Sr和Na改性对ZnZrO x /SAPO-34催化剂及催化合成气制低碳烯烃的影响

doi:10.16085/j.issn.1000-6613.2024-2036

摘要/Abstract

摘要：

通过共沉淀法制备了Sr、Na改性的ZnZrO _x 金属氧化物，考察了Sr和Na助剂的引入对ZnZrO _x /SAPO-34催化剂在合成气制低碳烯烃反应中性能的影响。采用XRD、BET、SEM、XPS和Py-FTIR等表征手段，系统研究了Sr和Na助剂对ZnZrO _x 金属氧化物表面氧空位、酸性和还原性等影响规律。结果表明，Sr和Na提高了ZnZrO _x 氧化物表面氧空位浓度，并且通过Na-ZrO₂界面促进了金属氧化物表面有更多氧缺陷的形成，同时提高了其路易斯酸性，因此在合成气制低碳烯烃反应中，具有较高的CO转化率（21.4%）和低碳烯烃选择性（80.7%）。此外，Sr和Na改性ZnZrO _x 金属氧化物与SAPO-34分子筛混合比例及“亲密度”对CO转化率和低碳烯烃选择性都有重要影响，合适的质量比（1∶1）和较高的“亲密度”（粉末研磨混合）能够使两种活性位点的协同作用达到最佳，且具有较好的催化稳定性。

关键词: 合成气, 低碳烯烃, 催化剂, 界面, 氧空位, 稳定性

Abstract:

Sr- and Na-modified ZnZrO _x metal oxides were prepared by the co-precipitation method. The influence of Sr and Na modification on ZnZrO _x /SAPO-34 bifunctional catalysts for the conversion of syngas to lower olefins was investigated. Characterization techniques such as XRD, BET, SEM, XPS and Py-FTIR were employed to investigate the influence of Sr and Na promoters on ZnZrO _x metal oxides, its surface oxygen vacancies, acidity and reducibility, etc. The results showed that the introduction of Sr and Na led to the increase of the surface oxygen vacancies of the ZnZrO _x oxides. Moreover, the Na-ZrO₂ interface promoted the formation of more oxygen defects on the surface of metal oxides and improved its Lewis acidity. Sr and Na modified ZnZrO _x /SAPO-34 bifunctional catalysts possessed a relatively high CO conversion of 21.4% and lower olefins selectivity of 80.7% in the conversion of syngas to lower olefins. Both the mass ratio and the intimacy between the Sr and Na modified ZnZrO _x_{metal oxide and the molecular sieve SAPO-34 played crucial roles. Specifically, a mass ratio of 1∶1 and a relatively high level of intimacy achieved by grinding and mixing the powders could give the best synergistic effect between the two active sites, thereby endowing the catalyst with good catalytic stability.}

Key words: syngas, lower olefins, catalyst, interface, oxygen vacancy, stability

中图分类号:

TQ013

王廷, 孙燕, 孙启文. Sr和Na改性对ZnZrO _x /SAPO-34催化剂及催化合成气制低碳烯烃的影响[J]. 化工进展, 2025, 44(12): 6953-6962.

WANG Ting, SUN Yan, SUN Qiwen. Influence of Sr and Na modification on ZnZrO _x /SAPO-34 bifunctional catalysts and its performance in catalytic conversion of syngas to lower olefins[J]. Chemical Industry and Engineering Progress, 2025, 44(12): 6953-6962.

图/表 17

图1 不同金属改性的ZnZr氧化物和SAPO-34分子筛的XRD谱图

图2 不同金属改性的ZnZr氧化物TEM图和粒径分布

图3 SAPO-34分子筛的SEM图

图4 NaSrZnZr氧化物和双功能催化剂的SEM和元素分布

图5 SAPO-34分子筛的NH3-TPD图

表1 不同金属改性的ZnZr氧化物和SAPO-34分子筛的织构性质

样品	比表面积/m²·g^-1	孔体积/cm³·g^-1	平均孔径/nm
ZnZr	59.7	0.2	9.4
SrZnZr	68.6	0.1	4.3
NaSrZnZr	56.1	0.1	5.9
SAPO-34	656.5	0.2	1.4

图6 不同催化剂的O 1s XPS谱图

表2 不同催化剂表面O物种的含量

样品	晶格氧（O_L）		氧空位（O_V）		化学吸附氧（O_C）
样品	结合能/eV	含量/%	结合能/eV	含量/%	结合能/eV	含量/%
ZnZr	530.1	61.9	531.6	32.2	533.2	5.9
SrZnZr	529.9	55.8	531.2	35.2	532.8	9.0
NaSrZnZr	529.4	45.6	530.9	43.1	532.4	11.3

图7 不同催化剂的Zr 3d XPS谱图

图8 不同催化剂的吡啶红外谱图

图9 不同催化剂的CO-TPD谱图

图10 不同催化剂的H2-TPR谱图

图11 不同金属改性的ZrZr氧化物对双功能催化剂催化性能的影响

图12 反应空速对NaSrZnZr/SAPO-34双功能催化剂催化性能的影响

图13 金属氧化物和分子筛混合比例对双功能催化剂催化性能的影响

图14 装填方式对双功能催化剂催化性能影响

图15 NaSrZnZr/SAPO-34双功能催化剂的稳定性评价结果

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