甲醇水蒸气重整制氢CuAl<sub>2</sub>O<sub>4</sub>催化材料的研究

乔韦军; 张楷文; 张娜; 张磊; 庆绍军; 高志贤

甲醇水蒸气重整制氢CuAl₂O₄催化材料的研究

乔韦军¹,
张楷文¹,
张娜²,
张磊^1, ,,
庆绍军³,
高志贤^1, ,

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
2.
抚顺职业技术学院化学工程系, 辽宁抚顺 113122
3.
中国科学院山西煤炭化学研究所, 山西太原 030001

基金项目:

国家自然科学基金 21376237

辽宁省教育厅科学研究经费项目 L2019038

辽宁省自然科学基金面上项目 2019-MS-221

详细信息

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2020-07-09
- 修回日期: 2020-07-28
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-08-10

Study on CuAl₂O₄ catalytic material for methanol steam reforming

1.
Institute of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Department of Chemical Engineering, Fushun Vocational Technology Institute, Fushun 113122, China
3.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds:

the National Natural Science Foundation of China 21376237

Scientific Research Funds project of Liaoning Education Department L2019038

the Natural Science Fund in Liaoning Province 2019-MS-221

More Information

Corresponding author: ZHANG Lei, E-mail: lnpuzhanglei@163.com; GAO Zhi-xian, E-mail: gaozx@sxicc.ac.cn

摘要

摘要: 以γ-Al₂O₃为原料采用原位合成法制备CuAl₂O₄催化材料，通过XRF、XRD、BET和H₂-TPR等手段对催化材料进行表征，考察铜铝物质的量比对CuAl₂O₄催化材料结构、性质及其催化甲醇水蒸气重整制氢性能的影响。结果表明，不同铜铝物质的量比主要影响了铜物种的还原性能，从而影响了其催化甲醇水蒸气重整制氢的性能。当铜铝物质的量比为1：2时，CuAl₂O₄催化材料的催化性能较好，在反应温度为260℃，水醇物质的量比为1.2，甲醇气体空速为800 h^-1时，甲醇转化率为100%，产氢速率为895 mL/（kg·s）。
- CuAl₂O₄ /
- 甲醇水蒸气重整 /
- 氢气 /
- 原位合成法
Abstract: The CuAl₂O₄ catalytic material was in-situ synthesized using γ-Al₂O₃ as raw material. The catalytic material was characterized by XRF, XRD, BET and H₂-TPR. The effect of the copper-aluminum molar ratios on the structure and properties of CuAl₂O₄ spinel catalytic material and its performance in hydrogen production from methanol steam reforming were investigated. The results show that the copper-aluminum molar ratios affects reduction performance of copper species, which affects its performance in catalyzing methanol steam reforming to produce hydrogen. When the copper-aluminum molar ratios is 1:2, CuAl₂O₄ catalytic material has better catalytic performance. When the reaction temperature is 260℃, with a water-methanol molar ratio of 1.2 and methanol gas hourly space velocity of 800 h^-1, the methanol conversion reaches 100%, the hydrogen production rate is 895 mL/(kg·s).
- CuAl₂O₄ /
- methanol steam reforming /
- hydrogen /
- in-situ synthesis

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图 1 CuAl₂O₄-t催化材料的XRD谱图

Figure 1 XRD spectra of CuAl₂O₄-t catalytic materials

a: CuAl₂O₄-1; b: CuAl₂O₄-2; c: CuAl₂O₄-4; d: CuAl₂O₄-16; e: γ-Al₂O₃

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图 3 CuAl₂O₄-t催化材料的氢气程序升温还原谱图

Figure 3 H₂-TPR spectra of CuAl₂O₄-t catalytic materials

a: CuAl₂O₄-1; b: CuAl₂O₄-2; c: CuAl₂O₄-4; d: CuAl₂O₄-16

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图 2 CuAl₂O₄-t催化材料的N₂吸附-脱附等温线

Figure 2 N₂ adsorption-desorption isotherms of CuAl₂O₄-t catalytic materials

a: CuAl₂O₄-1; b: CuAl₂O₄-2; c: CuAl₂O₄-4; d: CuAl₂O₄-16; e: γ-Al₂O₃

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图 4 CuAl₂O₄-t催化材料催化活性曲线

Figure 4 Catalytic activity curve of CuAl₂O₄-t catalytic materials (reaction conditions: atmospheric, GHSV=800 h^-1, W/M=1.2 :1, no carrier gas)

a: CuAl₂O₄-1; b: CuAl₂O₄-2; c: CuAl₂O₄-4; d: CuAl₂O₄-16; e: equil

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图 5 反应温度对催化剂CO摩尔含量的影响

Figure 5 Effect of reaction temperature on catalyst CO content

(reaction conditions: atmospheric, GHSV=800 h^-1, W/M=1.2 :1, no carrier gas)

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表 1 CuAl₂O₄-t催化材料的元素含量

Table 1 Elemental content of CuAl₂O₄-t catalytic materials

Catalyst	Content of element w/%						Al /Cu (mol ratio)
Catalyst	Cu^a	Cu^b	Al^a	Al^b	O^a	O^b	Al /Cu (mol ratio)
CuAl₂O₄-1	45.9	48.9	21.6	20.6	32.5	30.5	0.99
CuAl₂O₄-2	34.7	35.1	28.3	29.7	37.0	35.2	1.99
CuAl₂O₄-4	21.7	22.5	38.6	38.0	39.7	39.5	3.97
CuAl₂O₄-16	6.7	7.1	48.5	48.2	44.8	44.7	15.97
^a: theoretical content；^b: actual content

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表 2 CuAl₂O₄-t催化材料和γ-Al₂O₃的比表面积及孔结构参数

Table 2 Specific surface area and pore structure parameters of CuAl₂O₄-t catalytic materials and γ -Al₂O₃

Catalyst	A_BET /(m²·g^-1)	Bore diameter d/nm
CuAl₂O₄-1	18.6	3.42
CuAl₂O₄-2	26.2	3.04
CuAl₂O₄-4	57.6	18.14
CuAl₂O₄-16	89.9	18.15
γ-Al₂O₃	145.6	17.89

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表 3 CuAl₂O₄-t催化材料还原峰面积及峰面积占比

Table 3 Reduction peak area and area content of CuAl₂O₄-t catalytic materials

Catalyst	Peak area A/(a.u.)			Area /%
Catalyst	peak α	peak β	peak γ	peak α	peak β	peak γ
CuAl₂O₄-1	43242	18474	4562	65	28	7
CuAl₂O₄-2	6430	25594	1737	19	76	5
CuAl₂O₄-4	6170	9583	3125	33	51	16
CuAl₂O₄-16	3934	1209	325	72	22	6

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表 4 催化材料的产氢速率对比

Table 4 Hydrogen production rate compare of catalytic materials

Catalyst	Reaction temperature t/℃	Water/methanol w_mol/%	GHSV /h^-1	H₂ production rate^b w/(mL·kg^-1·s^-1)
CuAl₂O₄-1	260	1.2:1	800	633
CuAl₂O₄-2	260	1.2:1	800	895
CuAl₂O₄-4	260	1.2:1	800	820
CuO/CeO₂-R^[18]	240	1.2:1	800	378
CuO/CeO₂^[20]	280	1.2:1	800	380
CuZnCeZr^[21]	240	1.2:1	1200	510
Zn_0.5Ce₁Zr₉O_x^[22]	450	1.4:1	1500	808
GHSV: methanol gas hourly space velocity

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