Influence of Structure Evolution of CuY Catalyst During the Reaction Process on Its Catalytic Performance for Oxidative Carbonylation of Methanol†

doi:10.7503/cjcu20180790

Abstract

Abstract:

Chloride-free CuY catalyst prepared by solid state reaction with NH₄Y zeolites as support and copper acetylacetone as copper source was evaluated for oxidative carbonylation of methanol to dimethyl carbonate(DMC). Combining the results of X-ray diffraction(XRD), N₂ adsorption-desorption isotherm, thermogravimetric(TG) analysis, NH₃-temperature-programmed desorption(NH₃-TPD), transmission electroon microscopy(TEM) and X-ray photoelectron spectroscopy(XPS) characterization, the influence of copper species evolution during the reaction process on its catalytic performance was disclosed. The results indicated that Cu⁺was the dominant Cu species of fresh catalyst with the percentage of 48%. As the reaction proceeded, the active center Cu⁺ was gradually oxidized to Cu²⁺, and then formed CuO, part of which gradually migrated to the outer surface of the catalyst. With the reaction time extended to 100 h, the percentage of Cu⁺ gradually decreased to 36.7%, while the percentage of CuO continued to increase, accordingly resulting in the decrease of the space-time yield and selectivity of DMC and the increase of the selectivity of byproducts dimethoxymethane(DMM) and methyl formate(MF). With the reaction time extended to 190 h, the percentage of Cu⁺ decreased slowly to 33.6%, the space time yield and selectivity of DMC tended to be stable. When the reaction time extended to 300 h, the copper species in the catalyst remained unchanged, and the catalytic performance of the catalyst remained stable.

Key words: Oxidative carbonylation of methanol, Dimethyl carbonate, CuY catalyst, Copper species, Valence variation

CLC Number:

O643

TrendMD:

YIN Jiao, ZHANG Guoqiang, YAN Lifei, JIA Dongsen, ZHENG Huayan, LI Zhong. Influence of Structure Evolution of CuY Catalyst During the Reaction Process on Its Catalytic Performance for Oxidative Carbonylation of Methanol^†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1510.

Figures/Tables 13

Fig.1 Space time yield(STY) of DMC, conversion(X) of CH3OH and CO as a function of time on stream(A), selectivity(S) of DMC, DMM, DME and MF based on CH3OH as a function of time on stream(B) and selectivity of DMC and CO2(C) based on CO as a function of time on stream

Fig.2 TG curves of CuY catalystsa. CuY; b. CuY-20 h; c. CuY-100 h; d. CuY-190 h; e. CuY-300 h.

Fig.3 XRD patterns of NH4Y zeolite and CuY Catalystsa. NH4Y; b. CuY; c. CuY-20 h; d. CuY-100 h; e. CuY-190 h; f. CuY-300 h.

Fig.4 TEM images(A1—E1) and particle size distribution(A2—E2) of CuY(A1, A2), CuY-20 h(B1, B2), CuY-100 h(C1, C2), CuY-190 h(D1, D2), CuY-300 h(E1, E2) and HRTEM images of CuY-190 h(F1, F2)(F2) is the enlarged part of (F1).

Fig.5 N2 adsorption-desorption isotherms(A) and pore size distribution(B) of CuY catalysts

Table 1 Textural properties of CuY catalysts

Sample	$S BET a$ /(m²·g^-1)	$S micro b$ /(m²·g^-1)	$V total c$ /(cm³·g^-1)	$V micro b$ /(cm³·g^-1)	D_meso/nm
CuY	685	632	0.43	0.28	1.85
CuY-20 h	632	582	0.38	0.26	1.84
CuY-100 h	626	577	0.36	0.25	1.84
CuY-190 h	608	560	0.33	0.24	1.86
CuY-300 h	612	557	0.34	0.24	1.85

Table 1 Textural properties of CuY catalysts

Sample	$S BET a$ /(m²·g^-1)	$S micro b$ /(m²·g^-1)	$V total c$ /(cm³·g^-1)	$V micro b$ /(cm³·g^-1)	D_meso/nm
CuY	685	632	0.43	0.28	1.85
CuY-20 h	632	582	0.38	0.26	1.84
CuY-100 h	626	577	0.36	0.25	1.84
CuY-190 h	608	560	0.33	0.24	1.86
CuY-300 h	612	557	0.34	0.24	1.85

Fig.6 Cu2p3/2 XPS spectra(A) and Cu AES(B) of CuY catalystsa. CuY; b. CuY-20 h; c. CuY-100 h; d. CuY-190 h; e. CuY-300 h.

Table 2 Quantitative analysis of the XPS curve-fitting of CuY catalysts

Catalyst	E_b of C $u 2 p 3 / 2$ /eV		Area percentage of surface C $u 2 p 3 / 2$ (%)
Catalyst	Cu⁺	Cu²⁺+CuO	Cu⁺	Cu²⁺+CuO
CuY	933.2	935.6	49.6	50.4
CuY-20 h	933.5	935.7	43.2	56.8
CuY-100 h	933.4	935.6	41.5	58.5
CuY-190 h	933.9	935.7	33.4	66.6
CuY-300 h	933.6	935.7	33.6	66.4

Table 2 Quantitative analysis of the XPS curve-fitting of CuY catalysts

Catalyst	E_b of C $u 2 p 3 / 2$ /eV		Area percentage of surface C $u 2 p 3 / 2$ (%)
Catalyst	Cu⁺	Cu²⁺+CuO	Cu⁺	Cu²⁺+CuO
CuY	933.2	935.6	49.6	50.4
CuY-20 h	933.5	935.7	43.2	56.8
CuY-100 h	933.4	935.6	41.5	58.5
CuY-190 h	933.9	935.7	33.4	66.6
CuY-300 h	933.6	935.7	33.6	66.4

Fig.7 H2-TPR profiles of CuY catalysts

Table 3 Quantitative analysis of the H2-TPR profiles of CuY catalysts

Catalyst	H₂ consumption /(mmol·g^-1)			CuO/Cu_sum(%)	Cu²⁺/Cu_sum(%)	Cu⁺/Cu_sum(%)
Catalyst	Cu²⁺	CuO	Cu⁺	CuO/Cu_sum(%)	Cu²⁺/Cu_sum(%)	Cu⁺/Cu_sum(%)
CuY	0.22	0.24	0.54	17.9	34.1	48.0
CuY-20 h	0.17	0.36	0.40	31.4	28.9	39.7
CuY-100 h	0.13	0.45	0.33	41.1	22.2	36.7
CuY-190 h	0.12	0.42	0.29	42.2	24.2	33.6
CuY-300 h	0.14	0.46	0.32	41.7	25.1	33.2

Fig.8 NH3-TPD patterns of CuY catalysts

Table 4 Quantitative analysis of the NH3-TPD profiles of CuY catalysts

Catalyst	Desorption capacity of NH₃/(mmol·g^-1)
Catalyst	Peak a+b	Peak c	Peak d	Peak c+d	Total
CuY	3.42	2.57	1.47	4.04	7.46
CuY-20 h	3.71	2.13	1.57	3.70	7.41
CuY-100 h	3.36	1.59	1.64	3.23	6.59
CuY-190 h	3.41	1.38	1.65	3.03	6.44
CuY-300 h	3.40	1.37	1.65	3.02	6.42

Fig.9 Structure evolution of CuY catalyst in oxidative carbonylation process

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