Fe-Ce/SiO2固体碱催化剂用于制备碳酸二甲酯

doi:10.11949/0438-1157.20191152

摘要/Abstract

摘要：

采用化学还原法制备亚价负载铁催化剂，通过空气氧化为Fe³⁺碱性活性中心。考察了该催化剂在碳酸丙烯酯与甲醇酯交换制备碳酸二甲酯反应中的活性和选择性。采用N₂吸附-脱附、TEM、XRD、XPS和CO₂-TPD等对所制备的催化剂进行了表征。结果表明：催化剂的表面结构与碱性是影响其活性的重要因素。相对于Fe或Ce单金属催化剂，Fe-Ce/SiO₂催化剂的碱量大幅度提升，且Fe与Ce通过相互作用形成了稳定的非晶态结构。在醇酯比为15∶1、反应温度为140℃、催化剂用量为反应物总质量的0.5%、 Ce/Fe原子比为2∶1的反应条件下，碳酸丙烯酯转化率为88%，碳酸二甲酯的选择性为92%。催化剂在循环使用10次之后，其活性保持不变。

关键词: 固体碱, 催化剂, 碳酸丙烯酯, 酯交换, 碳酸二甲酯, 活性, 稳定性

Abstract:

A tetravalent supported iron catalyst is prepared by chemical reduction and oxidized to a Fe³⁺ basic active center by air. The activity and selectivity of the catalyst in the transesterification of propylene carbonate with methanol to prepare dimethyl carbonate were evaluated. The prepared catalysts were characterized by N₂ adsorption-desorption, TEM, XRD, XPS and CO₂-TPD. Compared with Fe or Ce single metal catalyst, the basic amount of Fe-Ce/SiO₂ catalyst is greatly improved, and the interaction between Fe and Ce formed a stable amorphous structure. Propylene carbonate conversion of 88% and dimethyl ester selectivity of 92% were reached under the reaction conditions of alcohol ester molar ratio of 15∶1, reaction temperature of 140℃, catalyst dosage of 0.5% of the total mass of the reactants, and Ce/Fe atomic ratio of 2∶1. The activity of the catalyst remained unchanged after 10 cycles of use.

Key words: solid base, catalyst, propylene carbonate, transesterification, dimethyl carbonate, reactivity, stability

中图分类号:

O 643.36

吴辰亮, 李小青, 张超, 张荷丰, 严新焕. Fe-Ce/SiO₂固体碱催化剂用于制备碳酸二甲酯[J]. 化工学报, 2020, 71(1): 297-305.

Chenliang WU, Xiaoqing LI, Chao ZHANG, Hefeng ZHANG, Xinhuan YAN. Fe-Ce/SiO₂solid base catalyst for preparing dimethyl carbonate[J]. CIESC Journal, 2020, 71(1): 297-305.

图/表 14

图1 催化剂的TEM图

Fig.1 TEM images of catalysts

图2 催化剂的EDX-mapping图

Fig.2 EDX-mapping images of catalyst

表1 催化剂的孔隙结构参数

Table 1 Textural properties of different catalysts

催化剂	S_BET^① /(m²·g^-1)	D^② /(nm)	V^③ /(cm³·g^-1)
SiO₂	193.7	14.84	1.37
10Ce/SiO₂	162.9	7.35	1.12
2.5Fe-10Ce/SiO₂	172.4	7.18	1.15
5Fe-10Ce/SiO₂	171.8	8.06	1.09
7.5Fe-10Ce/SiO₂	199.6	7.97	1.15
10Fe-10Ce/SiO₂	224.5	8.56	1.04

图3 催化剂的XRD谱图

Fig.3 XRD patterns of catalystsa—5Fe/SiO2; b—10Ce/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2; f—10Fe+10Ce/SiO2

图4 催化剂的Ce 3d XPS谱图

Fig.4 Ce 3d XPS spectra of catalystsa—5Fe/SiO2; b—10Ce/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2

图5 催化剂的Fe 2p XPS谱图

Fig.5 Fe 2p XPS spectra of catalystsa—5Fe/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2; f—10Fe+10Ce/SiO2

图6 催化剂的CO2-TPD谱图

Fig.6 CO2-TPD patterns of catalysta—5Fe/SiO2; b—10Ce/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2; f—10Fe+10Ce/SiO2

表2 催化剂的CO2吸附量

Table 2 Absorbed CO2 of catalysts

催化剂	CO₂吸附量/(mmol/g)			总CO₂吸附量/(mmol/g)
催化剂	弱(<200℃)	中等(200~450℃)		总CO₂吸附量/(mmol/g)
5Fe/SiO₂	0.04	0.71	0.75
10Ce/SiO₂	0.76	0.78	1.54
2.5Fe-10Ce/SiO₂	0.90	0.93	1.83
5Fe-10Ce/SiO₂	0.97	0.90	1.87
7.5Fe-10Ce/SiO₂	0.91	0.94	1.85
10Fe-10Ce/SiO₂	0.96	0.95	1.91

表3 催化剂的活性评价

Table 3 Catalytic performance test results

催化剂	Ce/Fe比例	PC转化率/%	DMC选择性/%
5Fe/SiO₂	—	78	77
10Ce/SiO₂	—	69	75
2.5Fe-10Ce/SiO₂	4:1	83	84
5Fe-10Ce/SiO₂	2:1	88	92
7.5Fe-10Ce/SiO₂	4:3	81	84
10Fe-10Ce/SiO₂	1:1	79	77

图7 反应温度的影响（反应压力 0.5 MPa，醇酯比 15∶1，催化剂质量分数0.5%，反应时间8 h）

Fig.7 Effect of reaction temperature on transesterification of propylene carbonate with methanol

图8 醇酯比的影响（反应压力0.5 MPa，反应温度140℃，催化剂质量分数0.5%，反应时间8 h）

Fig.8 Effect of methanol/PC molar ratio on transesterification of propylene carbonate with methanol

图9 催化剂用量的影响（反应压力0.5 MPa，反应温度140℃，醇酯比=15∶1，反应时间8 h）

Fig.9 Effect of catalyst dosage on transesterification of propylene carbonate with methanol

图10 5Fe-10Ce/SiO2催化剂的稳定性测试（反应压力0.5 MPa，反应温度140℃，醇酯比15∶1，催化剂质量分数0.5%，反应时间8 h）

Fig.10 Stability of 5Fe-10Ce/SiO2 catalyst

图11 反应后催化剂的XRD谱图

Fig.11 XRD patterns of recycled catalyst

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Fe-Ce/SiO₂固体碱催化剂用于制备碳酸二甲酯

Fe-Ce/SiO₂solid base catalyst for preparing dimethyl carbonate

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