In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene p...In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.展开更多
In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and e...In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and effective separation method, and selecting an extraction agent is the key to extraction technology research. In this paper, a design method of extractants based on elements and chemical bonds was proposed. A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups. The molecules were automatically synthesized according to specific combination rules to avoid the problem of “combination explosion” of molecules. The target properties of the extractant were set, and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules. Based on the separation performance of the extractant in liquid-liquid extraction and the relative importance of each index, the fuzzy comprehensive evaluation membership function was established, the analytic hierarchy process determined the mass ratio of each index, and the consistency test results were passed. The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzene-cyclohexane systems. The results unanimously prove that the method has important theoretical significance and application value.展开更多
A novel methodology is presented for simultaneously optimizing synthesis and cleaning schedule of flexible heat exchanger network(HEN)by genetic/simulated annealing algorithms(GA/SA).Through taking into account the ef...A novel methodology is presented for simultaneously optimizing synthesis and cleaning schedule of flexible heat exchanger network(HEN)by genetic/simulated annealing algorithms(GA/SA).Through taking into account the effect of fouling process on optimal network topology,a preliminary network structure possessing two-fold oversynthesis is obtained by means of pseudo-temperature enthalpy(T-H)diagram approach prior to simultaneous optimization.Thus,the computational complexity of this problem classified as NP(Non-deterministic Polynomial)-complete can be significantly reduced.The promising matches resulting from preliminary synthesis stage are further optimized in parallel with their heat exchange areas and cleaning schedule.In addition,a novel continu- ous time representation is introduced to subdivide the given time horizon into several variable-size intervals according to operating periods of heat exchangers,and then flexible HEN synthesis can be implemented in dynamic manner.A numerical example is provided to demonstrate that the presented strategy is feasible to decrease the total annual cost(TAC)and further improve network flexibility,but even more important,it may be applied to solve large-scale flexible HEN synthesis problems.展开更多
The heat exchanger network(HEN) synthesis problem based on entransy theory is analyzed. According to the characteristics of entransy representation of thermal potential energy, the entransy dissipation represents the ...The heat exchanger network(HEN) synthesis problem based on entransy theory is analyzed. According to the characteristics of entransy representation of thermal potential energy, the entransy dissipation represents the irreversibility of the heat transfer process, the temperature difference determines the entransy dissipation, and four HEN design steps based on entransy theory are put forward. The present study shows how it is possible to set energy targets based on entransy and achieve them with a network of heat exchangers by an example of heat exchanger network design for four streams. In order to verify the correctness of the heat exchanger networks design method based on entransy theory, the synthesis of the HEN for the diesel hydrogenation unit is studied. Using the heat exchange networks design method based on entransy theory, the HEN obtained is consistent with energy targets. The entransy transfer efficiency of HEN based on entransy theory is 92.29%, higher than the entransy transfer efficiency of the maximum heat recovery network based on pinch technology.展开更多
A T-Q diagram based on entransy theory is applied to graphically and quantitatively describe the irreversibility of the heat transfer processes.The hot and cold composite curves can be obtained in the T-Q diagram.The ...A T-Q diagram based on entransy theory is applied to graphically and quantitatively describe the irreversibility of the heat transfer processes.The hot and cold composite curves can be obtained in the T-Q diagram.The entransy recovery and entransy dissipation that are affected by temperature differences can be obtained through the shaded area under the composite curves.The method for setting the energy target of the HENs in T-Q diagram based on entransy theory is proposed.A case study of the diesel oil hydrogenation unit is used to illustrate the application of the method.The results show that three different heat transfer temperature differences is 10 K,15 K and 20 K,and the entransy recovery is 5.498×10~7k W·K,5.377×10~7k W·K,5.257×10~7k W·K,respectively.And the entransy transfer efficiency is 92.29%,91.63%,90.99%.Thus,the energy-saving potential of the HENs is obtained by setting the energy target based on the entransy transfer efficiency.展开更多
