CaO-Ca3Al2O6@Ni-SiO2复合催化剂制备及制氢性能

许凯; 刘璐; 荆洁颖; 冯杰; 李文英

doi:10.19906/j.cnki.JFCT.2022057

CaO-Ca₃Al₂O₆@Ni-SiO₂复合催化剂制备及制氢性能

doi: 10.19906/j.cnki.JFCT.2022057

太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 山西太原 030024

基金项目: 国家重点研发计划（2019YFC1906804-03）资助

详细信息

作者简介:
许凯（1997-），男，山西临汾人，硕士研究生，化学工程专业，主要从事能源化工领域催化剂的研制

通讯作者:
Tel: 86-351-6018453, E-mail: jingjieying@tyut.edu.cn

中图分类号: TQ426
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出版历程
- 收稿日期: 2022-05-02
- 修回日期: 2022-06-27
- 录用日期: 2022-07-04
- 网络出版日期: 2022-07-11
- 刊出日期: 2022-12-28

Preparation and hydrogen production performance of CaO-Ca₃Al₂O₆@Ni-SiO₂ composite catalyst

State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China

Funds: The project was supported by National Key Research and Development Program of China (2019YFC1906804-03)

摘要

摘要: 吸附强化CH₄/H₂O重整制氢技术通过原位移除反应产生的CO₂实现一步法制备高浓度H₂，但该技术常用复合催化剂中的吸附组分CaO在吸脱附CO₂时的体积变化会造成复合催化剂结构的坍塌，同时活性组分Ni也被反应生成的CaCO₃包埋，造成催化和吸附性能的下降，严重影响制取H₂的浓度。本研究利用阳离子表面活性剂辅助刻蚀的机理采用自模板法制备了CaO-Ca₃Al₂O₆@Ni-SiO₂复合催化剂。在吸附强化CH₄/H₂O重整制氢实验中，该复合催化剂制氢浓度达到99.6%，且10次循环后制氢浓度为97.3%，其高活性高稳定性归因于复合催化剂中的吸附组分CaO-Ca₃Al₂O₆在反应-再生循环过程中体积反复膨胀收缩的过程均在SiO₂空腔内进行，不会造成复合催化剂结构的坍塌，同时复合催化剂制备过程中采用SiO₂包覆活性组分Ni防止了其在脱碳再生过程中团聚失活，但结构表征发现，复合催化剂的催化组分中仅有一部分是以Ni为核、SiO₂为壳的核壳结构，还存在部分Ni直接负载在壳层SiO₂上，这是导致10次循环反应中CH₄转化率从99.5%降至91.8%的原因。
- 吸附强化 /
- 制氢 /
- 复合催化剂 /
- CO₂吸附 /
- 循环稳定性
Abstract: Sorption-enhanced steam methane reforming achieves one-step production of high purity hydrogen by in-situ removal of CO₂. However, the volume change of the adsorption component CaO in the composite catalyst during the adsorption and desorption of CO₂ generally caused the structure collapse of the composite catalyst. At the same time, the active component Ni would also be embedded by the generated CaCO₃, resulting in the decline of catalytic and adsorption performance and seriously affecting the purity of hydrogen production. How to prepare bifunctional composite catalyst with high stability is one of the key problems to be solved in the industrial application of this technology. In this work, CaO-Ca₃Al₂O₆@Ni-SiO₂ composite catalyst was prepared by the self-template approach using the cationic surfactant-assisted etching mechanism. In the experiment of hydrogen production by adsorption enhanced CH₄/H₂O reforming, the hydrogen production concentration over the composite catalyst reached 99.6%, and it still remained 97.3% after 10 cycles, which was closely related to the special structure of the prepared CaO-Ca₃Al₂O₆@Ni-SiO₂ composite catalyst. When the reaction was proceeded, the repeated expansion and contraction of CaO-Ca₃Al₂O₆ volume in the composite catalyst was performed in the SiO₂ cavity and would not cause the structure collapse of the composite catalyst. At the same time, the SiO₂ coating on catalytic component Ni could prevent its agglomeration and deactivation during the decarburization and regeneration process. However, it was found that only part of the catalytic component Ni possessed a core-shell structure with Ni as the core and SiO₂ as the shell, and there were some Ni directly loaded on the shell SiO₂, leading to CH₄ conversion dropping from 99.5% to 91.8% in 10 cycles.
- sorption-enhanced /
- hydrogen production /
- composite catalyst /
- CO₂ adsorption /
- stability

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FIG. 2028. FIG. 2028.

