A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-b...A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.展开更多
Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing l...Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing lower alcohols. Experimental techniques and ab initio approaches can produce accurate results;however, these two processes are time consuming and labor intensive. Although thermodynamic equations such as UNIFAC are widely used, experimental values are required, and it is difficult to choose the best groups to represent a complex system. Because of their high efficiency and fast calculation speed, quantitative structure–property relationship(QSPR) tools were used in this work to predict the azeotropic temperatures and compositions of binary azeotropes containing lower alcohols. The QSPR models for 64 binary azeotropes based on centroid approximation and weighted-contribution-factor approximation were established using the genetic function approximation(GFA) procedure in Materials Studio software, and a leave-one-out cross-validation procedure was conducted.External tests of an additional 16 azeotropes were also investigated, and high determination coefficient values were obtained. The best QSPR models were explained in terms of the molecular structure of the azeotropes,and good predictive ability was obtained within acceptable prediction error levels.展开更多
Continuous homogenous azeotropic distillation(CHAD) and pressure-swing distillation(PSD) are explored to separate a minimum-boiling azeotropic system of ethyl acetate and n-hexane. The CHAD process with acetone as the...Continuous homogenous azeotropic distillation(CHAD) and pressure-swing distillation(PSD) are explored to separate a minimum-boiling azeotropic system of ethyl acetate and n-hexane. The CHAD process with acetone as the entrainer and the PSD process with the pressures of 0.1 MPa and 0.6 MPa in two columns are designed and simulated by Aspen Plus. The operating conditions of the two processes are optimized via a sequential modular approach to obtain the minimum total annual cost(TAC). The computational results show that the partially heat integrated pressure-swing distillation(HIPSD) has reduced in the energy cost and TAC by 40.79% and 35.94%, respectively, than the conventional PSD, and has more greatly reduced the energy cost and TAC by 62.61% and 49.26% respectively compared with the CHAD process. The comparison of CHAD process and partially HIPSD process illustrates that the partially HIPSD has more advantages in averting the product pollution, energy saving, and economy.展开更多
In this work, an industrial acetic acid dehydration system via heterogeneous azeotropic distillation is simulated by Aspen Plus software. Residue curves are used to analyze the distillating behavior, and appropriate o...In this work, an industrial acetic acid dehydration system via heterogeneous azeotropic distillation is simulated by Aspen Plus software. Residue curves are used to analyze the distillating behavior, and appropriate operating region of the system is determined. Based on steady states simulation, a sensitivity analysis is carried out to detect the output multiple steady states in the system. Different solution branches are observered when the flow rates of the feed stream and the organic reflux stream are selected as manipulated variables. The performance of the column under different steady states is different. A method is oroposed to achieve the desired steady state.展开更多
Azeotropic distillation is a special distillation method for separating liquid mixtures, which has better distillation effect and obvious advantages of energy saving and consumption reduction compared with traditional...Azeotropic distillation is a special distillation method for separating liquid mixtures, which has better distillation effect and obvious advantages of energy saving and consumption reduction compared with traditional distillation. In this paper, the latest research progress of azeotropic distillation technology in separation, synthesis and energy saving at home and abroad is reviewed. The research progress in separation is reflected in product separation and product purification, and the research progress in energy saving is reflected in heat pump distillation and dividing wall column distillation respectively. Existing studies have shown that azeotropic distillation technology can produce higher purity target products than conventional distillation for the separation and purification of azeotropic or near-boiling compounds. Heat pump distillation and dividing wall column distillation are used in azeotropic distillation field, resulting in obvious energy-saving effect for distillation equipment. The follow-up research direction of new separation technology with the goal of reducing energy consumption and exploring new materials as entraining agents should be studied in detail, which provides certain guidance for the development of distillation technology in China’s chemical industry.展开更多
