固相反应制备无氯CuY催化剂及其催化氧化羰基化—固相反应温度和铜负载量的影响

doi:10.7503/cjcu20150285

摘要/Abstract

摘要：

以乙酰丙酮铜Cu(acac)₂为铜源、 NH₄Y分子筛为载体, 采用固相反应制备了无氯CuY催化剂, 考察了在甲醇氧化羰基化合成碳酸二甲酯过程中固相反应温度和Cu负载量对CuY催化剂催化性能的影响, 分析了CuY催化剂物相结构、可还原性Cu物种和织构性质对催化性能的影响. 结果表明, 随着固相反应温度的升高, 与NH₄Y中N $H 4 +$ 发生离子交换的Cu²⁺交换度和活性中心Cu⁺含量先增大后降低, CuY催化剂活性也呈现出相同的变化趋势; 负载量(质量分数)低于10%时, 受分子筛残留B酸位影响, 碳酸二甲酯的选择性较低, 而负载量高于12%时, CuY催化剂中出现了CuO物种, 且粒子逐渐长大, 覆盖部分活性中心, 甚至堵塞孔道, 使催化剂活性降低. 当固相反应温度为250 ℃, Cu负载量为12%时, 活性中心Cu⁺含量最高, 催化剂表现出最佳的催化活性, 碳酸二甲酯基于甲醇的时空收率为267.3 mg·g^-1·h^-1, 甲醇转化率为6.9%, 碳酸二甲酯(DMC)的选择性为69.2%.

关键词: 甲醇氧化羰基化, 碳酸二甲酯, 固相反应温度, 无氯CuY催化剂, Cu负载量

Abstract:

Copper(Ⅱ) acetylacetonate Cu(acac)₂ as copper source and NH₄Y zeolite as support, the chloride-free CuY catalyst was prepared by solid state reaction. The influence of the solid state reactive temperature and the copper loading(mass fraction) on the catalytic activity for oxidative carbonylation of methanol was studied. And the effect of the phase structure, reducible copper species and texture on catalytic activity was investigated. The results indicates that the exchange degree between N $H 4 +$ and Cu²⁺ at first increases and then decreases with the increasing of the solid state reactive temperature, and the catalytic activity of the as-prepared CuY catalyst has the same changing tendency. When copper loading is below 10%, the selectivity of dimethyl carbonate is low by the effect of the residual Brϕnsted acid. However, copper loading is above 12%, the unexchanged Cu(acac)₂ decomposed to form CuO nano-particles and the nanometer-sized particles grow up, covered some active centers, even blocked pore, resulting in the decrease of catalytic activity. The as-prepared CuY catalyst with 12% copper loading at 250 ℃ solid state reaction exhibits an excellent catalytic activity. Space-time yield(STY) of dimethyl carbonate(DMC) up to 267.3 mg·g^-1·h^-1 was achieved.

Key words: Oxidative carbonylation of methanol, Dimethyl carbonate, Solid state reactive temperature, Chloride-free CuY catalyst, Cu loading

中图分类号:

O643

TrendMD:

王玉春, 郑华艳, 刘斌, 张国强, 李忠. 固相反应制备无氯CuY催化剂及其催化氧化羰基化—固相反应温度和铜负载量的影响. 高等学校化学学报, 2015, 36(12): 2540.

WANG Yuchun, ZHENG Huayan, LIU Bin, ZHANG Guoqiang, LI Zhong. Chloride-free CuY Catalyst Prepared by Solid State Reaction for Oxidative Carbonylation of Methanol^†— Effect of Solid State Reactive Temperature and Copper Loading. Chem. J. Chinese Universities, 2015, 36(12): 2540.

图/表 12

Fig.1 XRD patterns of NH4Y and catalysts 10CuY with different temperature of solid state reaction(SSR) a. NH4Y; b. 10CuY170; c.10CuY200; d. 10CuY250;e. 10CuY280.

Fig.2 H2-TPR patterns and Gaussian fitting of low temperature peaks (A) a. Cu2+-Y(6.3); b. CuY(6.3); c. 6CuY250; d. CuY(10.6); e. 10CuY250.(B) a. 10CuY170; b. 10CuY200; c. 10CuY250; d. 10CuY280.

Table 1 Cu species content of 10CuYT catalysts

Catalyst	Mass fraction(%)
Catalyst	Cu²⁺(Supercage)	Cu²⁺(Sodalite cage)	CuO	Cu⁺	Cu_sum
10CuY₁₇₀	2.99	0.84	2.36	3.30	9.49
10CuY₂₀₀	3.30	1.39	1.31	3.39	9.39
10CuY₂₅₀	3.38	1.40	0.98	3.76	9.52
10CuY₂₈₀	2.78	0.91	2.68	3.04	9.41

Fig.3 STYDMC and conversion(A) and selectivities of DMC, DME, DMM and MF(B) vs. SSR temperature Feed composition(volume fraction): 31.8%CH3OH, 62.5%CO, 5.7%O2; GHSV 3250 h-1.