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图 1 复合催化剂CaO-Ca₃Al₂O₆@Ni-SiO₂的形成过程

Figure 1 Formation process of composite catalyst CaO-Ca₃Al₂O₆@Ni-SiO₂

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图 2 SiO₂对复合催化剂CO₂吸附性能的影响

Figure 2 Effect of SiO₂ on CO₂ adsorption performance of composite catalyst

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图 3 单次反应和10次反应的各产物含量和CH₄转化率

Figure 3 Concentration of each product and CH₄ conversion in the first and tenth reactions (a): the first reaction; (b): 10 reactions

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图 4 Ni/ CaO-Ca₃Al₂O₆重整反应中各产物含量和CH₄转化率

Figure 4 Concentration of each product and CH₄ conversion in the reforming reaction of Ni/ CaO-Ca₃Al₂O₆

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图 5 反应前后复合催化剂的XRD谱图

Figure 5 XRD patterns of the composite catalyst before and after the reaction

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图 6 不同预处理温度下复合催化剂的H₂-TPR谱图

Figure 6 H₂-TPR profiles of composite catalysts at different pretreatment temperatures

(a): H₂-TPR profile of CaO-Ca₃Al₂O₆@Ni-SiO₂ and CaO-Ca₃Al₂O₆ under 300 ℃ pretreatment; (b): H₂-TPR profile of CaO-Ca₃Al₂O₆@Ni-SiO₂ under 600 ℃ pretreatment

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图 7 复合催化剂CaO-Ca₃Al₂O₆@Ni-SiO₂的失重

Figure 7 Weight loss of composite catalyst CaO-Ca₃Al₂O₆@Ni-SiO₂

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图 8 反应前后CaO-Ca₃Al₂O₆@Ni-SiO₂的SEM图和EDS图

Figure 8 SEM and EDS mapping of CaO-Ca₃Al₂O₆@Ni-SiO₂

((a), (b)): Before reaction；((c), (d)): After reaction

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图 9 反应前后复合催化剂的TEM照片（（a）、（b））反应前CaO-Ca₃Al₂O₆@Ni-SiO₂；（（c）、（d））反应后CaO-Ca₃Al₂O₆@Ni-SiO₂）

Figure 9 TEM images of composite catalysts

((a), (b): Before reaction CaO-Ca₃Al₂O₆@SiO₂；((c), (d)): After reaction CaO-Ca₃Al₂O₆ @Ni-SiO₂)

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图 10 CaO-Ca₃Al₂O₆@Ni-SiO₂复合催化剂的结构

Figure 10 Structure of CaO-Ca₃Al₂O₆@Ni-SiO₂ composite catalyst

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表 1 不同复合催化剂的制氢性能

Table 1 Hydrogen production performance of different composite catalysts

Catalysis	Reaction condition		Regeneration condition		CH₄ conversion/%		H₂ concentration/%		Tenth cyclic reaction		Number of cycles
Catalysis	temp./℃	H₂O/CH₄	temp./ ℃	atmosphere /(mL·min⁻¹)	initial	stabilization	initial	stabilization	CH₄/ %	H₂/ %	Number of cycles
CaO-Ca₃Al₂O₆@Ni-SiO₂	600	4.8	750	N₂(100)	99.5	91.8	99.6	97.3	91.8	97.3	10
Ru/Ca₃Al₂O₆-CaO^[20]	550	4	750	N₂(50)	98.0	97.0	98.1	96.0	97.0	96.0	10
Ni-CaO-Ca₁₂Al₁₄O₃₃^[21]	600	3	−	−	−	−	88.0	−	−	−	1
CaO-Ca₁₂Al₁₄O₃₃-Ni^[22]	600	3	750	N₂	96.5	93.2	90.9	87.5	93.5	87.7	10
CaO-NiO/CaZrO₃^[23]	650	3	800	air	95.4	97.5	94.3	85.6	97.0	95.3	10
Ni-CaO-Ca₁₂Al₁₄O₃₃^[24]	650	3	−	−	96.0	−	90.0	−	−	−	1
Ce-Ni₁₀Co₃₀/HTlc^[25]	500	6	500	excessive H₂O	95.7	−	99.0	90.0	−	93.4	21
Co₃O₄/SiO₂/CeO₂-CaO^[26]	550	3	750	Ar	98.8	97.6	96.0	93.0	−	−	8
Ni/Al₂O₃/CaO^[27]	600	3	−	−	98.0	−	95.0	−	−	−	1
Ni-CaO-Ca₁₂Al₁₄O₃₃^[28]	640	3	900	N₂	89.0	82.0	90.0	85.0	−	−	4
CaO-Ca₉Al₆O₁₈@ Ca₅Al₆O_14/Ni^[11]	650	3	800	N₂(100)	93.3	90.5	93.5	93.5	−	93.5	60
Ni@TiO₂-CaO/Al₂O₃^[12]	650	4	800	N₂	86.3	92.7	88.0	92.0	87.2	91.5	36

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表 2 复合催化剂CaO-Ca₃Al₂O₆@Ni-SiO₂的组成

Table 2 Composition of composite catalyst CaO-Ca₃Al₂O₆@Ni-SiO₂

Substance	Ni	CaO	Ca₃Al₂O₆	SiO₂
Content*w/%	8.98	66.84	19.98	4.2
*The composition measured by ICP-OES and calculated by normalization method

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