咪唑/镍(II)改性SAPO-34的制备及其催化CO2加氢制备乙烯

doi:10.15541/jim20170021

摘要/Abstract

摘要：

按异丙醇铝 : 磷酸 : 硅溶胶 : 四乙基氢氧化铵 : 水 : 改性剂=1.0 : 0.8 : 0.6 : 2.0 : 52 : 0.01的质量比, 先将异丙醇铝和磷酸溶于水, 再加入硅溶胶和四乙基氢氧化铵的混合液, 30℃搅拌4 h后加入摩尔比为1 : 1的咪唑和硝酸镍, 60℃搅拌8 h, 室温陈化24 h, 在不锈钢水热合成反应釜中200℃晶化24 h, 固体在120℃干燥12 h, 550℃焙烧 6 h, 制得咪唑/镍(II)改性SAPO-34分子筛。用X射线粉末衍射(XRD)、扫描电镜(SEM)、能量色散X射线(EDS)和N₂吸脱附对咪唑/镍(II)改性SAPO-34进行了表征。将改性后的SAPO-34分子筛与CuO-ZnO-Al₂O₃按质量比1 : 1机械混合制备了复合催化剂。在固定床微分反应器上测定了复合催化剂对CO₂加氢制备低碳烯烃的催化性能。在温度400℃, 压强3.0 MPa, 碳氢体积比为1 : 3, 空速为1800 mL/(g_cat·h), 复合催化剂用量为1.0 g时, 二氧化碳的转化率达到73.8%, 乙烯的选择性为67.7%, 显示了较高的催化活性, 并且当温度继续升高至450℃时, 乙烯的选择性并未下降, 显示了一定的耐高温性能。

关键词: SAPO-34分子筛, 复合催化剂, 二氧化碳加氢, 乙烯, 改性

Abstract:

Imidazole and nickel (II) modified SAPO-34 was synthesized according to the mass ratio of aluminum isopropoxide: phosphoric acid: silica sol: tetraethylammonium hydroxide : water : modified agents = 1.0 : 0.8 : 0.6 : 2 : 52 : 0.01. Specified amount of aluminum isopropoxide was mixed with distilled water and phosphoric acid was added to present the white homogenous gel. Tetraethylammonium hydroxide was Also mixed with specified amount of silica sol to form homogenous solution. The homogenous solution was added to the white homogenous gel. After stirring at 30℃ for 4 h, specified amount of imidazole and nickel nitrate (mole ratio = 1 : 1) was added in and kept at 60℃ with a constant stirring speed for 8 h to result in a semi-transparent homogenous white gel. The white gel was transferred into a high-pressure stainless steel autoclave and maintained at 200℃ for 24 h without stirring. As precipitate was recovered from the autoclave, it was dried at 120℃ for 12 h and calcined at 550℃ for 6 h to acquire imidazole and nickel modified SAPO-34. It was characterized by means of N₂ adsorption/desorption, X-ray powder diffraction (XRD), scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS). The modified SAPO-34 was mechanically mixed with CuO-ZnO-Al₂O₃ prepared by co-precipitation process to form composited catalyst (CZA/SAPO-34_x). The activity of CZA/SAPO-34_x for CO₂ hydrogenation to light olefins was investigated in a differential fixed reactor. Under reaction pressure of 3.0 Mpa, temperature of 400℃, space velocity (SV) of 1800 mL/(g_cat·h), volume ratio of CO₂ to H₂ of 1 : 3, and composited catalyst mass of 1.0 g, the one-way conversion of CO₂ and selectivity of ethylene are 73.8% and 67.7%, respectively. Compared with SAPO-34, imidazole and nickel (II) modified SAPO-34 keeps high catalytic activity when reaction temperature rises to 450℃, showing the high temperature resistance.

Key words: SAPO-34, composited catalyst, CO₂ hydrogenation, ethylene, modification

中图分类号:

TQ426

唐小华, 李辉, 杨爱梅, 查飞, 常玥. 咪唑/镍(II)改性SAPO-34的制备及其催化CO₂加氢制备乙烯[J]. 无机材料学报, 2017, 32(11): 1209-1214.

TANG Xiao-Hua, LI Hui, YANG Ai-Mei, ZHA Fei, CHANG Yue. Imidazole and Nickel (II) Modified SAPO-34 and Its Catalytic Activity in CO₂ Hydrogenation to Ethylene[J]. Journal of Inorganic Materials, 2017, 32(11): 1209-1214.

