Solvent extraction of La(III) with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (EHEHPA) by membrane dispersion micro-extractor

The conventional rare earth solvent extraction equipments have many problems such as long mixing time, low processing capacity, large factory area occupation, high energy consumption and so on. In order to solve the problems, many types of equipments were brought out. In this work, studies were carried out on the La（III） extraction process with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor. Equilibrium studies showed that the initial aqueous pH value 4.15 with the saponification rate 40%was the optimal operation condition. The effects of membrane dispersion micro-extractor operational conditions such as dispersion mode, bulk flow rate and organic phase flow rate on the extraction efficiency were studied. The results showed that when the organic solution was the dispersed phase, the extraction efficiency was higher than that of others. Increasing bulk flow ratio could enhance the extraction efficiency greatly. When the ratio of organic phase flow rate to that of aque-ous phase was 80：80, the extraction efficiency was over 95%. The effect of stripping phase acidity on the La（III） recovery was studied. The results showed that when the stripping phase pH was 2.0, organic phase flow rate to stripping phase flow rate was 20：80;the re-covery efficiency of La（III） can reach 82%.

Solvent extraction performance of Ce(Ⅲ) from chloride acidic solution with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester(EHEHPA) by using membrane dispersion micro-extractor

By using membrane dispersion micro-extractor, Ce（IIl） solvent extraction experiments were conducted. Cerium chloride solution with certain acidity was used as aqueous phase and 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） kerosene solution as organic phase. The effects of system physicochemical properties and operational conditions, such as initial EHEHPA concentration, initial aqueous acidity, total flow rate and continuous phase flow rate, etc., on the extraction efficiency and the overall volume mass transfer coefficient were evaluated. As the total flow rate increased fi＇om 20 to 160 mL/min, the overall volume mass transfer coefficient was enhanced from 0.1 to 0.54 S1. Under the optimal conditions, the Ce（III） extraction efficiency could reach 99.92% in 2.98 s. A mathematical model was set up to predict the overall volume mass transfer coefficient, and the calculation results agreed well with the experimental results, most relative error was within ＋10%.

Efficient extraction and stripping of Nd(Ⅲ),Eu(Ⅲ) and Er(Ⅲ) by membrane dispersion micro-extractors

The extraction of low concentration rare earth elements at high phase ratio was investigated. The traditional extraction set-up, such as mixer-settler, have drawbacks of easy emulsification, difficult separation and low efficiency if operated at the above condition. Membrane dispersion micro-extractor,owing to its well-dispersed, high surface-to-volume ratio and fast mass transfer rate, was employed in our work. Nd（Ⅲ）,Eu（Ⅲ）,Er（Ⅲ） were chosen to represent light, medium,heavy rare earth elements（REEs）. The extraction process of REEs with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester（P507） was investigated by membrane dispersion micro-extractors. Firstly, the extraction equilibrium of these three elements was explored in the stirred conical flasks, and it is indicated that the extraction efficiencies can be 0.95, 0.97 and 0.98, respectively within 40 min at phase ratio of 100：1. Then the effects of operational conditions such as the residence time, organic and aqueous flow rates on extraction efficiency were also explored in micro-extractors. The results indicate that the efficiency decreases and then increases if increasing aqueous phase flow rate, residence time and droplets＇ diameter are the key factors of this process. Increasing the phase ratio reduces the extraction efficiency significantly. When the REEs solution has an initial pH of 4.00, the flow rates of continuous and dispersed phase are 40 and 1.6 mL/min,respectively, and 90 mg/L Nd（Ⅲ）, Eu（Ⅲ） and Er（Ⅲ） is extracted by 1 mol/L P507 at the out-let length of8 m. The extraction efficiencies are 0.978,0.983 and 0.991, respectively. Finally the stripping process was also studied with the micro-extractor. The stripping efficiencies of Nd（Ⅲ）, Eu（Ⅲ） and Er（Ⅲ） can reach0.99, 0.96 and 0.91, respectively when the out-let length is 8 m and the concentration of hydrochloric acid is 1 mol/L. The developed approach offers a novel and simple strategy on the fast extraction and enrichment of low concentration rare earth elements from waste water.

