Co3O4-CeO2氧化物对丙烷完全氧化的催化性能

引用本文: 朱文军, 陈霄, 金建辉, 邸鑫, 梁长海, 刘中民. Co₃O₄-CeO₂氧化物对丙烷完全氧化的催化性能[J]. 催化学报, 2020, 41(4): 679-690. doi: S1872-2067(19)63523-0 shu

Citation: Wenjun Zhu, Xiao Chen, Jianhui Jin, Xin Di, Changhai Liang, Zhongmin Liu. Insight into catalytic properties of Co₃O₄-CeO₂ binary oxides for propane total oxidation[J]. Chinese Journal of Catalysis, 2020, 41(4): 679-690. doi: S1872-2067(19)63523-0 shu

Co₃O₄-CeO₂氧化物对丙烷完全氧化的催化性能

朱文军 ^a,b, ,
陈霄 ^a, ,
金建辉 ^a, ,
邸鑫 ^a, ,
梁长海 ^a, ,
刘中民 ^b,

a 大连理工大学精细化工国家重点实验室, 先进材料与催化工程实验室, 辽宁大连 116024;
b 中国科学院大连化学物理研究所, 中国科学院洁净能源创新研究院, 甲醇制烯烃国家工程实验室, 辽宁大连 116023
基金项目:
国家重点研发计划（2016YFB0600305）.

摘要: 挥发性有机化合物（VOCs）是全球大气污染物的主要来源，近年来已造成严重的环境问题.催化氧化是一种有效的、经济可行的VOCs去除技术，其研究的关键在于开发高效、稳定的催化剂.在本文中，我们采用柠檬酸法合成了一系列具有不同Co/（Ce+Co）摩尔比的Co₃O₄-CeO₂二元氧化物催化剂，研究了其对丙烷（低碳VOCs）的催化氧化性能.
在催化活性测试中，反应气的组成为0.2 vol.% C₃H₈和5 vol.% O₂，Ar为平衡气，气体总流速为200mL min^-1.实验结果表明，Ce的掺入能够明显提高Co₃O₄的丙烷催化氧化性能，Co₃O₄-CeO₂催化剂的丙烷催化氧化活性顺序为CoCeO_x-70 > CoCeO_x-90 > Co₃O₄ > CoCeO_x-50 > CoCeO_x-20 > CeO₂.当Co/（Ce+Co）摩尔比为70%时，CoCeO_x-70催化剂的丙烷催化氧化性能最好.在丙烷转化率达到90%时，CoCeO_x-70催化剂的反应温度为310℃（GHSV=120000mL h^-1 g^-1），相比于单一的Co₃O₄催化剂的反应温度降低了25℃.
XRD和TEM表征结果显示，在Co₃O₄-CeO₂二元氧化物催化剂中存在Co₃O₄和CeO₂两种晶型，同时随着Ce的掺入，催化剂的粒径明显降低.Raman光谱图显示，Ce的掺入使催化剂的晶格发生畸变，促进催化剂表面氧空位的产生，为催化剂中氧的迁移提供晶格位点.H₂-TPR和C₃H₈-TPSR结果表明，Co₃O₄与CeO₂间存在相互作用，能够提高催化剂的低温还原性能，以促进催化剂的丙烷催化氧化.O₂-TPD和O 1s XPS结果表明，Ce的掺入能够增加催化剂表面活性氧物种的产生，提高催化剂中氧的移动性，从而提高了催化剂对丙烷的催化氧化活性.在对Co₃O₄和CoCeO_x-70催化剂进行in-situDRIFTS表征和简单的动力学研究，我们发现Ce的掺入不改变催化剂的丙烷催化氧化反应路径，其存在能够促进丙烷在催化剂表面的吸附和活化，以提高催化剂的丙烷催化氧化活性.同时，丙酮和酯作为中间物参与到丙烷的催化氧化反应过程中.
此外，我们考察了反应气氛中水蒸气和CO₂的存在对催化剂催化性能的影响.结果表明，CO₂和水蒸气的存在都抑制了催化剂的丙烷催化氧化活性，催化性能随着CO₂和水蒸气浓度的增加而降低.在相同条件下，水蒸气对催化剂催化性能的抑制作用明显大于CO₂的抑制作用，但这种抑制作用会随着反应气中水蒸气和CO₂的消失而消失.在稳定性测试中，CoCeO_x-70催化剂表现出优异的抗水蒸气和CO₂性能.在反应气中存在5 vol.%水蒸气和5 vol.% CO₂的条件下，CoCeO_x-70催化剂在50 h的稳定性测试中均未出现明显的失活现象.同时，经过10次加热和降温循环测试后，催化剂的催化活性也没有发生明显变化，这为CoCeO_x-70催化剂的未来工业化的应用提供了可能.

关键词:

English

Insight into catalytic properties of Co₃O₄-CeO₂ binary oxides for propane total oxidation

a State Key Laboratory of Fine Chemicals & Laboratory of Advanced Materials and Catalytic Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
b Methanol to Olefins National Engineering Laboratory, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
Received Date: 22 August 2019
Revised Date: 30 September 2019
Fund Project:
This work was supported by the National Key R&

Abstract: A series of Co₃O₄-CeO₂ binary oxides with various Co/(Ce+Co) molar ratios were synthesized using a citric acid method, and their catalytic properties toward the total oxidation of propane were examined. The activities of the catalysts decrease in the order CoCeO_x-70 > CoCeO_x-90 > Co₃O₄ > CoCeO_x-50 > CoCeO_x-20 > CeO₂. CoCeO_x-70 (Co/(Ce+Co)=70% molar ratio) exhibits the highest catalytic activity toward the total oxidation of propane, of which the T₉₀ is 310℃ (GHSV=120000 mL h^-1 g^-1), which is 25℃ lower than that of pure Co₃O₄. The enhancement of the catalytic performance of CoCeO_x-70 is attributed to the strong interaction between CeO₂ and Co₃O₄, the improvement of the low-temperature reducibility, and the increase in the number of active oxygen species. In-situ DRIFTS and reaction kinetics measurement reveal that Ce addition does not change the reaction mechanism, but promotes the adsorption and activation of propane on the catalyst surface. The addition of water vapor and CO₂ in reactant gas has a negative effect on the propane conversion, and the catalyst is more sensitive to water vapor than to CO₂. In addition, CoCeO_x-70 exhibits excellent stability and reusability in water vapor and CO₂ atmosphere.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

Co₃O₄-CeO₂氧化物对丙烷完全氧化的催化性能

English

Insight into catalytic properties of Co₃O₄-CeO₂ binary oxides for propane total oxidation

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