In many chemical processes, large amounts of wastewater containing butanol and isobutanol are produced.Given that n-butanol-isobutanol-water can form triple azeotrope, high-purity butanol cannot be recovered from the ...In many chemical processes, large amounts of wastewater containing butanol and isobutanol are produced.Given that n-butanol-isobutanol-water can form triple azeotrope, high-purity butanol cannot be recovered from the wastewater by ordinary distillation. To economically and effectively recover butanol from this kind of wastewater, 1,4-butanediol is selected as an extractant to break the formation of the azeotropes, and a doubleeffect extractive distillation process is proposed. The conceptual design of the proposed process is accomplished based on process simulation. With the proposed process, the purity of recovered butanol and water is greater than 99.99 wt%. In comparison with the conventional azeotropic distillation process, economic analysis shows that the operating cost of the proposed process is lower: when the capacity of wastewater treatment is 100 t·h^(-1), the total operating cost decreases by 5.385 ×10~6 USD per year, and the total annual cost of the new process decreases by 5.249 ×10~6 USD per year. In addition, in the extractive distillation system, variable effects on separation purities and cost are more complex than those in the ordinary distillation system. The method and steps to optimize the key variables of the extractive distillation system are also discussed in this paper and can provide reference for similar studies.展开更多
[Objective] This study was conducted to extract the scarce natural liquor flavorings desired by many liquor factories from yellow water. [Method] Strong water absorbent resin was used to absorb moisture from the yello...[Objective] This study was conducted to extract the scarce natural liquor flavorings desired by many liquor factories from yellow water. [Method] Strong water absorbent resin was used to absorb moisture from the yellow water in order to concentrate it into dense yellow water at first, followed by azcotropic dis- tillation of the previously concentrated yellow water, and then, catalytic esterification was performed to the remaining liquid after the distillation. [ Results] The 7. 066 7 fractions of concentrated yellow water with 56.7% ethanol could be obtained after the treatment of 100 fractions of yellow water with strong water absorbent resin. Azeotrope of 0.432 8 fraction of natural acetaldehyde, 0. 269 4 fraction of ethyl formate and methyl alcohol, 0. 975 0 fraction of ethyl acetate and methyl alco- hol could be obtained after the azeotropic distillation per 100 fractions of concentrated yellow water. After the addition of CaC12, O. 220 7 fraction of ethyl formate and 0. 514 2 fraction of ethyl acetate could be obtained after distillation of the azeotrope. Finally, 92. 094 8 fractions of esterification liquid with 38 kinds of flavor- ing compound could be obtained after catalytic esterification of 100 fractions of concentrated yellow water, and the content of ethyl acetate, ethyl propionate, ethyl- butyrate, ethyl valerate, ethyl lactate and ethyl bexanoate were as much as 142.9, 22.2, 54.2, 3.3,75.4 and 158.9 g/L, respectively. [ Conclusion] Top-grade Luzhou-flavor liquor could be made by mixing 6.5 fractions of common liquor with acetaldehyde, ethyl formate, ethyl acetate and esterification liquid which were ob- tained from 1 fraction of yellow water. Therefore, the yellow water has a great recycling value, and it tells us that the technique of extracting liquor flavorings from yellow water has tremendous market value.展开更多
Till now, most part of the biodiesel is produced from the refined vegetable oils using methanol as feedstock in the presence of an alkali catalyst. However, large amount of waste edible oils and grease are available. ...Till now, most part of the biodiesel is produced from the refined vegetable oils using methanol as feedstock in the presence of an alkali catalyst. However, large amount of waste edible oils and grease are available. The difficulty with alkali-catalyzed esterification of these oils is that they often contain large amount of free fatty acids （FFA）, polymers and decomposition products. These free fatty acids can quickly react with the alkali catalyst to produce soaps that inhibit the separation of the ester and glycerine. An esterification and transesterification process is developed to convert the high FFA oil to its monoesters, The first step, the acidcatalyzed esterification with glycerine and these FFA reduces the FFA content of the oil and grease to less than 3%, and then an azeotropic distillation solvent is used to remove the water. The major factors affecting the conversion efficiency of the process such as glycerol to free fatty acid molar ratio, catalyst amount, reaction temperature and reaction duration are analyzed, The second step, alkali-catalyzed transesterificatiou process converts the products of the first step to its monoesters and glycerol, and then the glycerol is recycled for utilization in the first step. Technical indicators of the biodiesel product can meet the ASTM 6751 standard.展开更多