Molecular property depends on the property, the number of the elements, and the interaction between elements(such as chemical bonds). Based on the above-mentioned idea, two methods to estimate the isobaric heat capaci...Molecular property depends on the property, the number of the elements, and the interaction between elements(such as chemical bonds). Based on the above-mentioned idea, two methods to estimate the isobaric heat capacity of liquids organic compounds were developed. Ten elements groups and 32 chemical bond groups were defined by considering the structure of organic compounds. The group contribution values and correlation parameters were regressed by the ridge regression method with the experiment data of 1137 compounds. The heat capacity can be calculated by summating the contributions of the elements and chemical bond groups. The two methods were compared with existing group contribution methods, such as Chickos, Zabransky-Ruzicka, and Zdenka Kolska. The results show that those new estimation methods' overall average relative deviations were 5.81% and 5.71%, which were lower than the other three methods. Those methods were more straightforward in compound splitting.Those new methods can be used to estimate the liquid heat capacity of silicon-containing compounds,which the other three methods cannot estimate. The new methods are more accessible, broader, and more accurate. Therefore, this research has important scientific significance and vast application prospects.展开更多
The title complex is widely used as an efficient key component of Ziegler-Natta catalyst for stereospecific polymerization of dienes to produce synthetic rubbers. However, the quantitative structure-activity relations...The title complex is widely used as an efficient key component of Ziegler-Natta catalyst for stereospecific polymerization of dienes to produce synthetic rubbers. However, the quantitative structure-activity relationship（QSAR） of this kind of complexes is still not clear mainly due to the difficulties to obtain their geometric molecular structures through laboratory experiments. An alternative solution is the quantum chemistry calculation in which the comformational population shall be determined. In this study, ten conformers of the title complex were obtained with the function of molecular dynamics conformational search in Gabedit 2.4.8, and their geometry optimization and thermodynamics calculation were made with a Sparkle/PM7 approach in MOPAC 2012. Their Gibbs free energies at 1 atm. and 298.15 K were calculated. Population of the conformers was further calculated out according to the theory of Boltzmann distribution, indicating that one of the ten conformers has a dominant population of 77.13%.展开更多
Matrix expression of finite orthogonal wavelet transform of finite impulse response signal is more valuable for theoretical analysis and understanding. However, clear deduction for matrix expression has not been provi...Matrix expression of finite orthogonal wavelet transform of finite impulse response signal is more valuable for theoretical analysis and understanding. However, clear deduction for matrix expression has not been provided yet. In this paper, the formulation to generate the re-lated matrix is put forward and the theorem on the orthogonality of this matrix proved. This effort deploys a basis for more deeper and wider applications in chemical processes. *展开更多
基金supported by the National Natural Science Foundation of China(22178190)。
文摘In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.
基金supported by the National Natural Science Foundation of China(22178190).
文摘In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and effective separation method, and selecting an extraction agent is the key to extraction technology research. In this paper, a design method of extractants based on elements and chemical bonds was proposed. A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups. The molecules were automatically synthesized according to specific combination rules to avoid the problem of “combination explosion” of molecules. The target properties of the extractant were set, and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules. Based on the separation performance of the extractant in liquid-liquid extraction and the relative importance of each index, the fuzzy comprehensive evaluation membership function was established, the analytic hierarchy process determined the mass ratio of each index, and the consistency test results were passed. The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzene-cyclohexane systems. The results unanimously prove that the method has important theoretical significance and application value.
基金Supported by the National Natural Science Foundation of China （20976022） and Dalian University of Technology for Constructing Interdiscipline ＇Energy＋X＇. ACKNOWLEDGEMENTS The authors gratefully acknowledge financial support from Lanzhou Petrochemical Company, PetroChina Company Limited.
文摘A novel methodology is presented for simultaneously optimizing synthesis and cleaning schedule of flexible heat exchanger network(HEN)by genetic/simulated annealing algorithms(GA/SA).Through taking into account the effect of fouling process on optimal network topology,a preliminary network structure possessing two-fold oversynthesis is obtained by means of pseudo-temperature enthalpy(T-H)diagram approach prior to simultaneous optimization.Thus,the computational complexity of this problem classified as NP(Non-deterministic Polynomial)-complete can be significantly reduced.The promising matches resulting from preliminary synthesis stage are further optimized in parallel with their heat exchange areas and cleaning schedule.In addition,a novel continu- ous time representation is introduced to subdivide the given time horizon into several variable-size intervals according to operating periods of heat exchangers,and then flexible HEN synthesis can be implemented in dynamic manner.A numerical example is provided to demonstrate that the presented strategy is feasible to decrease the total annual cost(TAC)and further improve network flexibility,but even more important,it may be applied to solve large-scale flexible HEN synthesis problems.
