基于蒸发诱导自组装法的高比表面介孔Al2O3的制备及在CO2-CH4重整催化剂中的应用

doi:10.7503/cjcu20150444

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (12): 2475.doi: 10.7503/cjcu20150444

基于蒸发诱导自组装法的高比表面介孔Al₂O₃的制备及在CO₂-CH₄重整催化剂中的应用

莫文龙, 马凤云(), 刘月娥, 刘景梅, 钟梅, 艾沙·努拉洪

煤炭清洁转化与化工过程自治区重点实验室, 新疆大学化学化工学院, 乌鲁木齐 830046

收稿日期:2015-06-05 出版日期:2015-12-10 发布日期:2015-11-17
作者简介:联系人简介: 马凤云, 女, 博士生导师, 主要从事煤、石油和天然气的催化转化利用的研究. E-mail:ma_fy@126.com
基金资助:
国家“八六三”计划项目(批准号: 2015AA050502)、新疆大学博士研究生创新项目(批准号: XJUBSCX-2013008)和先进功能材料新疆维吾尔自治区重点实验室开放课题(No.XJDX0902-2012-02)资助

Preparation of Mesoporous Al₂O₃ with High Specific Surface Area by Evaporation-induced Self-assembly Stategy and Its Application as Ni-Al₂O₃ Catalysts for CO₂-CH₄ Reforming^†

MO Wenlong, MA Fengyun^*(), LIU Yue’e, LIU Jingmei, ZHONG Mei,

Key Laboratory of Coal Clean Conversion & Chemical Engineering Process(Xinjiang Uyghur Autonomous Region),College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China

Received:2015-06-05 Online:2015-12-10 Published:2015-11-17
Contact: MA Fengyun E-mail:ma_fy@126.com
Supported by:
† Supported by the National High Technology Research and Development Program of China(No.2015AA050502), the Xinjiang University Science and Technology Innovation Project for Doctoral Student, China(No.XJUBSCX-2013008) and the Open Project of Key Laboratory of Advanced Functional Materials of Xinjiang Uygur Autonomous Region(No.XJDX0902-2012-02).

摘要/Abstract

摘要：

为提高镍基催化剂的干法重整活性, 采用蒸发诱导自组装法制备了PA0.01, PA0.02, PA0.03和PA0.05系列Al₂O₃载体, 并以水热沉积法制备了相应的4种催化剂, 在800 ℃考察了其在CO₂-CH₄重整反应中的催化性能, 并对载体和催化剂进行了表征分析. 结果表明, P123与异丙醇铝(ISO-AL)摩尔比为0.02时, 所制备的PA0.02载体比表面积最大, 为320.12 m²/g, 相应PAC0.02催化剂比表面积高达280.15 m²/g, 可为反应提供较多的活性位, PAC0.02催化剂的CH₄和CO₂转化率最高, 分别达到91.92%和94.69%; 该催化剂具有较多的NiAl₂O₄尖晶石结构, 其还原峰面积占总还原峰面积的82%, 还原后可获得更多的稳定的活性组分Ni. PAC0.02稳定性好, 反应154 h后CH₄转化率才降至50%以下.

关键词: 介孔Al2O3, Ni基催化剂, CH4-CO2重整反应, 蒸发诱导自组装法

Abstract:

To improve the catalytic performance of nickel-based catalysts for carbon dioxide reforming of methane, four supports, PA0.01, PA0.02, PA0.03 and PA0.05, were prepared by evaporation-induced self-assembly strategy, and the same contents of Ni of the four corresponding catalysts were prepared by hydrothermal-precipitation method. The catalytic performance of these samples for CO₂-CH₄ reforming was tested at 800 ℃. The supports and catalysts were characterized with ICP-AES, N₂ absorption-desorption method, NH₃-TPD, XRD, H₂-TPR, TG-DTG and TEM techniques. It was shown that the specific surface area of PA0.02 was large(320.12 m²/g), and the corresponding PAC0.02 catalyst with area of 280.15 m²/g, which could provide more active sites and improve the activity of samples(the conversion of CH₄ and CO₂ of PAC0.02 was up to 91.92% and 94.69%); the reduction peak area of NiAl₂O₄ in PAC0.02 catalyst was higher than 80% of the total reduction area, indicating that the catalyst had better stability(the conversion of CH₄ for PAC0.02 was about 50% after 154 h experiment).

Key words: Mesoporous alumina, Ni-Al2O3 catalyst, CH4/CO2 reforming, Evaporation-induced self-assembly strategy

中图分类号:

O643.32

TrendMD:

莫文龙, 马凤云, 刘月娥, 刘景梅, 钟梅, 艾沙·努拉洪. 基于蒸发诱导自组装法的高比表面介孔Al₂O₃的制备及在CO₂-CH₄重整催化剂中的应用. 高等学校化学学报, 2015, 36(12): 2475.

