Study On The Esterification Of Pyrolysis Oil Of Waste Oil Catalyzed By Solid Acid

Biofuel is reproductive environmental-friendly and it could be used as alternativetraditional fossil diesel without transformation of present engine. The research anddevelopment of biofuel has very important significance to alleviate the energy crisis,guarantee energy security and protect the environment. This paper explored catalyticpyrolysis, methyl esterification of waste oil to prepare biofuel. The properties ofesterification products of pyrolysis oil from waste oil were also investigated. Thisstudy not only provides good catalysts for deep processing and utilization of waste oilbut also offer groundwork in improving preparation process of biofuel.The methyl esterification of pyrolysis oil of waste oil using SO42-/ZrO2soild acidas catalyst was studied. Effects of sources of zirconium, calcination time andcalcination temperature on the catalyst activity were investigated. The acidity and acidtype of catalysts was analyzed by temperature programmed desorption of ammonia(NH3-TPD) and fourier infrared absorption spectroscopy (Py-IR) technology. Thecomposition of pyrolysis oil and esterification products were characterized usingGC-MS techniques and the properties were studied and the performance ofesterification product was investigated. The results showed SO42-/ZrO2prepared byusing ZrOCl2as the source of zirconium, calcinations temperature550℃andcalcinations time4h had the highest catalyst activity and the performance is stableamong all the prepared samples. The properties of esterification products were similarto bio-diesel and0#diesel. Effects of reaction time, reaction temperature, material ratioand the amount of catalyst on esterification of pyrolysis oil through singer factor testsand orthogonal experiments were researched. The optimal conditions were obtained as follows: reaction time4h, reaction temperature100℃, m(methanol):m(oil)=1.25:1,m(catalyst):m(oil)=5%, m(oil)=3g. The methyl esterification reaction kinetics ofpyrolysis oil of waste oil was explored. The kinetics calculation of the methylesterification using pyrolysis oil of rubber seed oil as raw material indicated that thereaction order is1.058, and Arrhenius equation can be expressed as1=7.711×106e47R.9T13. The kinetics calculation of the methyl esterification using pyrolysis oil ofillegal cooking oil as raw material indicated that it is a zero order reaction, andArrhenius equation can be expressed as=48.627×e19R.7T21.The methyl esterification of pyrolysis oil of rubber seed oil usingZr(SO4)2/SBA-15mesoporous molecular sieve as catalyst was studied. Effects ofsources of zirconium and the amount of zirconium source on the catalyst activity wereinvestigated. The acidity and acid type of catalysts was analyzed by NH3-TPD andPy-IR technology. The structure of catalysts was characterized by X-ray diffractionand nitrogen adsorption-desorption methods. The composition of pyrolysis oil andesterification products were characterized using GC-MS techniques and the propertieswere studied and the performance of esterification product was investigated. Theresults showed that Zr(SO4)2/SBA-15mesoporous molecular sieve using40%Zr(SO4)2as zirconium source which accounted for40%of total amount of Zr(SO4)2and SBA-15had well catalytic performance and service life. The optimal conditionswere obtained as follows: reaction time4h, reaction temperature100℃,m(methanol):m(oil)=1.25:1, m(catalyst):m(oil)=5%, m(oil)=3g. What’s more, thereaction time can be shortened to40min. The density and kinematic viscosity ofesterification products have reached the standard range of0#diesel and otherproperties were superior to bio-diesel.