固体酸表面B酸和L酸与果糖转化制乳酸甲酯产物分布

doi:10.11949/j.issn.0438-1157.20150837

化工学报 ›› 2015, Vol. 66 ›› Issue (9): 3428-3436.DOI: 10.11949/j.issn.0438-1157.20150837

• 催化、动力学与反应器 • 上一篇下一篇

固体酸表面B酸和L酸与果糖转化制乳酸甲酯产物分布

常翠荣, 王华, 韩金玉

天津大学化工学院, 天津 300072

收稿日期:2015-06-05 修回日期:2015-06-15 出版日期:2015-09-05 发布日期:2015-09-05
通讯作者: 王华
基金资助:
国家自然科学基金项目(21276191)。

Relationship between Brønsted and Lewis acid sites on solid acid surface and product distribution from transformation of fructose to methyl lactate

CHANG Cuirong, WANG Hua, HAN Jinyu

School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2015-06-05 Revised:2015-06-15 Online:2015-09-05 Published:2015-09-05
Supported by:
supported by the National Natural Science Foundation of China (21276191).

摘要/Abstract

摘要：

制备了γ-Al₂O₃、HZSM-5、SnOPO₄、SnZrOPO₄(1:1)、SO₄^2-/ZrO₂5种不同的固体酸催化剂,采用NH₃程序升温脱附、吡啶原位吸附红外对催化剂进行了表征。考察了固体酸催化果糖在甲醇中转化的催化性能,结果表明,果糖的转化率均高于98%,产物分布与固体酸表面L酸、B酸酸量具有显著的相关性,乳酸甲酯的收率随着L酸量的减少而降低,L酸催化剂γ-Al₂O₃催化,主产物只有乳酸甲酯,收率为24.4%。而L酸位和B酸位共存的固体酸,产物中有乳酸甲酯、乙酰丙酸甲酯,并且乙酰丙酸甲酯的收率随着B酸量的增多而升高。最后考察了典型L酸γ-Al₂O₃及B酸L酸共存的固体酸HZSM-5不同反应时间的产物分布,结合气相-质谱联用对产物定性分析,得出了果糖转化过程L酸位催化和B酸位催化的反应路径。

关键词: 固体酸催化剂, 果糖, 乳酸甲酯, 乙酰丙酸甲酯, B酸位, L酸位

Abstract:

Catalytic conversion of fructose directly into alkyl lactate is one of the effective ways for use of biomass to produce high value-added chemicals. Research shows that one of main factors influencing the alkyl lactate yield is Lewis and Brønsted acid sites on the surface of solid acid catalysts. A series of solid acid catalysts with different acid sites and concentration is prepared, including γ-Al₂O₃, HZSM-5 zeolite, SnOPO₄, SnZrOPO₄(1:1), and SO₄²^-/ZrO₂. All of catalysts was characterized by using NH₃ temperature-programmed desorption(NH₃-TPD) and infrared spectroscopy with pyridine adsorption(Py-FTIR) techniques to figure out their total acid concentration, Lewis and Brønsted acid concentrations. The catalytic conversion of fructose in methanol over the five solid acid catalysts was studied. The results showed that the conversions of fructose can be higher than 98%; product distribution obtained depends greatly on Lewis and Brønsted acid amounts; and yield of methyl lactate lessened with the decrease of Lewis acid concentration. For γ-Al₂O₃ catalyst that contains only Lewis acid sites, the yields of methyl lactate achieved is 24.4%, while for these solid acid catalyst that contain both Lewis and Brønsted acid sites, the product obtained is not only methyl lactate but also methyl levulinate, and yield of methyl levulinate improves with increase of Brønsted acid concentration. Finally, the product distribution from the reactions catalyzed by typical Lewis acid solid catalyst γ-Al₂O₃ and HZSM-5 catalyst with both Brønsted and Lewis acid sites at different reaction time was investigated. Combined with the qualitative analysis obtained by gas chromatography-mass spectrometry(GC-MS), the reaction pathway for fructose conversion catalyzed by Lewis and Brønsted acid sites was proposed.

Key words: solid acid catalyst, fructose, methyl lactate, methyl levulinate, Brø, nsted acid sites, Lewis acid sites

中图分类号:

TQ032.4

常翠荣, 王华, 韩金玉. 固体酸表面B酸和L酸与果糖转化制乳酸甲酯产物分布[J]. 化工学报, 2015, 66(9): 3428-3436.

CHANG Cuirong, WANG Hua, HAN Jinyu. Relationship between Brønsted and Lewis acid sites on solid acid surface and product distribution from transformation of fructose to methyl lactate[J]. CIESC Journal, 2015, 66(9): 3428-3436.

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固体酸表面B酸和L酸与果糖转化制乳酸甲酯产物分布

Relationship between Brønsted and Lewis acid sites on solid acid surface and product distribution from transformation of fructose to methyl lactate

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