ZnCaZr固溶体催化异丁烷-CO<sub>2</sub>氧化脱氢制异丁烯的研究

刘玉鹏; 刘玲技; 蔚晓盛; 王永钊; 李国强; 李磊; 王长真

doi:10.19906/j.cnki.JFCT.2024003

ZnCaZr固溶体催化异丁烷-CO₂氧化脱氢制异丁烯的研究

doi: 10.19906/j.cnki.JFCT.2024003

刘玉鹏^{1, #,},
刘玲技^{1, #,},
蔚晓盛^1,,
王永钊^1,,
李国强^2,,
李磊^2, ,,
王长真^1, ,

1.
山西大学精细化学品教育部工程研究中心, 山西太原 030006
2.
中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室, 山西太原 030001

基金项目: 国家自然科学基金 (22178202, 21603127), 山西省科技创新团队项目(202204051001012), 煤炭高效低碳利用全国重点实验室开放课题基金(J23-24-609-2), 天津市科技计划项目(22YFYSHZ00290)和中国科学院山西煤炭化学研究所自主创新项目(SCJC-DT-2023-03)资助

详细信息

通讯作者:
E-mail: lilei@sxicc.ac.cn

czwang@sxu.edu.cn

^#：共同第一作者
中图分类号: O643.36
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出版历程
- 收稿日期: 2024-01-06
- 修回日期: 2024-02-11
- 录用日期: 2024-02-27
- 网络出版日期: 2024-03-13

CO₂ Assistant Oxidative Dehydrogenation of Isobutane to Isobutene Catalyzed by ZnCaZr Solid Solution

LIU Yupeng^{1, #
,},
LIU Lingji^{1, #
,},
YU Xiaosheng^1
,,
WANG Yongzhao^1
,,
LI Guoqiang^2
,,
LI Lei^{2
, ,},
WANG Changzhen^{1
, ,}

1.
Engineering Research Center of Ministry of Education for Fine Chemicals, Shanxi University, Taiyuan 030006, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by National Natural Science Foundation of China (22178202, 21603127), the Science and Technology Innovation Teams of Shanxi Province (202204051001012), the foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal (J23-24-609-2), the Science and Technology Plan Project of Tianjin (22YFYSHZ00290), independent innovation project of ICCCAS (SCJC-DT-2023-03).

