Effects of Acetylacetone Ligand on Catalytic Performance of SnCl2/AC in Acetylene Hydrochlorination

doi:10.3969/j.issn.1006-396X.2022.02.006

Abstract

Abstract:

Supported SnCl₂ is a mercury?ree catalyst for acetylene hydrochlorination.5.0%Sn(acac)₂Cl₂/AC catalyst was prepared by introducing acetylacetone ligand to enhance the catalytic performance of SnCl₂ in acetylene hydrochlorination.The results show that the acetylene conversion of 5.0%Sn(acac)₂Cl₂/AC catalyst is up to 96% under the conditions of acetylene?to?hydrogen chloride molar ratio of 1∶1.1,170 ℃ and GHSV(C₂H₂) of 90 h^-1, which is higher than that of the 5.0%SnCl₂/AC catalyst. The physical and chemical properties of the catalysts before and after the reaction also proved that the introduction of acetylacetone ligand can enhance the acetylene adsorption capacity of the SnCl₂ catalyst and inhibit Sn loss during the reaction.Therefore,the activity and stability of the SnCl₂ catalyst were effectively improved.

Key words: Hydrochlorination, SnCl₂/AC catalyst, Acetylacetone ligand, Activity, Stability

摘要：

负载型SnCl₂是一种无汞乙炔氢氯化催化剂，为了增强SnCl₂催化剂的乙炔氢氯化反应性能，通过引入乙酰丙酮配体(acetylacetone)制备了5.0%Sn(acac)₂Cl₂/AC催化剂，并对催化剂的物化性能进行了分析。结果表明，在乙炔体积空速为90 h^-1、乙炔与HCl物质的量比为1∶1.1、反应温度为170 ℃的条件下，5.0%Sn(acac)₂Cl₂/AC催化剂的乙炔转化率达到96%，高于5.0%SnCl₂/AC催化剂的乙炔转化率；结合反应前后催化剂的性能表征，证实引入乙酰丙酮配体可增强SnCl₂催化剂的乙炔吸附能力，同时还可起到抑制反应过程中锡流失的作用，有效地提高了SnCl₂催化剂的反应活性和稳定性。

关键词: 氢氯化反应, SnCl₂/AC催化剂, 乙酰丙酮配体, 活性, 稳定性

CLC Number:

TQ032.4

Wei Zhou, Jian Zhang, Wenqiang Qiao, Xi Sun, Yucai Qin, Lijuan Song. Effects of Acetylacetone Ligand on Catalytic Performance of SnCl₂/AC in Acetylene Hydrochlorination[J]. Journal of Petrochemical Universities, 2022, 35(2): 37-42.

周维, 张健, 乔文强, 孙玺, 秦玉才, 宋丽娟. 乙酰丙酮配体对SnCl₂/AC催化乙炔氢氯化反应的影响[J]. 石油化工高等学校学报, 2022, 35(2): 37-42.

Figures/Tables 9

Table 1 Experimental materials and reagents

名称	规格	来源
乙炔	纯度≥99.9%	大连光明特气研究所
氯化氢	纯度≥99.9%	淄博万达利特气有限公司
椰壳活性炭	-	文昌琼池活性炭有限公司
氯化亚锡	AR	国药集团化学试剂有限公司
乙酰丙酮	AR	国药集团化学试剂有限公司
二氯乙烷	AR	国药集团化学试剂有限公司
硝酸	GR，质量分数68%	沈阳新西试剂厂
浓盐酸	质量分数38%	沈阳新西试剂厂

Fig.1 The schematic diagram of introduction of acetylacetone ligand

Fig.2 XRD pattern of the 5.0%Sn(acac)2Cl2/AC catalysts before and after the reaction

Fig.3 C2H2?TPD pattern of the catalysts

Table 2 Texture properties data of catalysts and AC

样品名称	比表面积/（m² $⋅$ g^-1）	孔容/（cm³ $⋅$ g^-1）	平均孔径/nm
AC	892	0.5	4.2
硝酸处理AC	981	0.6	4.4
5.0%SnCl₂/AC	886	0.4	4.3
5.0%Sn(acac)₂Cl₂/AC	806	0.4	4.4

Table 2 Texture properties data of catalysts and AC

样品名称	比表面积/（m² $⋅$ g^-1）	孔容/（cm³ $⋅$ g^-1）	平均孔径/nm
AC	892	0.5	4.2
硝酸处理AC	981	0.6	4.4
5.0%SnCl₂/AC	886	0.4	4.3
5.0%Sn(acac)₂Cl₂/AC	806	0.4	4.4

Fig.4 Thermogravimetric curves of the Sn catalysts

Fig.5 XPS energy spectrogram of 5.0%Sn(acac)2Cl2/AC before and after the reaction

Table 3 Surface mass composition of catalysts before and after the reaction, determined by XPS

反应前5.0%Sn(acac)₂Cl₂/AC

反应后5.0%Sn(acac)₂Cl₂/AC

80.30

65.31

76.31

19.70

25.92

18.30

4.08

4.83

4.69

1.26

Fig.6 Acetylene hydrochlorination performance of 5.0%SnCl2/AC and 5.0%Sn(acac)2Cl2/AC catalysts

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Effects of Acetylacetone Ligand on Catalytic Performance of SnCl₂/AC in Acetylene Hydrochlorination

乙酰丙酮配体对SnCl₂/AC催化乙炔氢氯化反应的影响

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