A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of c...A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.展开更多
Vanillin 1, 2-propylene glycol acetal was synthesized from vanillin and 1, 2-propylene glycol using H3PMo6W6O40·nH2O as catalyst, The factors influencing the synthesis were discussed and the better reaction condi...Vanillin 1, 2-propylene glycol acetal was synthesized from vanillin and 1, 2-propylene glycol using H3PMo6W6O40·nH2O as catalyst, The factors influencing the synthesis were discussed and the better reaction conditions were found as follows： The amount of vanillin was 3.8 g, the molar ratio of vanillin was 1, 2-propylene glycol 1.0 to 2.4, the amount of catalyst was 1.6% in proportion to the total reacting materials, the volume ofcyclohexane as the water-carrying agent 4 mL, the refluxing time was 2 h at 88-96℃ and thus the product yield reached over 87%. The results show that the catalyst＇s activity is high and the reaction time is short.展开更多
To facilitate the recovery of Pb/SiO_(2) catalyst,magnetic Pb/Fe_(3)O_(4)/SiO_(2) samples were prepared separately by emulsification,sol-gel and incipient impregnation methods.The catalyst samples were characterized b...To facilitate the recovery of Pb/SiO_(2) catalyst,magnetic Pb/Fe_(3)O_(4)/SiO_(2) samples were prepared separately by emulsification,sol-gel and incipient impregnation methods.The catalyst samples were characterized by means of X-ray diffraction and N_(2) adsorption-desorption,and their catalytic activity was investigated in the reaction for synthesizing propylene carbonate from urea and 1,2-propylene glycol.When the gelatin was applied in the preparation of Fe_(3)O_(4) at 60℃ and the pH value was controlled at 4 in the preparation of Fe_(3)O_(4)/SiO_(2),the Pb/Fe_(3)O_(4)/SiO_(2) sample shows good catalytic activity and magnetism.Under the reaction conditions of a reaction temperature of 180℃,reaction time of 2h,catalyst percentage of 1.7 wt-% and a molar ratio of urea to PG of 1∶4,the yield of propylene carbonate attained was 87.7%.展开更多
It is difficult to separate the methanol and hydrocarbons in the propylene oxide(PO)purification process due to their forming azeotrope.As for this,a novel PO separation process,in that the deionized water is employed...It is difficult to separate the methanol and hydrocarbons in the propylene oxide(PO)purification process due to their forming azeotrope.As for this,a novel PO separation process,in that the deionized water is employed as extractant and 1,2-propylene glycol(MPG)that is formed from the PO hydrolysis reaction is recovered,is presented in this work.The salient feature of this process is that both the non-catalyzed reactions of PO hydrolysis to form MPG and dipropylene glycol(DPG)are simultaneously considered and MPG by-product with high purity is obtained in virtue of the deionized water as reflux liquid and side take-off in MPG column.In addition,the ionic liquid(IL)extractant is screened through the conductorlike screening model for segment activity coefficient(COSMO-SAC)and the comparisons of separation efficiency between the IL and normal octane(nC_(8))extractant for the separation of PO and 2-methylpentane are made.With the non-random two-liquid(NRTL)thermodynamic model,the simulation and optimization design for the full flow sheet are performed and the effects of the key operation parameters such as solvent ratio,theoretical stages,feeding stage etc.on separation efficiency are detailedly discussed.The results show that the mass purity and the mass yield of PO can be up to 99.99%and 99.0%,and the condenser duty,reboiler duty and PO loss in the process with IL extractant can be decreased by 69.66%,30.21%and 78.86%compared to ones with nC_(8).The total annual cost(TAC)calculation also suggests that the TAC would be significantly reduced if using IL in replace of nC_(8) for the investigated process.The presented results would provide a useful guide for improving the quality of PO product and the economic efficiency of industrial plant.展开更多
基金Supported by the Changcheng Scholars Program of Beijing(CIT&TCD 20150316)
文摘A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.
文摘Vanillin 1, 2-propylene glycol acetal was synthesized from vanillin and 1, 2-propylene glycol using H3PMo6W6O40·nH2O as catalyst, The factors influencing the synthesis were discussed and the better reaction conditions were found as follows： The amount of vanillin was 3.8 g, the molar ratio of vanillin was 1, 2-propylene glycol 1.0 to 2.4, the amount of catalyst was 1.6% in proportion to the total reacting materials, the volume ofcyclohexane as the water-carrying agent 4 mL, the refluxing time was 2 h at 88-96℃ and thus the product yield reached over 87%. The results show that the catalyst＇s activity is high and the reaction time is short.
基金This work has been supported by the National Natural Science Foundation of China(Grant No.20576025)the Hebei Provincial Fund for Natural Science(B2007000010).
文摘To facilitate the recovery of Pb/SiO_(2) catalyst,magnetic Pb/Fe_(3)O_(4)/SiO_(2) samples were prepared separately by emulsification,sol-gel and incipient impregnation methods.The catalyst samples were characterized by means of X-ray diffraction and N_(2) adsorption-desorption,and their catalytic activity was investigated in the reaction for synthesizing propylene carbonate from urea and 1,2-propylene glycol.When the gelatin was applied in the preparation of Fe_(3)O_(4) at 60℃ and the pH value was controlled at 4 in the preparation of Fe_(3)O_(4)/SiO_(2),the Pb/Fe_(3)O_(4)/SiO_(2) sample shows good catalytic activity and magnetism.Under the reaction conditions of a reaction temperature of 180℃,reaction time of 2h,catalyst percentage of 1.7 wt-% and a molar ratio of urea to PG of 1∶4,the yield of propylene carbonate attained was 87.7%.
基金provided by the National Key Research and Devolopment Program of China(2017YFB0702800)the National Natural Science Foundation of China (21878025, 22078026)。
文摘It is difficult to separate the methanol and hydrocarbons in the propylene oxide(PO)purification process due to their forming azeotrope.As for this,a novel PO separation process,in that the deionized water is employed as extractant and 1,2-propylene glycol(MPG)that is formed from the PO hydrolysis reaction is recovered,is presented in this work.The salient feature of this process is that both the non-catalyzed reactions of PO hydrolysis to form MPG and dipropylene glycol(DPG)are simultaneously considered and MPG by-product with high purity is obtained in virtue of the deionized water as reflux liquid and side take-off in MPG column.In addition,the ionic liquid(IL)extractant is screened through the conductorlike screening model for segment activity coefficient(COSMO-SAC)and the comparisons of separation efficiency between the IL and normal octane(nC_(8))extractant for the separation of PO and 2-methylpentane are made.With the non-random two-liquid(NRTL)thermodynamic model,the simulation and optimization design for the full flow sheet are performed and the effects of the key operation parameters such as solvent ratio,theoretical stages,feeding stage etc.on separation efficiency are detailedly discussed.The results show that the mass purity and the mass yield of PO can be up to 99.99%and 99.0%,and the condenser duty,reboiler duty and PO loss in the process with IL extractant can be decreased by 69.66%,30.21%and 78.86%compared to ones with nC_(8).The total annual cost(TAC)calculation also suggests that the TAC would be significantly reduced if using IL in replace of nC_(8) for the investigated process.The presented results would provide a useful guide for improving the quality of PO product and the economic efficiency of industrial plant.