图/表 9

图1 咪唑/镍(II)改性SAPO-34分子筛的XRD图谱

Fig. 1 XRD patterns of modified SAPO-34

图2 SAPO-34X的SEM照片

Fig. 2 SEM images of SAPO-34X

图3 SAPO-34T的SEM照片和EDS分析

Fig. 3 SEM image and EDS analysis of SAPO-34T

图4 SAPO-34P的N2吸脱附和孔径分布曲线

Fig. 4 N2 adsorption/desorption and pore diameter distribution curves of SAPO-34P

表1 不同含量咪唑和硝酸镍改性SAPO-34X的比表面积、孔容和孔径

Table 1 Surface area, pore volume and pore diameter of SAPO-34X

Catalyst	Specific surface/ (m²•g^-1)	Pore volume/ (cm³•g^-1)	Pore diameter/ nm
SAPO-34_M	530.0	0.36	0.20
SAPO-34_S	526.9	0.34	0.22
SAPO-34_P	520.2	0.31	0.26
SAPO-34_T	511.8	0.29	0.29
SAPO-34_R	506.3	0.28	0.30
SAPO-34_N	471.4	0.27	0.38

表2 CZA/SAPO-34X的催化活性

Table 2 Catalytic performance of CZA/SAPO-34X

Catalyst	CO₂ conversion/%	Selectivity/%
Catalyst	CO₂ conversion/%	CH₄	C₂H₄	C₂H₆	C₃H₆	C₄H₈	CO
CZA/SAPO-34	52.6	13.2	52.8	1.00	10.5	0.07	22.4
CZA/SAPO-34_M	53.4	12.2	53.5	0.12	9.6	0.08	24.5
CZA/SAPO-34_S	69.0	12.7	58.2	0.10	9.2	0.10	19.9
CZA/SAPO-34_P	73.8	8.1	67.7	0.06	6.3	0.10	17.8
CZA/SAPO-34_T	72.7	9.2	66.4	0.30	6.6	0.10	17.5
CZA/SAPO-34_R	71.8	9.8	65.2	0.50	6.8	0.10	17.6
CZA/SAPO-34_N	71.1	9.9	64.3	0.90	7.0	0.16	17.6

