稀土改性CuO-ZnO-ZrO2/SAPO-34分子筛催化CO2加氢合成低碳烯烃

doi:10.7503/cjcu20150693

摘要/Abstract

摘要：

采用共沉淀法分别制备了Y₂O₃, La₂O₃和CeO₂改性的CuO-ZnO-ZrO₂, 表征结果表明, 稀土改性的CuO-ZnO-ZrO₂分散性良好, 比表面积增大. 将稀土改性的CuO-ZnO-ZrO₂与SAPO-34分子筛机械混合用于催化CO₂加氢一步法合成了低碳烯烃, 在反应温度400 ℃, 压力3 MPa, 空速为1800 mL· $g cat - 1$ ·h ^-1, 氢碳体积比为3∶1, CeO₂改性CuO-ZnO-ZrO₂与SAPO-34质量比为1∶1, 催化剂用量为1.0 g时, CO₂的单程转化率为54.6%, 低碳烯烃的选择性和产率分别为51.1%和27.9%.

关键词: 稀土改性CuO-ZnO-ZrO2催化剂, SAPO-34分子筛, 低碳烯烃, CO2加氢反应

Abstract:

Y₂O₃, La₂ $O 3$ and Ce₂O₃ modified CuO-ZnO-ZrO₂ catalysts were prepared by co-precipitation method. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), Brunauer-Emmett-Teller(BET), temperature programmed reduction(TPR) and thermogravimetry(TG). Rare earth metals modified CuO-ZnO-ZrO₂ catalyst have good dispersion and higher specific surface area. The activity of biofunctional prepared by mechanical mixing of modified CuO-ZnO-ZrO₂ with SAPO-34 for the hydrogenation of carbon dioxide to light olefins was investigated.Under the conditions of reaction temperature of 400 ℃, pressure of 3.0 MPa, space velocity(SV) of 1800 mL· $g cat - 1$ ·h^-1, CO₂/H₂(volume ratio) of 1∶3, mass ratio of Ce-CuO-ZnO-ZrO₂/SAPO-34 to 1∶1 and the quality of multiple catalyst of 1.0 g, the conversion of CO₂ could reach to 54.6%, with a light olefins selecti-vity and yield of 51.1% and 27.9%, respectively.

Key words: Rare earths modified CuO-ZnO-ZrO2 catalyst, SAPO-34 molecular sieve, Light olefins, Carbon dioxide hydrogenation(Ed.: V, Z)

中图分类号:

O643

TrendMD:

刘蓉, 查飞, 杨爱梅, 常玥. 稀土改性CuO-ZnO-ZrO₂/SAPO-34分子筛催化CO₂加氢合成低碳烯烃. 高等学校化学学报, 2016, 37(5): 964.

LIU Rong, ZHA Fei, YANG Aimei, CHANG Yue. Synthesis of Light Olefins from CO₂ Hydrogenation Catalyzed over Rare Earths Modified CuO-ZnO-ZrO₂/SAPO-34^†. Chem. J. Chinese Universities, 2016, 37(5): 964.

图/表 14

Fig.1 XRD patterns of CZZ(A), SAPO-34 and composite catalyst(B)(A) a. 350 ℃; b. 400 ℃; c. 500 ℃. (B) a. SAPO-34; b. CZZ/SAPO-34.

Fig.2 XRD patterns of Ce-CZZa. CZZ; b. 3%Ce-CZZ; c. 6%Ce-CZZ; d. 9%Ce-CZZ.

Fig.3 SEM images of CZZ(A, C, E) and Ce-CZZ(B, D, F) at different calcination temperatures(A, B) 500 ℃; (C, D) 400 ℃; (E, F) 350 ℃.

Fig.4 TEM images of CZZ(A) and Ce-CZZ(B) with calcination temperature of 400 ℃

Table 1 Surface area, pore volume and pore size data of catalysts

Catalyst	Surface area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Pore diameter/nm	Catalyst	Surface area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Pore diameter/nm
CZZ(350)	64.0	0.25	8.15	La-CZZ	66.4	0.28	8.17
CZZ(400)	58.5	0.22	8.14	Ce-CZZ	77.1	0.30	8.19
CZZ(500)	45.3	0.21	8.11	SAPO-34	549.6	0.23	0.90
Y-CZZ	59.6	0.23	8.17

Table 2 Average size and polydispersity index(PDI) of catalysts

Catalyst	Average particle size/nm	PDI	Catalyst	Average particle size/nm	PDI
CZZ	1170	0.349	La-CZZ	860	0.202
Y-CZZ	956	0.344	Ce-CZZ	804	0.115

Fig.5 Particle size distributions of CZZ(A), Ce-CZZ(B), Y-CZZ(C) and La-CZZ(D)

Fig.6 H2-TPR profiles of various catalystsa. CZZ; b. Y-CZZ; c. La-CZZ ; d. Ce-CZZ.

Fig.7 TG curves of composite catalysts CZZ/SAPO-34(a) and Ce-CZZ/SAPO-34(b)

Table 3 Catalytic performance of the different catalysts*

Catalyst	Conversion of CO₂(%)	Yield of C₂— $C 4 =$ (%)	Selectivity(%)
Catalyst	Conversion of CO₂(%)	Yield of C₂— $C 4 =$ (%)	CO	CH₄	C₂— $C 4 =$	C₂— $C 40$
CZZ/SAPO-34	49.4	24.9	11.9	14.2	50.5	23.4
Y-CZZ/SAPO-34	51.7	25.8	12.0	14.4	50.0	23.6
La-CZZ/SAPO-34	52.0	25.9	12.2	14.7	49.8	23.3
Ce-CZZ/SAPO-34	54.6	27.9	13.0	13.9	51.1	22.0

Table 3 Catalytic performance of the different catalysts*

Catalyst	Conversion of CO₂(%)	Yield of C₂— $C 4 =$ (%)	Selectivity(%)
Catalyst	Conversion of CO₂(%)	Yield of C₂— $C 4 =$ (%)	CO	CH₄	C₂— $C 4 =$	C₂— $C 40$
CZZ/SAPO-34	49.4	24.9	11.9	14.2	50.5	23.4
Y-CZZ/SAPO-34	51.7	25.8	12.0	14.4	50.0	23.6
La-CZZ/SAPO-34	52.0	25.9	12.2	14.7	49.8	23.3
Ce-CZZ/SAPO-34	54.6	27.9	13.0	13.9	51.1	22.0

Fig.8 Effect of calcining temperature on the catalytic performance(A) 350 ℃; (B) 400 ℃; (C) 500 ℃.

Fig.9 Effect of pressure on CO2 hydrogenationa. Conv. of CO2; b. sel. of CO; c. sel. of CH4; d. sel. of C2—C4=; e. sel. of C2—C40;f. yield of C2—C4=.

Fig.10 Effect of temperature on CO2 hydrogenationa. Conv. of CO2; b. sel. of CO; c. sel. of CH4; d. sel. of C2—C4=; e. sel. of C2—C40;f. yield of C2—C4=.

Fig.11 Effect of mass ratio of catalyst on CO2 hydrogenationa. Conv. of CO2; b. sel. of CO; c. sel. of CH4; d. sel. of C2—C4=; e. sel. of C2—C40;f. yield of C2—C4=.

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稀土改性CuO-ZnO-ZrO₂/SAPO-34分子筛催化CO₂加氢合成低碳烯烃

Synthesis of Light Olefins from CO₂ Hydrogenation Catalyzed over Rare Earths Modified CuO-ZnO-ZrO₂/SAPO-34^†

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