Preparation Of Ni-P/APO-11 Amorphous Catalyst And Its Catalytic Activity For Hydrogenation Of Turpentine Oil

Turpentine was biomass derived from metabolites.Its main components were?-pinene and ?-pinene which had active chemical properties.Therefore,they can be participated in many chemical reactions.The hydrogenation products of pinane were one of the important raw materials of spice industry,which can produce linalool,dihydromyrcene and so on.Pinane included two kinds of cis-and trans-pinane.Because of cis-pinane had much higher active than trans-pinane,cis-pinane was often applied in industrial production.Therefore,it was of great significance to research and prepare high performance for turpentine deep processing and utilization.At present,the catalyst for catalytic hydrogenation of pinene can be divided into non noble metal catalysts and noble metal catalysts.Because of low price,wide source,non noble metal nickel catalysts had been favored.In this study,the preparation of Ni-P/APO-11 catalst was made by chemical reduction method to catalytic the hydrogenation of pinene and other major components of turpentine.The following aspects were researched:(1)APO-11 aluminophosphate molecular sieve was prepared by hydrothermal method and determined the optimum conditions:the molar ratio of ?-Pr2NH/Al/P/H2O was 2:1:1:40,the crystallization time was 24 h,the crystallization temperature was 200 ?,the drying temperature was 110 ?.Meanwhile,the crystallization kinetics of APO-11 was studied and calculated apparent nucleation activation energy En and apparent growth activation energy Eg.(2)The preparation of Ni-P/APO-11 catalyst was made by chemical reduction method and investigated optimal preparation conditions by BBD response surface method at n(P)/n(Ni)=5.18,pH=8,m(Ni2+)/m(APO-11)?1:2.5,preparation temperature 29 ?.Meanwhile,the preparation conditions and catalytic performance were investigated by SEM,TEM,BET and XPS.Meanwhile,the optimal reaction conditions were investigated by the BBD response surface method and obtained:reaction pressure 4.9 MPa,reaction temperature 124.8 ?,the reaction time 1.5 h,the amount of catalyst 6.3wt%,the conversion rate of a-pinene was 99.45%,the selectivity of cis-pinane was 97.35%.Under these conditions,the repeatability was better and the catalyst could be used for 5 times.Meanwhile,the catalyst was applied in the hydrogenation of other components,the conversion of raw material can reach more than 99%and the selectivity is more than 65%.(3)The hydrogenation products were analyzed by GC and GC-MS,the carrier and catalyst were characterized by XRD,SEM-EDX,TEM,HRTEM,XPS,BET and ICP.The results showed that aluminophosphate molecular sieve APO-11 with AEL was successfully synthesized,it showed a columnar aggregates,length 15-20 ?m,width 5-10 ?m and the surface area was 190.95 m2/g.however the catalyst was 127.67 m2/g.SEM and TEM results showed the amorphous Ni-P catalyst had been successfully loaded on APO-11.There are several reasons for the deactivation of the catalyst:(a)The aggregation of Ni-P nanoparticles had different dispersion,the former had better dispersion and smaller particle size,however,the latter was serious,and the particle size was larger.(b)The active component Ni was lost.(c)Because of Ni valence state changing,the Ni0 content was significantly decreased and the proportion of Ni2+ was increased by XPS spectrums,Ni0 was oxidized to Ni2+.