Page 51 - 《精细化工》2022年第11期

第 11 期 邓志勇，等: 甲醇直接氧化羰基化合成碳酸二甲酯催化剂的研究进展 ·2201·

原气活化催化剂；在 150 ℃、压力为 1.5 MPa 时， of Cleaner Production, 2021, 279: 123344.
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甲醇的转化率达到 13.5%。
Synthesis and optimization of fatty alkyl trimethyl ammonium
相较于 Cu/活性炭和 Cu/石墨烯催化剂，CuY 分 oxalates[J]. Fine Chemicals (精细化工), 2019, 36(8): 1556-1559.
子筛催化剂的甲醇转化率较高，但 DMC 选择性明 [6] YANG H (杨浩), XIAO Z L (肖忠良), CHEN T (陈彤), et al.
TiO 2-GO composites catalyst for the transesterification of dimethyl
显较低，仅有 60%左右 [46,51-60] 。这是因为，CuY 分 carbonate with phenol to diphenyl carbonate[J]. Fine Chemicals (精
子筛催化剂有较多酸性位点，负载的 Cu 也表现出 细化工), 2020, 37(1): 92-97.
中强酸的吸附性质 [63] ，而酸性位点对副产物二甲氧 [7] WANG Y B (王玉斌), CHEN T (陈彤), WANG G Y (王公应).
Synthesis of anisole from phenol and dimethyl carbonate catalyzed
基甲烷（DMM）和甲酸甲酯（MF）有催化活性。 by solid base KF/MgAl-LDO[J]. Fine Chemicals (精细化工), 2021,
此外，由于反应物在 CuY 分子筛催化剂中扩散阻力 38(8): 1590-1596.
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较大，DMC 的时空收率也较低。 Green and effective synthesis of N,N,N-trimethyladamantan1- aminium
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3 结束语与展望 [9] SUN Y H (孙予罕), WEI W (魏伟), YANG H J (杨海金), et al.
Method for synthesizing dimethyl carbonate by using urea and
methanol and adopting heterogeneous catalyst: CN1428329A[P].
中国 DMC 产能持续增加，直接氧化羰基化合
2003-07-09.
成 DMC 具有生产成本低、反应条件温和等优点， [10] GILPIN J A, EMMONS A H. Synthesis of dimethyl carbonate:
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素铜基催化剂的开发是近年的研究热点。对于碳基 producing dimethylcarbonate: US4318862A[P]. 1982-03-09.
载体负载的催化剂，将 Cu 限域在介孔孔道中，以 [13] WU X J (吴晓金), ZHANG X L (张学岭), XU Y F (许叶飞), et al.
Method for indirectly synthesizing dimethyl carbonate by CO gas
及利用载体表面基团对 Cu 的锚定作用等，可以有
phase oxidative coupling and decarbonylation: CN102079709A[P].
效提高 Cu 的分散度，增加活性 Cu 物种的含量，从 2011-06-01.
而提高其催化性能。对于 CuY 催化剂，则应打开 Y [14] ROMANO U, TESEL R, MAURI M M, et al. Synthesis of dimethyl
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氛或载体表面性质，可以增加 Cu(Ⅰ)和 Cu(0)物种
copper catalyzed aerobic oxidative carbonylation of methanol to
的含量。Cu 的团聚和流失以及 Cu(Ⅰ)和 Cu(0)的氧 dimethyl carbonate (DMC)[J]. Journal of Molecular Catalysis A:
化是催化剂失活的主要原因，通过调变 Cu 与载体 Chemical, 2001, 175(1): 51-63.
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间的相互作用，可以有效抑制 Cu 的团聚和流失。 Catalyst for synthesizing dimethyl carbonate by oxidative carbonylation
分析发现，相比含卤素催化剂和 CuY 分子筛催化剂， of liquid phase methanol and method: WO2018/028505Al[P]. 2018-
02-15.
碳基载体负载 Cu 催化剂在甲醇直接氧化羰基化合 [17] MO W L, XIONG H, LI T, et al. The catalytic performance and
成 DMC 反应中，不存在腐蚀设备、催化剂难回收 corrosion inhibition of CuCl/Schiff base system in homogeneous
oxidative carbonylation of methanol[J]. Journal of Molecular Catalysis
等问题，且表现出较高的 DMC 选择性，通过优化
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催化剂载体的表面性质，也成功制备了有较高 DMC [18] MO W L, LIU H T, XIONG H, et al. Preparation of CuCl/
时空收率的催化剂，是最有潜力的催化剂。未来的 1,10-phenanthroline immobilized on polystyrene and catalytic
performance in oxidative carbonylation of methanol[J]. Applied
研究方向可能是更精确地调控 Cu 粒子或团簇在载 Catalysis A: General, 2007, 333(2): 172-176.
体表面结构上的空间位置和局部环境。 [19] DONG W S, ZHOU X S, XIN C S, et al. Ionic liquid as an efficient
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