Ru-K-NaY催化草酸二甲酯脱羰基制备碳酸二甲酯

doi:10.16085/j.issn.1000-6613.2024-0360

摘要/Abstract

摘要：

以NaY分子筛为载体，通过KNO₃溶液对NaY分子筛进行预处理，记为K-NaY。之后采用过量浸渍的方法，制备了一系列不同Ru含量的Ru-K-NaY催化剂。并首次将其用于草酸二甲酯（DMO）脱羰基制备碳酸二甲酯（DMC）的反应中。研究了Ru负载量和催化剂碱量对反应的影响。采用X射线光电子能谱（XPS）、BET和CO₂程序升温脱附（CO₂-TPD）等测试对Ru-K-NaY催化剂的表面、结构性能以及碱性性能进行了表征，确定了增加催化剂弱碱活性位点数量以及Ru⁰物种数量可以提高催化剂的催化活性，促进碳酸二甲酯的生成。以Ru-K-NaY作为催化剂，对反应条件进行了优化，在最佳反应条件下，DMO转化率和DMC选择性分别为83%和69%。最后研究了催化剂的稳定性，Ru-K-NaY催化剂循环使用5次后催化活性基本不变。

关键词: 沸石, 催化剂, 催化剂载体, 碳酸二甲酯, 钌

Abstract:

A series of Ru-K-NaY catalysts with different Ru contents were prepared by using the method of excess impregnation which used NaY molecular sieves as carriers and pretreated by KNO₃ solution. The catalysts were used for the first time in the reaction of decarbonylation of dimethyl oxalate(DMO) to prepare dimethyl carbonate(DMC). The effects of Ru loading and catalyst base on the reaction were investigated. The surface and structural properties as well as the alkaline properties of the Ru-K-NaY catalysts were characterized using XPS, BET and CO₂-TPD, and it was determined that increasing the number of weak alkaline active sites as well as the number of Ru⁰ species of the catalysts could improve their catalytic activity and promote the generation of dimethyl carbonate. The reaction using Ru-K-NaY catalyst was optimized, yielding the DMO conversion and DMC selectivity were 83% and 69%, respectively. Finally, the stability test showed that the catalytic activity of the Ru-K-NaY catalyst was almost unchanged after 5 cycles.

Key words: zeolite, catalyst, catalyst support, dimethyl carbonate, ruthenium

中图分类号:

TQ032.41

张日东, 吕建华, 刘继东, 郭豹, 李文松. Ru-K-NaY催化草酸二甲酯脱羰基制备碳酸二甲酯[J]. 化工进展, 2024, 43(S1): 382-390.

ZHANG Ridong, LYU Jianhua, LIU Jidong, GUO Bao, LI Wensong. Ru-K-NaY catalyzed decarbonylation of dimethyl oxalate to dimethyl carbonate[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 382-390.

图/表 12

表1 不同载体的催化剂对DMO转化率和DMC选择性的影响

催化剂	DMO转化率/%	DMC选择性/%
Ru-NaY	65	53
Ru-K-NaY	83	69

图1 5%Ru-K-NaY的SEM图像

图2 Ru-K-NaY的TEM图像

图3 不同负载量的催化剂XRD谱图

图4 不同Ru负载量的Ru-K-NaY催化剂的H2-TPR图像

表2 NaY分子筛及Ru-K-NaY的结构性质

样品	Ru实际负载量^①/%	比表面积^② /m²∙g^-1	孔径^③ /nm	孔容^④ /cm³∙g^-1	碱量^⑤ /mmol∙g^-1
NaY	—	1080.8	0.557	0.371	—
K-NaY	—	1043.5	0.583	0.397	0.23
2%Ru-K-NaY	1.73	1037.1	0.572	0.373	0.17
5%Ru-K-NaY	4.91	1033.8	0.568	0.354	0.34
8%Ru-K-NaY	7.89	1011.0	0.533	0.343	0.26

图5 不同Ru负载量的Ru-K-NaY催化剂的XPS谱图

表3 不同Ru负载量的Ru-K-NaY催化剂中的不同价态Ru物种的比例

样品	不同价态Ru物种比例/%
样品	$R u 0 R u 0 + R u δ +$	$R u δ + R u 0 + R u δ +$
2%Ru-K-NaY	53.81	46.19
5%Ru-K-NaY	61.4	38.6
8%Ru-K-NaY	59.61	40.39

表3 不同Ru负载量的Ru-K-NaY催化剂中的不同价态Ru物种的比例

样品	不同价态Ru物种比例/%
样品	$R u 0 R u 0 + R u δ +$	$R u δ + R u 0 + R u δ +$
2%Ru-K-NaY	53.81	46.19
5%Ru-K-NaY	61.4	38.6
8%Ru-K-NaY	59.61	40.39

图6 不同负载量催化剂CO2-TPD谱图

图7 不同条件对DMO转化率和DMC选择性的影响

图8 Ru-K-NaY催化剂的循环利用（催化剂用量7%，反应温度220℃，120min，Ru负载量5%）

图9 反应机理

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