The separation of ternary mixture of butanol, butyl acetate, and methyl isobutyl ketone(MIBK) was initially analyzed by the residual curve. In this process, MIBK was chosen as the azeotropic agent during the first ste...The separation of ternary mixture of butanol, butyl acetate, and methyl isobutyl ketone(MIBK) was initially analyzed by the residual curve. In this process, MIBK was chosen as the azeotropic agent during the first step of separation. The optimum mass ratio of extra MIBK was 1.6 in the modified feed stream according to the residual curve. Thus on this condition the top product was butanol-MIBK azeotrope while the bottom product was butyl acetate in the preliminary separation of the mixture. Then the butanol and MIBK azeotrope was separated by the double effect pressureswing distillation with the low pressure column performing at 30 kPa and the atmospheric pressure column at 101 kPa. The optimal operating conditions were then obtained by using Aspen Plus to simulate and optimize the process. The results showed that the mass purities of butanol, butyl acetate, and MIBK were all more than 99% and reached the design requirements. Additionally, compared with the traditional distillation with outside heating, the double effect pressure swing distillation saved the reboiler duty by 48.6% and the condenser duty by 44.6%.展开更多
The molar heat capacity of the azeotropic mixture composed of water and benzene was measured by an adia-batic calorimeter in the temperature range from 80 to 320 K. The phase transitions took place in the temperature ...The molar heat capacity of the azeotropic mixture composed of water and benzene was measured by an adia-batic calorimeter in the temperature range from 80 to 320 K. The phase transitions took place in the temperature range from 265.409 to 275.165 K and 275.165 to 279.399 K. The phase transition temperatures were determined to be 272.945 and 278.339 K, which were corresponding to the solid-liquid phase transitions of water and benzene, respectively. The thermodynamic functions and the excess thermodynamic functions of the mixture relative to stan-dard temperature 298.15 K were derived from the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.展开更多
γ-Al2O3 with high surface area and large pore volume combined with high thermal stability was synthe- sized by a reverse precipitation-azeotropic distillation method. The effects of azeotropic distillation on the cha...γ-Al2O3 with high surface area and large pore volume combined with high thermal stability was synthe- sized by a reverse precipitation-azeotropic distillation method. The effects of azeotropic distillation on the characte- ristics of γ-Al2O3 were studied by means of X-ray diffraction（XRD）, Fourier transform infrared（FTIR） spectroscopy, transmission electron microscopy（TEM） and N2 adsorption-desorption. The results show that γ-Al2O3 dried by azeo- tropic distillation has excellent structure characteristics with a high surface area of 426 m2/g and a large pore volume of 2.56 cm3/g. After calcination at 1100 ℃, the surface area of γ-Al2O3 was still 92 mE/g with a large pore volume of 1.00 cma/g, indicating the potential application in catalyst and petroleum industry.展开更多
基金Supported by the Innovation Fund of Tianjin University
文摘A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.
基金Supported by the National Natural Science Foundation of China(21776145,21676152)Key Research Project of Shandong Province(2016GSF116004)
文摘Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing lower alcohols. Experimental techniques and ab initio approaches can produce accurate results;however, these two processes are time consuming and labor intensive. Although thermodynamic equations such as UNIFAC are widely used, experimental values are required, and it is difficult to choose the best groups to represent a complex system. Because of their high efficiency and fast calculation speed, quantitative structure–property relationship(QSPR) tools were used in this work to predict the azeotropic temperatures and compositions of binary azeotropes containing lower alcohols. The QSPR models for 64 binary azeotropes based on centroid approximation and weighted-contribution-factor approximation were established using the genetic function approximation(GFA) procedure in Materials Studio software, and a leave-one-out cross-validation procedure was conducted.External tests of an additional 16 azeotropes were also investigated, and high determination coefficient values were obtained. The best QSPR models were explained in terms of the molecular structure of the azeotropes,and good predictive ability was obtained within acceptable prediction error levels.
基金Supported by the Education Foundation of Chongqing(KJ1712307)the Application Technology Research and Developments Foundation of Fuling Technology Board(FLKJ,2016ABA1026)the Young Foundation of Yangtze Normal University(2015XJXM03)
文摘Continuous homogenous azeotropic distillation(CHAD) and pressure-swing distillation(PSD) are explored to separate a minimum-boiling azeotropic system of ethyl acetate and n-hexane. The CHAD process with acetone as the entrainer and the PSD process with the pressures of 0.1 MPa and 0.6 MPa in two columns are designed and simulated by Aspen Plus. The operating conditions of the two processes are optimized via a sequential modular approach to obtain the minimum total annual cost(TAC). The computational results show that the partially heat integrated pressure-swing distillation(HIPSD) has reduced in the energy cost and TAC by 40.79% and 35.94%, respectively, than the conventional PSD, and has more greatly reduced the energy cost and TAC by 62.61% and 49.26% respectively compared with the CHAD process. The comparison of CHAD process and partially HIPSD process illustrates that the partially HIPSD has more advantages in averting the product pollution, energy saving, and economy.