Acid precipitation coupled membrane-dispersion advanced oxidation process(MAOP)to treat crystallization mother liquor of pulp wastewater

Treatment to crystallization mother liquor containing high concentration of organic and inorganic substances is a challenge in zero liquid discharge of industrial wastewater.Acid precipitation coupled membrane-dispersion advanced oxidation process(MAOP)was proposed for organics degradation before salt crystallization by evaporation.With acid-MAOP treatment CODCrin mother liquor of pulping wastewater was eliminated by 55.2%from ultrahigh initial concentration up to 12,500 mg·L^-1.The decolorization rate was 96.5%.Recovered salt was mainly NaCl(83.3 wt%)having whiteness 50 brighter than industrial baysalt of whiteness 45.The oxidation conditions were optimized as CO3=0.11 g·L^-1 and CH2O2=2.0 g·L^-1 with dispersing rate 0.53 ml·min^-1 for 100 min reaction toward acidified liquor of p H=2.Acidification has notably improved evaporation efficiency during crystallization.Addition of H2O2 made through membrane dispersion has eliminated hydroxyl radical"quench effect"and enhanced the degradation capacity,in particular,the breakage of carbon-chloride bonds(of both aliphatic and aromatic).As a result,the proposed coupling method has improved organic pollutant reduction so as the purity of salt from the wastewater mixture which can facilitate water and salt recycling in industry.

Tb(III) Transport in Dispersion Supported Liquid Membrane System with D2EHPA as Carrier in Kerosene

The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（2-ethylhexyl） phosphoric acid（D2EHPA） dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb（III） and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the transport of Tb（III） have also been investigated, respectively. As a result, the optimum transport conditions of Tb（III） were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb（III）. Under the optimum conditions, the transport percentage of Tb（III） was up to 96.1% in a transport time of 35 min when the initial concentration of Tb（IIl） was 1.0× 10 -4 mol/L. The diffusion coefficient of Tb（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10 -8 m2/s and 5.61 um, respectively. The calculated results were in good agreement with the literature data.

Study on transport of Dy(Ⅲ) by dispersion supported liquid membrane

The transport of Dy（III） through a dispersion supported liquid membrane （DSLM） consisting of polyvinylidene fluoride membrane （PVDF） as the liquid membrane support and dispersion solution including HCI solution as the stripping solution and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester （PC-88A） dissolved in kerosene as the membrane solution, was studied. The effects of pH value, initial concentration of Dy（III） and different ionic strength in the feed phase, volume ratio of membrane solution and stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on transport of Dy（III） were also investigated, respectively. As a result, when the concentration of HCI solution was 4.0 mol/L, concentration of PC-88A was 0.10 mol/L, and volume ratio of membrane solution and stripping solution was 40：20 in the dispersion phase, and pH value was 5.0 in the feed phase, the transport effect of Dy（III） was the best. Ionic strength had no obvious effect on transport of Dy（III）. Under the optimum condition studied, when initial concentration of Dy（III） was 0.8×10^-4 mol/L, the transport rate of Dy（III） was up to 96.2% during the transport time of 95 rain. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Dy（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.99×10^-7 m^2/s and 15.97 μm, respectively. The results were in good agreement with experimental results.

Separation of Eu(Ⅲ) with supported dispersion liquid membrane system containing D2EHPA as carrier and HNO_3 solution as stripping solution

The Eu（III） separation in supported dispersion liquid membrane （SDLM）, with polyvinylidene fluoride membrane （PVDF） as the support and dispersion solution containing HNO3 solution as the stripping solution and Di（2-ethylhexyl） phosphoric acid （D2EHPA） dis- solved in kerosene as the membrane solution, was studied. The effects ofpH value, initial concentration of Eu（III） and different ionic strengths in the feed phase, volume ratio of membrane solution and stripping solution, concentration of HNO3 solution, concentration of carrier, different stripping agents in the dispersion phase on the separation of Eu（III） were also investigated, respectively. As a result, the optimum separation conditions of Eu（III） were obtained as the concentration of HNO3 solution was 4.00 mol/L, concentration of D2EHPA was 0.160 mol/L, and volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase, and pH value was 5.00 in the feed phase. Ionic strength had no obvious effect on the separation of Eu（III）. Under the optimum conditions studied, when initial concentration of Eu（III） was 1.00× 10^-4 mol/L, the separation rate of Eu（III） was up to 94.2% during the separation period of 35 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The results were in good agreement with the literature data.

