具有羧酸官能团的功能性离子液体萃取分离钇的研究(英文)

A new kind of hydrophobic ionic liquids [1-alkyl-3-(1-carboxylpropyl)im][PF6] has been synthesized,and their extraction properties for Y(III) in the nitric acid medium was also investigated.The effects of extractant concentration,equilibrium pH of aqueous phase,salt concentration,temperature etc.were discussed.The results show that this kind of Task-Specific Ionic Liquid(TSIL) needs to be saponified before being used for the Y(III) ex-traction,and the extraction is acid dependent,and the extraction efficiency increases with the aqueous phase acidity decreasing.Furthermore,the loaded organic phase is easy to be stripped;more than 95% Y(III) could be stripped from the loaded organic phase when the stripping acidity is higher than 0.07 mol?L?1.The slope analysis technique is used to investigate the extraction mechanism,and a possible cation-exchange extraction mechanism is proposed in the present extraction system.     

Direct extraction of Mo(Ⅵ) from sulfate solution by synergistic extractants in the rotation column

Direct extraction of molybdenum from sulfate solution with synergistic extractants(mixture of D_2EHPA and TBP)was studied in the rotation column. The influence of extractant concentration and initial pH of aqueous phase was studied in the bench scale experiments. The outcomes demonstrated that the synergistic solvent extraction enhances the constancy of the extracted complexes for transfer into the organic phase. In the continuous experiments, the effect of different operating parameters such as speed of agitation, inlet solvent flow rate and inlet aqueous flow rate on the holdup, mean drop size, drop size distribution, slip and characteristic velocities and extraction percentage were examined. Modified correlations were proposed for prediction of hydrodynamic parameters with consideration of reaction extraction condition in the rotation column. Furthermore, these correlations were compared with the experimental data. According to the results, the direct extraction of Mo(Ⅵ) from aqueous solution and sulfuric media with extraction efficiency of 90.4% was obtained at higher rotor speed(240 r·min~(–1) rpm) in this column.     

A NEW ARRANGEMENT OF EXTRACTION CASCADE——MULTIPLE STAGE COUNTER-CURRENT EXTRACTION PROCESS WITH ALTERNATING EXTRACTION AND STRIPPING

In this article a new arrangement of extraction cascade—multiple stage counter-current extraction processwith alternating extraction and stripping is presented.The effects of increasing mass-transfer rate and decreas-ing the number of extraction stage in an extraction process may be obtained by adopting this new arrange-ment.Extraction cascade calculation for two extraction systems-extraction of iron with N,N-bis-(l-methl-heptyl)acetyl amide(N-503)* and extraction of H_3PO_4 with DBSO has been carried out and the experi-ment has been done with the former system.The results of calculation and experiment show that the extraction efficiency increases significantly byadopting this new alternating arrangement,compared with a commun multiple stage counter-current process.The new alternating extraction and stripping arrangement may be called alternating extraction process.     

IN SITU SEPARATION OF ETHANOL DURING BATCH FERMENTATION WITH CO_2 STRIPPING AND ACTIVATED CARBON ADSORPTION

In situ separation of ethanol during batch fermentation with CO_2 stripping and activated carbon adsorption was studied. The higher initial glucose concentration and fermentation rate were reached due to the elimination of ethanol inhibition on the cell growth by means of CO_2 stripping. The stripped ethanol vapor was selectively adsorbed by an activated carbon column. The conde(?)sate desorbed from the adsorption column can be higher than 50% by weight. Ar unstructured model was used to simulate the experimental data satisfactorily.     

Kinetics of Forward Extraction of Boric Acid from Salt Lake Brine by 2-Ethyl-1,3-hexanediol in Toluene Using Single Drop Technique

The kinetics of forward extraction of boric acid from salt lake brine by 2-ethyl-1,3-hexanediol in tolu-ene was investigated using the single drop technique. The factors affecting the extraction rate include interfacial area between aqueous phase and organic phase, initial concentration of boric acid in aqueous phase, initial concen-tration of 2-ethyl-1,3-hexanediol in organic phase, and extraction temperature. The experimental results show that the extraction rate increases with the increase of the initial concentration of boric acid and 2-ethyl-1,3-hexanediol, interfacial area of two phases, and temperature. With the temperature-dependence study, it is showed that the ex-traction is a diffusion-controlled process. The kinetic equation is presented for pH 1.0 in the aqueous phase and temperature of 318 K.     

