Study of methanol shape-selective aromatization over ZnO/SiO2/ZSM-5 modified with mental oxide and silicon deposition
-
摘要: 采用真空浸渍法对ZSM-5分子筛进行硅沉积和负载金属修饰,制备了复合改性的ZnO/SiO2/ZSM-5催化剂,并将它应用于甲醇择形芳构化反应中。采用XRD、BET、NH3-TPD、SEM、TEM等方法对制备的催化剂进行了物化表征。考察硅沉积次数和ZnO负载量对甲醇芳构化反应(MTA)中对二甲苯(PX)的选择性和收率的影响。结果表明,两次硅沉积改性并负载2.0%金属ZnO的ZSM-5分子筛具有较高的PX收率,在优化的反应温度420 ℃、反应压力0.2 MPa、甲醇空速WHSV为1.25 h-1下,PX收率在28%以上。Abstract: ZnO/SiO2/ZSM-5 zeolites were prepared from ZSM-5 by vacuum metal impregnation of metallic oxides and silicon deposition. The resulted zeolite were characterized by XRD, BET, NH3-TPD, SEM and TEM. Furthermore, the influence of silicon deposition time and the content of impregnated ZnO to the selectivity and yield of p-xylene (PX) on the reaction of aromatization of methanol was investigated. The results indicated that by twice silicon deposition and 2.0% ZnO, the modified ZSM-5 had the highest PX selectivity. The yield of PX could reach up to 28% at 420 ℃, 0.2 MPa and 1.25 h-1 of methanol WHSV.
-
Key words:
- ZSM-5 /
- methanol /
- aromatization /
- shape-selective /
- p-xylene
-
温倩. 甲醇芳构化技术和经济性分析[J]. 煤化工, 2012, 2(159): 1-4. (WEN Qian. Technical and economic analysis of the aromatization of methanol[J]. Coal Chem Ind, 2012, 2(159): 1-4.) 田树勋, 朱伟平. 甲醇制烯烃催化剂研究进展[J]. 天然气化工, 2009, 34(6): 66-72. (TIAN Shu-xun, ZHU Wei-ping. Advances in research of catalysts for methanol to light olefins[J]. Nat Gas Chem Ind, 2009, 34(6): 66-72.) 苗青, 董梅, 牛宪军, 王浩, 樊卫斌, 王建国, 秦张峰. 含镓ZSM-5分子筛的制备及其在甲醇芳构化反应中的催化性能[J]. 燃料化学学报, 2012, 40(10): 1230-1239. (MIAO Qing, DONG Mei, NIU Xian-jun, WANG Hao, FAN Wei-bin, WANG Jian-guo, QIN Zhang-feng. Synthesis of gallium-containing ZSM-5 molecular sieves and their catalytic performance in methanol aromatization[J]. J Fuel Chem Technol, 2012, 40(10): 1230-1239.) 王金英, 李文怀, 胡津仙. ZnHZSM-5上甲醇芳构化反应的研究[J]. 燃料化学学报, 2009, 37(5): 607-612. (WANG Jin-ying, LI Wen-huai, HU Jin-xian. Study of methanol to aromatics on ZnHZSM-5 catalyst[J]. J Fuel Chem Technol, 2009, 37(5): 607-612.) 刘维桥, 雷卫宁, 尚通明. Zn对HZSM-5分子筛催化剂物化及甲醇芳构化反应性能的影响[J]. 化工进展, 2011, 30(9): 1967-1976. (LIU Wei-qiao, LEI Wei-ning, SHANG Tong-ming. Physicochemical and methanol aromatization property of HZSM-5 catalyst promoted by Zn[J]. Chem Ind Eng Prog, 2011, 30(9): 1967-1976.) 张建祥, 关乃佳, 李伟. 非金属、第二金属改性对ZnZSM-5上丙烷芳构化的影响[J]. 