Application of Annular Centrifugal Contactor on Separating Indium from Iron

Abstract

It is hard to separate indium from iron in sulfuric acid leachate without reducing Fe³⁺ to Fe²⁺ with di(2-ethylhexyl) phosphoric acid (HDEHP) by the equilibrium extraction process. A nonequilibrium extraction process with annular centrifugal contactors is studied through the extraction kinetics difference between In and Fe. The mass transfer velocities of In and Fe were determined. Laboratory- and industry-scale extraction tests with miniature and industry scale annular centrifugal contactors, respectively, were conducted. The results indicate the mass transfer velocity of In is much faster than that of Fe, the contact time between the two phases is very short in the contactor, and the In can be well separated from Fe in the nonequilibrium extraction process with annular centrifugal contactors.     

Separation of cobalt and nickel from sulfate media using P507-N235 system

Separation of cobalt and nickel from sulfate media was investigated, using a extraction system of 30% 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507)+15% trioctyl/decylamine (N235)+55% sulfonated kerosene. About 41 wt% Co²⁺ was extracted with 1.6 wt% co-extraction of Ni²⁺ at O/A ratio of 2:1. Scrubbing of Ni²⁺ and stripping of Co²⁺ could be achieved from the loaded organic phase, using water and 0.05 mol/L H₂SO₄, respectively. Cobalt extraction percentage decreased with increasing Mg²⁺ concentration, but this influence was negligible as [Mg²⁺] < 0.1g/L. The favorable equilibrium pH was 4–4.8. A different E-pH curve was observed in the P507-N235 system compared to the saponified P507 system.     

SOLVENT EXTRACTION OF ANTIMONY (III), BISMUTH (HI), LEAD (II) AND TIN (IV) WITH BIS(2,4,4-TRIMETHYLPENTYL)PHOSPHINODITHIOIC ACID (CYANEX 301®)

The solvent extraction of antimony (in), bismuth (111), lead (II) and tin (IV) from aqueous hydrochloric acid solutions by bis(2,4,4-trimethylpentyl) phosphinodithioic acid (Cyanex 301® denoted HL) in kerosene + 10 % v/v n-decanol was investigated. Lead (II), tin (IV), bismuth (III) and antimony (III) are efficiently extracted by Cyanex 301® up to about 5, 6, 9 and 11 mol.L^1? HCl, respectively. The corresponding extracted species were identified as PbL₂, SnCl₂L₂, BiL₃ and SMvj. However, it was observed that Sn (IV) can be moderately extracted from the aqueous phase by the mere mixture of kerosene and n-decanol above 9 mol.L^1?HCl. In all cases, extraction equilibrium was reached within a few minutes. Finally, a thermodynamic modelling of the extraction system was developed in the particular case of lead (II).     

Extraction of Caffeine with Annular Centrifugal Contactors

Abstract

An extraction process for caffeine has been developed with annular centrifugal contactors. The caffeine distribution ratio in the mother solution effluent‐chloroform system was measured to be about 18.6. Both the pilot tests and the plant tests have been completed with Φ20 mm and Φ230 mm annular centrifugal contactors, respectively. The extraction rate higher than 99% was achieved in the pilot tests, when the rotor speed was 3000‐4500 r/min, the total flow was 20‐80 mL/min, and the flow ratio (A/O) was 2/1. When the rotor speed was 1800 r/min, the mother solution flow was 2000 L/h, and the chloroform flow was 1000 L/h; the extraction rate was also more than 99% in the plant tests.     

Homogeneous Liquid–Liquid Extraction and Determination of Cobalt,Copper, and Nickel in Water Samples by Flame Atomic Absorption Spectrometry

Abstract

A simple and effective homogeneous liquid–liquid extraction method has been used for the simultaneous extraction and preconcentration of cobalt, copper, and nickel after the formation of complex with 4‐benzylpiperidinedithiocarbamate potassium salt (K‐4‐BPDC), and later they were determined by flame atomic absorption spectrometry (FAAS) using (water/tetrabutylammonium ion (TBA⁺)/chloroform) as a ternary component system. The phase separation phenomenon occurred by an ion‐pair formation of TBA⁺ and perchlorate ion. After the optimization of complexation and extraction conditions ([K‐4‐BPDC]=2.0×10^?4 mol l^?1, [TBA⁺]=2.0×10^?2 mol l^?1, [CHCl₃]=60.0 µl, [ClO₄ ^?]=2.0 ×10^?2 mol l ^?1 and pH=6.0), a preconcentration factor of 200 was obtained for only 10 ml of the sample.

