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

doi:10.11949/j.issn.0438-1157.20181455

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 8

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

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

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

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

Fig.5 Effect of GO on catalyst stability

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

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

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

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