石油学报, 2000, 15(3): 7-11. (ZHANG Jian-xiang, GUAN Nai-jia, LI Wei. Aromatization of propane over ZnZSM-5 modified by non-metal and second metal components[J]. Acta Pet Sin, 2000, 15(3): 7-11.) 田涛, 骞伟中, 孙玉建, 崔宇, 卢俨俨, 魏飞. Ag/ZSM-5催化剂上甲醇芳构化过程[J]. 现代化工, 2009, 29(1): 55-58. (TIAN Tao, QIAN Wei-zhong, SUN Yu-jian, CUI Yu, LU Yan-yan, WEI Fei. Aromatization of methanol on Ag/ZSM-5 catalyst[J]. Mod Chem Ind, 2009, 29(1): 55-58.) 田涛, 骞伟中, 汤效平. 甲醇芳构化反应中Ag/ZSM-5催化剂的失活特性[J]. 物理化学学报, 2012, 26(12): 3305-3309. (TIAN Tao, QIAN Wei-zhong, TANG Xiao-ping. Deactivation of Ag/ZSM-5 catalyst in the aromatization of methanol[J]. Acta Phys-Chim Sin, 2010, 26(12): 3305-3309.) 朱志荣. ZSM-5分子筛择形功能的化学修饰及其对二甲苯催化合成的研究. 上海: 上海石油化工研究院, 2006. (ZHU Zhi-rong. Chemical modification of the shape-selective functionalization of ZSM-5 zeolite for the catalytic synthesis of para-xylene. Shanghai: Shanghai Research Institute of Petrochemical Technology, 2006.) 姜健准, 张明森, 柯丽, 杨菁, 王焕茹, 黄文氢. 超细ZSM-5分子筛的制备及其形貌表征[J]. 化工进展, 2012, 31(9): 1980-1984. (JIANG Jian-zhun, ZHANG Ming-sen, KE Li, YANG Jing, WANG Huan-ru, HUANG Wen-qing. Synthesis and characterization of ultra-fine ZSM-5 zeolite[J]. Chem Ind Eng Prog, 2012, 31(9): 1980-1984.) 刘金香, 蔡光宇, 杨立新, 高秀英, 季平, 陈国权. 热重法研究甲醇在沸石催化剂上转化为低级烯烃过程中的积炭行为[J]. 催化学报, 1985, 6(3): 218-223. (LIU Jin-xiang, CAI Guang-yu, YANG Li-xin, GAO Xiu-ying, JI Ping, CHEN Guo-quan. The coking behaviour of zeolite catalysts during the conversion of methanol to lower olefins[J]. Chin J Catal, 1985, 6(3): 218-223.) 钟炳, 罗庆云, 肖有燮, 张威. 甲醇在HZSM-5上转化为烃类的催化反应机理[J]. 燃料化学学报, 1986, 14(1): 9-16. (ZHONG Bing, LUO Qing-yun, XIAO You-xie, ZHANG Wei. Reaction mechanism of methanol to hydrocarbons on HZSM-5[J]. J Fuel Chem Technol, 1986, 14(1): 9-16.) SONG Y Q, ZHU X X, XU L Y. Study on the process of transformation of olefin into aromatics over HZSM-5[J]. Appl Catal, 2006, 7(4): 218-223. 张超, 陆志强, 陈万里. 二甲基硅油生产状况及研究进展[J]. 科技信息, 2010, 11: 47-48. (ZHANG Chao, LU Zhi-qiang, CHEN Wan-li. Production status and research progress of dimethicone[J]. Sci Technol Inf, 2010, 11: 47-48.) KOMATSU T. Aromatization of butane on Pt-Ge intermetallic compounds supported on HZSM-5[J]. Appl Catal, 2000, 194-195: 333-339. CHANG C D, LANG W H, SMITH R L. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts[J]. J Catal, 1979, (56): 169-173.
点击查看大图
计量
- 文章访问数: 414
- HTML全文浏览量: 31
- PDF下载量: 798
- 被引次数: 0