基金Supported by the National Natural Science Foundation of China （20976048） and Shanghai Leading Academic Discipline Project （B504）.
文摘In this work, an industrial acetic acid dehydration system via heterogeneous azeotropic distillation is simulated by Aspen Plus software. Residue curves are used to analyze the distillating behavior, and appropriate operating region of the system is determined. Based on steady states simulation, a sensitivity analysis is carried out to detect the output multiple steady states in the system. Different solution branches are observered when the flow rates of the feed stream and the organic reflux stream are selected as manipulated variables. The performance of the column under different steady states is different. A method is oroposed to achieve the desired steady state.
文摘Azeotropic distillation is a special distillation method for separating liquid mixtures, which has better distillation effect and obvious advantages of energy saving and consumption reduction compared with traditional distillation. In this paper, the latest research progress of azeotropic distillation technology in separation, synthesis and energy saving at home and abroad is reviewed. The research progress in separation is reflected in product separation and product purification, and the research progress in energy saving is reflected in heat pump distillation and dividing wall column distillation respectively. Existing studies have shown that azeotropic distillation technology can produce higher purity target products than conventional distillation for the separation and purification of azeotropic or near-boiling compounds. Heat pump distillation and dividing wall column distillation are used in azeotropic distillation field, resulting in obvious energy-saving effect for distillation equipment. The follow-up research direction of new separation technology with the goal of reducing energy consumption and exploring new materials as entraining agents should be studied in detail, which provides certain guidance for the development of distillation technology in China’s chemical industry.
基金Supported by the National Key Technology Support Program of China(2014BAC10B01)the National Natural Science Foundation of China(21406123)the Key Scientific and Technological Project of Shanxi Province(MH2014-10)
文摘In many chemical processes, large amounts of wastewater containing butanol and isobutanol are produced.Given that n-butanol-isobutanol-water can form triple azeotrope, high-purity butanol cannot be recovered from the wastewater by ordinary distillation. To economically and effectively recover butanol from this kind of wastewater, 1,4-butanediol is selected as an extractant to break the formation of the azeotropes, and a doubleeffect extractive distillation process is proposed. The conceptual design of the proposed process is accomplished based on process simulation. With the proposed process, the purity of recovered butanol and water is greater than 99.99 wt%. In comparison with the conventional azeotropic distillation process, economic analysis shows that the operating cost of the proposed process is lower: when the capacity of wastewater treatment is 100 t·h^(-1), the total operating cost decreases by 5.385 ×10~6 USD per year, and the total annual cost of the new process decreases by 5.249 ×10~6 USD per year. In addition, in the extractive distillation system, variable effects on separation purities and cost are more complex than those in the ordinary distillation system. The method and steps to optimize the key variables of the extractive distillation system are also discussed in this paper and can provide reference for similar studies.
基金Supported by Shandong Provincial Major Research and Development Program(2017GSF216009)
文摘[Objective] This study was conducted to extract the scarce natural liquor flavorings desired by many liquor factories from yellow water. [Method] Strong water absorbent resin was used to absorb moisture from the yellow water in order to concentrate it into dense yellow water at first, followed by azcotropic dis- tillation of the previously concentrated yellow water, and then, catalytic esterification was performed to the remaining liquid after the distillation. [ Results] The 7. 066 7 fractions of concentrated yellow water with 56.7% ethanol could be obtained after the treatment of 100 fractions of yellow water with strong water absorbent resin. Azeotrope of 0.432 8 fraction of natural acetaldehyde, 0. 269 4 fraction of ethyl formate and methyl alcohol, 0. 975 0 fraction of ethyl acetate and methyl alco- hol could be obtained after the azeotropic distillation per 100 fractions of concentrated yellow water. After the addition of CaC12, O. 220 7 fraction of ethyl formate and 0. 514 2 fraction of ethyl acetate could be obtained after distillation of the azeotrope. Finally, 92. 094 8 fractions of esterification liquid with 38 kinds of flavor- ing compound could be obtained after catalytic esterification of 100 fractions of concentrated yellow water, and the content of ethyl acetate, ethyl propionate, ethyl- butyrate, ethyl valerate, ethyl lactate and ethyl bexanoate were as much as 142.9, 22.2, 54.2, 3.3,75.4 and 158.9 g/L, respectively. [ Conclusion] Top-grade Luzhou-flavor liquor could be made by mixing 6.5 fractions of common liquor with acetaldehyde, ethyl formate, ethyl acetate and esterification liquid which were ob- tained from 1 fraction of yellow water. Therefore, the yellow water has a great recycling value, and it tells us that the technique of extracting liquor flavorings from yellow water has tremendous market value.
