负载镉离子ZSM-5分子筛膜脱硫性能的研究
|
摘要
采用二次水热合成法制备出硅铝比为100的ZSM-5分子筛膜,用于脱除模拟汽油中的噻吩类硫化物。用X射线衍射仪和扫描电子显微镜对改性后的分子筛膜进行表征。考察了脱硫次数对脱硫效果的影响,测试了膜稳定脱硫时间,并进行再生实验。结果表明,经过Cd~(2+)改性的ZSM-5分子筛膜的骨架和形貌未发生改变,负载Cd~(2+)浓度为0.2 mol/L时,膜脱除噻吩类硫化物效果最佳,负载Cd~(2+)浓度为0.3 mol/L时,脱硫过程中分子筛膜出现堵塞情况。经0.2 mol/L Cd~(2+)改性过的ZSM-5分子筛膜两次脱硫后,噻吩的脱硫率可以达到81%,苯并噻吩的脱除率可以达到85%,稳定脱硫能持续32 h,再生后的膜脱硫效果良好。
The ZSM-5 zeolite membranes,the Si/Al ratios of which is 100,were prepared on the surface of Al_2O_3 tubes using second-step hydrothermal synthesis method. The membranes separated the thiophenetype sulfide from the model gasoline. The desulfurization performance of the ZSM-5 zeolite membrane loaded with cadmium ion was investigated. The membranes modified were characterized by X-ray diffraction and scanning electron microscope. Furthermore,the experiment to text the sustainability and renewability of membrane desulfurization was conducted. The results showed the desulphurization ratio of membrane modified by 0. 2 mol/L Cd~(2+)solution was optimal. The ZSM-5 zeolite membrane modified by0. 3 mol/L Cd~(2+)solution could be blocked sometimes. Approximately the 81% of thiophene and 85% of benzothiophene can be removed when the desulfurization process was conducted twice. The time of sulfide being removed stably could continued for about 32 h. The good desulfurization performance can be recovered by calcination.
The ZSM-5 zeolite membranes,the Si/Al ratios of which is 100,were prepared on the surface of Al_2O_3 tubes using second-step hydrothermal synthesis method. The membranes separated the thiophenetype sulfide from the model gasoline. The desulfurization performance of the ZSM-5 zeolite membrane loaded with cadmium ion was investigated. The membranes modified were characterized by X-ray diffraction and scanning electron microscope. Furthermore,the experiment to text the sustainability and renewability of membrane desulfurization was conducted. The results showed the desulphurization ratio of membrane modified by 0. 2 mol/L Cd~(2+)solution was optimal. The ZSM-5 zeolite membrane modified by0. 3 mol/L Cd~(2+)solution could be blocked sometimes. Approximately the 81% of thiophene and 85% of benzothiophene can be removed when the desulfurization process was conducted twice. The time of sulfide being removed stably could continued for about 32 h. The good desulfurization performance can be recovered by calcination.
引文
[1]达如汉.我国汽油脱硫技术的发展及展望[J].化工管理,2014(8):96.
[2]刘玉良.FCC汽油脱硫工艺及发展现状[J].广州化工,2010(2):16-19.
[3]曹冬梅.我国SO2污染,危害及控制技术[J].环境科学导刊,2013,32(2):73-74.
[4]唐晓东,张永汾,李晶晶,等.FCC汽油烷基化脱硫催化剂新进展[J].现代化工,2014,34(8):41-44.
[5]国外汽油标准[J].标准生活,2014,22(1):40-42.
[6]秦启飞,孙江波,崔淼,等.ZSM-5分子筛膜的一次水热法合成及工艺探索[J].材料导报:纳米与新材料专辑,2010,24(1):64-66.
[7]耿丹,陈玉丽,居沈贵.模板剂对ZSM-5分子筛膜脱硫的影响[J].化工进展,2014(5):1230-1235.
[8]刘晴,张旭东,居沈贵.改性ZSM-5膜脱除汽油中多组分硫化物的研究[J].污染防治技术,2014(3):23-27.
[9]薛宁,居沈贵.改性ZSM-5分子筛膜对二元噻吩类硫化物分离性能[J].化工进展,2010(3):444-448.
[10]殷晓伟,冯辉,居沈贵.负载金属离子ZSM-5分子筛膜脱除噻吩的性能[J].石油化工,2008,37(11):1201-1205.
[11]刘晴,居沈贵.改性ZSM-5分子筛膜脱除苯并噻吩/2,5-二甲基噻吩[J].化工进展,2011,30(4):886-890.
[12]Gao Y,Chen M,Zhang T,et al.A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel[J].Materials Letters,2011,65(17):2789-2792.
[13]Zhang K,Liu Y,Tian S,et al.Preparation of bifunctional Ni Pb/Zn O-diatomite-ZSM-5 catalyst and its reactive adsorption desulfurization coupling aromatization performance in FCC gasoline upgrading process[J].Fuel,2013,104:201-207.
[14]Yang R T,Hernndez-Maldonado A J,Yang F H.Desulfurization of transportation fuels with zeolites under ambient conditions[J].Science,2003,301(5629):79-81.
[15]Smith T J.Mol View:a program for analyzing and displaying atomic structures on the Macintosh personal computer[J].Journal of Molecular Graphics,1995,13(2):122-125.
[2]刘玉良.FCC汽油脱硫工艺及发展现状[J].广州化工,2010(2):16-19.
[3]曹冬梅.我国SO2污染,危害及控制技术[J].环境科学导刊,2013,32(2):73-74.
[4]唐晓东,张永汾,李晶晶,等.FCC汽油烷基化脱硫催化剂新进展[J].现代化工,2014,34(8):41-44.
[5]国外汽油标准[J].标准生活,2014,22(1):40-42.
[6]秦启飞,孙江波,崔淼,等.ZSM-5分子筛膜的一次水热法合成及工艺探索[J].材料导报:纳米与新材料专辑,2010,24(1):64-66.
[7]耿丹,陈玉丽,居沈贵.模板剂对ZSM-5分子筛膜脱硫的影响[J].化工进展,2014(5):1230-1235.
[8]刘晴,张旭东,居沈贵.改性ZSM-5膜脱除汽油中多组分硫化物的研究[J].污染防治技术,2014(3):23-27.
[9]薛宁,居沈贵.改性ZSM-5分子筛膜对二元噻吩类硫化物分离性能[J].化工进展,2010(3):444-448.
[10]殷晓伟,冯辉,居沈贵.负载金属离子ZSM-5分子筛膜脱除噻吩的性能[J].石油化工,2008,37(11):1201-1205.
[11]刘晴,居沈贵.改性ZSM-5分子筛膜脱除苯并噻吩/2,5-二甲基噻吩[J].化工进展,2011,30(4):886-890.
[12]Gao Y,Chen M,Zhang T,et al.A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel[J].Materials Letters,2011,65(17):2789-2792.
[13]Zhang K,Liu Y,Tian S,et al.Preparation of bifunctional Ni Pb/Zn O-diatomite-ZSM-5 catalyst and its reactive adsorption desulfurization coupling aromatization performance in FCC gasoline upgrading process[J].Fuel,2013,104:201-207.
[14]Yang R T,Hernndez-Maldonado A J,Yang F H.Desulfurization of transportation fuels with zeolites under ambient conditions[J].Science,2003,301(5629):79-81.
[15]Smith T J.Mol View:a program for analyzing and displaying atomic structures on the Macintosh personal computer[J].Journal of Molecular Graphics,1995,13(2):122-125.