摘要

摘要: 本研究采用一锅式共沉淀法制备了xZn-CaZr固溶体催化剂并将其应用于CO₂-BDH反应，通过多种手段探明该系列催化剂的理化性质并结合催化性能阐述其构效关系及表面氧化还原机制。研究表明，xZn-CaZr催化剂在Zn含量为6%−12%的情况下形成了Zn物种高度分散的固溶体结构，且氧缺陷的数量与Zn的含量几乎成正比。在xZn-CaZr催化剂上，晶格氧的数量和氧迁移率是决定催化性能的关键因素，其中，0.4Zn-CaZr催化剂展示出最佳的催化活性，而0.2Zn-CaZr催化剂展示出最佳的反应稳定性。该研究为进一步开发绿色高性能的CO₂-BDH催化剂提供了参考价值。
- 异丁烷氧化脱氢 /
- CO₂ /
- ZnCaZr固溶体 /
- 氧化还原循环 /
- 活性与稳定性
Abstract: CO₂-assisted oxidative dehydrogenation of isobutane to isobutene (CO₂-BDH) is an environmentally friendly low-carbon dehydrogenation process, which can effectively utilize greenhouse gas CO₂ while producing value-added product isobutylene. Besides, the soft oxidizing property of CO₂ can break the thermodynamic limitation of dehydrogenation reaction and avoid the problem of deep oxidation, which makes isobutylene highly selective. However, its industrialization is still challenged by the lack of green and efficient catalysts. In this work, xZn-CaZr solid solution catalysts was prepared by one-pot co-precipitation method and applied to CO₂-BDH reaction. The physicochemical properties of all catalysts were investigated by various means, and the structure-activity relationship and surface redox mechanism were described in combination with catalytic performance. The results show that xZn-CaZr catalysts formed solid solution structure with Zn species (6%−12%) existing in highly dispersion state, and the "confinement effect" given by mesoporous skeleton and strong metal-support interactions contributes to the stable distribution of nanoscale sites and generates more Zn-O-Zr interfaces. When excessive Zn species (16%) is added, the ZnO crystal will have obvious phase separation from the solid solution phase. The surface chemical states of different catalysts were analyzed by XPS, and it was found that the relative content of O_β increased first and then decreased with the increase of Zn content. In addition, the surface reduction characteristics of the catalyst indicated that the promotion of an appropriate amount of Zn species can improve the mobility of lattice oxygen, thus 0.4Zn-CaZr catalyst showing the highest relative content of O_β and the best oxygen conductivity. In the activity evaluation of different xZn-CaZr catalyst, 0.4Zn-CaZr catalyst shows the best catalytic dehydrogenation activity but its stability is poor, while 0.2Zn-CaZr catalyst has the best reaction stability. Moreover, the catalytic performance of ZnCaZr catalyst under different C₄H₁₀-CO₂ ratios was also investigated, which indicated that the higher CO₂ content in the feed gas was helpful to improve the catalytic stability and isobutene selectivity. Combined with the surface chemical state and carbon deposition information of the spent catalyst, it was found that the relative content of O_β on the surface of 0.4Zn-CaZr catalyst decreases obviously, but the carbon deposition rate was slow. On the contrary, the relative content of O_β for 0.2Zn-CaZr catalyst decreased less, but its carbon deposition rate was faster. We believe that the amount and mobility of lattice oxygen over xZn-CaZr catalysts were revealed as key factors in determining the catalytic performance. Notably, higher content and superior mobility of lattice oxygen can enhance the redox function of the solid solution catalyst itself and improve the activation performance of CO₂. The strong oxygen supply capacity can ensure the continuous MvK catalytic cycle on the Zn-O-Zr interface, and avoid the deep accumulation of inert carbon deposits while improving the dehydrogenation activity of isobutane and selectivity of isobutene. This study shed lights on the further design and development of green and efficient CO₂-BDH catalysts.
- oxidative dehydrogenation of isobutane /
- CO₂ /
- ZnCaZr solid solution /
- redox mechanism /
- activity and stability
注释:

1) ^#：共同第一作者

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图 1 新鲜催化剂的物理结构表征

Figure 1 Physical structure of the fresh catalyst

(a): N₂ adsorption/desorption isotherms; (b): pore size distributions; (c): XRD patterns; (d): Raman patterns.

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图 2 xZn-CaZr催化剂的化学性质表征

Figure 2 XPS spectra of the xZn-CaZr catalysts

(a): Zn 2p_3/2; (b):O 1s; (c): H₂-TPR patterns; (d): the changing pattern of the relative content of O_β and H₂-TPR peak-1 temperature with the Zn content in xZn-CaZr.

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图 3 xZn-CaZr催化剂的（a）异丁烷转化率，（b）异丁烯选择性，（c）异丁烯收率和（d） CO₂转化率

Figure 3 (a) Isobutane conversion, (b) isobutene selectivity, (c) isobutene yield, and (d) CO₂ conversion of xZn-CaZr catalysts Reaction condition: C₄H₁₀∶CO₂∶N₂ = 1∶5∶4, 570 ℃, atmospheric pressure, GHSV = 6000 mL/(g·h)

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图 4 0.4Zn-CaZr催化剂在不同进气比条件下的CO₂-BDH反应性能

Figure 4 CO₂-BDH reaction performance of 0.4Zn-CaZr catalyst under different feed ratiosReaction condition: C₄H₁₀∶CO₂∶N₂ = 3∶0:27、3∶3:24、3∶9∶18、3∶15∶12, 570 ℃, atmospheric pressure, GHSV = 6000 mL/(g·h)

(a): Isobutane conversion; (b): isobutene selectivity; (c): isobutene yield; (d): Comparison of activity and selectivity at 1 h and 7 h.

