Page 153 - 《精细化工》2022年第8期

第 8 期 何沛航，等: 小尺寸 TS-1 的合成及其催化油酸甲酯环氧化 ·1653·

图 10 为油酸甲酯环氧化反应中 TS-1-s 催化剂 Fine Chemicals (精细化工), 2019, 36(10): 2155-2160.
[5] LI Z Y (李志莹) , JIANG P P (蒋平平), HUANG Y D (黄元旦), et al.
的稳定性和再生性能。
Preparation and evaluation of the environment-friendly plasticizer
di(2-propylheptyl)-1,2-cyclohexane dicarboxylate[J]. Fine Chemicals
(精细化工), 2015, 32(7): 794-840.
[6] WEI Y, LI G, LYU Q, et al. Green and efficient epoxidation of methyl
oleate over hierarchical TS-1[J]. Chinese Journal of Catalysis, 2018,
39(5): 964-972.
[7] ZHAO Y D (赵亚东), GAO L (郜蕾), GAO J (高健), et al. Synthesis
of methyl oleate using a silica-immobilized SO 3H-functionalized
ionic liquid as an efficient catalys[J]. Fine Chemicals (精细化工),
2018, 35(1): 81-86.
[8] BAI Y C, WANG J Y, LIU D H, et al. Conversion of fatty acid
methyl ester to epoxy plasticizer by auto-catalyzed in situ formation
of performic acid: Kinetic modeling and application of the model[J].
Journal of Cleaner Production, 2020, 259: 120791.
[9] SUN S F (孙守飞), DING Y (丁云), YANG H (杨欢), et al.

图 10 催化剂的稳定性和再生性能 Epoxidation of fatty acid methyl ester over phosphotungstic acid
Fig. 10 Stability and regeneration of catalyst pillared Zn-Ti hydrotalcites[J]. Fine Chemicals (精细化工), 2014,
31(5): 586-602.
由图 10 可知，TS-1-s 催化剂重复使用 5 次后， [10] OK D Y, JIANG N Z, PRASETYANTO E A, et al. Epoxidation of
cyclic-olefins over carbon template mesoporous TS-1[J]. Microporous
MO 转化率从 53.58%下降到 19.98%。因为催化剂表 and Mesoporous Materials, 2011, 141: 2-7.
面吸附的大分子油酸甲酯和环氧油酸甲酯堵塞固体 [11] SHI Y K, CHEN L, LI J, et al. Co supported on interparticle porosity
dominated hierarchical porous TS-1 as highly efficient heterogeneous
催化剂孔道或者覆盖了部分表面活性位点 [26-27] 。进 catalyst for epoxidation of styrene[J]. Chemical Physics Letters,
一步地，催化剂经过高温再生后再进行环氧化反应 2021, 762: 138116.
[12] LI Z S, SU Z Y, MA W H, et al. Competition of propylene
测试，结果显示，油酸甲酯转化率和环氧油酸甲酯 hydrogenation and epoxidation over Au-Pd/TS-1 bimetallic catalysts
选择性均接近新鲜 TS-1-s 催化剂的结果。 for gas-phase epoxidation of propylene with O 2 and H 2[J]. Applied
Catalysis A: General, 2021, 615: 118060.
[13] GAO X, ZHANG Y Q, HONG Y P, et al. Efficient and clean
3 结论 epoxidation of methyl oleate to epoxidized methyl oleate catalyzed
by external surface of TS-1 supported molybdenum catalysts[J].
为了开发一种高效、清洁催化油酸甲酯环氧化 Microporous Mesoporous Materials, 2022, 333: 111731.
制备绿色环氧油酸甲酯增塑剂的方法。首先，成功 [14] TEKLA J, TARACH K A, OLEJMICZAK Z, et al. Effective
hierarchization of TS-1 and its catalytic performance in cyclohexene
合成了 S-1、S-1-s、TS-1 和 TS-1-s 4 种催化剂，并 epoxidation[J]. Microporous and Mesoporous Materials, 2016, 233:
主要考察了水蒸气辅助晶化法合成 TS-1-s 沸石的操 16-25.
[15] CHEN H X, ZHANG R D, BAO W J, et al. Effective catalytic
作工艺条件（干燥温度、固液质量比、晶化温度和 abatement of indoor formaldehyde at room temperature over TS-1
晶化时间）对催化油酸甲酯环氧化反应性能的影响。 supported platinum with relatively low content[J]. Catalysis Today,
2020, 355: 547-554.
催化剂的多种表征结果显示，TS-1-s 含有典型的 [16] ZHANG J L, CAO P, YAN H Y, et al. Synthesis of hierarchical
MFI 结构，且具有更小的颗粒直径和更大的外表面 zeolite beta with low organic template content via the steam-assisted
conversion method[J]. Chemical Engineering Journal, 2016, 291:
积，尤其是更良好的四配位骨架 Ti 物种。所有催化 82-93.
剂的油酸甲酯环氧化性能测试结果显示，TS-1-s 催 [17] ZENG L G, YU Z C, SUN Z T, et al. Fast synthesis of SSZ-13 zeolite
by steam-assisted crystallization method[J]. Microporous and
化剂表现出最佳的催化活性，油酸甲酯的转化率为
Mesoporous Materials, 2020, 293: 109789.
53.58%，EMO 选择性为 85.48%。 [18] CHENG Y, PAN S L. Preparation and characterization of nanosized
silicalite-2 zeolites by steam-assisted dry gel conversion method[J].
参考文献： Materials Letters, 2013, 100: 289-291.
[19] CAI L, CHEN C, WANG W J, et al. Acid-free epoxidation of soybean
[1] LIU D K, SHEN Y R, JIANG P P, et al. An efficient cold-resistant oil with hydrogen peroxide to epoxidized soybean oil over titanium
strategy: Synthesis and application of green cold-resistant bio-based silicalite-1 zeolite supported cadmium catalysts[J]. Journal of Industrial
plasticizer for poly(vinyl chloride)[J]. European Polymer Journal, and Engineering Chemistry, 2020, 91: 191-200.
2021, 142: 110154. [20] ZHANG M, REN S Y, GUO Q X, et al. Synthesis of hierarchically
[2] XU Y Q, LIU X, ZHAO J R, et al. An efficient phthalate porous zeolite TS-1 with small crystal size and its performance of
ester-degrading Bacillus subtilis: Degradation kinetics, metabolic 1-hexene epoxidation reaction[J]. Microporous and Mesoporous
pathway, and catalytic mechanism of the key enzyme[J]. Materials, 2021, 326: 111395.
Environmental Pollution, 2021, 273: 116461. [21] SOEKIMAN C N, MIYAKR K, HAYASHI Y, et al. Synthesis of
[3] PARK M, CHOI I, LEE S, et al. Renewable malic acid-based titanium silicalite-1 (TS-1) zeolite with high content of Ti by a dry
plasticizers for both PVC and PLA polymers[J]. Journal of Industrial gel conversion method using amorphous TiO 2-SiO 2 composite with
and Engineering Chemistry, 2020, 88: 148-158. highly dispersed Ti species[J]. Materials Today Chemistry, 2020, 16:
[4] ZHANG W J (张文洁), ZHENG M L (郑美玲), ZHU Y Y (朱远洋), 100209.
et al. Transfer behavior of non-phenyl ester plasticizers in cigarettes[J]. （下转第 1721 页）