基金Supported the National Natural Science Foundation of China(21406124)
文摘The heat exchanger network(HEN) synthesis problem based on entransy theory is analyzed. According to the characteristics of entransy representation of thermal potential energy, the entransy dissipation represents the irreversibility of the heat transfer process, the temperature difference determines the entransy dissipation, and four HEN design steps based on entransy theory are put forward. The present study shows how it is possible to set energy targets based on entransy and achieve them with a network of heat exchangers by an example of heat exchanger network design for four streams. In order to verify the correctness of the heat exchanger networks design method based on entransy theory, the synthesis of the HEN for the diesel hydrogenation unit is studied. Using the heat exchange networks design method based on entransy theory, the HEN obtained is consistent with energy targets. The entransy transfer efficiency of HEN based on entransy theory is 92.29%, higher than the entransy transfer efficiency of the maximum heat recovery network based on pinch technology.
基金Supported by the National Natural Science Foundation of China(21406124)
文摘A T-Q diagram based on entransy theory is applied to graphically and quantitatively describe the irreversibility of the heat transfer processes.The hot and cold composite curves can be obtained in the T-Q diagram.The entransy recovery and entransy dissipation that are affected by temperature differences can be obtained through the shaded area under the composite curves.The method for setting the energy target of the HENs in T-Q diagram based on entransy theory is proposed.A case study of the diesel oil hydrogenation unit is used to illustrate the application of the method.The results show that three different heat transfer temperature differences is 10 K,15 K and 20 K,and the entransy recovery is 5.498×10~7k W·K,5.377×10~7k W·K,5.257×10~7k W·K,respectively.And the entransy transfer efficiency is 92.29%,91.63%,90.99%.Thus,the energy-saving potential of the HENs is obtained by setting the energy target based on the entransy transfer efficiency.
基金Financial support from the National Natural Science Foundation of China (22178190)the Major Science and Technology Innovation Project of Shandong Province (2018CXGC1102) is gratefully acknowledged。
文摘Molecular property depends on the property, the number of the elements, and the interaction between elements(such as chemical bonds). Based on the above-mentioned idea, two methods to estimate the isobaric heat capacity of liquids organic compounds were developed. Ten elements groups and 32 chemical bond groups were defined by considering the structure of organic compounds. The group contribution values and correlation parameters were regressed by the ridge regression method with the experiment data of 1137 compounds. The heat capacity can be calculated by summating the contributions of the elements and chemical bond groups. The two methods were compared with existing group contribution methods, such as Chickos, Zabransky-Ruzicka, and Zdenka Kolska. The results show that those new estimation methods' overall average relative deviations were 5.81% and 5.71%, which were lower than the other three methods. Those methods were more straightforward in compound splitting.Those new methods can be used to estimate the liquid heat capacity of silicon-containing compounds,which the other three methods cannot estimate. The new methods are more accessible, broader, and more accurate. Therefore, this research has important scientific significance and vast application prospects.
基金supported by the National Natural Science Foundation of China(No.21476119)
文摘The title complex is widely used as an efficient key component of Ziegler-Natta catalyst for stereospecific polymerization of dienes to produce synthetic rubbers. However, the quantitative structure-activity relationship（QSAR） of this kind of complexes is still not clear mainly due to the difficulties to obtain their geometric molecular structures through laboratory experiments. An alternative solution is the quantum chemistry calculation in which the comformational population shall be determined. In this study, ten conformers of the title complex were obtained with the function of molecular dynamics conformational search in Gabedit 2.4.8, and their geometry optimization and thermodynamics calculation were made with a Sparkle/PM7 approach in MOPAC 2012. Their Gibbs free energies at 1 atm. and 298.15 K were calculated. Population of the conformers was further calculated out according to the theory of Boltzmann distribution, indicating that one of the ten conformers has a dominant population of 77.13%.
文摘Matrix expression of finite orthogonal wavelet transform of finite impulse response signal is more valuable for theoretical analysis and understanding. However, clear deduction for matrix expression has not been provided yet. In this paper, the formulation to generate the re-lated matrix is put forward and the theorem on the orthogonality of this matrix proved. This effort deploys a basis for more deeper and wider applications in chemical processes. *
