噻吩和苯并噻吩在原位氢存在下的还原脱硫  

Reductive desulfurization of thiophene and benzothiophene over nickel boride using in situ generated hydrogen

作　　者：郭秀燕[1] 李术元[1] 刘峰[2] 岳长涛[1] 

机构地区：[1]中国石油大学重质油国家重点实验室,北京102249 [2]中国石油规划总院,北京100083

出　　处：《化学工程》2007年第10期27-29,38,共4页Chemical Engineering(China)

基　　金：中国石油科技中青年创新基金资助项目(04E7030);中国石油大学重油开放基金资助项目(2004-05)

摘　　要：研究了噻吩和苯并噻吩在原位氢和硼化镍存在下的还原脱硫。实验对操作条件进行了优化;研究了可能的反应机理。结果表明,六水合氯化镍与还原剂于质子溶剂中反应的对硫化物脱硫,产生的原位氢脱硫活性较高;还原剂用量为0.64 g时,脱硫率可达99%以上。噻吩和苯并噻吩脱硫主要发生直接氢解反应;少量苯并噻吩脱硫经由加氢途径进行,硫化物主要通过S原子'端连吸附'在硼化镍表面。推测反应机理为,反应中大量原位氢吸附在硼化镍表面并活化;硼化镍中富电子镍介入硫化物分子中C—S键形成加合物,与活性原位氢进一步作用,使C—S和C—C键断裂。A new desulfurization of thiophene （T） and benzothiophene （BT） using in situ generated hydrogen was evaluated. The results showed that hydrogen and nickel boride in situ generated from reaction of nickel chloride with reducing reagent in protic solvent and 0.64 g reducing reagent were developed with a desulfurization efficiency of more than 99%. The desulfurization of T and BT on metal boride proceeded through the direct hydrogenolysis of C--S bond basically, and the desulfurization of a small quantity of BT proceeded through the hydrogenation route. The probably reaction mechanism is deduced that the hydrogen is firstly adsorbed and activated on the surface of nickel boride, and the sulfur compounds are adsorbed on the active sites via ＂end-on adsorption＂ of sulfur atom, the nickel atoms on the surface of solid insert into the C--S bonds of sulfur compounds to form certain insertion adducts, reacting with adsorbed and activated hydrogen, followed by the cleavage of C--S bonds and C--C bonds.

关 键 词：原位氢 硼化镍 还原脱硫 

分 类 号：TE624.55[石油与天然气工程—油气加工工程]