Simultaneous Cell Disruption and Aqueous Two-Phase Extraction for Isolation of Intracellular Recombinant Proteins

A new technique was developed for the integrated processing of cell disruption and aqueous two-phase extraction in a high-speed bead mill to separate intracellular proteins form microbial cells. The process was narned as simultanecus cell disruption and aqueous two-phase extraction (ADATE). Advantages, such as high cell disruption efficiency, biochemical activities proservation of proteins, cell debris elimination, and preliminary puriffcation of the target protein were being clairmed. When this technique was employed for isolating recombinant Tumor Necrois Factor (TNF) from E.coli, overall protein codcentration and TNF activity were found to have been increased. More than 85% of TNF was partitioned into the top phase and all cell debris were in the bottom phase. The partition coefficinet was greater than 3 and the TNF puriflcation fsctop was greater than 6. It is zhown that less separation steps were being utilized in the new techniqne, meaning a reduction in separation time and less process extractors required.     

Liquid–liquid equilibrium extraction of ethanol with mixed solvent for bioethanol concentration

The extraction of ethanol with the solvents of aldehydes mixed with m-xylene was studied for the bioethanol concentration process.Furfural and benzaldehyde were selected as extraction solvents,with which the solubility of water is small,expecting large distribution coefficient of ethanol.The liquid–liquid two-phase region was the largest with m-xylene solvent,followed by benzaldehyde and furfural.The region of two liquid–liquid phase became larger with the mixed solvent of m-xylene and furfural than that with furfural solvent.The NRTL model was applied to the ethanol–water–furfural–m-xylene system,and the model could well express the liquid–liquid equilibrium of the system.For any solvent used in this study,the separation selectivity of ethanol relative to water decreased as the distribution coefficient of ethanol increased.The separation selectivity with m-xylene was the largest among the employed solvents,but the distribution coefficient was the smallest.The solvent mixture of furfural and m-xylene showed relatively high distribution coefficient of ethanol and separation selectivity,even in the higher mass fraction of m-xylene in the solvent phase.The ethanol extraction with a countercurrent multistage extractor by a continuous operation was simulated to evaluate the extraction performance.The ethanol content could be concentrated in the extract phase with relatively small number of extraction stages but low yield of ethanol was obtained.     

分段进水生物脱氮工艺稳态模型的开发与试验评价

In this article,a steady-state mathematical model was developed and experimentally evaluated to inves- tigate the effect of influent flow distribution and volume ratios of anoxic and aerobic zones in each stage on the to- tal nitrogen concentration of the effluent in the step-feed biological nitrogen removal process.Unlike the previous modeling methods,this model can be used to calculate the removal rates of ammonia and nitrate in each stage and thereby predict the concentrations of ammonia,nitrate,and total nitrogen in the effluent.To verify the simulation results,pilot-scale experimental studies were carried out in a four-stage step feed process.Good correlations were achieved between the measured data and the simulation results,which proved the validity of the developed model. The sensitivity of the model predictions was analyzed.After verification of the validity,the step feed process was optimally operated for five months using the model and the criteria developed for the design and operation.During the pilot-scale experimental period,the effluent total nitrogen concentrations were all below 5mg·L ^-1 ,with more than 90%removal efficiency.     

反应精馏合成乙酸丁酯的实验和模拟(英文)

In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.     

Recovery of Copper from Leaching Solution of Copper Smelting Ash

An efficient and reliable approach based on solvent extraction to selectively recover copper from leaching solution of Jinchuan copper smelting ash has been developed in this work. And the extraction isotherm of 50%(j) N902 with initial aqueous acidity of 19.6 g/L was determined at 25℃. The results show that the extractant, N902, has good selectivity to copper, and its saturated capacity of copper under the given conditions is over 23 g/L. The recovery rate of copper in the extraction is over 99%. And copper extraction equilibrium is reached in 90 s using 50% N902 with kerosene as the diluenting agent at an organic and aqueous volume phase ratio (O/A) of 1. Furthermore, over 99.5% of the loaded copper in the organic phase could be stripped by applying 196 g/L H2SO4 as the stripping agent.     

用磷酸三丁酯萃取分离硫酸铵母液中的HCN

研究了磷酸三丁酯(TBP)-磺化煤油体系从重庆某企业甘氨酸生产副产物硫酸铵母液中萃取分离HCN的工艺,考察了萃取体系、TBP体积分数、母液初始pH值、相比(Vorg∶Vaq)对萃取HCN的影响以及氢氧化钠浓度、相比(Vaq∶Vorg)和平衡pH值对HCN反萃的影响。结果表明:选用TBP作为萃取剂能够对硫酸铵母液中的HCN进行快速有效的萃取;TBP体积分数、母液初始pH值及相比对HCN萃取率影响显著;以含体积分数35%TBP的有机相作萃取剂,在相比(Vorg∶Vaq)为2∶1的条件下,pH值为2.92的含氰1.71 g/L的硫酸铵母液经3级错流萃取,萃余液中含氰低于0.5 mg/L,氰的萃取率接近100%;在相比(Vaq∶Vorg)为1∶1条件下,以0.6 mol/L的氢氧化钠为反萃液,控制反萃液平衡pH值大于13.0,氰的单级反萃率大于96%;含氰0.78 g/L的有机相在相比为1∶1条件下,经过2级错流反萃,氰基本上被反萃完全,贫有机相不经过处理可循环使用。     