The analytical curves were linear in the range of 20–1500, 15–2000, 35–1600 µg l^?1 and the limits of detection were 10, 5, and 15 µg l^?1 for Co²⁺, Cu²⁺, and Ni²⁺, respectively. The proposed method was applied for the extraction and determination of Co²⁺, Cu²⁺, and Ni²⁺ in natural water samples with satisfactory results.     

Solvent Extraction and Emulsion Separation in Magnetic Fields

Abstract

In two-phase emulsion separations, it is customary to employ large settling volumes (for mixer-settling apparatus) or large centrifugal forces (for centrifugal contactors). Improvement can sometimes be achieved by using an extractant with magnetic properties in the presence of a variable field. In the work reported in this paper, two different extractants (D-2EHPA and TBP) were employed in magnetic field experiments. These compounds are both stable and resistant to acid (15% H₂SO₄) and basic (NaOH, pH = 10) media. The test results for extraction of Cu²⁺ (with D-2EHPA) and UO₂ ²⁺ (with TBP) from aqueous media were positive. The emulsion separation for these two systems in the presence of a magnetic field was 160 times faster than in the gravitational field alone.     

Extraction and Separation of Germanium Using Cyanex 301/Cyanex 923. Its Recovery from Transistor Waste

Abstract

The extraction of Ge(IV) from HCl, HNO₃ and H₂SO₄ media in toluene solution of Cyanex 301 and Cyanex 923 is investigated. It is almost quantitatively extracted (～95%) in Cyanex 301 and Cyanex 923 at 8 molL^?1 HCl but the extractions from H₂SO₄ and HNO₃ are poor in the entire investigated range of acid molarity. Detailed investigations were carried out from HCl medium. Based on the slope analysis data the extracting species is identified as GeCl₄·2R (R=Cyanex 301/Cyanex 923). The extraction of Ge(IV) is higher and comparable in diluents like toluene, n‐hexane and kerosene (160–200°C) and there is no correlation between the dielectric constant and the percent extraction. The extractants are stable towards prolonged acid contact and there is negligible loss in their extraction efficiency even after recycling them for several cycles. The extraction behavior of commonly associated metal ions namely As(V)/(III), Sn(IV), Tl(III), In(III), Ga(III), Fe(III), Al(III), Hg(II), and Cu(II) has also been investigated. Based on the partition data conditions for attaining some binary and ternary separations involving Ge(IV) have been optimized. The separation data have been fused to develop a scheme for the recovery (93%) of pure germanium (～99%) from semi conductor waste.     

Extraction of Hydrocortisone from the Fermentation Liquor with Annular Centrifugal Contactors

Abstract

A continuous countercurrent extraction process for the recovery of hydrocortisone from the fermentation liquor has been developed with annular centrifugal contactors. When the hydrocortisone was extracted from the fermentation liquor with the butyl acetate, the distribution ratio increased with increase of the hydrocortisone concentration in the equilibrium aqueous phase. Both the laboratory tests and the plant tests have been finished with Φ20 mm and Φ230 mm annular centrifugal contactors respectively. In the laboratory tests, when the rotor speed was 3400～4200 r/min, the fermentation liquor flow was 30～50 mL/min and the phase ratio (V_O/V_A) was 0.36～0.50, the percent recovery of hydrocortisone was higher than 92%. In the plant tests, when the rotor speed was 2000 r/min, the fermentation liquor flow was 2000 L/h and the butyl acetate flow was 1000 L/h, the percent recovery of hydrocortisone was about 96.5～98%.     

