碱性离子液体协同配合剂催化葡萄糖异构化制备果糖

doi:10.11949/0438-1157.20191201

摘要/Abstract

摘要：

糖类是生物质的重要组成部分，可经催化转化制得一系列高附加值化学品，具有经济价值高、对环境友好和可持续性强等优点。葡萄糖异构为果糖是该过程的关键步骤。本文合成了四种碱功能性离子液体，用红外光谱、核磁共振谱仪和热重分析进行了表征，并用于催化葡萄糖异构化制备果糖，结果表明碱性离子液体具有较好的催化活性，但易使果糖进一步催化降解，同时加入硼酸钠可提高葡萄糖的转化率和果糖的产率，说明硼酸钠既起配合保护剂的作用，也有一定的协同催化作用。考察了离子液体用量、硼酸钠用量、时间、温度等因素对果糖选择性和产率的影响，结果表明，在离子液体和硼酸钠与葡萄糖的摩尔比分别为3∶1和0.08∶1、反应温度为70℃、反应时间为7 min的最佳反应条件下果糖的产率可高达64.7%，选择性为73.1%。

关键词: 碱性离子液体, 硼酸钠, 协同催化, 葡萄糖, 异构化, 果糖

Abstract:

Carbohydrates are an important part of biomass and can be converted into a series of high value-added chemicals through catalytic conversion, which has the advantages of high economic value, environmental friendliness and sustainability. Isomerization of glucose into fructose is a key step in the process. Herein, four basic functional ionic liquids: [HOEtMim]Phen, [EMim]Phen, [HOEtMim]Im, [Ch]Phen were synthesized and their catalytic performances on glucose isomerization were investigated. A comparison of direct transformation and catalysts combined with sodium borate complex was discussed. It showed that four basic ionic liquids exhibit good catalytic activities, but fructose is easily to be further degraded. While ionic liquids added with sodium borate obtain much higher fructose yields. It indicates that sodium borate plays an important role in both protective agent and synergistic catalysis. [Ch]Phen added with sodium borate is the most efficient. The basic structure parameters of [Ch]Phen were further characterized by ¹H NMR, FT-IR and TG-DTG techniques. The effects of reaction temperature, reaction time, the dosage of catalyst and sodium borate on the isomerization and the optimal reaction conditions were investigated by single factor method. The yield of fructose is up to 64.7% with a high selectivity of 73.1% under the optimum condition at 70℃ within 7 min.

Key words: basic ionic liquid, sodium borate, synergistic catalysis, glucose, isomerization, fructose

中图分类号:

O 643

项小燕, 危依, 裴宝有, 丘荣星, 陈晓燕, 赵朝阳, 罗小燕, 林金清. 碱性离子液体协同配合剂催化葡萄糖异构化制备果糖[J]. 化工学报, 2020, 71(1): 290-296.

Xiaoyan XIANG, Yi WEI, Baoyou PEI, Rongxing QIU, Xiaoyan CHEN, Zhaoyang ZHAO, Xiaoyan LUO, Jinqing LIN. Efficient isomerization of glucose to fructose co-catalyzed with basic ionic liquid and sodium borate[J]. CIESC Journal, 2020, 71(1): 290-296.

图/表 9

图1 [Ch]Phen的合成反应式（代表阴离子交换树脂）

Fig.1 Synthetic reaction equations of [Ch]Phen (represents anion exchange resin)

图2 [Ch]Phen的红外光谱图

Fig.2 Infrared spectra of [Ch]Phen

图3 离子液体的TG曲线

Fig.3 TG curves of basic ionic liquids

表1 催化剂对果糖产率的影响

Table 1 Effect of catalysts on fructose yield

催化剂种类	果糖产率Y/%
催化剂种类	催化剂	催化剂+ Na₂B₄O₇
NaOH	17.2	53.4
[EMim]Phen	23.1	55.0
[HOEtMim]Phen	21.8	48.2
[HOEtMim]Im	12.0	32.0
[Ch]OH	11.7	30.99
[Ch]Phen	26.6	62.08
Na₂B₄O₇	—	0