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图 5 反应后催化剂的表面氧缺陷及积炭信息分析

Figure 5 Analysis of surface relative content of O_β and carbon deposits of the used catalysts

(a): O 1s spectra of XPS; (b): TG; (c): Raman spectra; (d): C 1s spectra of XPS.

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图 6 （a）反应前后催化剂的表面O_β相对含量及异丁烷转化率损失量; （b）催化剂的表面O_β相对含量与积炭速率的关系; H₂-TPR中的1类还原峰值温度与催化剂的异丁烷起始转化速率（c）及积炭速率（d）的关系

Figure 6 (a) The relative content of O_β and the loss of isobutane conversion before and after reaction; (b) the relationship between the relative content of O_β on the catalyst surface and the coking rate. The relationship between the reduction temperature of peak-1 in H₂-TPR and (c) the initial isobutane conversion, (d) coking rate of the catalysts

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图 7 xZn-CaZr固溶体催化剂表面可能的氧化还原机制

Figure 7 Possible redox mechanism on the surface of xZn-CaZr solid solution catalysts

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表 1 xZn-CaZr催化剂的元素含量及织构参数

Table 1 Elemental content and texture parameters of xZnO-CaZr catalyst

Catalyst	Zn loading/%	Ca loading/%	Zr loading/%	A/(m² g⁻¹)	vp/(cm³ g⁻¹)	dp/nm	ZrO₂ crystal size/nm
CaZr	—	4.6	52.3	210.7	0.75	5.4	15
0.2Zn-CaZr	6.6	4.2	49.0	159.4	0.43	7.4	19
0.4Zn-CaZr	11.4	3.8	46.9	135.8	0.41	8.8	30
0.6Zn-CaZr	15.9	3.1	40.5	76.9	0.46	8.0	36

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表 2 催化剂的表面O_β相对含量和H₂-TPR峰值温度

Table 2 Surface relative content of O_β and H₂-TPR Peak temperature on the fresh catalysts

Catalyst	Relative content of O_β/%	H₂-TPR peak temperature/℃
Catalyst	Relative content of O_β/%	1	2	3
CaZr	20.2	584	738	—
0.2Zn-CaZr	22.1	589	729	824
0.4Zn-CaZr	27.2	575	602	663
0.6Zn-CaZr	25.6	578	708	—

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表 3 反应1h时的异丁烷和CO₂转化率、主要烃类产物选择性及异丁烯产率

Table 3 Conversion of isobutane and CO₂, selectivity of main hydrocarbon products and isobutene yield at 1h reaction

Catalyst	Conversion/%		Selectivity/%						i-C₄H₈ yield/%
Catalyst	i-C₄H₁₀	CO₂	i-C₄H₈	C₃H₈	C₃H₆	C₂H₆	C₂H₄	CH₄	i-C₄H₈ yield/%
CaZr	3.0	1.5	91.3	2.3	1.8	0.9	0.8	2.9	2.7
0.2Zn-CaZr	18.2	5.7	89.5	2.8	2.1	1.3	1.3	3.0	16.2
0.4Zn-CaZr	53.8	13.6	85.5	3.1	2.7	1.9	1.6	5.2	45.9
0.6Zn-CaZr	50.6	12.4	84.2	3.0	2.9	1.8	1.8	6.3	42.6

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表 4 反应后催化剂的XPS分析、表面碳信息及积炭速率

Table 4 Surface relative content of O_β, carbon information and coking rate of used catalysts

Catalyst	Relative content of O_β/%	Coke content/%	I_D/I_G	C_Ⅰ/C_Ⅱ	Coking rate/(mg·mol⁻¹)
CaZr	19.6	—	—	—	—
0.2Zn-CaZr	20.8	0.8	1.75	1.42	5.01
0.4Zn-CaZr	23.7	0.9	1.91	1.51	1.91
0.6Zn-CaZr	21.2	1.6	1.64	1.20	3.87

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