Staged Versions of Liquid Membrane Extraction Processes

The application of the liquid membrane technique to the system consisting of serially connected mixer-settler extractors is suggested and evaluated. A comparative theoretical analysis of various flow schemes of contacting liquids in series of mixer-settler extractors has been performed. It is shown that the scheme of a staged version of supported liquid membrane provides the highest extraction efficiency. One laboratory plant consisting of eight mixer-settler was examined with the standard extraction system water-acetone-toluene using two schemes: with internal (the extractant recycles between each pair of extraction and stripping stages) and external (the extractant first passes through all the stages of extraction, then through all stripping stages) circulation of the extractant. The effectiveness of the first variant (supported liquid membrane scheme) was considerably higher than that of the second scheme. Good agreement between theory and experiment was established.     

Solvent Extraction of Cyclohexanecarboxylic Acid From Waste Fluid by Using a Mixture of Toluene and 1-Octanol

Solvent extraction studies have been carried out for the recovery of cyclohexanecarboxylic acid (CCA) from simulated waste fluid. Influences of various parameters including extractant types, pH of the solution, equilibration time, and initial concentrations of CCA, etc., were studied. A mixture of toluene and 1-octanol (90:10, v/v) was found suitable for the extraction. The results showed that solution pH had a great effect on the distribution ratio, and CCA could be efficiently extracted when the pH was lower than 3.5. The extraction was found quite rapidly. The distribution ratio decreased as the initial concentration of CCA increased. The stripping rate of CCA using sodium hydroxide as stripping agent was found to be increased with the increase of alkali concentration. After back extraction once, more than 98% stripping efficiency was achieved with 0.8 mol/L sodium hydroxide solution at aqueous to organic phase (A/O) ratio 1:1 when CCA concentration was lower than 38.3 g/L. The practical extraction process was carried out for the waste fluid (concentration of CCA 36.5 g/L) discharged in the production of caprolactam from toluene. After four extraction stages at A/O ratio 1:1, the cumulative extraction recovery reached 99.3%. The practical stripping efficiency from loaded organic phase reached 98.2% in one single stage.     

中空纤维支撑液膜萃取法提铟工艺比较研究

采用中空纤维支撑液膜(SLM)技术,模拟酸性铟渣浸出液,以磷酸二异辛酯(P204)、磺化煤油体积比3:7为液膜萃取相,盐酸溶液为反萃相,研究了单组件膜萃取系统、双膜组件萃取-反萃系统、双膜组件萃取-超滤系统对酸性浸出液中In的提取与分离效率。结果表明,双膜组件萃取-超滤技术可同时实现浸出液中In的提取与反萃液中In的高纯度富集,浸出液中In的提取率可达90%以上,反萃液中In含量可达浸出液中In含量的70%,In的质量分数高于90%。     

On the application of liquid-membrane principle in a system of mixing-settling extractors

The paper is devoted to the possibilities of applying the liquid-membrane technique in extraction processes in a cascade of mixing-settling apparatuses. The process is performed in the cascade of N mass-exchange stages, each of which contains two mixing-settling extractors, one of which is used in the extraction of a component from the starting water solution, while the other is used in the its reextraction by the second (pure) water solution. Calculation dependences between the input and output concentrations in flows are represented. Experimental investigations were carried out on a laboratory plant consisting of eight glass cylindrical mixing-settling apparatuses with a standard extraction system water—acetone-toluene at two schemes of the stage assemblage: with the internal (between the stages of extraction and reextraction) and external (extractant flow passes first through all extraction stages and next reextraction those) extractant circulation. The efficiency of the first variant (liquid membrane scheme) was found to be two times higher than that of the second variant.     

Separation and Recovery of Cadmium from Acidic Leach Liquors of Spent Ni-Cd Batteries using Molten Paraffin Wax Solvent Extraction

Separation and recovery of cadmium from sulphate leach liquors of spent Ni-Cd batteries using TBP, HDEHP (D2EHPA), EHEHPA (PC 88A or Ionquest 801 or P507) have been investigated in a laboratory scale. Cadmium can be extracted into paraffin waxes from acidic solutions in the temperature range of 55–75°C using different extractants. The influence of various parameters on extraction and stripping were studied in detail. The feasibility of separation of cadmium from nickel using these extractants and their combination was studied. The mixture extractant of EHEHPA and TBP was found to be the best for the separation of Cd and Ni. A three-stage counter-current extraction simulation test for cadmium extraction was carried out at an A/O phase ratio of 4:1 and pH 2.5. More than 99.97% Cd²⁺ was extracted with the organic phase containing 0.7 mol L^?1 EHEHPA and 0.5 mol L^?1 TBP, while more than 99.97% nickel was left in the raffinate. The cadmium loaded organic phase was stripped with 2 mol L^?1 hydrochloric acid in the stripping stage. The present method can be applied to the separation and recovery of cadmium from acidic leach liquor of spent Ni-Cd batteries or related waste liquor.     

