| Turpentine is a kind of renewable natural resources which can be obtained rosin and turpentine after distillation. Disproportionated rosin amine is one of deep-processing products which has good biological activity and become an important natural organic synthesis raw material. Abietic type acid, which is short for "abietic acid", and pimaric type acid are the main components of rosin.The purification of abietic acid and the preparation of high content of dehydroabietic acid amine component of disproportionated rosin amine have important significance to increase the added value of rosin’s deep processing products. Fluid catalytic cracking FCC waste catalyst is an large amount of solid waste produced in the process of petroleum refining industry in the light of the heavy oil. This article first attempted at the FCC waste catalyst regeneration and applied to the preparation of disproportionated rosin amine, turned the FCC waste catalyst waste into treasure. The main research contents are as follows: By microwave strengthening rosin acid isomerization reaction, promoting rosin resin acid turned into abatic acid in a short time. Microwave fortified rosin isomerization optimum conditions were:hydrochloric acid as catalyst, microwave power500W, reaction temperature40℃, reaction time30min, the content of abetic acid measured by GC was86%.Using isomerous rosin as raw materical, microwave radiation enhanced isomerous rosin amination-crystallization reaction to prepare abetic acid. Microwave can make the amination process at a low temperature, break the homogeneous chemical equilibrium, achieving the coupling of reaction and crystallization separation. The optimal reaction conditions of purification of abietic acid were established by the single factor and orthogonal experiment as fllow:microwave power500W, reaction temperature35℃, reaction time25min, ratio of raw materials (n Rosin:n ethanolamine)=1:1. Abietic acid purity and yield were98.60%and54.47%, respectively. Using high-purity abietic acid as raw materials, it also can obtain disproportionated rosin nitrile with dehydroabietic nitrile content of90.86%by disproportionation reaction and ammoniated reaction.With FCC waste catalyst as carrier, FCC waste catalyst-supported nickel was prepared by incipient impregnation, and for the first time used in the catalytic hydrogenation reaction of disproportionated rosin nitrile to preparare disproportionated rosin amine. Using purity of primary amine and its conversion rate of disproportionated rosin amine as examining index, the effct of catalytic amount, promoter NaOH dosage, reaction temperature, reaction pressure, stirring speed, reaction time and other factors on catalytic hydrogenation of disproportionated rosin nitriles by Single factor and orthogonal experiment. Using purity of primary amine as indicator, the significant degree of each factor as follows:reaction pressure> reaction time> stirring speed> catalyst amount> reaction temperature. Using conversion rate of primary amine as indicator, the degree of impact:reaction pressure> stirring speed> catalyst amount> reaction time> reaction temperature.Combined with the comprehensive analysis of single factor experiment and orthogonal experiment, using disproportionated rosin nitrile as raw material and FCC waste catalyst-supported nickel as catalyst, the optimum conditions of FCC waste catalyst supported-nickel for catalytic hydrogenation to prepare disproportionated rosin amine were:FCC waste catalyst-supported nickel catalyst15wt%, NaOH dosage0.1wr%, reaction temperature130℃, reaction pressure5Mpa, stirring speed500r·min-1, the reaction time4h, and validated the optimal conditions. The results showed that in the optimal experimental conditions, the purity and conversion of primary amine were90.58%and98.14%, respectively, which the content of dehydroabietic acid amine is60.29%. Using disproportionated rosin nitrile with high content of dehydroabietic acid nitrile as raw material to prepare disproportionated rosin amine, its purity and conversion rate of primary amine were94.58%and98.00%, respectively, which dehydroabietic acid amine content was86.52%. Compared with conventional methods, the content of dehydroabietic acid amine had improved significantly. |
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