图5 反应压强对CZA/SAPO-34P催化性能的影响

Fig. 5 Effect of reaction pressure on the catalytic activity of CZA/SAPO-34P

图6 反应温度对CZA/SAPO-34P催化性能的影响

Fig. 6 Effect of reaction temperature on the catalytic activity of CZA/SAPO-34P

图7 反应温度对CZA/SAPO-34催化性能的影响

Fig. 7 Effect of reaction temperature on the catalytic activity of CZA/SAPO-34

参考文献 26

[1]	SITTICHAI N, LEKSE J W, BALTRUS J P,et al. Active sites and structure-activity relationships of copper-based catalysts for carbon dioxide hydrogenation to methanol. ACS Catal., 2012, 2(8): 1667-1676.
[2]	LIU X M, LU G Q, YAN Z F,et al. Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO2. Ind. Eng. Chem. Res., 2003, 42(25): 6518-6530.
[3]	GAYUBO A G, VICENTE J, ERE A J, et al. Causes of deactivation of bifunctional catalysts made up of CuO-ZnO-Al2O3 and desilicated HZSM-5 zeolite in DME steam reforming.Appal. Catal. A-Gen., 2014, 483: 76-84.
[4]	DUBOIS D R, OBRZUT D L, LIU J,et al. Conversion of methanol to olefins over cobalt-, manganese- and nickel-incorporated SAPO-34 molecular sieves. Fuel Proces. Technol., 2003, 83(1/2/3): 203-218.
[5]	JABBARI Z, FATEMI S, DAVOODPOUR M.Improvement of SAPO-34 fine layer formation on ceramic and steel supports by applying uniform-size synthesized seed particles. Asia-Pac J.Chem. Eng., 2013, 8(2): 301-310.
[6]	SLOCZYNSKI J, GRABOWSKI R, OLSZEWSKI P, et al. Effect of metal oxide additives on the activity and stability of Cu/ZnO/ ZrO2 catalysts in the synthesis of methanol from CO2 and H2.Appal. Catal. A-Gen., 2006, 310: 127-137.
[7]	YOU ZHENYA, DENG WEIPING, ZHANG QINGHONG,et al. Hydrogenation of carbon dioxide to light olefins over non-supported iron catalyst. Chinese J. Catal., 2013, 34(5): 956-963.
	HIRSA M, TORRES G, KRIGE P,et al. Catalysts for production of lower olefins from synthesis gas: a review. ACS Catal., 2013, 3(9): 2130-2149.
[8]	NISHIYAMA N, ICHIOKA K, PARK D H,et al. Reactant-selective hydrogenation over composite silicalite-1-coated Pt/TiO2 particles. Ind. Eng. Chem. Res., 2004, 43(5): 1211-1215.
[9]	PARK J W, SEO G.IR study on methanol-to-olefin reaction over zeolites with different pore structures and acidities.Appl. Catal. A-Gen., 2009, 356(2): 180-188.
[10]	CHEN D, REBO H P, MOLJORD K,et al. Influence of coke deposition on selectivity in zeolite catalysis. Ind. Eng. Chem. Res., 1997, 36(9): 3473-3479.
[11]	TAN JUAN, LIU ZHONGMIN, BAO XINHE,et al. Crystallization and Si incorporation mechanisms of SAPO-34. Micropor. Mesopor. Mat., 2002, 53(1/2/3): 97-108.
[12]	MISOOK K.Methanol conversion on metal-incorporated SAPO- 34s (MeAPSO-34s).J. Mole. Catal. A. 2000, 160(2): 437-444.
[13]	SALMASI M, FATEMI S, TAHERI NAJAFABADI A.Improvement of light olefins selectivity and catalyst lifetime in MTO reaction; using Ni and Mg-modified SAPO-34 synthesized by combination of two templates.J. Ind. Eng. Chem., 2011, 17(4): 755-761.
[14]	CORMA L, NEMETH T, RENZ M,et al. Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-viliger oxidations. Nature, 2001, 412: 423-425.
[15]	GARSUCH O, KLEPEL R, SATTLER R, et al. Synthesis of a carbon replica of zeolite Y with large crystallite size.Carbon, 2006, 44(1): 593-596.
[16]	WANG K, CAO G KENNEDY G J, et al. Pore modification of H-SAPO-34 using dialkyl zinc: structural characterization and reaction pathway. J. Phys. Chem. C, 2011, 115(38): 18611-18617.
[17]	TIAN HAIFENG, YANG AIMEI, ZHA FEI,et al. Preparation of imidazole-modified HZSM-5 zeolite and its application in the catalytic synthesis of dimethyl ether from hydrogenation of carbon dioxide. Fine Chem., 2014, 31(2): 186-192.
[18]	ZHAO YANQIAO, CHEN JIXIANG, ZHANG JIYAN.Effects of precipitation temperature on performance of the catalyst for dimethyl ether synthesis from carbon dioxide hydrogenation.Chem. React. Eng. Technol., 2007, 23(5): 456-461.
[19]	EREN J, GARON R, ARANDES J M, et al. Effect of operating conditions on the synthesis of dimethyl ether over a CuO-ZnO- Al2O3/NaHZSM-5 bifunctional catalyst. Catal. Today#/magtechI#. Effect of operating conditions on the synthesis of dimethyl ether over a CuO-ZnO- Al2O3/NaHZSM-5 bifunctional catalyst. Catal. Today, 2005, 107- 108: 467-473.
[20]	LIU ZHIJIAN, LIAO JIANJUN, TAN JINGPIN,et al. A method for evaluating the activity of CO2 hydrogenation catalyst for methanol synthesis. Chemical Engineering of Oil and Gas, 2000, 29(5): 268-271.
[21]	DAI W L, WANG X, WU G J,et al. Methanol-to-olefin conversion on silicoaluminophosphate catalysts: effect of bronsted acid sites and framework structures. ACS Catal., 2011, 1(4): 292-299.
[22]	JAROMIEC M, SOLOVYOV L A.Improvement of the kruk-jaroniec- sayar method for pore size analysis of ordered silicas with cylindrical mesopores.Langmuir, 2006, 22: 6757-6760.
[23]	POP G, BOZGA G, GANEA R,et al. Methanol conversion to dimethyl ether over H-SAPO-34 catalyst. Ind. Eng. Chem. Res., 2009, 48(15): 7065-7071.
[24]	BAEK S C, LEE Y J, JUN K W,et al. Influence of catalytic functionalities of zeolites on product selectivities in methanol conversion. Energy Fuel, 2009, 23(2): 593-598.
[25]	FUJIWARA M, SAKURAI H, SHIOKAWA K,et al. Synthesis of C2+ hydrocarbons by CO2 hydrogenation over the composite catalyst of Cu-Zn-Al oxide and HB zeolite using two-stage reactor system under low pressure. Catal. Today, 2015, 242: 255-260.
[26]	QI GUOZHEN, XIE ZAIKU, YANG WEIMIN,et al. Kinetic modeling of coke formation on SAPO-34 catalyst in the transformation of methanol to olefins. Journal of Fuel Chemistry & Technology, 2006, 34(2): 205-208.