Modeling of Ce（IV） transport through a dispersion flat combined liquid membrane with carrier P507

A mathematical model for the transport of Ce （IV） from hydrochloric acid solutions through dispersion flat combined liquid membrane （DFCLM） with contain 2- ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester （P507） as the carrier, dissolved in kerosene as the membrane solution have been studied. This process of facilitated transport, based on membrane technology, is a variation on the conventional technique of solvent extraction and may be described mathematically using Fick＇s second law. The equations for transport velocity are derived considering the diffusion of P507 and its metallic complexes through the liquid membrane. In this work, the system is considered to be in a transient state, and chemical reaction between Ce（IV） and the carrier to take place only at the solvent-aqueous interfaces. Model concentration profiles are obtained for the Ce（IV）, from which extraction velocities are predicted. The experimental and simulated Ce（IV） extractions showed similar tendencies for a high Ce （IV） concentration and acidity case.The model results indicate that high initial Ce（IV） concentrations and acidity both have detrimental effects on Ce（IV） extraction and stripping. The diffusion coefficient of Ce（IV） in the membrane and the thickness of diffusion layer between feed phase and membrane phase are obtained and the values are 6.31 × 10-8m2·s-1 and 31.2 μm, respectively. The results are in good agreement with experimental results.

Separation of Trivalent Samarium through Facilitated Stripping Dispersion Hollow Fiber Liquid Membrane Using p204 as Mobile Carrier

The separation of Sm（III） through stripping dispersion hollow fiber liquid membrane system （SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HC1 solution as the stripping solution and membrane solution of di（2-ethylhexyl） phosphoric acid （p204） dissolved in kerosene, has been studied. A set of factors were studied, including pH value, initial concentration of Sm（III） and different ionic strength of feed phase, volume ratio of membrane solution and stripping solution （O/W）, HC1 concentration, carrier concentration, different stripping agents of dispersion phase on Sm（III） separation. Experimental results indicate that the optimum separa- tion conditions of Sm（III） were obtained as that HC1 concentration was 4.00 tool/L, p204 concentration was 0.150 mol/L, and volume ratio of membrane solution and stripping solution （O/W） was 1.00 in the dispersion phase, and pH value was 4.60 in the feed phase. Ionic strength had no obvious effect on separation of Sm（III）. When initial Sm（III） concentration was 1.00 × 10^-4 mol/L, the separation rate of Sm（III） was up to 93.5% in 85 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The modeled results were in good agreement with the experiment data.

Stripping dispersion hollow fiber liquid membrane containing carrier PC-88A and HNO_3 for the extraction of Sm^(3+)

Stripping dispersion hollow fiber liquid membrane system（SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HNO_3 solution as the stripping solution and membrane solution of 2-ethyl hexyl phosphoric acid-mono-2-ethylhexyl ester（PC-88A） dissolved in kerosene,has been studied for the extraction of Sm^（3＋）.Many factors including pH value, volume ratio of membrane solution to stripping solution（OAV） and carrier concentration on Sm^（3＋） extraction were investigated. Experimental results indicate that the optimum extraction conditions of Sm^（3＋） were obtained as that PC-88A concentration was 0.120 mol/L,and OAV was 1.00 in the dispersion phase,and pH value was 4.80 in the feed phase.When initial Sm^（3＋） concentration was 1.20×10^（-4） mol/L,the extraction percentage of Sm^（3＋） was up to 92.8%in 160 min.