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

doi:10.11949/j.issn.0438-1157.20150837

Abstract

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

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

CLC Number:

TQ032.4

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.

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.

References 24

[1]	Dusselier M, van Wouwe P, Dewaele A, Makshina E, Sels B F. Lactic acid as a platform chemical in the biobased economy: the role of chemocatalysis [J]. Energy & Environmental Science, 2013, 6(5): 1415-1442.
[2]	Taarning E, Osmundsen C M, Yang Xiaobo, Voss B, Andersena S I, Christensena C H. Zeolite-catalyzed biomass conversion to fuels and chemicals [J]. Energy & Environmental Science, 2011, 4(3): 793-804.
[3]	Román-Leshkov Y, Davis M E. Activation of carbonyl-containing molecules with solid Lewis acids in aqueous media [J]. ACS Catal., 2011, 1(11): 1566-1580.
[4]	Hayashi Y, Sasaki Y. Tin-catalyzed conversion of trioses to alkyl lactates in alcohol solution [J]. Chemical Communications, 2005, (21): 2716-2718.
[5]	West R M, Holm M S, Saravanamurugan S, Xiong Jianmin, Beversdorf Z, Taarning E, Christensen C H. Zeolite H-USY for the production of lactic acid and methyl lactate from C3-sugars [J]. Journal of Catalysis, 2010, 269(1): 122-130.
[6]	Pescarmona P P, Janssen K P, Stroobants C, Molle B, Paul J S, Jacobs P A, Sels B F. A high-throughput experimentation study of the synthesis of lactates with solid acid catalysts [J]. Topics in Catalysis, 2010, 53(1-2): 77-85.
[7]	Holm M S, Saravanamurugan S, Taarning E. Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts [J]. Science, 2010, 328(5978): 602-605.
[8]	Li L, Stroobants C, Lin K, Jacobs P A, Sels B F, Pescarmona P P. Selective conversion of trioses to lactates over Lewis acid heterogeneous catalysts [J]. Green Chemistry, 2011, 13(5): 1175- 1181.
[9]	de Clippel F, Dusselier M, van Rompaey R, Vanelderen P, Dijkmans J, Makshina E, Giebeler L, Oswald S, Baron G V, Denayer J F, Pescarmona P P, Jacobs P A, Sels B F. Fast and selective sugar conversion to alkyl lactate and lactic acid with bifunctional carbon-silica catalysts [J]. Journal of the American Chemical Society, 2012, 134(24): 10089-10101.
[10]	Yuan Quan, Luo Chen, Sun Lingdong, Zhang Yawen, Duan Wentao, Liu Haichao, Yan Chunhua. Facile synthesis for ordered mesoporous gamma-aluminas with high thermal stability [J]. Journal of the American Chemical Society, 2008, 130(11): 3465-3472.
[11]	Hino M K S, Arata K. Solid catalyst treated with anion(Ⅱ): Reactions of butane and isobutane catalyzed by zirconium oxide treated with sulfate ion solid superacid catalyst [J]. J. Am. Chem. Soc., 1979, 101(21): 6439-6441.
[12]	Gu M, Yu D, Zhang H, Sun P, Huang H. Metal (Ⅳ) phosphates as solid catalysts for selective dehydration of sorbitol to isosorbide [J]. Catalysis Letters, 2009, 133(1/2): 214-220.
[13]	Emeis C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts [J]. Journal of Catalysis, 1993, 141(2): 347-354.
[14]	Kasprzyk-Hordern B. Chemistry of alumina, reactions in aqueous solution and its application in water treatment [J]. Advances in Colloid and Interface Science, 2004, 110(1/2): 19-48.
[15]	Okuhara T. Water-tolerant solid acid catalysts [J]. Chem. Rev., 2002, 102(10): 3641-3666.
[16]	Mal N K, Ichikawa S, Fujiwara M. Synthesis of a novel mesoporous tin phosphate, SnPO4 [J]. Chemical Communications, 2002, (2): 112-113.
[17]	Rao K N, Sridhar A, Lee A F, Tavener S J, Young N A, Wilson K. Zirconium phosphate supported tungsten oxide solid acid catalysts for the esterification of palmitic acid [J]. Green Chemistry, 2006, 8(9): 790-797.
[18]	Hammache S, Goodwin Jr J G. Characteristics of the active sites on sulfated zirconia for n-butane isomerization [J]. Journal of Catalysis, 2003, 218(2): 258-266.
[19]	Liu Zhen(刘镇). Catalytic conversion of biomass-derived carbohydrates to methyl lactate [D]. Hangzhou: Zhejiang University, 2012
[20]	Chambon F, Rataboul F, Pinel C, Cabiac A, Guillon E, Essayem N. Cellulose hydrothermal conversion promoted by heterogeneous Brønsted and Lewis acids: remarkable efficiency of solid Lewis acids to produce lactic acid [J]. Applied Catalysis B: Environmental, 2011, 105(1/2): 171-181.
[21]	Osmundsen C M, Holm M S, Dahl S, Taarning E. Tin-containing silicates: structure-activity relations [J]. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2012, 468(2143): 2000-2016.
[22]	Pescarmona P P, Janssen K P F, Delaet C, Stroobants C, Houthoofd K, Philippaerts A, de Jonghe C, Paul J S, Jacobs P A, Sels B F. Zeolite-catalysed conversion of C3 sugars to alkyl lactates [J]. Green Chemistry, 2010, 12(6): 1083-1089.
[23]	Saravanamurugan S, Riisager A. Zeolite catalyzed transformation of carbohydrates to alkyl levulinates [J]. ChemCatChem, 2013, 5(7): 1754-1757.
[24]	Taarning E, Saravanamurugan S, Holm M S, Xiong J, West R M, Christensen C H. Zeolite-catalyzed isomerization of triose sugars [J]. ChemSusChem, 2009, 2(7): 625-627.