The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the to...The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the toxicity of phthalate esters.In this study,a new,efficient and environmentally friendly plasticizer of hydrogenated rosin dodecyl ester was prepared by an esterification reaction of hydrogenated rosin and dodecanol.The influences of different reaction conditions(including different catalysts,the catalyst concentration,the ratio of the reactants,reaction temperature,and reaction time)on the esterification yield are examined and discussed.Hydrogenated rosin dodecyl ester with 71.8%yield was synthesized under the optimized reaction conditions(1:0.8 molar ratio of rosin to dodecanol,1 mol%tetrabutyl titanate concentration,and 210℃for 6 h).The esterification reaction is a second-order reaction,and kinetic calculations showed that the activation energy is 39.77 KJ·mol^(−1).The structure of the hydrogenated rosin dodecyl ester was confirmed by FT-IR spectroscopy and^(13)C NMR spectrum.Besides,the thermal stability of target product(hydrogenated rosin dodecyl ester)was also tested by thermal gravimetric analysis(TGA),which showed a good thermal stability.展开更多
大连石化分公司400万t/a柴油加氢装置采用Shell Global Solution工艺技术。为使产品满足国V排放标准,反应器于2017年停检期间更换Axens公司生产的Impulse^(TM) HR1246催化剂及ACT069、ACT077、ACT935、ACT955保护剂。通过对原料性质、...大连石化分公司400万t/a柴油加氢装置采用Shell Global Solution工艺技术。为使产品满足国V排放标准,反应器于2017年停检期间更换Axens公司生产的Impulse^(TM) HR1246催化剂及ACT069、ACT077、ACT935、ACT955保护剂。通过对原料性质、反应温度与加权平均温度、主要操作条件等相关数据进行评估,Impulse^(TM) HR1246催化剂在加氢脱硫、加氢脱氮以及提高十六烷值等方面均表现较好的加氢活性。装置反应温度与加权平均温度长时间趋于稳定,表明Impulse^(TM) HR1246催化剂具有较好的稳定性。此外,大连石化公司采用降低装置加工负荷、产品部分转循环、降低原料硫含量等方面的举措,为催化剂长周期运行创造了较好的运行条件。展开更多
The reaction mechanism of catalytic hydrogenation of rosin was investigated in a high-pressure agitated autoclave(type FYX-2G),using gum rosin as raw material,200# as solvent,and Pd/C as catalyst.When the effects of i...The reaction mechanism of catalytic hydrogenation of rosin was investigated in a high-pressure agitated autoclave(type FYX-2G),using gum rosin as raw material,200# as solvent,and Pd/C as catalyst.When the effects of internal and external diffusion were eliminated,the relationship between reactant concentrations and reaction time was traced on line at temperatures ranging from 130℃ to 160℃ and under pressures ranging from 3.0MPa to 7.0MPa,and the parameters were regressed by using EVIEWS.Based on the experimental results,a suitable reaction model was selected from Hougen-Warson 17 reaction mechanism models to show the reaction between molecules of abietic-type resin acids and atomic hydrogen adsorbed on the catalyst surface.The dissociative adsorption of hydrogen could be the controlling step,the reaction rate is proportional to the pressure of hydrogen and in inverse proportion to the square of concentration of product.The activation energy is 20.773 kJ/mol,and the reason of using solvent in catalytic hydrogenation of rosin was also explained according to the reaction mechanism.展开更多
基金the financial support From the Open Fund Project of Key Lab.of Biomass Energy and Material,Jiangsu Province(JSBEM201907)the Ordinary University Young Innovative Talents Project of Guangdong Province(2018KQNCX119)+4 种基金Provincial Science and Technology Planning Projects of Guangdong Province(2017A040405055)Guangdong-Hong Kong Cooperation Project(2017A050506055)Guangdong Provincial Education Department Project(Natural Science,2017KZDXM045)Guangzhou major special project for collaborative innovation of industry,University and research(201604020074)the fund project of Yele Science and Technology Innovation(YL201807).
文摘The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the toxicity of phthalate esters.In this study,a new,efficient and environmentally friendly plasticizer of hydrogenated rosin dodecyl ester was prepared by an esterification reaction of hydrogenated rosin and dodecanol.The influences of different reaction conditions(including different catalysts,the catalyst concentration,the ratio of the reactants,reaction temperature,and reaction time)on the esterification yield are examined and discussed.Hydrogenated rosin dodecyl ester with 71.8%yield was synthesized under the optimized reaction conditions(1:0.8 molar ratio of rosin to dodecanol,1 mol%tetrabutyl titanate concentration,and 210℃for 6 h).The esterification reaction is a second-order reaction,and kinetic calculations showed that the activation energy is 39.77 KJ·mol^(−1).The structure of the hydrogenated rosin dodecyl ester was confirmed by FT-IR spectroscopy and^(13)C NMR spectrum.Besides,the thermal stability of target product(hydrogenated rosin dodecyl ester)was also tested by thermal gravimetric analysis(TGA),which showed a good thermal stability.
文摘The reaction mechanism of catalytic hydrogenation of rosin was investigated in a high-pressure agitated autoclave(type FYX-2G),using gum rosin as raw material,200# as solvent,and Pd/C as catalyst.When the effects of internal and external diffusion were eliminated,the relationship between reactant concentrations and reaction time was traced on line at temperatures ranging from 130℃ to 160℃ and under pressures ranging from 3.0MPa to 7.0MPa,and the parameters were regressed by using EVIEWS.Based on the experimental results,a suitable reaction model was selected from Hougen-Warson 17 reaction mechanism models to show the reaction between molecules of abietic-type resin acids and atomic hydrogen adsorbed on the catalyst surface.The dissociative adsorption of hydrogen could be the controlling step,the reaction rate is proportional to the pressure of hydrogen and in inverse proportion to the square of concentration of product.The activation energy is 20.773 kJ/mol,and the reason of using solvent in catalytic hydrogenation of rosin was also explained according to the reaction mechanism.