图4 Na2B4O7用量的影响

Fig.4 Effect of amount of Na2B4O7 on isomerization of glucose

图5 反应温度的影响

Fig.5 Effect of reaction temperatures on isomerization of glucose

图6 离子液体用量的影响

Fig.6 Effect of ionic liquid dosage on isomerization of glucose

图7 反应时间的影响

Fig.7 Effect of reaction time on isomerization of glucose

表2 反应条件和果糖产率与文献结果比较

Table 2 Comparison of fructose yield with literature results

催化剂	时间/min	温度/℃	产率Y/%	选择性S/%	参考文献
[Ch]Phen +Na₂B₄O₇	7	70	64.7	73.1	本论文
HTs	30	90	56	80	[11]
TEA	20	100	32	63	[12]
[N_4,4,4,4]Pro	30	80	36.8	73.8	[23]
[Ch]Pro	30	70	37.6	77.2	[25]
BBTA	240	80	33.0	93.5	[30]
PS - TBD	30	100	25	59	[31]
Cr(OH)₄/MIL-101	1440	100	59.3	—	[32]

参考文献 32

1	Sudarsanam P , Peeters E , Makshina E V , et al . Advances in porous and nanoscale catalysts for viable biomass conversion[J]. Chem. Soc. Rev., 2019, 48(8): 2366-2421.
2	Steinbach D , Kruse A , Sauer J . Pretreatment technologies of lignocellulosic biomass in water in view of furfural and 5-hydroxymethylfurfural production—a review[J]. Biomass Convers. Bior., 2017, 7(2):1-28.
3	Lei H , Lu L , Zhen W , et al . Recent advances in catalytic transformation of biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals[J]. Renew Sust. Energ. Rev., 2017, 74: 230-257.
4	Bosilj M , Schmidt J , Fischer A , et al . One pot conversion of glucose to ethyl levulinate over a porous hydrothermal acid catalyst in green solvents[J]. RSC Adv., 2019, 9(35): 20341-20344.
5	Villanueva N I , Marzialetti T G . Mechanism and kinetic parameters of glucose and fructose dehydration to 5-hydroxymethylfurfural over solid phosphate catalysts in water[J]. Catal. Today, 2018, 302: 100-107.
6	Wang X , Liang F , Huang C , et al . Siliceous tin phosphates as effective bifunctional catalysts for selective conversion of dihydroxyacetone to lactic acid[J]. Catal. Sci. Technol., 2016， (6): 6551-6560.
7	Luo Q , Zhang Y , Qi L , et al . Glucose isomerization and epimerization over metal- organic frameworks with single-site active centers[J]. ChemCatChem, 2019, 11(7): 1903-1909.
8	Olson N , Deshpande N , Gunduz S , et al . Utilizing imogolite nanotubes as a tunable catalytic material for the selective isomerization of glucose to fructose[J]. Catal. Today, 2019, 323: 69-75.
9	Pienkoß F , Ochoa-Hernández C , Theyssen N , et al . Kaolin: a natural low-cost material as catalyst for isomerization of glucose to fructose[J]. ACS Sust. Chem. Eng., 2018, 6(7): 8782-8789.
10	Qi T , He M , Zhu L , et al . Cooperative catalytic performance of Lewis and Brønsted acids from AlCl₃ salt in aqueous solution toward glucose-to-fructose isomerization[J]. J. Phys. Chem. C, 2019, 123(8): 4879-4891.
11	Yabushita M , Shibayama N , Nakajima K , et al . Selective glucose-to-fructose isomerization in ethanol catalyzed by hydrotalcites[J]. ACS Catal., 2019, (9): 2101-2109.
12	Liu C , Carraher J M , Swedberg J L , et al . Selective base-catalyzed isomerization of glucose to fructose[J]. ACS Catal., 2014, 4 (12): 4295-4298.
13	Bruyn C A L D , Ekenstein W A V . Action des alcalis sur les sucres: Ⅱ[J]. Recueil des Travaux Chimiques des Pays-Bas, 1895, 14: 203-216.
14	Knill C J , Kennedy J F . Degradation of cellulose under alkaline conditions[J]. Carbohyd. Polym., 2003, 51(3): 281-300.