Fig.4 XRD patterns of NH4Y and catalysts with different copper loadings a. NH4Y; b. 6CuY250; c. 8CuY250; d. 10CuY250; e. 12CuY250; f. 15CuY250; g. 20CuY250.

Fig.5 N2 adsorption-desorption isotherms of catalysts with different copper loadings

Table 2 Specific surface area and pore volume of catalysts with different Cu loadings*

Catalyst	S_BET/(m²·g^-1)	S_micro/(m²·g^-1)	S_meso/(m²·g^-1)	V_micro/(cm³·g^-1)	V_meso/(cm³·g^-1)
NH₄Y	791.9	746.4	45.5	0.36	0.10
6CuY₂₅₀	737.5	690.9	46.7	0.34	0.13
8CuY₂₅₀	718.0	668.4	49.6	0.33	0.18
10CuY₂₅₀	705.0	656.3	48.9	0.32	0.12
12CuY₂₅₀	560.3	514.2	46.1	0.26	0.12
15CuY₂₅₀	549.6	507.9	41.7	0.25	0.12
20CuY₂₅₀	530.1	481.9	48.2	0.24	0.12

Fig.6 TEM images of catalysts with different Cu loadings (A) 6CuY250; (B) 12CuY250; (C) 20CuY250.

Fig.7 Hydrogen TPR profiles for the catalysts with different copper loadings a. 6CuY250; b. 8CuY250; c. 10CuY250; d. 12CuY250;e. 15CuY250; f. 20CuY250.

Fig.8 XPS spectra of Cu2P3/2orbits(A) and Auger electron spectroscopy(B) of Cu in CuY catalysts a. 6CuY250; b. 12CuY250; c. 20CuY250.

Fig.9 Influence on catalysis of copper loading STYDMC and XCH3OH vs. copper loading(A), selectivities of DMC, DME, DMM and MF vs. copper loading(B) and time-on-stream performance of xCuY250 catalysts(C) Feed composition(volume fraction): 31.8% CH3OH, 62.5% CO, 5.7% O2; GHSV 3250 h-1.

Table 3 Catalytic activities of CuY catalysts in the oxidative carbonylation of methanol

Catalyst	Preparation method	Mass fraction of Cu loading(%)	STY_DMC /(mg·g^-1·h^-1)	S_DMC(%)	$X C H 3 OH$
6CuY₂₅₀	SSR	6.1	11.3^a	33.9	0.6
8CuY₂₅₀	SSR	8.0	50.5^a	58.7	1.5
10CuY₂₅₀	SSR	9.5	192.7^a	67.6	5.1
12CuY₂₅₀	SSR	11.3	267.3^a	69.2	6.9
15CuY₂₅₀	SSR	13.9	211.7^a	69.6	5.4
20CuY₂₅₀	SSR	16.1	204.5^a	72.1	5.0
CuHY-3^[40]	IEIM	11.9	200.5^b	51.7	13.0
CuCl₂/HY^[41]	SSIE	12.2	97.3^b	74.6	4.4
Cu₂(OH)₃Cl/AC^[42]	DP	18.7	139.1^b	67.3	6.9
12Cu- $Y 700 16$	DP	12.0	152.1^c	56.3	8.4

Table 3 Catalytic activities of CuY catalysts in the oxidative carbonylation of methanol

Catalyst	Preparation method	Mass fraction of Cu loading(%)	STY_DMC /(mg·g^-1·h^-1)	S_DMC(%)	$X C H 3 OH$
6CuY₂₅₀	SSR	6.1	11.3^a	33.9	0.6
8CuY₂₅₀	SSR	8.0	50.5^a	58.7	1.5
10CuY₂₅₀	SSR	9.5	192.7^a	67.6	5.1
12CuY₂₅₀	SSR	11.3	267.3^a	69.2	6.9
15CuY₂₅₀	SSR	13.9	211.7^a	69.6	5.4
20CuY₂₅₀	SSR	16.1	204.5^a	72.1	5.0
CuHY-3^[40]	IEIM	11.9	200.5^b	51.7	13.0
CuCl₂/HY^[41]	SSIE	12.2	97.3^b	74.6	4.4
Cu₂(OH)₃Cl/AC^[42]	DP	18.7	139.1^b	67.3	6.9
12Cu- $Y 700 16$	DP	12.0	152.1^c	56.3	8.4

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