Characterization of Copper–Cobalt Ores and Quantification of Cu2+, Co2+, Co3+, and Fe3+ in Aqueous Leachates Using UV/Visible Spectrophotometry

Ultraviolet/visible (UV/vis) spectroscopy was used to determine qualitatively and quantitatively Cu²⁺, Co²⁺, Co³⁺, and Fe³⁺ in oxidized Cu–Co ore leachates. The mineralogical and chemical characteristics of the three oxidized Cu–Co ore samples considered were determined using Fourier transform infrared spectroscopy (FTIR), X-ray powder diffractometry (XRD), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and X-ray fluorescence spectrometry (XRF). The results showed that Cu and Co in the samples were in the form of carrollite (Co₂CuS₄), malachite (Cu₂CO₃(OH)₂, and heterogenite (CoO(OH)). The samples contained (2.73% Cu and 0.19% Co), (2.82% Cu and 0.07% Co), and (0.03% Cu and 0.05% Co), respectively. Gangues were mainly constituted of quartz, goethite, and hematite. The ultraviolet/visible (UV/vis) results indicated that the wavelengths of absorbance of the metal ions in dilute ethylenediaminetetraacetic acid aqueous solution (pH ≈ 3.5) were Fe³⁺ (293 nm), Cu²⁺ (821 nm), Co³⁺ (344 nm), and Co²⁺ (512 nm). The molar concentrations of the metal ions obtained using the UV/vis method compared well with the results obtained using the atomic absorption spectroscopy (AAS) method. UV/vis spectroscopy was also used to monitor the conversion of Co³⁺ into Co²⁺ using different reducing agents. The results showed that the molar concentration of Co²⁺ in the aqueous solutions increased with the addition of reducing agents, of about 80.95% (copper foil), 61.22% (ferrous sulfate), and 20.35% (sodium sulfite), respectively.     

Back-extraction Of Pu4 + From 20% Tributyl Phosphate – 20% Mixed Trialkyl Phosphine Oxides/kerosene In The Presence Of

Back-extraction of Pu^4 +  from a mixture of 20% tributyl phosphate (TBP) and 20% mixed trialkyl phosphine oxides (TRPO) in kerosene in the presence of UO²⁺ ₂was studied. The back-extractants investigated may be divided into three groups: carboxylic acids and salts, amino polycarboxylates, and phosphonic acid. The distribution coefficients of both Pu^4 +  and UO²⁺ ₂using a number of different back-extractants were measured and compared. The results obtained suggest that the only practical back-extractants are carboxylic acids. Among the carboxylic acids tested, oxalic acid is suitable when the UO²⁺ ₂ concentration in the organic phase is less than 2 g/L. For UO²⁺ ₂concentrations between 2 and 10 g/L, oxalic acid-nitric acid mixtures may be used. For UO²⁺ ₂concentrations greater than 10 g/L, the only practical back-extractant is glycolic acid. The results obtained here may be used to further develop a new process for separation of Pu^4 +  and UO²⁺ ₂ from TBP-TRPO/kerosene mixture.     

膜接触器中乳化液膜脱除Ni2+的研究

研究了以D2EHPA/煤油/HC1形成的微乳液体系在中空纤维膜接触器中萃取NiCl2水溶液中Ni2的过程,考察了D2EHPA和Ni2+浓度、水溶液酸度、两相流速对溶液中Ni2+的萃取率和传质性能的影响.结果表明,用D2EHPA/煤油/HCl形成的微乳液体系能有效萃取NiCl2水溶液中的微量Ni2+,增大微乳液中载体D2EHPA浓度和料液pH都能提高Ni2的萃取率和过程的总质系数,增加料液流速能显著提高Ni2+的萃取率和过程的总质系数,表明过程的传质阻力主要在水溶液相.     

Uranium and Zirconium Mass Transfer Testing of 5.5-CM-DIAM Centrifugal Contactors

Abstract

As part of the Consolidated Fuel Reprocessing Program of the Oak Ridge National Laboratory, compact centrifugal contactors were designed and prototypes built for the Breeder Reprocessing Engineering Test (BRET) facility with a throughput capacity of 0.1 t/d of heavy metals. While the construction of BRET has been put on hold indefinitely, development of the 5.5-cm-diam centrifugal contactors has advanced due to the contactor's broad applicability in other areas of fuel reprocessing and liquid-liquid extraction. Due to the short residence time of the process fluids in a centrifugal contactor, it was necessary to measure the mass transfer efficiency for a typical process flowsheet. This was done with depleted uranium and ⁹¹Zr. The results of mass transfer tests with uranium and zirconiun are reported in this paper.     