15	Yang B Y , Montgomery R . Alkaline degradation of glucose: effect of initial concentration of reactants[J]. Carbohyd. Res., 1996, 280(1): 27-45.
16	Rendleman J A , Hodge J E . Complexes of carbohydrates with aluminate ion aldose-ketose interconversion on anion-exchange resin (aluminate and hydroxide forms)[J]. Carbohyd. Res., 1979, 75: 83-99.
17	Berg R V D , Peters J A , Bekkum H V . The structure and (local) stability constants of borate esters of mono- and di-saccharides as studied by ¹¹B and ¹³C NMR spectroscopy[J]. Carbohyd. Res., 1994, 253: 1-12.
18	Sayago C M , González E A , Ivanova S , et al . Epimerization of glucose over ionic liquid/phosphomolybdate hybrids: structure-activity relationship[J]. Green Chem., 2018, 20(5): 1042-1049.
19	Singh S , Simmons B A , Vogel K P . Visualization of biomass solubilization and cellulose regeneration during ionic liquid pretreatment of switchgrass[J]. Biotechnol. Bioeng., 2010, 104(1):68-75.
20	Hou Q , Ju M , Li W , et al . Pretreatment of lignocellulosic biomass with ionic liquids and ionic liquid-based solvent systems[J]. Molecules, 2017, 22(3): 490.
21	Yang Y , Zhang C , Zhang Z C . Advances in catalytic transformations of carbohydrates and lignin in ionic liquids and mechanistic studies[J]. WIREs: Energy Environ., 2018, 7(3):e284.
22	Saravanamurugan S , Paniagua M , Melero J A , et al . Efficient isomerization of glucose to fructose over zeolites inconsecutive reactions in alcohol and aqueous media[J]. J. Am. Chem. Soc., 2013, 135(14): 5246 -5249.
23	Zhang X , Li H , Li X , et al . Glucose aqueous isomerization catalyzed by basic ionic liquids[J]. ACS Sust. Chem. Eng., 2019, 7: 13247-13256.
24	张雄 . 碱性离子液体催化葡萄糖化学异构制备果糖的研究[D]. 广州: 华南理工大学, 2017.
	Zhang X . The isomerization of glucose into fructose over alkaline ionic liquids[D]. Guangzhou: South China University of Technology, 2017.
25	Ståhlberg T , Rodriguez-Rodriguez S , Fristrup P , et al . Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter[J]. Chem. Eur. J., 2011, 17: 1456-1464.
26	李文侠 . 葡萄糖化学催化法异构为果糖及其分离研究[D]. 厦门: 厦门大学， 2015.
	Li W X . Study on the glucose isomerization and separation of glucose and fructose[D]. Xiamen: Xiamen University, 2015.
27	Liu Q P , Hou X D , Li N , et al . Ionic liquids from renewable biomaterials: synthesis, characterization and application in the pretreatment of biomass[J]. Green Chemistry, 2012, 14(2):304-307.
28	Guan Q , Lei T , Wang Z , et al . Preparation of ethyl levulinate from wheat straw catalysed by sulfonate ionic liquid[J]. Ind. Crop. Prod., 2018, 113: 150-156.
29	Ma H , Wang F , Yu Y , et al . Autocatalytic production of 5-hydroxymethylfurfural from fructose-based carbohydrates in a biphasic system and its purification[J]. Ind. Eng. Chem. Res., 2015. 54(10): 2657-2666.
30	Zhang N , Meng X , Wu Y , et al . Highly selective isomerization of glucose into fructose catalyzed by a mimic glucose isomerase[J]. ChemCatChem, 2019, 11(9): 2355-2361.
31	Yang Q , Zhou S , Runge T . Magnetically separable base catalysts for isomerization of glucose to fructose[J]. J. Catal., 2015, 330: 474-484.
32	Tsapatsis M , Guo Q , Ren L , et al . A chromium hydroxide/MIL-101(Cr) composite catalyst and its use for selective glucose isomerization to fructose[J]. Angew. Chem. Int. Edit., 2018, 57: 4926-4930.

