制备方法对InZr复合氧化物/SAPO-34催化剂CO<sub>2</sub>加氢制备低碳烯烃性能的影响

郭帅; 冯礼奎; 于志勇; 许狄; 刘凯迪; 宋小宁; 程一杰; 曹求洋; 王光辉; 定明月

doi:10.1016/S1872-5813(24)60433-0

制备方法对InZr复合氧化物/SAPO-34催化剂CO₂加氢制备低碳烯烃性能的影响

doi: 10.1016/S1872-5813(24)60433-0

郭帅^{1, 2,},
冯礼奎^2,,
于志勇^{1, 2,},
许狄^3, ,,
刘凯迪^3,,
宋小宁²,
程一杰^{1, 2,},
曹求洋^2,,
王光辉^1,,
定明月^3, ,

1.
杭州意能电力技术有限公司, 浙江杭州 310014
2.
国网浙江省电力有限公司电力科学研究院, 浙江杭州 310014
3.
武汉大学动力与机械学院, 湖北武汉 430072

基金项目: 校企合作项目“电厂烟气中二氧化碳捕集制备低碳烯烃的催化剂与工艺研究”资助

详细信息

通讯作者:
x_d@whu.edu.cn

E-mail: dingmy@whu.edu.cn

中图分类号: O643.3
计量
- 文章访问数: 15
- HTML全文浏览量: 19
- PDF下载量: 9
- 被引次数: 0
出版历程
- 收稿日期: 2023-12-05
- 修回日期: 2024-01-07
- 录用日期: 2024-01-16
- 网络出版日期: 2024-03-26

Effects of preparation methods on the performance of InZr/SAPO-34 composite catalysts for CO₂ hydrogenation to light olefins

GUO Shuai^{1, 2
,},
FENG Likui^2
,,
YU Zhiyong^{1, 2
,},
XU Di^{3
, ,},
LIU Kaidi^3
,,
SONG Xiaoning²,
CHENG Yijie^{1, 2
,},
CAO Qiuyang^2
,,
WANG Guanghui^1
,,
DING Mingyue^{3
, ,}

1.
E-energy Technology Co., LTD, Hangzhou 310014, China
2.
State Grid Zhejiang Electric Power Co., LTD. Research Institute, Hangzhou 310014, China
3.
School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, China

Funds: The project was supported by the School-Enterprise Cooperation Project “Study on catalyst and process for light olefins synthesis from carbon dioxide in flue gas of power plant”.

摘要

摘要: 低碳烯烃是重要的化工原料，乙烯更是作为衡量一个国家石油化工发展水平的重要标志，使用CO₂催化加氢制备低碳烯烃是实现CO₂高值化利用的重要途径。在众多催化剂中，InZr复合氧化物/SAPO-34催化剂因其高低碳烯烃选择性和高稳定性展现出潜在的研究和应用前景。本工作研究了不同制备方法对InZr复合氧化物/SAPO-34催化剂CO₂加氢制备低碳烯烃的影响，结果表明，共沉淀法制备的催化剂具有最高的催化活性，溶胶凝胶-沉积法制备的催化剂具有最高的低碳烯烃选择性，并结合多种表征手段揭示了InZr复合氧化物/SAPO-34催化剂内在构效关系。
- CO₂催化加氢 /
- 低碳烯烃 /
- InZr复合氧化物 /
- SAPO-34 /
- 构效关系
Abstract: Light olefins are of great importance as chemical raw materials, and ethylene is a crucial symbol to evaluate the development level of petrochemical industry. Catalytic hydrogenation of CO₂ to light olefins is one of the most vital approaches to utilize CO₂with high added valued. InZr/SAPO-34 composite catalyst shows prominent potential in research and application because of their high light olefins selectivity and high stability in CO₂ hydrogenation. In this study, the effects of different preparation methods of InZr/SAPO-34 composite catalyst for CO₂ hydrogenation to light olefins were studied in depth. The catalyst prepared by co-precipitation method showed the highest catalytic activity, and the catalyst prepared by sol-gel-precipitation method showed the highest light olefins selectivity. The structure-activity relationship of InZr/SAPO-34 catalysts were revealed by various characterization methods.
- CO₂ hydrogenation /
- light olefins /
- InZr composite oxide /
- SAPO-34 /
- structure-activity relationship

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图 1 （a）不同方法制备InZr复合氧化物和（b）商业SAPO-34分子筛的XRD谱图

