The comprehensive utilization and environment-friendliness of processes for recovering fresh water or valuable salt from seawater, salt-lakes, or mineral deposits are of utmost importance for sustainable development.O...The comprehensive utilization and environment-friendliness of processes for recovering fresh water or valuable salt from seawater, salt-lakes, or mineral deposits are of utmost importance for sustainable development.One primitive sustainable process for recovering salt from sodium-sulfate-type brine in Yuncheng salt lake had been considered one of the greatest inventions of ancient China, however, the replaced process of mass extraction of single Na_2SO_4 in recent years, has reduced a large amount of residual brine.In this research, relying on the salt-forming diagram in the non-equilibrium state, the technical secrets of ancient salt processes were uncovered, and a new comprehensive utilization system was proposed and tested experimentally.The new system includes a vacuum salt-making process and a normal pressure kieserite process, which can gradually eliminate the existed waste liquid and aid in the sustainable development of the Yuncheng salt-lake.The continuous experiment of salt-making process running stably in the double salt region without double salt formation, which proves the feasibility of salt-forming diagram applied in industrial process.Thus salt-forming diagram would be extremely valuable to industry process design and control, especially, the treatment of concentrated brine.展开更多
Salt-forming regions for a complex salt-water system in non-equilibrium state of evaporation process are usually different from those in solubility diagrams.To understand the solid-forming region of NaCl and improve t...Salt-forming regions for a complex salt-water system in non-equilibrium state of evaporation process are usually different from those in solubility diagrams.To understand the solid-forming region of NaCl and improve the utilization of bittern resources,experiments were carried out to evaporate 20 representative mixture solution samples of Na ^＋,Mg ^2＋ //Cl^-, SO4^2--H2O system with an average evaporation intensity of（1.4±0.4） g·L^-1 ·min^-1（water） at boiling temperature 348 K,and determine the NaCl solid-forming regions in non-equilibrium state.Because of the complexity of salt-forming region,a maximal region and a minimal region were proposed to express the non-equilibrium state salt-forming region with different crystal seed,and a conditional salt-forming region was proposed to present the characteristic region of non-equilibrium salt-forming phase diagram.The areas of the maximal and minimal regions are 2.00 and 1.56 times those in solubility diagram,so it is possible to utilize bittern resources in high efficiency.The recovery rates of NaCl were 99.65%,93.14%,88.57%,72.76%,and 83.68%for six typical bittern sources from Tulantai Salt Lake（China）,Dongtai Salt Lake（China） ,Jilantai Salt Lake（China）,Qarun Salt Lake（Egypt） and seawater,respectively.It is testified that the non-equilibrium state salt-forming phase diagram can be used in industrial processes.展开更多
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The cataly...A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.展开更多
Phosgene is highly toxic, and it plays a role in the depletion of the ozone layer. The ground state geometric structure and spectral characteristic of phosgene in various external electric fields were calculated via t...Phosgene is highly toxic, and it plays a role in the depletion of the ozone layer. The ground state geometric structure and spectral characteristic of phosgene in various external electric fields were calculated via the density-functional theory (DFT) and time-dependent density-functional theory (TDDFT) with the B3LYP/6-31+G(d) basis set. With external electric field, the structure of phosgene changed significantly. With increasing electric field, the bond lengths of 1C-3Cl and 1C-4Cl increased;the total energy and energy gap initially increased and then decreased, whereas the dipole moment initially decreased and then increased. Most of the IR vibrational frequencies were redshifted. The wavelength of the singlet excited state increased, reflecting a red shift, and the oscillator strengths of most transitions belonged to forbidden transitions. These results are of great significance for studying the dissociation of phosgene in external electric field.展开更多
基金Supported by the National Natural Science Foundation of China(U1407204)the Yangtze Scholarsand Research Team in university of Ministry of Education of China(IRT_17R81)+1 种基金the Innovative Research Team of Tianjin Municipal Education Commission(TD12-5004)the Foundation of Tianjin Key Laboratory of Marine Resources and Chemistry(201602)
文摘The comprehensive utilization and environment-friendliness of processes for recovering fresh water or valuable salt from seawater, salt-lakes, or mineral deposits are of utmost importance for sustainable development.One primitive sustainable process for recovering salt from sodium-sulfate-type brine in Yuncheng salt lake had been considered one of the greatest inventions of ancient China, however, the replaced process of mass extraction of single Na_2SO_4 in recent years, has reduced a large amount of residual brine.In this research, relying on the salt-forming diagram in the non-equilibrium state, the technical secrets of ancient salt processes were uncovered, and a new comprehensive utilization system was proposed and tested experimentally.The new system includes a vacuum salt-making process and a normal pressure kieserite process, which can gradually eliminate the existed waste liquid and aid in the sustainable development of the Yuncheng salt-lake.The continuous experiment of salt-making process running stably in the double salt region without double salt formation, which proves the feasibility of salt-forming diagram applied in industrial process.Thus salt-forming diagram would be extremely valuable to industry process design and control, especially, the treatment of concentrated brine.
