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Preparation of 5-Hydroxymethylfurfural from High Fructose Corn Syrup Using Organic Weak Acid in Situ as Catalyst
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2020-02-19 , DOI: 10.1021/acs.iecr.9b06602
Changqu Lin 1 , Hongli Wu 1 , Junyi Wang 1 , Jinsha Huang 1 , Fei Cao 1 , Wei Zhuang 1 , Yanyu Lu 1 , Jiao Chen 1 , Honghua Jia 1 , Pingkai Ouyang 1
Affiliation  

The acidic catalysts play pivotal roles in the dehydration of hexose into 5-hydroxymethylfurfural (HMF). However, these acidic catalysts were usually exogenously added or self-made, which increase the cost of preparation of HMF. Herein, a novel route to prepare HMF from high fructose corn syrup (HFCS-55) using gluconic acid in situ produced by bio-oxidation as a catalyst has been investigated. In the process of bio-oxidation of HFCS-55, the introducing of ε-polylysine (EPL) can effectively improve the acid tolerance of the coimmobilized glucose oxidase and catalase. The immobilized enzymes can keep activity in the existence of a large amount of gluconic acid. Through the chelation of gluconic acid and calcium ions, the degree of gluconic acid ionization was raised and enough protons were released to convert fructose to HMF without the addition of acid. Using 2-methyltetrahydrofuran (2-MeTHF) as an extractor and adding 2 wt % CaCl2, the HMF’s yield reached 85% from fructose–gluconic acid mixture solution at 150 °C for 10 min with 200 W microwave irritations. Furthermore, we also used nuclear magnetic titration to investigate the complexation mechanism of the calcium ion and gluconic acid.

中文翻译:

有机弱酸原位催化高果糖玉米糖浆制备5-羟甲基糠醛

酸性催化剂在己糖脱水成5-羟甲基糠醛(HMF)中起关键作用。然而,这些酸性催化剂通常是外源添加或自制的,这增加了制备HMF的成本。在本文中,已经研究了一种利用高果糖玉米糖浆(HFCS-55)来制备HMF的新方法,该方法使用通过生物氧化法原位产生的葡萄糖酸作为催化剂。在HFCS-55的生物氧化过程中,引入ε-聚赖氨酸(EPL)可以有效提高共固定的葡萄糖氧化酶和过氧化氢酶的耐酸性。固定的酶可以在存在大量葡萄糖酸的情况下保持活性。通过葡萄糖酸和钙离子的螯合,葡萄糖酸离子化的程度提高了,并且释放了足够的质子,从而在不添加酸的情况下将果糖转化为HMF。使用2-甲基四氢呋喃(2-MeTHF)作为萃取剂并添加2 wt%的CaCl如图2所示,在200 W微波刺激下,在150°C的果糖-葡萄糖酸混合溶液中处理10分钟,HMF的产率达到了85%。此外,我们还使用核磁滴定法研究了钙离子和葡萄糖酸的络合机理。
更新日期:2020-02-19
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