晶化时间对Cs-La/SBA-15催化丙酸甲酯与甲醛缩合反应的影响

doi:10.7523/j.issn.2095-6134.2016.06.004

中国科学院大学学报 ›› 2016, Vol. 33 ›› Issue (6): 741-747.DOI: 10.7523/j.issn.2095-6134.2016.06.004

晶化时间对Cs-La/SBA-15催化丙酸甲酯与甲醛缩合反应的影响

王亚男¹, 闫瑞一², 李增喜¹

1. 中国科学院大学化学与化工学院, 北京 100049;
2. 中国科学院过程工程研究所多相复杂系统国家重点实验室, 北京 100190

收稿日期:2016-02-02 发布日期:2016-11-15
通讯作者: 李增喜,E-mail:lizengxi@ucas.ac.cn
基金资助:
国家自然科学基金（21406244，21276267）资助

Effects of crystallization time on the catalysis of Cs-La/SBA-15 for aldol condensation of methyl propionate and formaldehyde

WANG Yanan¹, YAN Ruiyi², LI Zengxi¹

1. School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
2. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2016-02-02 Published:2016-11-15

摘要/Abstract

摘要：

丙酸甲酯（MP）和甲醛（FA）缩合反应制备甲基丙烯酸甲酯（MMA）是一条绿色可持续的生产MMA的工艺路线，该路线的关键是开发高效的催化剂，而载体的性质直接影响着催化剂的性能.采用水热合成法制备晶化时间不同的SBA-15，用等体积浸渍法制备负载型的Cs-La/SBA-15催化剂.利用XRD、SEM、IR、BET和TPD等手段对载体和催化剂进行表征，并评价相应的催化剂活性.结果表明，当晶化时间为24 h时，由于载体具有稳定的孔结构（孔径为6 nm左右）和大的比表面积（1 000 m²/g左右），且催化剂表面的中等强度碱性活性位的数量较多，导致催化剂的活性最好.当原料配比为MP/FA=1/1时，反应转化率达到30.9%，选择性达到90.3%.

关键词: 晶化时间, 催化剂, 羟醛缩合

Abstract:

Aldol condensation of methyl propionate (MP) and formaldehyde (FA) is a green and sustainable route to synthesize methyl methacrylate (MMA). The key to the route is to develop effective catalysts, and the supports of catalysts play an important role in the catalytic performance. SBA-15 with different crystallization time was synthesized by the hydrothermal method and the Cs-La/SBA-15 catalysts were prepared by wetness impregnation method. The catalysts were characterized by XRD, SEM, IR, BET, TPD, etc. The effect of crystallization time of SBA-15 on the catalytic performance of Cs-La/SBA-15 for aldol condensation was studied. The results showed that regular mesoporous materials with 2D-hexogonal rod-like structure were obtained when the crystallization time was more than 24 h. The Cs-La/24SBA-15 (with SBA-15 crystallized 24 h) exhibited higher catalytic activity than the other catalysts because of the higher density of medium base sites as well as the great surface area of SBA-15 (around 1 000 m²/g) and uniform pore size (6 nm). When the MP/FA=1/1, the conversion of MP is 30.9% and the selectivity of MMA reachs 90.3%.

Key words: crystallization time, catalysts, aldol condensation

中图分类号:

TQ225.24

王亚男, 闫瑞一, 李增喜. 晶化时间对Cs-La/SBA-15催化丙酸甲酯与甲醛缩合反应的影响[J]. 中国科学院大学学报, 2016, 33(6): 741-747.

WANG Yanan, YAN Ruiyi, LI Zengxi. Effects of crystallization time on the catalysis of Cs-La/SBA-15 for aldol condensation of methyl propionate and formaldehyde[J]. , 2016, 33(6): 741-747.

