负载型Pd催化剂催化草酸二甲酯脱羰基制备碳酸二甲酯

摘要/Abstract

摘要： 为开发高效、成本低廉的碳酸二甲酯(DMC)合成工艺，以Naβ(25)、NaZSM-5(25)、NaY(6)、NaY(8)和NaY(10)分子筛为载体，采用浸渍法制备了负载型Pd催化剂，并将其首次用于草酸二甲酯(DMO)脱羰基反应。采用X射线衍射、X射线光电子能谱、透射电镜和傅里叶变换红外光谱等表征方法对催化剂的组成、价态、孔结构、形貌以及晶型进行分析，并对其催化性能进行评价。结果表明，使用Pd/NaY(6)催化剂催化DMO脱羰基合成DMC，在反应温度220 ℃、反应时间90 min、催化剂用量1.0 g、1,4-二氧六环与DMO质量比4:1、Pd负载量（w）0.2%的条件下，DMO转化率可达82.59%，DMC选择性可达62.33%。通过对催化剂稳定性的研究发现，经过5次循环再生后，催化剂对DMO脱羰基反应仍具有良好的催化活性。最后，合理推测出Pd/NaY(6)催化剂催化DMO脱羰基合成DMC的反应机理。

关键词: 沸石分子筛, Pd催化剂, 草酸二甲酯, 脱羰基反应, 碳酸二甲酯

Abstract: In order to develop a high efficient and low cost synthetic process for dimethyl carbonate (DMC), supported Pd catalysts were prepared by impregnation method on Naβ(25), NaZSM-5(25), NaY(6), NaY(8),NaY(10) zeolites, and it was first used in the decarbonylation reaction of dimethyl oxalate (DMO). The composition, valence, pore structure, morphology and crystal of the catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The results showed that DMC was synthesized by the decarbonylation of DMO over Pd/NaY (6) catalyst. Under the optimum conditions such as a reaction temperature of 220 ℃,a reaction time of 90 min,a catalyst dosage of 1.0 g, a mass ratio of 1,4-dioxane to DMO of 4:1, and Pd loading 0.2%, the conversion of DMO and the selectivity of DMC were 82.59% and 62.33%, respectively. After five cycles of regeneration, the catalyst showed good catalytic activity for DMO decarboxylation. Finally, the reaction mechanism of DMC synthesis by DMO decarbonylation over Pd/NaY (6) catalyst was reasonably deduced.

Key words: zeolite, Pd catalyst, dimethyl oxalate, decarbonylation, dimethyl carbonate

刘鹏李文松郭豹刘继东吕建华. 负载型Pd催化剂催化草酸二甲酯脱羰基制备碳酸二甲酯[J]. 石油炼制与化工, 2024, 55(8): 74-83.

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