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

doi:10.7503/cjcu20150693

Abstract

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)

CLC Number:

O643

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2016, 37(5): 964.

Figures/Tables 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=.

References 32

[1]	Fujiwara M., Sakurai H., Shiokawa K., Iizuka Y., Catal.Today, 2015, 242, 255—260
[2]	Wang J. J., You Z. Y., Zhang Q. H., Deng W. P., Wang Y., Catal.Today, 2013, 215, 186—193
[3]	Dorner R. W., Hardy D. R., Williams F. W., Willauer H. D., Catal.Commun., 2011, 15, 88—92
[4]	Venter J., Kaminsky M., Geoffroy G. L., Vannice M. A., J. Catal., 1987, 105, 155—162
[5]	Park Y., Park K., Ihm S., Catal.Today, 1998, 44, 165—173
[6]	Hu B. X., Frueh S., Garces H. F., Zhang L. C., Aindow M., Brooks C., Kreidler E., Suib S. L., Appl. Catal.B, 2013, 132/133, 54—61
[7]	Su C. Y., Tan J. Q., Wang C. X., Nat. Gas. Chem.Ind., 2013, 38(3), 34—38
	(苏春彦, 檀建群, 王承学. 天然气化工, 2013, 38(3), 34—38)
[8]	Tian S. C., Han L. L., Hou J. Q., Bian W. Y., Tian X. G., Li Y. C., Lian P. Y., J. Liaoning ShihuaUniversity, 2011, 31(3), 4—11
	(田世超, 韩丽丽, 侯俊琦, 卞婉莹, 田晓光, 李永超, 连丕勇. 辽宁石油化工大学学报, 2011, 31(3), 4—11)
[9]	Wang C. X., Tan J. Q., Su C. Y., Nat. Gas. Chem.Ind., 2012, 37(2), 21—23
	(王承学, 檀建群, 苏春彦. 天然气化工, 2012, 37(2), 21—23)
[10]	Hirsa M.T. G., Krijn P. J., ACS Catal., 2013, 3, 2130—2149
[11]	Chena D., Moljord K., Holmen A., Microporous MesoporousMater., 2012, 164, 239—250
[12]	Sedighi M., Bahrami H., Towfighi J., J. Ind. Eng.Chem., 2014, 20(5), 3108—3114
[13]	Witoon T., Bumrungsalee S., Chareonpanich M., Limtrakul J., Energy Convers.Manage., 2015, 103, 886—894
[14]	Li Z. X., Na W., Wang H., Gao W. G., Chem. J. Chinese Universities,2014, 35(12), 2616—2623
	(李志雄, 纳薇, 王华, 高文桂. 高等学校化学学报, 2014, 35(12), 2616—2623)
[15]	Zhang X. B., Zhong L., Guo Q. H., Fan H., Zheng H. Y., Xie K. C., Fuel,2010, 89, 1348—1352
[16]	Shang M. J., Chen S. Y., Li G. M., Zhang Y. C., Mod. Chem.Ind., 2011, 31(7), 50—54
	(商敏静, 陈绍云, 李桂民, 张永春. 现代化工, 2011, 31(7), 50—54)
[17]	Liu J. D., Huang Z. G., Li Z., Guo Q. Q., Li Q. Y., Chem. J. Chinese Universities,2014, 35(3), 589—595
	(刘建东, 黄张根, 李哲, 郭倩倩, 李巧艳. 高等学校化学学报, 2014, 35(3), 589—595)
[18]	Zhang X. X., Wu C. Z., Zhou J. F., Yang G. H., Liu Y. H., Zhang Y. W., Ding W. Z., Chem. J. Chinese Universities,2015, 36(7), 1246—1253
	(张星星, 吴成章, 周建芳, 杨恭辉, 刘银河, 张玉文, 丁伟中. 高等学校化学学报, 2015, 36(7), 1246—1253)
[19]	Guo X. M., Ma D. S., Lu G. Z., Wang S., Wu G. S., J. Mol. Catal. A: Chem., 2011, 345, 60—68
[20]	Tang X. B., Noritatsu T., Xie H. J., Han Y. Z., Tan Y. S., J. Fuel Chem.Technol., 2014, 42(6), 704—709
[21]	Bana H. Y., Li C. M., Asami K. J., Fujimoto K., Catal.Commun., 2014, 54, 50—54
[22]	Kong L. Z., Wang Q., Xu L., Yan Y. S., Li H. M., Yang X. G., Chem. J. Chinese Universities,2015, 36(7), 1372—1377
	(孔令智, 王谦, 徐丽, 闫永胜, 李华明, 杨向光. 高等学校化学学报, 2015, 36(7), 1372—1377)
[23]	Zha F., Tian H. F, Yan J., Chang Y., Appl. Surf.Sci., 2013, 285P, 945—951
[24]	Zha F., Ding J., Chang Y., Ding J. F., Wang J. Y., Ma J., Ind. Eng. Chem.Res., 2012, 51, 345—352
[25]	Rasmussen D. B., Janssens T. V. W., Temel B., Bligaard T., Hinnemann B., Helveg S., Sehested J., J. Catal., 2012, 293, 205—214
[26]	Matsumura Y., J. Power Sources, 2013, 238, 109—116
[27]	Bonura G., Cordaro M., Cannilla C., Arena F., Frusteri F., Appl.Catal., B,2014, 152/153, 152—161
[28]	Wang J. Z., Luo L. T., Chinese RareEarths, 2007, 28(4), 25—29
	(王菊枝, 罗来涛. 稀土, 2007, 28(4), 25—29)
[29]	Bai Y. G., He D. H., Ge S. H., Catal.Today, 2010, 149(1/2), 111—116
[30]	Li B. X., Xie Y., Wu C. Z., Mater. Chem.Phys., 2006, 99(2/3), 479—486
[31]	Pop G., Bozga G., Ganea R., Ind. Eng. Chem.Res., 2009, 48, 7065—7071
[32]	Aghaei E., Haghighi M., Microporous MesoporousMater., 2014, 196, 179—190