参考文献

[1] Nagai K. New developments in the production of methyl methacrylate[J]. Applied Catalysis A:General, 2001, 221(1/2):367-377.
[2] Nagai K, Ui T. Trends and future of monomer-MMA technologies[J]. Sumitomo Chemicals, 2004, 2:4-13.
[3] 智研资讯集团.2010-2015年中国甲基丙烯酸甲酯(MMA)市场运行态势与投资战略咨询报告.北京:智研资讯集团,2015:17-22.
[4] Böhnke H, Gaube J, Petzoldt J. Selective oxidation of methacrolein towards aethacrylic acid on mixed oxide (Mo, V, W) catalysts. Part 1. Studies on kinetics[J]. Industrial & Engineering Chemistry Research, 2006, 45(26):8801-8806.
[5] Kanno M, Yasukawa T, Ninomiya W, et al. Catalytic oxidation of methacrolein to methacrylic acid over silica-supported 11-molybdo-1-vanadophosphoric acid with different heteropolyacid loadings[J]. Journal of Catalysis, 2010, 273(1):1-8.
[6] Langpape M, Millet J-M M. Effect of iron counter-ions on the redox properties of the Keggin-type molybdophosphoric heteropolyacid:Part I. An experimental study on isobutane oxidation catalysts[J]. Applied Catalysis A:General, 2000, 200(1/2):89-101.
[7] 丁爽. 丙酸甲酯与甲醛缩合催化剂的制备及性能研究.大连:大连工业大学, 2012.
[8] 赖崇伟,李洁,熊国炎,等. 丙酸甲酯和甲醛合成甲基丙烯酸甲酯的Cs-SiO₂催化剂的研究[J]. 天然气化工, 2014, 39(6):1-4.
[9] 李斌. 丙酸甲酯与甲醛缩合反应制备甲基丙烯酸甲酯.北京:中国科学院大学, 2014.
[10] Ai M. Reaction of methyl propionate with methylal over V-Si-P ternary oxide catalysts[J]. Bulletin of the Chemical Society of Japan, 1990, 63(12):3722-3724.
[11] Li B, Yan R Y, Wang L, et al. Synthesis of methyl methacrylate by aldol condensation of methyl propionate with formaldehyde over acid-base bifunctional catalysts[J]. Catalysis Letter, 2013, 143(8):829-838.
[12] Suzuki K, Kiyozumi Y, Matsuzaki K, et al. Effect of crystallization time on the physicochemical and catalytic properties of a ZSM-5 type zeolite[J]. Applied Catalysis, 1988, 42(1):35-45.
[13] Xu L, Ma Y, Ding W, et al. Effect of crystallization time on the physico-chemical and catalytic properties of the hierarchical porous materials[J]. Materials Research Bulletin, 2010, 45(9):1293-1298.
[14] Li B, Yan R, Wang L, et al. SBA-15 supported cesium catalyst for methyl methacrylate synthesis via condensation of methyl propionate with formaldehyde[J]. Industrial & Engineering Chemistry Research, 2014, 53(4):1386-1394.
[15] Zhao D, Feng J, Huo Q, et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998, 279(5350):548-552.
[16] Zhao D, Huo Q, Feng J, et al. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures[J]. Journal of the American Chemical Society, 1998, 120(24):6024-6036.
[17] Gogate M R, Spivey J J, Zoeller J R. Synthesis of methyl methacrylate by vapor phase condensation of formaldehyde with propionate derivatives[J]. Catalysis Today, 1997, 36(3):243-254.
[18] Chen H, Xue M, Hu S, et al. The effect of surface acidic and basic properties on the hydrogenation of lauronitrile over the supported nickel catalysts[J]. Chemical Engineering Journal, 2012, 181/182(2):677-684.
[19] Hu S, Xue M, Chen H, et al. The effect of surface acidic and basic properties on the hydrogenation of aromatic rings over the supported nickel catalysts[J]. Chemical Engineering Journal, 2010, 162(1):371-379.
[20] Meloni D, Sini M F, Cutrufello M G, et al. Acid-base features of ex-hydrotalcites Mg-containing and Mg-free mixed oxides[J]. Journal of Thermal Analysis and Calorimetry, 2013, 112(1):489-498.
[21] 刘旗,李奕怀,燕溪溪,等. 晶化时间对SAPO-34分子筛合成及性能的影响[J].上海第二工业大学学报, 2015, 32(2):114-119.
[22] 史忠华,刘华,陈耀强,等. 耐高温高比表面积载体对密偶催化剂性能的影响[J].石油化工, 2004, 33(z1):1393-1394.
[23] 毕玉水,赵晓红.不同载体负载的Pd催化剂上的CO氧化性能比较[J].稀有金属材料工程, 2009, 38(5):870-875.
[24] 于兹灜."吸附增进法"在甲烷水蒸汽重整、水煤气变换制氢工艺中的应用.金华:浙江师范大学, 2010.
[25] 李应成,闫世润,杨为民,等.载体比表面积及孔径对Nb₂O₅/α-Al₂O₃催化剂酸性及反应性能的影响[J].石油化工, 2006, 35(3):221-225.

晶化时间对Cs-La/SBA-15催化丙酸甲酯与甲醛缩合反应的影响

Effects of crystallization time on the catalysis of Cs-La/SBA-15 for aldol condensation of methyl propionate and formaldehyde

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 5

编辑推荐

Metrics

本文评价

访问统计

联系我们

[1]	陈凤霞, 马家海. Fe₃O₄@PCDP纳米复合材料的制备及其在类芬顿体系中的应用[J]. 中国科学院大学学报, 2020, 37(5): 593-598.
[2]	张君伍, 杨丽, 张玉秀, 舒新前, 邓增社. 掺钾对镁铝复合氧化物四效催化性能的影响[J]. 中国科学院大学学报, 2018, 35(3): 308-313.
[3]	薛琼, 张志昆, 何裕建, 杨镜奎, 杨志勇. 玻碳电极上真实铂载量的直接测定[J]. 中国科学院大学学报, 2015, 32(4): 468-475.
[4]	黄碧玉, 吴海臣, 杨镜奎. 缺电子Rh-BINAP催化剂催化氢化富电性底物的机理研究[J]. 中国科学院大学学报, 2012, 29(4): 571-575.
[5]	李强, 王蕾, 李增喜, 闫瑞一, 张锁江, 成卫国. 异丁烯选择氧化制备甲基丙烯醛催化反应的研究[J]. 中国科学院大学学报, 2008, 25(1): 28-34.