Synthesis Of Ethyl Acetate And Butyl Acetate By Fluidized Catalyst Reaction Distillation

Chemical reaction process is the core of the chemical conversion technology so that improving chemical reaction process efficiency is an important task for the scientists and the engineers. The development of the reaction and separation coupling techniques is a kind of trend for chemical conversion technology research. Catalytic distillation technology developed in the past30years is a strengthening the reaction process in which the heterogeneous catalyst reaction is coupled with the distillation process. Catalytic distillation has the advantages of low energy consumption, simplicity of operation and less investment, this technology has good practical prospects for the acetate production industry.The best catalytic performance of gel-type strong acid resin A in synthesis of ethyl acetate and butyl acetate was picked from the four commercial strong acid ion exchange resins. Through the characterizations of acidic ion exchange resin, the catalytic esterification reaction differences were explained primarily by the content and the activity of group—SO3H. The effects of smashing, combined with some metal ions, temperature resistance, re-use and regeneration on the catalytical performance of the resin A were investigated. The results showed that the resin A catalyst had good selectivity and the smashing had little impact on its catalytical performance. The catalytic activity decreased to the respective degree after complex to the different metal ions such as Fe2+, Ni+, Mn2+, Cr3+, Cu2+et al. The catalytic activity of resin A interacted with ions of Fe2+and Ni+decreased to the most degree. The catalytic activity of resin combining with ions of Fe2+and Mn2+recovered well after acidactivation but did bad combining with ions of Cr3+, Cu2+and Ni+. The catalytic activity of resin A increased when it was combined with ion of Fe3+. The catalytic activity of resin A had no significant decline after reusing15times. The dissolved loss of resin A in the reaction systems synthesizing ethyl acetate and butyl acetate were0.35%and0.15%respectively. Resin A can be effectively used at180℃.The effects of the resin A on the synthesis process of ethyl acetate and butyl acetate were studied respectively. The conversion of ethanol was above90%when catalyst amount was0.05gcat·gA-1, reaction temperature was67.7℃, the initial mole ratio of acetic acid to ethanol was3:1, reaction time was2hours. The conversion of butanol was above90%when catalyst amount was0.08gcat·gA-1, reaction temperature was80.5℃, the initial mole ratio of acetic acid to butanol was3:1, reaction time was2hours. The conversion of ethanol and butanol in the esterification of acetic acid with ethanol and butanol simultaneously were less than the conversion in the single reaction respectively at same conditions. When initial mole ratios of acetic acid, ethanol and butanol were2:0.8:1, the conversion rates of ethanol and butanol were72.73%and64.4%respectively after2hours. When the initial mole ratios were2:1:0.8, the conversion of ethanol and butanol were69.94%and63.04%respectively after2hours.The kinetics of synthesizing ethyl acetate and butyl acetate with resin A catalyst were respectively investigated in batch reactor. The pseudo homogeneous kinetics model for two esterification reactions were obtained using the method of initial reaction rate by eliminating internal and external diffusion conditions. When the catalyst amount range was0.01665～0.08333gcat·gA-1and reaction temperature range was between320.5K～340.7K, the pseudo homogeneous kinetics model synthesizing ethyl acetate was following form:When the catalyst amount range was0.01665～0.08333gcat·gA-1and the temperature range was between320.5K and340.7K, the pseudo homogeneous kinetics model synthesizing butyl acetate was following form:In kinetic model for synthesis of ethyl acetate, the maximum relative deviation between the calculating value and the experimental value was8.3%. In kinetic model for synthesis of butyl acetate, the maximum relative deviation was8.5%. Both of confidence coefficients in two models were equal to98%.The hydrodynamic performance and separation performance of the catalytic distillation column packed small size ceramic Rasching rings at the diameter of34mm with the fluidized resin powder in liquid phase were investigated by air-water system. The results showed that the resin powder had little effect on the pressure drop of the packed column. The increase of content resin powder in liquid phase increased, the liquid holdup of packing bed and increased the separation performance of the column at the same operating conditions. Compared with those without resin powder in the liquid phase, the separation performance of the pack column increased20percent with the resin powder content of4%.The continuous synthesis processes of ethyl acetate and butyl acetate were investigated in a diameter of34mm fluidized catalytic distillation column. When ethanol fed in at Y10near tower bottom, acetic acid fed in at Y3near tower top, catalyst amount was0.05gcat·gA-1,mole ratios of acetic acid to ethanol was2.5:1, reflux ratio of99.5%ethyl acetate to taken out column top was2.5times, the proportion of ethyl acetate, acetic acid, ethanol and water in the organic phase from the column top were95.71%,0.028%,1.09%and2.95%respectively, almost did not contain acid. The conversion per pass of ethanol was97.35%and the yield of ethyl acetate was98.27%. When butanol fed in at Y9near tower bottom, acetic acid fed in at Y3near tower top, catalyst amount was0.05gcat·gA-1, mole ratios of acetic acid to ethanol was3:1, reflux ratio was2.0, the proportion of butyl acetate, butanol and water in the organic phase from the column top were97.46%,1.9%and1.45%respectively, almost did not contain acid. The conversion per pass of butanol was97.15%and the yield of butyl acetate was97.88%.