咪唑/镍(II)改性SAPO-34的制备及其催化CO₂加氢制备乙烯

Imidazole and Nickel (II) Modified SAPO-34 and Its Catalytic Activity in CO₂ Hydrogenation to Ethylene

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	马晓森, 张丽晨, 刘砚超, 汪全华, 郑家军, 李瑞丰. 13X@SiO₂合成及其甲苯吸附性能[J]. 无机材料学报, 2023, 38(5): 537-543.
[2]	焦博新, 刘兴翀, 全子威, 彭永姗, 周若男, 李海敏. L-精氨酸掺杂钙钛矿太阳电池性能研究[J]. 无机材料学报, 2022, 37(6): 669-675.
[3]	董淑蕊, 赵笛, 赵静, 金万勤. 离子化氨基酸对氧化石墨烯膜渗透汽化过程中水选择性渗透的影响[J]. 无机材料学报, 2022, 37(4): 387-394.
[4]	周港怀, 刘耀, 石原, 刘绍军. 活性氧化铝催化剂载体的光固化浆料制备与成型[J]. 无机材料学报, 2022, 37(3): 297-302.
[5]	王潇, 朱智杰, 吴之怡, 张城城, 陈志杰, 肖梦琦, 李超然, 何乐. 钴等离激元超结构粉体催化剂的制备及其光热催化应用[J]. 无机材料学报, 2022, 37(1): 22-28.
[6]	付宇坤, 曾敏, 饶先发, 钟盛文, 张慧娟, 姚文俐. 锂离子电池高镍LiNi_0.8Mn_0.2O₂正极材料的微波合成及其Co、Al共改性[J]. 无机材料学报, 2021, 36(7): 718-724.
[7]	梁凤青, 温兆银. 固态锂电池用MOF/聚氧化乙烯复合聚合物电解质[J]. 无机材料学报, 2021, 36(3): 332-336.
[8]	董少杰,王旭东,沈国芳,王晓虹,林开利. 生物陶瓷支架的功能改性及应用研究进展[J]. 无机材料学报, 2020, 35(8): 867-881.
[9]	彭章美,赵安婷,付茂芬. Q[6]/CdS-Ag₂S复合光催化剂的合成及光催化性质[J]. 无机材料学报, 2020, 35(6): 703-708.
[10]	季邦, 赵文锋, 段洁利, 马立哲, 付兰慧, 杨洲. 泡沫镍网负载TiO₂/WO₃薄膜对乙烯的光催化降解[J]. 无机材料学报, 2020, 35(5): 581-588.
[11]	陈钧,马培华,张诚,劳伦·鲁尔曼,吕耀康. 新型多功能无机/有机复合薄膜的制备及电化学性能研究[J]. 无机材料学报, 2020, 35(2): 217-223.
[12]	方美蓉,秦利梅,贾晓博,李永生,牛德超,胡泽岚. 聚乙烯亚胺改性的双介孔氧化硅基因载体构建[J]. 无机材料学报, 2020, 35(2): 187-192.
[13]	程福强,吉田田,薛敏,孟子晖,吴玉凯. 巯基改性SBA-15的制备及其对Cr⁶⁺的吸附[J]. 无机材料学报, 2020, 35(2): 193-198.
[14]	范佳锋,张小锋,周克崧,刘敏,邓畅光,邓春明,牛少鹏,邓子谦. 镀铝改性对PS-PVD 7YSZ热障涂层抗CMAS腐蚀影响机制[J]. 无机材料学报, 2019, 34(9): 938-946.
[15]	李昊耕,谷红宇,章俞之,宋力昕,吴岭南,齐振一,张涛. 聚合物材料表面原子氧防护技术的研究进展[J]. 无机材料学报, 2019, 34(7): 685-693.