Mg量影响的纳米片负载Pt-In催化异丁烷脱氢性能

doi:10.11949/0438-1157.20230258

化工学报 ›› 2023, Vol. 74 ›› Issue (6): 2427-2435.DOI: 10.11949/0438-1157.20230258

• 催化、动力学与反应器 • 上一篇下一篇

Mg量影响的纳米片负载Pt-In催化异丁烷脱氢性能

张希庆¹(), 王琰婷¹(), 徐彦红², 常淑玲¹, 孙婷婷¹, 薛定³, 张立红¹()

^1.天津大学化工学院，天津 300350
^2.平顶山学院化学与环境工程学院，河南平顶山 467000
^3.天津市工业尾气资源综合利用技术工程中心，天津 300271

收稿日期:2023-03-20 修回日期:2023-05-28 出版日期:2023-06-05 发布日期:2023-07-27
通讯作者: 张立红
作者简介:张希庆（1997—），男，硕士研究生，zhangxiqing1997@163.com
王琰婷（1998—），女，硕士研究生，w2016016061@163.com
基金资助:
国家自然科学基金项目(21776214)

Effect of Mg content on isobutane dehydrogenation properties over nanosheets supported Pt-In catalysts

Xiqing ZHANG¹(), Yanting WANG¹(), Yanhong XU², Shuling CHANG¹, Tingting SUN¹, Ding XUE³, Lihong ZHANG¹()

^1.School of Chemical Engineering, Tianjin University, Tianjin 300350, China
^2.School of Chemical and Environmental Engineering, Pingdingshan University, Pingdingshan 467000, Henan, China
^3.Tianjin Industrial Exhaust Resources Comprehensive Utilization Technology Engineering Center, Tianjin 300271, China

Received:2023-03-20 Revised:2023-05-28 Online:2023-06-05 Published:2023-07-27
Contact: Lihong ZHANG

摘要/Abstract

摘要：

采用一步法在Al₂O₃表面原位生长一系列Mg含量不同的超薄水滑石纳米片，并采用分步浸渍复原法逐步引入助剂In和活性组分Pt，进一步通过焙烧和还原处理制备了负载Pt-In双金属催化剂PtIn/HTR-x(x = 0.05，0.1，0.15，0.2 mol·L^-1)。探究了催化剂及其前体的结构、物化性能与异丁烷直接脱氢性能之间的关系。结果表明，制备母液中Mg²⁺浓度会影响纳米片厚度，进而影响催化剂结构、还原能力、表面化学状态、表面酸性和脱氢性能。当Mg²⁺浓度为0.15 mol·L^-1时，催化剂获得最佳脱氢性能，其中异丁烯产率高达58%。催化剂PtIn/HTR-0.15优异的活性、选择性、稳定性及良好的抗积炭性能与催化剂高的比表面积、低的强酸量和酸强度、强的金属载体相互作用以及高的表面In³⁺/In⁰原子比有关。

关键词: 异丁烷, 脱氢, 催化剂, 水滑石纳米片, Mg浓度, 积炭

Abstract:

A series of hydrotalcite nanosheets with different Mg content were in-situ constructed on the surface of Al₂O₃ support by one-step synthesis method. And promoter In and active component Pt were introduced in the nanosheets by consecutive impregnation-reconstruction method. Furthermore, the supported Pt-In bimetallic catalysts PtIn/HTR-x (x = 0.05, 0.1, 0.15, 0.2 mol·L^-1) were prepared by calcination and reduction. The relationship between the structure, physical and chemical properties of the catalyst and its precursor and the direct dehydrogenation performance of isobutane was explored. The results show that the Mg²⁺ concentrations determine the nanosheets thickness, which affects the structure, reducibility, surface chemical states, and surface acidity and dehydrogenation properties of these catalysts. The catalyst with Mg²⁺ concentration of 0.15 mol·L^-1exhibits the optimum dehydrogenation performance, of which the isobutene yield reaches 58%. The excellent activity, selectivity and stability of PtIn/HTR-0.15 are attributed to the maximum specific surface area, strong metal-support interaction and high surface In³⁺/In⁰ atomic ratio, and the good anti-carbon deposition performance is related to the low concentration and weak strength of surface strong acid sites.

Key words: isobutane, dehydrogenation, catalyst, hydrotalcite nanosheets, Mg concentration, carbon deposition

中图分类号:

TQ 032.4

张希庆, 王琰婷, 徐彦红, 常淑玲, 孙婷婷, 薛定, 张立红. Mg量影响的纳米片负载Pt-In催化异丁烷脱氢性能[J]. 化工学报, 2023, 74(6): 2427-2435.

Xiqing ZHANG, Yanting WANG, Yanhong XU, Shuling CHANG, Tingting SUN, Ding XUE, Lihong ZHANG. Effect of Mg content on isobutane dehydrogenation properties over nanosheets supported Pt-In catalysts[J]. CIESC Journal, 2023, 74(6): 2427-2435.