基金Supported by the National Natural Science Foundation of China（20776110） the Natural Science Foundation of Tianjin（06YFJMJC04100）
文摘Salt-forming regions for a complex salt-water system in non-equilibrium state of evaporation process are usually different from those in solubility diagrams.To understand the solid-forming region of NaCl and improve the utilization of bittern resources,experiments were carried out to evaporate 20 representative mixture solution samples of Na ^＋,Mg ^2＋ //Cl^-, SO4^2--H2O system with an average evaporation intensity of（1.4±0.4） g·L^-1 ·min^-1（water） at boiling temperature 348 K,and determine the NaCl solid-forming regions in non-equilibrium state.Because of the complexity of salt-forming region,a maximal region and a minimal region were proposed to express the non-equilibrium state salt-forming region with different crystal seed,and a conditional salt-forming region was proposed to present the characteristic region of non-equilibrium salt-forming phase diagram.The areas of the maximal and minimal regions are 2.00 and 1.56 times those in solubility diagram,so it is possible to utilize bittern resources in high efficiency.The recovery rates of NaCl were 99.65%,93.14%,88.57%,72.76%,and 83.68%for six typical bittern sources from Tulantai Salt Lake（China）,Dongtai Salt Lake（China） ,Jilantai Salt Lake（China）,Qarun Salt Lake（Egypt） and seawater,respectively.It is testified that the non-equilibrium state salt-forming phase diagram can be used in industrial processes.
基金Supported by the National Natural Science Foundation of China(21476244,21406245)Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21030600)the Youth Innovation Promotion Association CAS(2016046)
文摘A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
基金National Natural Science Foundation of China(Grant Number:21763027)Innovation Team for Monitoring of Emerging Contaminants and Biomarkers(Grant Number:2021D14017)+2 种基金Xinjiang Regional Collaborative Innovation Project(Grant Number:2019E0223)Scientific Research Program of Colleges and Universities in Xinjiang(Grant Number:XJEDU2020Y029)“13th Five-Year”Plan for Key Discipline Physics Bidding Project of Xinjiang Normal University(Grant Number:17SDKD0602).
文摘Phosgene is highly toxic, and it plays a role in the depletion of the ozone layer. The ground state geometric structure and spectral characteristic of phosgene in various external electric fields were calculated via the density-functional theory (DFT) and time-dependent density-functional theory (TDDFT) with the B3LYP/6-31+G(d) basis set. With external electric field, the structure of phosgene changed significantly. With increasing electric field, the bond lengths of 1C-3Cl and 1C-4Cl increased;the total energy and energy gap initially increased and then decreased, whereas the dipole moment initially decreased and then increased. Most of the IR vibrational frequencies were redshifted. The wavelength of the singlet excited state increased, reflecting a red shift, and the oscillator strengths of most transitions belonged to forbidden transitions. These results are of great significance for studying the dissociation of phosgene in external electric field.
