THFS-2硫化型重整预加氢催化剂的工业应用  

Industrial application of THFS-2 sulfurized reforming prehydrogenation catalysts

作　　者：王超 宋国良 肖寒 WANG Chao;SONG Guoliang;XIAO Han(CNOOC Huizhou Petrochemical Company Limited,Huizhou 516086,China;CenterTech Tianjin Chemical Research and Design Institute Co.Ltd.,Tianjin 300131)

机构地区：[1]中海石油惠州石化有限公司,广东惠州516086 [2]中海油天津化工研究设计院有限公司,天津300131

出　　处：《无机盐工业》2024年第5期94-100,共7页Inorganic Chemicals Industry

摘　　要：基于高氮环烷基直馏石脑油加氢生产重整原料的需求,通过自主研发的原位活化技术开发了THFS-2硫化型重整预加氢催化剂,采用N_(2)吸附-脱附、H_(2)-程序升温还原、X射线衍射、NH_3-程序升温脱附、吡啶吸附红外光谱和高分辨率透射电镜等方法进行分析表征。结果表明,相比THFS-1加氢催化剂,有机磷助剂的引入优化了催化剂的孔道结构,增加了强酸和B酸(质子酸)量,提高了金属硫化度和原子利用率,形成了更多的“Ni—Mo—S”II类活性中心相。THFS-2催化剂应用于中海油惠州石化有限公司80万t/a重整预加氢装置,开工过程高效环保,活化时间缩短至18 h,循环氢中硫化氢最高含量小于2 000μg/g。在反应器入口温度为289℃、氢分压为2.4 MPa、反应空速为5.0 h^(-1)、氢油比(气液体积比,Nm^(3)/m^(3))为130的满负荷工况下,加氢石脑油中硫、氮含量均小于0.5μg/g,溴指数小于100 mg/100 g,砷含量小于1.0μg/kg,氯含量小于0.5μg/g。工业运行结果表明,THFS-2硫化型重整预加氢催化剂性能优异,可以满足高氮石脑油在高空速条件下的加氢活性,为重整装置提供合格原料。According to the demand on hydrogenation of the high nitrogen and naphthenic base of traight naphtha for reform-ing raw materials,THFS-2 sulfurized reforming pre-hydrogenation catalyst was developed through the independently devel-oped in-situ activation technique.The catalysts were characterized by BET,H_(2)-TPR,XRD,NH3-TPD,Py-FTIR and TEM techniques.The results showed that compared to the THFS-1 hydrogenation catalyst,the addition of organic phosphorus as-sistant optimized the pore structure of the catalyst,increased the distributions of medium strong acid and B acid,improved the metal sulfide and atomic utilization rate,and formd more active“NiMoS-Ⅱ”phases.THFS-2 catalyst achieved indus-trial application on 800000 t/a reforming pre-hydrogenation unit of CNOOC Huizhou Petrochemical Co.,Ltd.The activation process was more efficient and environmentally friendly,the activation time was reduced to 18 h,and the highest hydrogen sulfide content in recycle hydrogen was less than 2000µg/g.Under the full load conditions of reaction inlet temperature of 289℃,hydrogen partial pressure of 2.4 MPa,the GHSV of 5.0 h^(-1),and hydrogen-oil ratio of 130 Nm^(3)/m^(3),the sulfur and ni-trogen contents in hydrogenated naphtha were less than 0.5µg/g,the bromine index was less than 100 mg/100 g,the arsenic content was less than 1.0µg/kg,and the chlorine content was less than 0.5µg/g.The result of industrial operation showed that THFS-2 sulfurized reforming prehydrogenation catalyst had excellent performance.It could meet the hydrogenation ac-tivity of the high nitrogen straight-run naphtha under the condition of high GHSV,and provided qualified raw materials for reforming plant.

关 键 词：硫化 重整预加氢 催化剂 工业应用 

分 类 号：O643.3[理学—物理化学]