TiO2掺杂CuMnCe/Al2O3催化剂对甲烷催化燃烧脱氧反应的影响

袁善良; 兰海; 薄其飞; 张彪; 肖熙; 蒋毅

TiO₂掺杂CuMnCe/Al₂O₃催化剂对甲烷催化燃烧脱氧反应的影响

袁善良^{1, 2},
兰海^{1, 2},
薄其飞^{1, 2},
张彪¹,
肖熙^{1, 2},
蒋毅^1, ,

1.
中国科学院成都有机化学有限公司, 中国科学院成都有机化学研究所, 四川成都 610041
2.
中国科学院大学, 北京 100049

详细信息

通讯作者:
Tel:13678048407,E-mail:yjiang@cioc.ac.cn

中图分类号: TQ426;TQ519
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- 被引次数: 0
出版历程
- 收稿日期: 2016-11-10
- 修回日期: 2016-12-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-02-10

Effect of TiO₂ doping on methane catalytic combustion deoxidation of CuMnCe/Al₂O₃ catalyst

YUAN Shan-liang^{1, 2},
LAN Hai^{1, 2},
BO Qi-fei^{1, 2},
ZHANG Biao¹,
XIAO Xi^{1, 2},
JIANG Yi^{1
, ,}

1.
Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences, Chengdu Institute of Organic Chemistry, Chengdu 610041, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 以掺杂了不同TiO₂含量的Al₂O₃作为载体，通过等体积浸渍法制备了一系列不同TiO₂含量的CuMnCe/TiO₂-Al₂O₃催化剂，用BET、H₂-TPR、XRD和XPS表征技术对催化剂物理化学性质进行表征，并考察了催化剂在含甲烷气脱氧反应中的催化性能。结果表明，在载体中添加TiO₂对催化剂活性组分的晶相结构和分散度没有明显影响；但有效改善了Al₂O₃载体抗烧结能力；增加了CuMnCe/Al₂O₃催化剂表面Ce³⁺/（Ce³⁺+Ce⁴⁺）的相对含量，从而提高了活性氧的移动性，且使催化剂表面可氧化还原物种含量和表面吸附氧O_sur/（O_sur+O_latt）的含量增多。有效改善了催化剂在含甲烷气催化燃烧脱氧上的催化活性。其中，CuMnCe/4% TiO₂-Al₂O₃表现出最优的催化活性，在387℃时可使含甲烷气中氧气的转化率达到100%。
- TiO₂ /
- Al₂O₃ /
- 脱氧 /
- CuMnCe催化剂 /
- 吸附氧
Abstract: CuMnCe/TiO₂-Al₂O₃ catalysts with different TiO₂ contents were prepared by the co-impregnation method and characterized by BET, XRD, XPS and H₂-TPR techniques.The catalytic performance in methane deoxidation reaction were investigated using CGK-5A fixed bed reactor.Results showed that doping some TiO₂ in the Al₂O₃support has no effect on the crystalline structure of the active ingredient.But it can effectively improve Al₂O₃ support sintering resistance and thermal stability, furthermore, it increases content of Ce³⁺/(Ce³⁺+Ce⁴⁺) in the CuMnCe/Al₂O₃ catalysts, which improves the mobility of oxygen.Besides, the content of adsorbed oxygen O_sur/(O_sur+O_latt) and reducible species in the catalyst surface are increased.Thus, effectively, doping some TiO₂ into the Al₂O₃support improved the catalytic activity of deoxygenation catalyst for methane combustion.CuMnCe/4% TiO₂-Al₂O₃ exhibited optimum catalytic activity and oxygen conversion rate reached 100% at 387℃.
- titania /
- alumina /
- deoxygenation /
- CuMnCe catalyst /
- adsorbed oxygen

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图 1 不同催化剂氧转化率随温度的变化

Figure 1 Oxygen conversion vs reaction temperature over different catalysts

■: CuMnCe/Al₂O₃; ●: CuMnCe/4%TiO₂-Al₂O₃;▲: CuMnCe/8%TiO₂-Al₂O₃

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图 2 CuMn₂Ce_1.5/xTiO₂-Al₂O₃的XRD谱图

Figure 2 XRD patterns of the CuMn₂Ce_1.5/xTiO₂-Al₂O₃ catalysts

a: CuMnCe/Al₂O₃; b: CuMnCe/4%TiO₂-Al₂O₃; c: CuMnCe/8%TiO₂-Al₂O₃

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图 3 不同催化剂的Ce 3d和O 1s XPS谱图

Figure 3 Ce 3d and O 1s XPS spectra for diffent catalysts

a: CuMnCe/Al₂O₃; b: CuMnCe/4%TiO₂-Al₂O₃; c: CuMnCe/8%TiO₂-Al₂O₃

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图 4 催化剂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of different catalysts

a: CuMnCe/Al₂O₃; b: CuMnCe/4%TiO₂-Al₂O₃; c: CuMnCe/8%TiO₂-Al₂O₃

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表 1 载体的比表面积和孔结构特性

Table 1 Surface area and pore characteristics of different support

Sample	Surface area A/(m²·g^-1)	Pore volume v/(mL·g^-1)	Average pore size d/nm
Al₂O₃(450 ℃)	199.77	0.442 9	8.87
Al₂O₃(600 ℃)	172.08	0.459 1	10.67
Al₂O₃(800 ℃)	144.19	0.456 2	12.56
TiO₂-Al₂O₃ (450 ℃)	163.48	0.404 6	9.89
TiO₂-Al₂O₃ (600 ℃)	151.54	0.412 1	10.87
TiO₂-Al₂O₃ (800 ℃)	125.31	0.405 7	12.95

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表 2 催化剂表面Ce³⁺以及O_sur的含量和150-350 ℃ 的H₂-TPR氢气消耗峰的面积

Table 2 Ratio of Ce³⁺and O_sur in the catalyst surface by XPS and relative H₂ consumption peak area during H₂-TPR experiment from 150 ℃ up to 350 ℃

Sample	Ce³⁺/( Ce³⁺+ Ce⁴⁺)/%^a	O_sur/(O_sur+O_latt)/%^a	H₂ consume(peak area^b)
CuMnCe/Al₂O₃	45.14	40.65	3 683
CuMnCe/4%TiO₂-Al₂O₃	46.28	41.95	4 421
CuMnCe/8%TiO₂-Al₂O₃	39.62	42.76	4 216
^a： calculated by XPS results; ^b: calculated by H₂-TPR results

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表 3 不同催化剂表相中各元素结合能及各组分的浓度

Table 3 Content and binding energy on the surface of different catalysts

Sample	Binding energy E/eV				Content of catalysts surface w/%
Sample	Cu 2p_3/2	Mn 2p_3/2	O 1s	Al 2p	Cu	Mn	O	Al
CuMnCe/Al₂O₃	933.4	642.2	531.1	74.2	0.24	0.45	52.7	34.3
CuMnCe/4%TiO₂-Al₂O₃	933.2	641.8	531.1	74.2	0.38	0.59	52.1	34.4
CuMnCe/8%TiO₂-Al₂O₃	933.4	642.1	531.1	74.2	0.45	0.80	51.2	35.4

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