[1]	张静, 刘涛, 张伟, 储震宇, 金万勤. 一种新型分离传感膜的制备及其血糖的动态监测[J]. 化工学报, 2023, 74(1): 459-468.
[2]	马荣, 孙杰, 李东辉, 魏进家. 基于Cu/TiO₂/C-Wood复合材料的聚光太阳能驱动自漂浮高效海水汽化催化分解制氢体系[J]. 化工学报, 2022, 73(4): 1695-1703.
[3]	徐飞翔, 蒋丽群, 郑安庆, 赵增立. 碳基固体酸催化纤维素热解制备左旋葡聚糖和左旋葡萄糖酮[J]. 化工学报, 2022, 73(3): 1166-1172.
[4]	谢晶, 舒歌平, 杨葛灵, 高山松, 王洪学, 卢晗锋, 陈银飞. Mo修饰的钼铁复合催化剂及其煤直接液化催化性能[J]. 化工学报, 2021, 72(9): 4675-4684.
[5]	王刚,段学志,袁渭康,周兴贵. 钛硅分子筛TS-1催化环氧丙烷异构反应的机理探究[J]. 化工学报, 2021, 72(10): 5150-5158.
[6]	韩建年, 王刚, 杨梅, 刘美佳, 高成地, 高金森. 费托蜡催化裂化反应生产清洁汽油的热力学分析[J]. 化工学报, 2020, 71(S1): 38-45.
[7]	徐坤, 方阳, 宫梦, 陈应泉, 陈旭, 王贤华, 杨海平, 陈汉平. 葡萄糖催化热解制备左旋葡萄糖酮特性研究[J]. 化工学报, 2020, 71(8): 3594-3601.
[8]	宫梦, 方阳, 陈伟, 陈应泉, 陆强, 杨海平, 陈汉平. 纤维素组分对氨基酸热解的影响[J]. 化工学报, 2020, 71(5): 2312-2319.
[9]	谢雨珩, 李智, 杨明磊, 杜文莉. 基于自适应采样算法的芳烃异构化代理模型[J]. 化工学报, 2020, 71(2): 688-697.
[10]	胡凤腾, 姚建龙, 李小青, 李思汉, 严新焕. Sr改性Cu催化剂的果糖加氢制备甘露醇性能[J]. 化工学报, 2019, 70(4): 1420-1428.
[11]	王丽, 王兴杰, 李浩, 陈永伟, 李忠. 葡萄糖基多孔碳材料对CO₂/CH₄的分离性能[J]. 化工学报, 2018, 69(2): 733-740.
[12]	芮泽宝, 杨晓庆, 陈俊妃, 纪红兵. 光热协同催化净化挥发性有机物的研究进展及展望[J]. 化工学报, 2018, 69(12): 4947-4958.
[13]	芮泽宝, 纪红兵. 有机废气催化燃烧过程中多尺度效应和催化剂设计[J]. 化工学报, 2018, 69(1): 317-326.
[14]	苏叶, 鲍宗必, 张治国, 邢华斌, 杨启炜, 苏宝根, 杨亦文, 任其龙. L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水制备5-羟甲基糠醛[J]. 化工学报, 2016, 67(7): 2799-2807.
[15]	张冬梅, 程文萍, 张明胜, 崔杏雨, 马静红, 李瑞丰. AC/X-G吸附剂的制备及CH₄/N₂吸附分离性能[J]. 化工学报, 2016, 67(6): 2386-2392.