Demonstration of a SANEX Process in Centrifugal Contactors using the CyMe4‐BTBP Molecule on a Genuine Fuel Solution

Efficient recovery of minor actinides from a genuine spent fuel solution has been successfully demonstrated by the CyMe₄‐BTBP/DMDOHEMA extractant mixture dissolved in octanol. The continuous countercurrent process, in which actinides(III) were separated from lanthanides(III), was carried out in laboratory centrifugal contactors using an optimized flow‐sheet involving a total of 16 stages. The process was divided into 9 stages for extraction from a 2 M nitric acid feed solution, 3 stages for lanthanide scrubbing, and 4 stages for actinide back‐extraction. Excellent feed decontamination factors for Am (7000) and Cm (1000) were obtained and the recoveries of these elements were higher than 99.9%. More than 99.9% of the lanthanides were directed to the raffinate except Gd for which 0.32% was recovered in the product.     

Kinetics of Exchange of Cs+, Co2+ and Sr2+ on Synthetic Hydrous Titanium Oxides

Abstract

In the present work, a study of the kinetics of adsorption of Cs⁺, Co²⁺, and Sr²⁺ on four hydrous titanium oxides, prepared in different media, and designated as Ti‐I, Ti‐II, Ti‐III, and Ti‐IV, was carried out. In the aqueous medium, the internal diffusion coefficients, D_i for Cs⁺ were found to be equal to 3.7×10^?9, 3.7×10^?9, 2.3×10^?9, and 1.5?10^?9 cm²/s, in Ti‐I, Ti‐II, Ti‐III, and Ti‐IV, respectively. For Co²⁺ and Sr²⁺, these values are equal to 0.96×10^?9 and 0.64×10^?9 cm²/s, respectively for Ti‐IV. In Ti‐IV, D_i for all ions generally increases on adding methanol or propanol. This is probably due to greater dehydration, leading to faster ion diffusion, and, hence, to a decrease of ion mobility due to stronger interaction with the surface. In all media in Ti‐IV, the order: D_i(Cs⁺)>D_i(Co²⁺)≥D_i(Sr²⁺) was found which is due to a stronger interaction of the bivalent ions with the exchange sites.     

Experimental study of the hydraulic operation of an annular centrifugal contactor with various mixing vane geometries

The annular centrifugal contactor is a combination mixer/centrifuge that has been developed for solvent extraction processes for recycling used nuclear reactor fuel. The experimental observations presented were part of a simulation‐focused research effort aimed at providing a more complete understanding of the fluid flow within these contactors to enable further advancements in design and operation of future units and greater confidence for use of such contactors in a variety of other solvent extraction applications. Laser doppler velocimetry (LDV), particle image velocimetry (PIV), pressure measurements, and high‐speed video imaging for a range of flow rates and rotor speeds were performed to characterize the flow of water in the annular mixing region of the contactor using three different mixing vane geometries. It was found that the geometry of the mixing vanes has a significant impact on the annular liquid height and general flow in the contactor mixing zone. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Effect of Co2+, Ni2+, Cu2+, or Zn2+ on properties of polyaniline nanoparticles

Uniform polyaniline (PANI) nanoparticles with typical sizes of about 50 nm were electropolymerized on indium tin oxide surfaces in the presence of Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. According to shaping theory, we first suggest the reason forming PANI spherical particles. Their conductivity, UV‐vis spectra, FTIR spectra, X‐ray diffraction, and thermogravimetric analysis were investigated. The conductivities and crystallinity of PANI doped with these ions are higher than those of PANI doped with HCl (PANI/HCl). Both UV‐vis absorption spectra and FTIR spectra indicate the interactions between Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ and PANI chains. TG analysis also shows that the thermal stability of PANI doped by Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ is lower than that of PANI/HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Membrane Gas-Solvent Contactor Pilot Plant Trials of CO2 Absorption from Flue Gas

Membrane gas-solvent contactors have received much attention for CO₂ absorption, as the approach incorporates advantages from both solvent absorption and membrane gas separation. This study reports on pilot plant trials of three membrane contactors for the separation of CO₂ from flue gas. The contactors were porous polypropylene (PP), porous polytetrafluoroethylene (PTFE), and non-porous polydimethylsiloxane (PDMS), with the solvent PuraTreatTM F^TM. To enable performance comparison, laboratory measurements based on a gas mixture of 10% CO₂ in N₂ were also undertaken on the same contactor–solvent systems. It was found that the PP contactor experienced significant pore wetting in both laboratory and pilot plant studies. In contrast, the PTFE contactor experienced only minor pore wetting in the laboratory. However, in the pilot plant trial of the PTFE contactor extensive pore wetting was observed, and the overall mass transfer coefficient measured was comparable with the PP contactor. The non-porous PDMS contactor had an overall mass transfer coefficient two orders of magnitude less than the PP contactor, due to the greater mass transfer resistance of the polymeric film. However, the non-porous membrane does not experience pore wetting, which resulted in the overall mass transfer coefficient being similar for both laboratory and pilot plant measurements.     

