficult. We reported a green synthetic route of cellulose formate and its efficient conversion into HMF. Ball milled cellulose formate (BCF) was synthesized via ball milling followed by formylation in formic acid at 80 °C for 0.5 h. The structure of BCF was thoroughly characterized and BCF was subsequently converted to HMF catalyzed by AlCl3 and HCl in dimethyl sulfoxide (DMSO)-H₂O media. Results showed that ball milling of cellulose for 1–1.5 h efficiently deconstructed its crystallinity and degree of polymerization, boosting its further formylation and catalytic conversion. An overall 66.9% HMF yield from cellulose was achieved at 150 °C for 20 min using BCF derived from cellulose ball milled for 1.5 h as the substrate. BCF exhibits high reactivity toward HMF due to its excellent solubility and accessibility in DMSO-H₂O media, and the release of formic acid in reaction further facilitates HMF production. BCF synthesized with different ball milling times shows different degrees of substitution of formyl groups, which could serve as an indicator and regulate the HMF production. The green synthesis of cellulose formate creates an efficient pathway for HMF production.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: China Postdoctoral Science Foundation; National Natural Science Foundation of China; Natural Science Foundation of the Jiangsu Higher Education Institutions of China; Postdoctoral Exchange Fellowship Program; USDOE; Zhejiang University

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1968672

Journal Information:: Industrial Crops and Products, Journal Name: Industrial Crops and Products Journal Issue: 1 Vol. 192; ISSN 0926-6690

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

5-hydroxymethylfurfural
59 BASIC BIOLOGICAL SCIENCES
ball milled cellulose formate
cellulose
dimethyl sulfoxide

Green synthesis of cellulose formate and its efficient conversion into 5-hydroxymethylfurfural

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