氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能

doi:10.11949/j.issn.0438-1157.20181455

化工学报 ›› 2019, Vol. 70 ›› Issue (4): 1401-1408.DOI: 10.11949/j.issn.0438-1157.20181455

• 催化、动力学与反应器 • 上一篇下一篇

氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能

宋宇淙¹(),丁晓墅¹(),闫亚辉²,王淑芳¹,王延吉¹()

1. 河北工业大学化工学院，绿色化工和高效节能河北省重点实验室，天津 300130
2. 中国船舶重工集团公司第七一八研究所，河北邯郸 056027

收稿日期:2018-12-05 修回日期:2019-01-24 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 丁晓墅,王延吉
作者简介:<named-content content-type="corresp-name">宋宇淙</named-content>（1993—），女，博士研究生，<email>yucong0508@163.com</email>|丁晓墅（1985—），女，博士，副教授，<email>dxshu@hebut.edu.cn</email>|王延吉（1962—），男，博士，教授，<email>yjwang@hebut.edu.cn</email>
基金资助:
国家青年自然科学基金项目(21606070);河北省青年科学基金项目(B2016202256);国家自然科学基金重点项目(21236001);国家自然科学基金项目(21576069)

Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis

Yucong SONG¹(),Xiaoshu DING¹(),Yahui YAN²,Shufang WANG¹,Yanji WANG¹()

1. Hebei Provincial Key Laboratory of Green Chemical Technology and High Efficiency Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
2. China Shipbuilding Industry Corp., Handan 056027, Hebei, China

Received:2018-12-05 Revised:2019-01-24 Online:2019-04-05 Published:2019-04-05
Contact: Xiaoshu DING,Yanji WANG

摘要/Abstract

摘要：

针对甲醇气相氧化羰基化直接合成碳酸二甲酯（DMC）反应中催化剂活性低和稳定性差的问题，制备了一系列氧化石墨烯复合金属催化剂，并对其进行活性评价。结果表明：催化剂PdCl₂-CuCl₂-KOAc/AC@GO-HCl表现出最佳的催化活性和稳定性：DMC的空时收率（STY）为800~900 g·(L cat)^-1·h^-1，且反应16 h内活性无明显下降；甲醇选择性保持在95%以上，CO选择性为35%~40%。结合XRD和XPS表征发现，活性物种Cu₂Cl(OH)₃的生成，提高了催化剂催化活性，而CuO和KCl均可导致催化剂的失活。

关键词: 氧化石墨烯, 催化剂, 固定床, 多相反应, 氧化羰基化

Abstract:

A series of graphene oxide composite metal catalysts were prepared and evaluated for their activity in the direct synthesis of dimethyl carbonate (DMC) by methanol vapor phase oxidative carbonylation. The results show that the catalyst PdCl₂-CuCl₂-KOAc/AC@GO-HCl has the best catalytic activity and stability. The space time yield (STY) of DMC was between 800－900 g·(L cat) ^-1·h^-1, and the catalytic activity was stable in 16 h without significant decrease. Methanol selectivity was maintained above 95%, and CO selectivity was between 35%－40%. Combined with results of XRD and XPS analyses, it was found that the formation of the active species Cu₂Cl(OH)₃ improved the catalytic activity of the catalyst, while both CuO and KCl could cause the deactivation of the catalyst.

Key words: graphene oxide, catalyst, fixed-bed, multiphase reaction, oxidative carbonylation

中图分类号:

宋宇淙, 丁晓墅, 闫亚辉, 王淑芳, 王延吉. 氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能[J]. 化工学报, 2019, 70(4): 1401-1408.

Yucong SONG, Xiaoshu DING, Yahui YAN, Shufang WANG, Yanji WANG. Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis[J]. CIESC Journal, 2019, 70(4): 1401-1408.

图/表 8

图1 氧化石墨烯复合金属催化剂对合成碳酸二甲酯空时收率的影响

Fig.1 Effect of GO composite metal catalyst on space-time yield of synthetic dimethyl carbonate

图2 碳酸二甲酯对甲醇的选择性随运转时间的变化

Fig.2 Selectivity of dimethyl carbonate to methanol with running time

图3 碳酸二甲酯对CO的选择性随运转时间的变化

Fig.3 Selectivity of dimethyl carbonate to CO with running time

图4 GO与盐酸用量对合成碳酸二甲酯空时收率的影响

Fig.4 Effect of GO and hydrochloric acid dosage on space-time yield of dimethyl carbonate

图5 GO对催化剂稳定性的影响

Fig.5 Effect of GO on catalyst stability

图6 新鲜和反应后多相复合催化剂的X射线衍射图谱

Fig.6 X-Ray diffraction pattern of fresh and after reaction heterogeneous composite catalyst

表1 新鲜和反应后催化剂的孔结构参数

Table 1 Pore structure parameter of fresh and recovered catalyst

Catalyst		Surface area/(m²/g)	Pore volume/(cm³/g)	Pore diameter/nm
fresh	PdCl₂-CuCl₂-KOAc/AC	705.0	0.230	2.44
	PdCl₂-CuCl₂-KOAc/AC@GO-HCl	921.8	0.364	1.94
	PdCl₂-CuCl₂-KOAc/AC@HCl	937.4	0.413	2.02
recovered	PdCl₂-CuCl₂-KOAc/AC@GO-HCl	829.1	0.415	2.00
recovered	PdCl₂-CuCl₂-KOAc/AC@HCl	830.3	0.111	2.24

图7 新鲜和反应后多相复合催化剂的Cu2p3/2的XPS谱图

Fig.7 XPS spectra of Cu2p3/2 of fresh and after reaction heterogeneous composite catalyst

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氧化石墨烯复合金属催化剂催化碳酸二甲酯合成反应性能

Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis

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