Journal of University of Chinese Academy of Sciences >
Effects of crystallization time on the catalysis of Cs-La/SBA-15 for aldol condensation of methyl propionate and formaldehyde
Received date: 2016-02-02
Online published: 2016-11-15
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
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]. Journal of University of Chinese Academy of Sciences, 2016 , 33(6) : 741 -747 . DOI: 10.7523/j.issn.2095-6134.2016.06.004
[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.
/
| 〈 |
|
〉 |