MO Wenlong, MA Fengyun, LIU Yue’e, LIU Jingmei, ZHONG Mei, . Preparation of Mesoporous Al₂O₃ with High Specific Surface Area by Evaporation-induced Self-assembly Stategy and Its Application as Ni-Al₂O₃ Catalysts for CO₂-CH₄ Reforming^†. Chem. J. Chinese Universities, 2015, 36(12): 2475.

图/表 22

Table 1 ICP-AES data of the catalysts

Catalyst	Elemental content(molar fraction, %)
Catalyst	Ni	Al	O
PAC0	4.13	37.73	58.14
PAC0.01	4.10	37.75	58.15
PAC0.02	4.08	37.76	58.16
PAC0.03	4.07	37.74	58.19
PAC0.05	4.09	37.75	58.16

Fig.1 TEM images of PA0(A) and PA0.02(B)

Fig.2 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of PA0.02(a) and PA0(b) supports

Table 2 Structural parameters of the supports and catalysts

Support	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	D_BJH/nm	Catalyst	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	D_BJH/nm
PA0	197.25	0.41	3.71	PAC0	190.83	0.45	2.40
PA0.01	265.43	0.41	3.40	PAC0.01	222.21	0.43	3.12
PA0.02	320.12	0.39	3.32	PAC0.02	280.15	0.46	3.24
PA0.03	281.45	0.40	4.61	PAC0.03	250.26	0.51	3.52
PA0.05	254.26	0.39	5.30	PAC0.05	210.44	0.50	3.87

Fig.3 Small-angle(A) and wide-angle(B) XRD profiles of PA0(a) and PA0.02(b) supports

Fig.4 Small-angle XRD patterns of catalysts

Fig.5 Wide-angle XRD patterns of catalysts before(A) and after(B) reduction

Table 3 Reduction peak area proportions of different NiO species

Catalyst	α-NiO(%)	β-NiO(%)
PAC0	66	34
PAC0.01	45	55
PAC0.02	18	82
PAC0.03	35	65
PAC0.05	61	39

Fig.6 H2-TPR profiles of the catalysts

Fig.7 NH3-TPD profiles of the supports

Fig.8 Peak areas from NH3-TPD profiles a. Weak acid area; b. strong acid area;c. total acid area.

Fig.9 NH3-TPD profiles of the catalysts

Fig.10 H2-TPD profiles of the catalysts

Fig.11 Conversion of CH4(A) and CO2(B) T=800 ℃, P=1.01325×105 Pa, GHSV=18000 h-1, V(CH4)/V(CO2)=1.

Fig.12 Selectivity of H2(A) and the change of CH4 and CO2 conversions and β-NiO percentage with the increasing of PA/ISO-AL(B) T=800 ℃, P=1.01325×105 Pa, GHSV=18000 h-1, V(CH4)/V(CO2)=1.

Fig.13 Endurance test over PAC0(a), PAC0.01(b) and PAC0.02(c) catalysts T=800 ℃, P=1.01325×105 Pa, GHSV=18000 h-1, V(CH4)/V(CO2)=1.

Table 4 Conversion of CH4 and corresponding deactivation rate

Catalyst	Conversion(%)				Deactivation rate/(point·h^-1)
Catalyst	0 h				10 h	120 h	154 h
PAC0.02	95.02	91.89	80.02	50.44	0.313(Ⅰ)	0.108^*(Ⅱ)	0.870(Ⅲ)

Fig.14 TG(A) and DTG(B) curves of the endurance-tested catalysts PAC0(a) and PAC0.02(b)

Table 5 Carbon deposition rate of PAC0 and PAC0.02

Catalyst	w(%)	Reaction time/h	Carbon deposition rate/(mg·h^-1· $g cat - 1$ )
PAC0	15.85	60	0.002642
PAC0.02	22.10	154	0.001435

Table 5 Carbon deposition rate of PAC0 and PAC0.02

Catalyst	w(%)	Reaction time/h	Carbon deposition rate/(mg·h^-1· $g cat - 1$ )
PAC0	15.85	60	0.002642
PAC0.02	22.10	154	0.001435

Fig.15 TEM images of PAC0(A, B) and PAC0.02(C, D) before(A, C) and after(B, D) reaction

Table 6 Ni size before and after endurance test

Catalyst	Ni size^*/nm		Icreasing rate(%)
Catalyst	Before reaction	After reaction	Icreasing rate(%)
PAC0	7.56	13.53	78.97
PAC0.02	5.72	8.04	40.56

Fig.16 Industrial test over PAC0.02 catalyst T=800 ℃, P=1.01325×105 Pa, GHSV=108000 h-1,V(CH4)/V(CO2)=1.

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基于蒸发诱导自组装法的高比表面介孔Al₂O₃的制备及在CO₂-CH₄重整催化剂中的应用

Preparation of Mesoporous Al₂O₃ with High Specific Surface Area by Evaporation-induced Self-assembly Stategy and Its Application as Ni-Al₂O₃ Catalysts for CO₂-CH₄ Reforming^†

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