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†

doi:10.7503/cjcu20150444

Abstract

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

CLC Number:

O643.32

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(12): 2475.

Figures/Tables 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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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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