Experimental Investigation and Simulation of a Gas‐agitated Sieve Plate Column

The extraction of hydrogen peroxide by means of deionized water from anthraquinone working solution via anthraquinone process was carried out in a gas‐agitated sieve plate extraction column. The effects of the superficial velocity of air, dispersed phase and continuous phase on the overall plate extraction efficiency have been investigated. The corrections for the prediction of the overall plate extraction efficiency were presented. The correction proposed to predict the overall plate extraction efficiency in the air, water, anthraquinone working solution three‐phase system agreed satisfactory with experimental data with a maximum absolute deviation of 5.6 %. A new design method for gas‐liquid‐liquid three‐phase extractors is developed based on the multistage countercurrent extraction model. The calculated data by the model agreed well with experimental data and the average relative deviation was less than 10 %. Moreover, the model was used to predict a gas‐agitated sieve plate extraction column for industrial production of hydrogen peroxide. The results show that the plate numbers of gas‐agitated sieve plate extraction column are 30–40 % less than that of liquid‐liquid sieve plate column.     

萃取串级的新排列——萃反交替多级逆流萃取过程

本文从萃取传质过程的基本关系式出发,提出了采用萃取级和反萃级交替排列、以增大传质推动力,从而提高萃取传质速率、减少萃取级数的新的逐级萃取方式,具体交替排列方式视具体萃取工艺体系之不同而有所不同.从理论分析出发,采用了N,N-二(1-甲庚基)乙酰胺(N_(503))萃取铁和二丁基亚砜(DBSO)萃取磷酸两个萃取体系进行串级计算,并对前—萃取体系进行了实验验证.结果表明,采用萃、反交替排列的多级逆流萃取方式较之通用的多级逆流萃取方式确可收到提高萃取传质速率、减少萃取级数的效果.用小型萃取设备进行的连续流动实验还表明,实现萃、反交替的排列方式以采用逐级式萃取设备(如混合澄清槽或单台单级式的离心萃取器)为宜,在设备设计和布置方面不存在任何困难.     

Hydraulic and Mass-Transfer Performance of a 20-Mm-Diameter Annular Centrifugal Contactor for the Solvent Extraction of Cesium by Bis(2-Propyloxy)Calix[4]-Crown-6 in n-Octanol

A calixcrown extraction process using bis(2-propyloxy)calix[4]-crown-6 (iPr-C[4]C-6) as extractant and n-octanol as diluent for the separation of cesium from Chinese High Level Liquid Waste (HLLW) has been developed at INET. Chinese HLLW is acidic defense waste with high salt content, which is now stored in underground stainless steel tanks. The intention is to use a process to extract cesium from HLLW conducted on multistage 20-mm-diameter annular centrifugal contactors (ACCs), so it is necessary to study the hydraulic and mass-transfer performance of a 20-mm-diameter ACC for the extraction system. In this work, the effects of the parameters such as the rotor speed, the diameter of heavy weir, and the acid concentration on the hydraulic performance were investigated. An operational envelope of the 20-mm-diameter ACC for the n-octanol/aqueous solution system was identified. The mass-transfer efficiency of the single stage 20-mm-diameter ACC for the extraction and stripping of cesium with iPr-C[4]C-6 in n-octanol was studied by varying several parameters, such as the rotor speed, the total flow rate, and the flow ratio. The extraction stage efficiency is greater than 95% at suitable operating conditions for extracting Cs⁺ with 0.025 mol/L of iPr-C[4]C-6 in n-octanol from HNO₃ solution containing Cs⁺. The stripping stage efficiency of Cs⁺ (< 90%) is lower than the extraction stage efficiency of Cs⁺.     

钛白水解废酸中钪的回收

研究了钛白水解废酸中钪的回收及钪与钛的分离。在P204-TBP萃取体系中进行了钛白水解废酸提钪实验研究,在此基础上绘制了钪的萃取等温线,并进行了串级逆流萃取实验。针对萃取后含钪钛的有机相,提出了用洗脱剂EL洗脱负载有机相中的钛,并进行了相应的实验研究。对除钛后的有机相,考察了钪反萃的影响因素。实验结果表明：P204-TBP萃取体系基本可以实现钪的回收富集,经洗脱剂EL三级逆流洗脱,钛的洗脱率可达到98%,而钪的损失率仅为4%,钪钛的分离效果明显。洗脱钛后的有机相用氢氧化钠反萃,钪的单级反萃率能达到97%以上。钛白水解废酸经一次萃取、洗脱、反萃后得到的粗钪产品纯度可达到85%。