Preparation Of Nickel Phosphide Catalysts And The Catalytic Performances Of Hydrogenation Of Petroleum Resin

Hydrogenated C9 petroleum resins,which have good thermal stability,low acid value,low melting point,good adhesion,water resistance,chemical resistance and other characteristics,are widely used in hot-melt adhesive,paint,printing ink,paint,adhesives,rubber and other industries.Therefore,it is of great importance to accelerate the hydrogenation technology research of C9 petroleum resin,but the key is the study of hydrogenation catalyst.At present,Pd catalyst is widely used in C9 petroleum resin hydrogenation,but it is sensitive to S impurities in raw materials and easily poisoning deactivation.Therefore,it is significant to improve the service life of the Pd catalyst.In this paper,we tried to remove most S impurities in raw material through the study of the hydrodesulfurization pretreatment of C9 petroleum resin.We prepared CoMoPS series,NiMoS series and NiWS series hydrodesulfurization catalysts by co-impregnation and used in hydrodesulfurization reaction to investigate their catalytic properties.Experimental results show that:1,the product of bromine value has a corresponding relationship with the sulfur content:bigger bromine value with higher sulfur content,smaller bromine value with lower sulfur content.2,NiWS catalyst shows more excellent catalytic activity and stability than NiMoS catalyst and CoMoPS catalyst in C9 petroleum resin hydrogenation desulfurization reaction.After NiWS hydrodesulfurization pretreatment,bromine value is 200 mg Br2/100 g and S content is 3.54 ppm in the hydrogenated C9 petroleum resin,and the catalyst still keeps high activity after 240 h.In addition,for C9 petroleum resin with high space steric hindrance and much impurity,this paper attempts to prepare Ni2P catalyst by loading on the high specific surface area carrier which displayed good hydrogenation activity and sulfur resistance performance.In the beginning,we adopted H2-TPR method to prepare 10wt.%Ni2P/SiO2 catalyst and optimized the reaction conditions to investigate the catalytic hydrogenation of C9 petroleum resin.Reaction results show that,in the catalytic hydrogenation of C9 petroleum resin,Ni2P/SiO2 catalyst has excellent catalytic activity and stability.Under optimal conditions of 250?,6 MPa and 1 h-1,the product bromine value reduced from 3.67 g Br2/100 g to 300 mg Br2/100 g or less.After 300 h reaction,the catalyst still remains high activity and the product bromine value is about 250 mg Br2/100 g.It is not conducive to the formation and dispersion of Ni2P by H2-TPR method taken ?-Al2O3 as carrier for easily leading to generate A1P04 which will cover the surface of the carrier.Therefore,this paper also explored and prepared Ni2P/?-Al2O3 catalyst by thermal decomposition of hypophosphite precursor.After characterizing the Ni2P/SiO2 by XRD,BET,TEM,we find that Ni2P crystal dispersed evenly and the catalyst surface area,pore volume and pore size decreased slightly without AIPO4 formed.