柠檬酸络合浸渍法制备的Ag-Mn/γ-Al2O3-TiO2催化剂用于丙烷催化燃烧

程丽军; 刘照; 袁善良; 胡鑫; 张彪; 蒋毅

柠檬酸络合浸渍法制备的Ag-Mn/γ-Al₂O₃-TiO₂催化剂用于丙烷催化燃烧

程丽军^{1, 2},
刘照^{1, 2},
袁善良¹,
胡鑫^{1, 2},
张彪¹,
蒋毅^1, ,

1.
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

基金项目:

四川省科技计划项目 2018GZ0314

详细信息

中图分类号: TQ426
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- 被引次数: 0
出版历程
- 收稿日期: 2019-09-17
- 修回日期: 2019-09-29
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-11-10

Preparation of Ag-Mn/γ-Al₂O₃-TiO₂ catalysts by complexation-impregnation process with citric acid and its application in propane catalytic combustion

CHENG Li-jun^{1, 2},
LIU Zhao^{1, 2},
YUAN Shan-liang¹,
HU Xin^{1, 2},
ZHANG Biao¹,
JIANG Yi^{1
, ,}

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

Funds:

Sichuan Science and Technology Program 2018GZ0314

More Information

Corresponding author: JIANG Yi, Tel:028-85229457, E-mail:yjiang@cioc.ac.cn

摘要

摘要: 采用不同浸渍方法制备了系列Ag-Mn/γ-Al₂O₃-TiO₂催化剂，利用BET、XRD、TEM、XPS和H₂-TPR等技术对催化剂进行了表征，通过丙烷催化燃烧反应考察了催化性能。结果表明，与常规浸渍法相比，柠檬酸络合浸渍法促进了催化剂表面Ag与Mn颗粒的分散及加强了Ag与Mn之间的相互作用，从而提高了活性氧物种的相对含量和催化剂的低温还原性能，进而促进丙烷催化燃烧活性的提升。其中，络合浸渍法制备的Ag₁Mn₃/γ-Al₂O₃-TiO₂催化剂在263℃时丙烷转化率即可达90%。
- 络合浸渍法 /
- Ag-Mn催化剂 /
- 丙烷 /
- 催化燃烧 /
- 相互作用
Abstract: A series of Ag-Mn/γ-Al₂O₃-TiO₂ catalysts were prepared by different impregnation procedures. The catalysts were characterized by BET, XRD, TEM, XPS and H₂-TPR, and the catalytic properties were investigated by propane catalytic combustion. Results show that compared with the conventional impregnation method, complexation-impregnation procedure with citric acid promotes the dispersion of Ag and Mn particles on the surface of catalyst and strengthens the interaction between Ag and Mn, so as to increase the relative content of reactive oxygen species and improve the reducibility of catalysts, which further improves the catalytic activity of propane combustion reaction. Especially, the Ag₁Mn₃/γ-Al₂O₃-TiO₂ catalyst prepared by complexation-impregnation process with citric acid exhibits the best activity for propane catalytic combustion with 90% conversion at 263℃.
- complexation-impregnation /
- Ag-Mn catalysts /
- propane /
- catalytic combustion /
- interaction

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图 1 不同方法制备的Ag-Mn/AlTi催化剂的丙烷催化燃烧活性

Figure 1 Catalytic activity of Ag-Mn/AlTi catalysts with different methods for propane oxidation the feed gas was 0.3% C₃H₈ in air and GHSV=6000mL/(g·h)

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图 2 Ag/Mn物质的量比对丙烷转化的t₅₀和t₉₀的影响

Figure 2 Effect of Ag/Mn molar ratio on t₅₀, t₉₀ of propane conversion

the feed gas was 0.3% C₃H₈ in air and GHSV=6000mL/(g·h)

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图 3 Ag₁Mn₃/AlTi(CA)催化剂在不同空速下的丙烷催化燃烧活性

Figure 3 Propane conversion over the Ag₁Mn₃/AlTi(CA) catalyst under different GHSV conditions

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图 4 Ag₁Mn₃/AlTi(CA)催化剂的反应稳定性评价

Figure 4 Reaction stability with time for propane oxidation over Ag₁Mn₃/AlTi(CA) catalyst

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图 5 催化剂的XRD谱图

Figure 5 XRD patterns of catalysts

a: Ag₄/AlTi; b: Ag₄/AlTi(CA); c: Mn₄/AlTi; d: Mn₄/AlTi(CA); e: Ag₁Mn₃/AlTi; f: Ag₁Mn₃/AlTi(CA)

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图 6 (a) Ag₁Mn₃/AlTi和(b) Ag₁Mn₃/AlTi(CA)催化剂的TEM照片

Figure 6 TEM images of (a) Ag₁Mn₃/AlTi and (b) Ag₁Mn₃/AlTi(CA) catalysts

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图 7 不同催化剂的XPS谱图

Figure 7 XPS patterns of different catalysts

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图 8 催化剂的H₂-TPR谱图

Figure 8 H₂-TPR profiles of catalysts

a: Ag₄/AlTi; b: Ag₄/AlTi(CA); c: Mn₄/AlTi; d: Mn₄/AlTi(CA); e: Ag₁Mn₃/AlTi; f: Ag₁Mn₃/AlTi(CA)

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表 1 不同催化剂的织构性质

Table 1 Textural properties of different catalysts

Sample	Surface area A/ (m²·g^-1)	Pore volume v/ (cm³·g^-1)	Average pore diameter d/nm
AlTi	163	0.41	9.9
Ag₄/AlTi	105	0.31	11.4
Ag₄/AlTi(CA)	112	0.36	10.6
Mn₄/AlTi	94	0.30	10.5
Mn₄/AlTi(CA)	122	0.34	10.4
Ag₁Mn₃/AlTi	93	0.23	9.9
Ag₁Mn₃/AlTi(CA)	126	0.40	11.1

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表 2 催化剂的XPS数据

Table 2 XPS results of different catalysts

Sample	Surface element contents w_mol/%				Ag⁰/ (Ag⁺+Ag⁰)	Mn^δ+/Mn^total			O species contents
Sample	Ag	Mn	O	Al	Ag⁰/ (Ag⁺+Ag⁰)	Mn²⁺	Mn³⁺	Mn⁴⁺	O_Ⅰ	O_Ⅱ	O_Ⅲ
Ag₄/AlTi	1.80	-	64.80	33.40	42.52	-	-	-	32.55	47.65	19.80
Ag₄/AlTi(CA)	4.00	-	64.61	31.39	43.34	-	-	-	28.73	51.76	19.50
Mn₄/AlTi	-	1.08	75.41	23.51	-	22.12	45.18	32.70	34.89	49.23	15.88
Mn₄/AlTi(CA)	-	8.52	61.6	29.88	-	12.28	31.89	55.83	38.97	51.22	9.80
Ag₁Mn₃/AlTi	0.9	1.51	72.7	24.89	33.54	22.56	39.42	38.02	32.41	52.73	14.86
Ag₁Mn₃/AlTi(CA)	1.09	4.72	70.81	23.39	38.33	12.08	28.02	59.90	36.32	54.57	9.11

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