High‐throughput microporous tube‐in‐tube microreactor as novel gas–liquid contactor: Mass transfer study

High‐throughput microporous tube‐in‐tube microchannel reactor (MTMCR) was first designed and developed as a novel gas–liquid contactor. Experimentally measured k_Lα in MTMCR is at least one or two orders of magnitude higher than those in the conventional gas–liquid contactors. A high throughput of 500 L/h for gas and 43.31 L/h for liquid is over 60 times higher than that of T‐type microchannel. An increase of the gas or liquid flow rate, as well as a reduction of the micropore size and annular channel width of MTMCR, could greatly intensify the gas–liquid mass transfer. The interfacial area, α, in MTMCR was measured to be as high as 2.2 × 10⁵ m²/m³, which is much higher than those of microchannels (3400–9000 m²/m³) and traditional contactors (50–2050 m²/m³). The artificial neural network model was proposed for predicting α, revealing only an average absolute relative error of <5%. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

SEPARATION OF COBALT(II) AND NICKEL(II) IONS FROM ACID AQUEOUS SOLUTIONS BY Co IT ION-EXCHANGE INTO γ-TITANIUM PHOSPHATE

ABSTRACT

The Co²⁺-2H⁺, Ni²⁺-2H⁺, and Co²⁺-Ni²⁺-2H⁺ ion exchange processes into γ-Ti(H₂PO₄)(PO₄)2H₂O were studied. Exchange isothenns and titration curves were obtained. Monometallic half ion exchange phases were formed by using MC₂+HCl (M=Co,Ni) solutions. Equilibrium constants, free energy, enthalpy, and entropy of the Co²⁺-2H²⁺ ion exchange reaction were determined. In (Co,Ni)Cl₂ solutions, bimetallic a half ion exchange substitution solid solution is detected. Equilibrium constant of the Co²⁺-Ni²⁺ substitution process in the γ-Ti(Co_xNi_0.5?x.HPO₄)(PO₄)nH₂O phase at 85°C was determined. In (Co,Ni)Cl₂+HCl solutions, total separation of Co²⁺ and Ni²⁺ is obtained.     

Separation of Radiogallium from Zinc Using Membrane-Based Liquid-Liquid Extraction in Flow: Experimental and COSMO-RS Studies

ABSTRACT

A switch from batch to continuous manufacturing of gallium-68 (⁶⁸Ga) and ⁶⁸Ga-labeled pharmaceuticals can be advantageous, as it recycles isotopically-enriched zinc-68 (⁶⁸Zn), removes pre- and post-irradiation target manipulations, and provides scalability via dose-on-demand production. Herein we report efficient extraction of radiogallium (^66,67,68Ga = *Ga) from ZnCl₂/HCl solutions in batch and in flow using a membrane-based liquid-liquid separator. From 5.6 M ZnCl₂/3 M HCl, a 1/2 (v/v) diisopropyl ether (ⁱPr₂O)/trifluorotoluene (TFT) solvent extracts 76.3 ± 1.9% of *Ga and 1.9 ± 1.6% of Zn in flow using a single pass through. From 1 M ZnCl₂/6 M HCl, a 1/2 (v/v) n-butyl methyl ether (n-BuOMe)/TFT solvent extracts 95.7 ± 2.0% of *Ga and 0.005 ± 0.003% of Zn in flow. TFT plays a key role in controlling the interfacial tension between the aqueous and the organic phases, ensuring clean membrane-based separation. The process did not extract Cu, Mn, and Co but did extract Fe. Using HGaCl₄ and ZnCl₂ as the extractable species, the COSMO-RS theory predicts the solvation-driven extraction of Ga and Zn with a mean unsigned error of prediction of 4.0% and 3.4% respectively.