图/表 12

图1 不同Mg2+浓度制备的PtIn/HTR-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）催化剂异丁烷直接脱氢性能

Fig.1 Isobutane direct dehydrogenation performance of PtIn/HTR-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1) with different Mg2+ concentration

图2 HT-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）前体的XRD谱图

Fig.2 XRD patterns of HT-x precursors (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

图3 焙烧催化剂PtIn/HTC-x和还原催化剂PtIn/HTR-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）的XRD谱图

Fig.3 XRD patterns of calcined catalysts PtIn/HTC-x and reduced catalysts PtIn/HTR-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

图4 焙烧催化剂PtIn/HTC-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）的低温N2吸-脱附等温线和孔径分布曲线

Fig.4 Low temperature N2 adsorption-desorption isotherms and pore size distribution curves of calcined catalysts PtIn/HTC-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

表1 焙烧催化剂PtIn/HTC-x（x = 0.05， 0.1， 0.15， 0.2 mol·L-1）的织构数据

Table 1 Textural data of calcined catalysts PtIn/HTC-x （x = 0.05， 0.1， 0.15， 0.2 mol·L-1）

催化剂	比表面积/(m²·g^-1)	孔体积/(cm³·g^-1)	平均孔径/nm
PtIn/HTC-0.05	136	0.34	6.6
PtIn/HTC-0.1	173	0.58	6.6
PtIn/HTC-0.15	247	0.57	6.6
PtIn/HTC-0.2	203	0.56	7.8

图5 焙烧催化剂PtIn/HTC-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）的NH3-TPD谱图

Fig.5 NH3-TPD diagrams of calcined catalysts PtIn/HTC-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

表2 焙烧催化剂PtIn/HTC-x（x = 0.05， 0.1， 0.15， 0.2 mol·L-1）的NH3-TPD结果

Table 2 NH3-TPD results of calcined catalysts PtIn/HTC-x （x = 0.05， 0.1， 0.15， 0.2 mol·L-1）

催化剂	T_M /℃			总峰面积	峰面积占比/%
催化剂	Ⅰ	Ⅱ	Ⅲ	总峰面积	Ⅰ	Ⅱ	Ⅲ
PtIn/HTC-0.05	150	189	295	121	14.5	26.8	58.7
PtIn/HTC-0.1	147	187	263	111	13.3	29.7	57.0
PtIn/HTC-0.15	150	190	265	88	23.3	30.2	46.5
PtIn/HTC-0.2	144	184	315	64	20.4	32.3	47.3

图6 焙烧催化剂PtIn/HTC-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）的H2-TPR曲线

Fig. 6 H2-TPR curves of calcined catalysts PtIn/HTC-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

表3 焙烧催化剂PtIn/HTC-x（x = 0.05， 0.1， 0.15， 0.2 mol·L-1）的H2-TPR结果

Table 3 H2-TPR results of calcined catalysts PtIn/HTC-x （x = 0.05， 0.1， 0.15， 0.2 mol·L-1）

催化剂	T_M /℃		总峰面积 A_t	各峰面积		峰面积比
催化剂	Ⅰ	Ⅱ	总峰面积 A_t	A_Ⅰ	A_Ⅱ	A_II/A_I	A_II/A_t
PtIn/HTC-0.05	345	520	502	417	85	0.20	0.17
PtIn/HTC-0.1	398	529	761	637	124	0.19	0.16
PtIn/HTC-0.15	407	536	613	534	79	0.15	0.13
PtIn/HTC-0.2	446	570	419	329	90	0.27	0.21

图7 还原催化剂PtIn/HTR-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）的In 3d的XPS谱图

Fig.7 XPS spectra of In 3d region of reduced catalysts PtIn/HTR-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

表4 还原催化剂PtIn/HTR-x（x = 0.05，0.1，0.15，0.2 mol·L-1）的In 3d数据

Table 4 In 3d region data of reduced catalysts PtIn/HTR-x （x = 0.05，0.1，0.15，0.2 mol·L-1）

催化剂	In 3d_5/2 结合能 /eV		In 3d_3/2 结合能 /eV		In³⁺/In^0①
催化剂	In⁰	In³⁺	In⁰	In³⁺	In³⁺/In^0①
PtIn/HTR-0.05	444.5	445.8	452.2	453.2	1.57
PtIn/HTR-0.1	444.5	445.6	452.2	453.1	2.00
PtIn/HTR-0.15	444.7	445.6	452.3	453.3	2.87
PtIn/HTR-0.2	444.5	445.5	452.2	453.1	2.27

图8 反应后催化剂PtIn/HTU-x（x = 0.05, 0.1, 0.15, 0.2 mol·L-1）的TG曲线

Fig.8 TG curves of used catalysts PtIn/HTU-x (x = 0.05, 0.1, 0.15, 0.2 mol·L-1)

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Mg量影响的纳米片负载Pt-In催化异丁烷脱氢性能

Effect of Mg content on isobutane dehydrogenation properties over nanosheets supported Pt-In catalysts

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