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 14

References 32

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	QU Dawei, LI Xin, CHEN Guangming. Fabrication and Properties of Flexible Thermoelectric Devices^† [J]. Chem. J. Chinese Universities, 2019, 40(4): 617.
[2]	LUO Dajun, SHAO Huiju, JIN Jinbo, XIE Gaoyi, CUI Zhenyu, YU Jie, QIN Shuhao. Preparation of Hydrophilic Polypropylene/Polyvinyl Butyral Hollow Fiber Membranes by Melt-spinning-stretching^† [J]. Chem. J. Chinese Universities, 2018, 39(8): 1838.
[3]	WANG Peng, WU Xian, ZHANG Hanyu, YOU Kaiyuan, LIU Zhenchao, LIU Baijun. Preparation of the Blend Membranes Based on Sulfonated Polyetheretherketoneketone and Amine-terminated Hyperbranched Polyimide^† [J]. Chem. J. Chinese Universities, 2018, 39(3): 405.
[4]	YAN Kaibo,GUO Guibao,LIU Jinyan. Synthesis of Oil/Water Separation Membranes via Grafting Acrylic Acid onto Poly(vinylidene fluoride) Modified by Tetraethyl Ammonium Hydroxide^† [J]. Chem. J. Chinese Universities, 2016, 37(8): 1565.
[5]	LIU Xuewu,CHEN Shuhua,ZHAN Shiping. Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO₂-induced Phase Inversion^† [J]. Chem. J. Chinese Universities, 2016, 37(8): 1573.
[6]	CHEN Xiaolin, WU Hao, LIU Lifen, GAO Congjie. Synthesis and Characterization of Trimesoylamidoamine^† [J]. Chem. J. Chinese Universities, 2016, 37(5): 983.
[7]	QIN Yichao, YE Jian, JIANG Binbo, WANG Jingdai, YANG Yongrong. Ethylene Oligomerization and Friedel-Crafts Alkylation Tandem Action Catalyzed by Aryloxy Zirconium Catalysts^† [J]. Chem. J. Chinese Universities, 2015, 36(9): 1825.
[8]	ZHAO Xiaoxia, GAO Xiaoya, ZHANG Xiaochao, LI Rui, WANG Yawen, WANG Yunfang, FAN Caimei. Tunable Synthesis of Hierarchical BiOCl Microspheres for Efficient Photocatalytic Degradation of Pharmaceutical Wastewater^† [J]. Chem. J. Chinese Universities, 2015, 36(5): 955.
[9]	DUAN Xinli, ZHANG Xin, LEI Ming. QM/MM Molecular Dynamics Simulation on the Mechanisms for the Hydrolytic Deamination of Nicotinamidase^† [J]. Chem. J. Chinese Universities, 2015, 36(12): 2491.
[10]	SONG Min, ZHANG Linping, ZHONG Yi, XU Hong, MAO Zhiping. Catalytic Properties of Manganese Complex of Cyclic Polyamine Encapsulated in Ethyl Cellulose Microcapsules^† [J]. Chem. J. Chinese Universities, 2014, 35(9): 1941.
[11]	GE Kaikai, QIU Wenfeng, HAN Weijian, YE Li, ZHAO Aijun, ZHAO Tong. Synthesis, Characterization and Pyrolysis Behavior of ZrB₂/SiC Precursor^† [J]. Chem. J. Chinese Universities, 2014, 35(9): 2050.
[12]	ZHANG Lingna, TAO Jinhui, JI Kaiji, YUE Qunfeng. Synthesis of Mesoporous Carbon/Iron Carbide Material and Its Hydrogen Storage Capacity^† [J]. Chem. J. Chinese Universities, 2014, 35(6): 1318.
[13]	SUN Yan, WANG Bing. Molecular Recognition Mechanism of Chiral (S)-Ibuprofen’s Hydrogen Bonds Self-assembly Imprinted Polymer [J]. Chem. J. Chinese Universities, 2012, 33(04): 838.
[14]	WANG Hai-Bo, LIU Xi-Kui*. Novel Indole Alkaloid from the Flowers of Rauvolfia yunnanensis [J]. Chem. J. Chinese Universities, 2010, 31(10): 2005.
[15]	GAO Rong^1,2, MA Hai-Xia^1*, YAN Biao¹, SONG Ji-Rong¹, WANG Ying-Hui¹. Structure-Property Investigation on TDNAZ·HNO₃ and DNAZ·HCl [J]. Chem. J. Chinese Universities, 2009, 30(3): 577.