煤焦油加氢脱硫脱氮催化剂研究进展  

Research progress in desulfurization and denitrification catalysts for coal tar hydrogenation

作　　者：田梦[1] 周厚峰 张谦温[2] 

机构地区：[1]北京化工大学化学工程学院,北京100029 [2]北京石油化工学院化学工程学院,北京102617

出　　处：《工业催化》2014年第4期252-258,共7页Industrial Catalysis

摘　　要：随着石油资源的日趋减少,煤焦油加工技术受到关注。汽车尾气中含有的硫和氮污染环境,各国对油品中的硫和氮含量进行了严格限制,脱硫和脱氮成为煤焦油化工行业的重要课题。介绍煤焦油加氢工艺,综述金属碳化物、氮化物、磷化物和硫化物作为催化剂的研究现状。贵金属催化剂具有较强的加氢能力,并且通过使用强酸性载体分子筛和双金属催化剂的方法提高贵金属催化剂的抗硫毒性。碳化物催化剂具有较高的熔点和硬度、较好的机械稳定性和热稳定性,室温下几乎可以耐各种腐蚀性物质。根据金属源和碳源的不同,介绍使用程序升温还原法、气相法、热分解法和液相反应法制备碳化物催化剂的制备工艺。过渡金属磷化物催化剂具有优异的加氢脱硫和加氢脱氮选择性,添加钒的磷化物催化剂能改变加氢脱氮路径的选择性,明显增加咔唑加氢脱氮反应活性,钙的添加明显提高磷化物催化剂的加氢脱硫活性。工业上通常以ⅥB族和ⅧB族金属为活性物质制备过渡金属硫化物催化剂,使用的贵金属主要包括Pt、Pd和Ru,非贵金属主要包括W、Mo、Co和Ni等,其中,贵金属通常使用Al2O3或SiO2为载体。ZrO2载体可与活性组分产生较强的相互作用,热力学稳定性较高,但比表面积小,价格昂贵。Al2O3载体机械强度大,比表面积高,ZrO2-Al2O3复合载体将两者的优良性能结合,可以获得性能更加优异的载体。With the decrease of petroleum resources, the coal tar processing technology attracts more attention. The environment has been seriously polluted by sulfur and nitrogen contained in vihecle exhaust, so the contents of sulfur and nitrogen in oil are strictly restricted. Thus desulfurization and denitrification have become the important issues in Coal tar chemical industry. In the paper, the hydrogenation processes of coal tar were introduced, and the research status of the carbides, nitrides, phosphides and sulfides of the metals as the active components of the catalysts was also reviewed. The noble metal cata lysts had strong hydrogenation ability. The anti-sulfur properties of the noble metal catalysts were enhanced by using molecular sieves with strong acid carriers and bi-metal catalysts. The carbide catalysts had high melting points and hardness, good mechanical and thermal stability and were resistant to almost all kinds of corrosive substances at room temperature. Using different metal and carbon sources, the prepa- ration processes of carbide catalysts by adopting temperature programmed reduction, the vapor phase method, the thermal decomposition method, and liquid phase method were introduced. The transition metal phosphide catalysts possessed excellent selective hydrodesulfurization and hydrodenitrogenation proper- ties. Phosphide catalysts added with vanadium could change the selectivity of HDN path, which signifi- cantly increased HDN reactivity of carbazole. Furtheremore, phosphide catalysts added with calcium could also enhance the activity of hydrodesulfurization obviously. Transition metal sulfide catalysts were prepared using VI B and VI~ B groups metals as the active components in industry. Typically, Pt, Pd, and Ru were representatives of noble metal, while non-noble metal W, Mo, Co and Ni were utilized broadly. Al2O3 or SiO2 were used as the carriers for precious metals. High priced ZrO2 exhibited small surface area even though it showed higher thermodynamic stability and stronger interaction w

关 键 词：催化剂工程 煤焦油 加氢工艺 加氢脱硫 加氢脱氮 

分 类 号：TQ426.6[化学工程] O643.36[理学—物理化学]