Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) an...Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) and TBP was proposed for extraction.The results show the species extracted into the organic phase were found to be mainly BiCl_3·x TBP(x=2 or 3).Thermodynamic parameters of the extraction reaction were obtained from the thermodynamics analysis,which illustrates that higher temperatures show a negative effect on the extraction.Extraction isotherm was obtained with 2.16 mol/L TBP for a typical solution containing 0.1 mol/L of bismuth and 1.0 mol/L of hydrochloric acid.About 98.5 % of bismuth has been extracted from the leaching solution under the optimum condition.Moreover,oxalate was explored as a precipitation stripping agent for BiCl_3·x TBP(x=2 or 3) complexes,by which Bi(Ⅲ) was stripped in the form of Bi_2(C_2O_4)_3·7H_2O.A stripping efficiency of 99.3% was obtained in only one stage at the phase ratio of 1 and TBP also could be recycled.Therefore,the method is an efficient,effective and highly selective approach to extract Bi(Ⅲ) and to recover metal bismuth.展开更多
Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in che...Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.展开更多
A degradative solvent extraction(DSE)method was proposed to upgrade low-rank coals(LRC)for their cascaded utilizations in a highly-dispersed medium.The derived products exhibited well improved properties in comparison...A degradative solvent extraction(DSE)method was proposed to upgrade low-rank coals(LRC)for their cascaded utilizations in a highly-dispersed medium.The derived products exhibited well improved properties in comparison to the raw LRCs.Previously,the LRCs were pre-dried to eliminate the potential impact of the varied water content of raw LRCs,but in light of the abundant water in fresh coals,the hydrolyzing effect of water on coals under heating,and the energy cost to pre-dry the LRCs,it is consequently essential to clarify the effect of water so as to verify the necessity of pre-drying process.In this study,the roles of inherent water and extra-added water were respectively investigated,using dried,raw and wet coals from two typical LRCs.The results show that increasing the moisture content of raw LRCs contributed to the extraction ability of DSE method without noticeably changing the elemental composition,chemical structure and thermal decomposition behavior of extractable products,thus pre-drying of LRCs before DSE treatment was proven unnecessary.Additionally,the roles of the inherent water were concluded as:1)leading to the formation of stable covalent bond during drying process;and 2)acting as H donor to promote extraction ability,while the added water can only function as H donor.Since excessive water will increase the pressure during DSE treatment and lead to the waste water treatment,the LRCs with a water content between 10%and 30%were consequently recommended for the practical application of DSE treatment.展开更多
基金Project(2011AA061002)supported by the High-Tech Research and Development Program of ChinaProject(2010SK2010)supported by the Key Program of Science and Technology of Hunan Province,ChinaProject supported by the Hunan Nonferrous Metals Fund,China
文摘Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) and TBP was proposed for extraction.The results show the species extracted into the organic phase were found to be mainly BiCl_3·x TBP(x=2 or 3).Thermodynamic parameters of the extraction reaction were obtained from the thermodynamics analysis,which illustrates that higher temperatures show a negative effect on the extraction.Extraction isotherm was obtained with 2.16 mol/L TBP for a typical solution containing 0.1 mol/L of bismuth and 1.0 mol/L of hydrochloric acid.About 98.5 % of bismuth has been extracted from the leaching solution under the optimum condition.Moreover,oxalate was explored as a precipitation stripping agent for BiCl_3·x TBP(x=2 or 3) complexes,by which Bi(Ⅲ) was stripped in the form of Bi_2(C_2O_4)_3·7H_2O.A stripping efficiency of 99.3% was obtained in only one stage at the phase ratio of 1 and TBP also could be recycled.Therefore,the method is an efficient,effective and highly selective approach to extract Bi(Ⅲ) and to recover metal bismuth.
基金financially supported by Shanxi Province Natural Science Foundation of China(20210302123167)NSFC-Shanxi joint fund for coal-based low carbon(U1610223)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SX-TD006).
文摘Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.
基金the National Natural Science Foundation of China(21776109)the Foundation of State Key Laboratory of Coal Combustion(FSKLCCB1805).
文摘A degradative solvent extraction(DSE)method was proposed to upgrade low-rank coals(LRC)for their cascaded utilizations in a highly-dispersed medium.The derived products exhibited well improved properties in comparison to the raw LRCs.Previously,the LRCs were pre-dried to eliminate the potential impact of the varied water content of raw LRCs,but in light of the abundant water in fresh coals,the hydrolyzing effect of water on coals under heating,and the energy cost to pre-dry the LRCs,it is consequently essential to clarify the effect of water so as to verify the necessity of pre-drying process.In this study,the roles of inherent water and extra-added water were respectively investigated,using dried,raw and wet coals from two typical LRCs.The results show that increasing the moisture content of raw LRCs contributed to the extraction ability of DSE method without noticeably changing the elemental composition,chemical structure and thermal decomposition behavior of extractable products,thus pre-drying of LRCs before DSE treatment was proven unnecessary.Additionally,the roles of the inherent water were concluded as:1)leading to the formation of stable covalent bond during drying process;and 2)acting as H donor to promote extraction ability,while the added water can only function as H donor.Since excessive water will increase the pressure during DSE treatment and lead to the waste water treatment,the LRCs with a water content between 10%and 30%were consequently recommended for the practical application of DSE treatment.
基金the financial support from the National Natural Science Foundation of China(No.52104354)the Joint Fund for Nuclear Technology Innovation Sponsored by the National Natural Science Foundation of China and the China National Nuclear Corporation(No.U2067201)。