Figure 1 XRD pattens of (a) InZr composite oxides prepared by different methods and (b) commercial SAPO-34 zeolite

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图 2 系列InZr复合氧化物400 ℃ N₂处理后XPS谱图

Figure 2 XPS spectra of InZr composite oxides after treated at 400 ℃ in N₂

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图 3 系列InZr复合氧化物H₂-TPR谱图

Figure 3 H₂-TPR results of InZr composite oxides

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图 4 （a）InZr-cp/SAPO-34和（b）InZr-sgpr/SAPO-34催化剂在不同反应温度下的CO₂加氢性能

Figure 4 CO₂ hydrogenation performance of (a) InZr-cp/SAPO-34 and (b) InZr-sgpr/SAPO-34 catalysts at different reaction temperatures

Reaction conditions: H₂/CO₂=3, 2 MPa, 6000 mL/(g·h).

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图 5 InZr-cp/SAPO-34和InZr-sgpr/SAPO-34催化剂CO₂加氢制丙烯表观活化能

Figure 5 Apparent activation energy of CO₂ hydrogenation to propylene on InZr-cp/SAPO-34 and InZr-sgpr/SAPO-34 catalysts

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图 6 反应后催化剂的结构表征

Figure 6 Structural characterizations of spent catalysts: (a), (b) XPS, HR-TEM images of (c) InZr-cp and (d) InZr-sgpr, elemental distribution images of (e) InZr-cp and (f) InZr-sgpr

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图 7 （a）−（c）InZr-cp和（d）−（f）InZr-sgpr催化剂不同反应温度原位CO₂加氢DRIFTS谱图

Figure 7 In-situ DRIFTS spectra of CO₂ hydrogenation on (a)−(c) InZr-cp and (d)−(f) InZr-sgpr catalysts at different reaction temperatures

Reaction conditions: H₂/CO₂=3, 2 MPa, 30 mL/min.

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图 8 （a）InZr-cp和（b）InZr-sgpr催化剂时间分辨原位CO₂加氢DRIFTS谱图，（c）*H₃CO/*HCOO峰强度比值随反应时间变化

Figure 8 Time-resolved in-situ DRIFTS spectra of CO₂ hydrogenation on (a) InZr-cp and (b) InZr-sgpr catalysts and (c) *H₃CO/*HCOO peak intensity ratio as a function of reaction time

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图 9 新鲜SAPO-34和反应后复合催化剂SAPO-34的NH₃-TPD谱图

Figure 9 NH₃-TPD spectra of fresh and spent SAPO-34 zeolites

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表 1 系列InZr复合氧化物表面金属元素和氧物种含量

Table 1 Surface content of metal elements and oxygen species on InZr composite oxides

Catalyst	Surface element content/%		In/Zr ratio	O species content/%
Catalyst	In	Zr	In/Zr ratio	O_lattice	O_defect	OH
InZr-cp/SAPO-34	3.83	22.25	0.17	70.7	26.2	3.1
InZr-sg/SAPO-34	3.38	17.94	0.19	81.5	16.7	1.8
InZr-sgim/SAPO-34	5.3	21.13	0.25	77.2	19.1	3.7
InZr-sgpr/SAPO-34	12.52	13.93	0.90	68.1	27.5	4.4

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表 2 InZr复合氧化物/SAPO-34催化剂CO₂加氢制备低碳烯烃性能

Table 2 Catalytic performance of InZr/SAPO-34 catalysts for CO₂ hydrogenation to light olefins

Catalyst	CO₂ conversion/%	CO selectivity/%	Hydrocarbons selectivity/%				O/P ratio	C₂ ⁼−C₄ ⁼ yield/%
Catalyst	CO₂ conversion/%	CO selectivity/%	CH₄	C₂ ⁼−C₄ ⁼	C₂ ⁰−C₄ ⁰	C₅₊	O/P ratio	C₂ ⁼−C₄ ⁼ yield/%
InZr-cp/SAPO-34	26.2	60.9	17.4	41.0	34.0	7.6	1.12	4.20
InZr-sg/SAPO-34	16.8	69.0	3.6	55.9	33.8	6.7	1.49	2.91
InZr-sgim/SAPO-34	15.9	100	N.D.	N.D.	N.D.	N.D.	−	−
InZr-sgpr/SAPO-34	17.5	55.8	2.9	46.2	43.8	7.1	0.98	3.57
Reaction conditions: H₂/CO₂=3, 380 ℃, 3 MPa, 6000 mL/(g·h).

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