透水NaA分子筛膜强化的CO2加氢高效制甲醇

doi:10.16085/j.issn.1000-6613.2023-1936

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2834-2842.DOI: 10.16085/j.issn.1000-6613.2023-1936

• 二氧化碳捕集与资源化利用 • 上一篇

透水NaA分子筛膜强化的CO₂加氢高效制甲醇

李海鹏¹^,²(), 吴桐¹^,³, 王琪¹^,³, 郜时旺¹^,³(), 王晓龙¹, 李旭¹^,⁴, 高新华²(), 年佩², 魏逸彬²()

^1.中国华能集团清洁能源技术研究院有限公司，北京 102209
^2.宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^3.高效灵活煤电及碳捕集利用封存全国重点实验室，北京 100031
^4.二氧化碳捕集与处理北京市重点实验室，北京 102209

收稿日期:2023-11-03 修回日期:2024-03-27 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 郜时旺,高新华,魏逸彬
作者简介:李海鹏（1999—），男，硕士研究生，研究方向为CO₂催化转化。E-mail：2891861797@qq.com。
基金资助:
宁夏重点研发计划(2023BDE03001);华能国际科技项目(HNKJ20-H58);宁夏自然科学基金(2023AAC05003)

Effective methanol production by CO₂ hydrogenation using water-permeable NaA zeolite membrane

LI Haipeng¹^,²(), WU Tong¹^,³, WANG Qi¹^,³, GAO Shiwang¹^,³(), WANG Xiaolong¹, LI Xu¹^,⁴, GAO Xinhua²(), NIAN Pei², WEI Yibin²()

^1.Institute of Clean Energy Technology, China Huaneng Group Co. , Ltd. , Beijing 102209, China
^2.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^3.National Key Laboratory of Carbon Capture and Utilization Sequestration and Efficient and Flexible Coal Power Generation, Beijing 100031, China
^4.Beijing Key Laboratory for Treatment and Capture of Carbon Dioxide, Beijing 102209, China

Received:2023-11-03 Revised:2024-03-27 Online:2024-05-15 Published:2024-06-15
Contact: GAO Shiwang, GAO Xinhua, WEI Yibin

摘要/Abstract

摘要：

近年来，利用可再生能源产生的绿氢与CO₂反应制备甲醇备受关注。然而，由于CO₂催化加氢反应受热力学平衡限制，CO₂的转化率与甲醇选择性较低；另外，副产物水易导致催化剂失活。本研究采用母液晶种法在 α-Al₂O₃膜管外制备了无缺陷的单通道NaA分子筛外膜，通过在膜管外填充Cu基催化剂，构建了一种分子筛膜-催化剂反应分离双功能反应体系，以同时实现CO₂加氢生成甲醇和在线选择性除水。通过XRD、SEM、N₂等温吸附-脱附、H₂-TPR表征技术对NaA分子筛膜和催化剂进行理化性质表征，并在膜反应器上对催化剂的CO₂催化加氢性能进行评价。结果表明，与传统固定床反应器对比，本反应体系可有效拉动反应平衡，大幅提高CO₂转化率。在250℃、3MPa条件下，CO₂转化率由3.34%提高至28.78%，甲醇收率由3.28%提高至27.62%。

关键词: 二氧化碳, 加氢, 甲醇, Cu基催化剂, 膜, 反应器

Abstract:

In recent years, the production of methanol by CO₂ hydrogenation with green hydrogen produced from renewable energy sources has received a lot of attention. However, the CO₂ conversion and methanol selectivity of the reaction are limited by the thermodynamic equilibrium of CO₂ catalytic hydrogenation reaction. Moreover, the presence of water as a byproduct usually leads to catalyst deactivation. In this study, a mother liquid seeding method was used to prepare defect-free single-channel NaA zeolite membrane. Then Cu-based catalysts were filled on the membrane to create a zeolite membrane-catalyst bifunctional reaction system that allowed for the simultaneous hydrogenation of CO₂ to produce methanol and the on-line selective removal of water. XRD, SEM, N₂ isothermal adsorption-desorption, and H₂-TPR were used to characterize the physical and chemical properties of the NaA zeolite membranes and the catalysts. The catalysts performance for CO₂ hydrogenation were evaluated by the membrane reactor. The results showed that the reaction system can significantly increase the CO₂ conversion and effectively drive the reaction equilibrium forward compared with the conventional fixed-bed reactor. The CO₂ conversion was increased from 3.34% to 28.78% and the methanol yield was promoted from 3.28% to 27.62% at 250℃ and 3MPa.

Key words: carbon dioxide, hydrogenation, methanol, Cu-based catalysts, membranes, reactor

中图分类号:

O643

李海鹏, 吴桐, 王琪, 郜时旺, 王晓龙, 李旭, 高新华, 年佩, 魏逸彬. 透水NaA分子筛膜强化的CO₂加氢高效制甲醇[J]. 化工进展, 2024, 43(5): 2834-2842.

LI Haipeng, WU Tong, WANG Qi, GAO Shiwang, WANG Xiaolong, LI Xu, GAO Xinhua, NIAN Pei, WEI Yibin. Effective methanol production by CO₂ hydrogenation using water-permeable NaA zeolite membrane[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2834-2842.

图/表 12

图1 NaA分子筛膜反应器评价装置图

图2 NaA分子筛膜加氢反应前后的XRD谱图

图3 NaA分子筛膜反应前后的SEM图

图4 Cu基催化剂在还原前、还原后和反应后的XRD谱图

图5 Cu基催化剂不同尺度的SEM图

表1 Cu基催化剂的元素含量分布、比表面积及孔结构参数

催化剂

ICP（样品元素所占比例）/%

比表面积

/m²·g^-1

总孔容

/cm³·g^-1

平均孔径

/nm

图6 Cu基催化剂的N2等温吸附-脱附曲线

图7 Cu基催化剂的孔径分布

图8 Cu基催化剂的H2-TPR谱图

表2 不同反应器类型下CO2加氢制甲醇的催化活性评价

反应器类型

CO₂转化率

CH₃OH选择性

CO选择性

CH₃OH收率

α-Al₂O₃膜

图9 不同温度下的CO2加氢制甲醇的催化性能

表3 不同吹扫气流速下CO2加氢制甲醇的催化活性评价

流速 /mL·min^-1	CO₂转化率 /%	CH₃OH选择性 /%	CO选择性 /%	CH₃OH收率 /%
0	28.78	95.97	4.03	27.62
1.8	26.59	95.35	4.65	25.35
3.8	12.75	89.67	10.33	11.43
15.2	11.59	80.79	19.21	9.36
22.7	11.11	80.03	19.97	8.89

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透水NaA分子筛膜强化的CO₂加氢高效制甲醇

Effective methanol production by CO₂ hydrogenation using water-permeable NaA zeolite membrane

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