文摘Till now, most part of the biodiesel is produced from the refined vegetable oils using methanol as feedstock in the presence of an alkali catalyst. However, large amount of waste edible oils and grease are available. The difficulty with alkali-catalyzed esterification of these oils is that they often contain large amount of free fatty acids （FFA）, polymers and decomposition products. These free fatty acids can quickly react with the alkali catalyst to produce soaps that inhibit the separation of the ester and glycerine. An esterification and transesterification process is developed to convert the high FFA oil to its monoesters, The first step, the acidcatalyzed esterification with glycerine and these FFA reduces the FFA content of the oil and grease to less than 3%, and then an azeotropic distillation solvent is used to remove the water. The major factors affecting the conversion efficiency of the process such as glycerol to free fatty acid molar ratio, catalyst amount, reaction temperature and reaction duration are analyzed, The second step, alkali-catalyzed transesterificatiou process converts the products of the first step to its monoesters and glycerol, and then the glycerol is recycled for utilization in the first step. Technical indicators of the biodiesel product can meet the ASTM 6751 standard.
基金Supported by the National Natural Science Foundation of China(21306036)the Basic Research Program of Hebei Province(16964502D)
文摘The separation of ternary mixture of butanol, butyl acetate, and methyl isobutyl ketone(MIBK) was initially analyzed by the residual curve. In this process, MIBK was chosen as the azeotropic agent during the first step of separation. The optimum mass ratio of extra MIBK was 1.6 in the modified feed stream according to the residual curve. Thus on this condition the top product was butanol-MIBK azeotrope while the bottom product was butyl acetate in the preliminary separation of the mixture. Then the butanol and MIBK azeotrope was separated by the double effect pressureswing distillation with the low pressure column performing at 30 kPa and the atmospheric pressure column at 101 kPa. The optimal operating conditions were then obtained by using Aspen Plus to simulate and optimize the process. The results showed that the mass purities of butanol, butyl acetate, and MIBK were all more than 99% and reached the design requirements. Additionally, compared with the traditional distillation with outside heating, the double effect pressure swing distillation saved the reboiler duty by 48.6% and the condenser duty by 44.6%.
基金the National Natural Science Foundation of China (No. 20073047) and K. C. Wong Education Foundation, Hong Kong.
文摘The molar heat capacity of the azeotropic mixture composed of water and benzene was measured by an adia-batic calorimeter in the temperature range from 80 to 320 K. The phase transitions took place in the temperature range from 265.409 to 275.165 K and 275.165 to 279.399 K. The phase transition temperatures were determined to be 272.945 and 278.339 K, which were corresponding to the solid-liquid phase transitions of water and benzene, respectively. The thermodynamic functions and the excess thermodynamic functions of the mixture relative to stan-dard temperature 298.15 K were derived from the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.
文摘γ-Al2O3 with high surface area and large pore volume combined with high thermal stability was synthe- sized by a reverse precipitation-azeotropic distillation method. The effects of azeotropic distillation on the characte- ristics of γ-Al2O3 were studied by means of X-ray diffraction（XRD）, Fourier transform infrared（FTIR） spectroscopy, transmission electron microscopy（TEM） and N2 adsorption-desorption. The results show that γ-Al2O3 dried by azeo- tropic distillation has excellent structure characteristics with a high surface area of 426 m2/g and a large pore volume of 2.56 cm3/g. After calcination at 1100 ℃, the surface area of γ-Al2O3 was still 92 mE/g with a large pore volume of 1.00 cma/g, indicating the potential application in catalyst and petroleum industry.
