Process development for the direct solvent extraction of nickel and cobalt from nitrate solution:aluminum,cobalt,and nickel separation using Cyanex 272

A direct solvent extraction（DSX） process for purifying nickel and cobalt from the nitric acid leach solution of nickel laterite ores was conceived and experimentally probed. The proposed process consists of two solvent extraction（SX） steps but with only one extractant - bis（2,4,4-trimethylpentyl）phosphinic acid（Cyanex？ 272） - used in both steps. The first extraction step involved the removal of aluminum and zinc, whereas the second extraction step involved the separation of cobalt along with manganese from nickel. The experimental results showed essentially quantitative removal of aluminum（〉97%） and zinc（〉99%） in a single extraction stage using 20vol% Cyanex 272 at pH 2.1. Some cobalt（32%） and manganese（55%） were co-extracted but were easily scrubbed out completely from the loaded organic phase using dilute sulfuric acid at pH ≤ 1.38. Cobalt and manganese in the first extraction raffinate were extracted completely in four extraction stages at staggered pH values of 4.0, 4.4, 4.5, and 4.0 in the first, second, third, and fourth stages, respectively, using also 20vol% Cyanex 272. A small amount of nickel（up to 6.6%） was co-extracted but was easily scrubbed out completely with dilute sulfuric acid at pH 2.0. A flow diagram showing the input and output conditions and the metals separated under the deduced optimum conditions is presented.

Recovery of nickel,cobalt,copper and zinc in sulphate and chloride solutions using synergistic solvent extraction

A number of synergistic solvent extraction （SSX） systems have been developed to recover nickel, cobalt, zinc and copper from sulphuric and chloride leach solutions by the solvent extraction team of CSIRO, Australia. These in- clude （1） Versatic 10/CLXS0 system for the separation of Ni from Ca in sulphate solutions, （2） Versatic 10/4PC system for the separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, （3） Cyanex 471X/HRJ-4277 system for the separation of Zn from Cd in sulphate solutions, （4） Versatic 10/LIX63 system for the separation of Co from Mn/Mg/Ca in sulphate solutions, （5） Versatic 10/LIX63/TBP system for separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, （6） Versatic 10/LIX63 system for the separation of cobalt from nickel in sulphate solutions by difference in kinetics, （7） Cyanex 272/LIX84 system for the separation of Cu/Fe/Zn from Ni/Co in sulphate solutions, （8） Versatic 10/LIX63fFBP system to recover Cu/Ni from strong chloride solutions, and [9） Versatic 10/LIX63 system to separate Cu from Fe in strong chloride solutions. The synergistic effect on metal separation and efficiency is presented and possible industrial applications are demonstrated. The chemical stability of selected SSX systems is also reported.

Separation of nickel, cobalt and copper by solvent extraction with P204

Nickel, cobalt and copper were separated by solvent extraction with P204. The experimental results show that [Co(NH 3) 6] 3+ is an inert complex in extraction kinetics, therefore cobalt can be separated from nickel and copper by non equilibrium solvent extraction. Under the conditions of temperature 25?℃, contact time of two phases 10?min, phase ratio 1∶1, aqueous pH 10.10 and concentration of P204 20%, [Co(NH 3) 6] 3+ is hardly extracted by P204, while the percentage extractions of nickel and copper are 79.3% and 93.9% respectively. Nickel and copper are separated by equilibrium solvent extraction with P204. Under the conditions of temperature 25?℃, contact time of two phases 1?min, phase ratio 1∶1, equilibrium pH 4.01 and concentration of P204 20%, the separation factor of copper and nickel is 216.

Separation of cobalt and nickel by non-equilibrium solvent extraction

The separation of cobalt and nickel in the ammoniacal sulfate solution by non equilibrium solvent extraction with a phosphate (P303) as extractant was studied. In the experiment, the effects of equilibrium pH value in aqueous phase, contact time of the two phases, the air blowing time for feed liquor in the open beaker on percentage extraction of cobalt and nickel and percentage reextraction of nickel from the loaded organic phase with dilute H 2SO 4. etc were studied. The results showed that: Co(Ⅱ) can be oxidized to Co(Ⅲ) ammino complex by adding (NH 4) 2S 2O 8 or blowing air to the aqueous phase, and Co(Ⅲ) ammino complex is a kind of kinetically inert complex. Its extractive speed is very slow, while the nickel′s is much faster than that of cobalt. By controlling the contact time of the two phases, nickel can be separated from cobalt by non equilibrium solvent extraction. Then nickel was reextracted from the loaded organic phase with dilute H 2SO 4.

Solvent Extraction of Nickel and Cobalt from Ammonia-Ammonium Carbonate Solution by Using LIX 84-ICNS

In the present paper, separation of nickel and cobalt in ammonia-ammonium carbonate solution that simulates pregnant leach solution of Caron Process by solvent extraction using LIX 84-ICNS was studied. LIX 84-ICNS is a novel extractant which is still being studied, especially for nickel and cobalt separation in ammonia-ammonium carbonate solution. A series of solvent extraction tests were performed at various equilibrium pH, temperature, extractant concentration, and volume ratio of organic to aqueous solution (O/A ratio). The investigation results show that the highest nickel and cobalt extraction percentages of 99.8% and 90.3% were obtained from the extraction test at equilibrium pH of 8.75, temperature of 55°C, extractant concentration of 40% (v/v) and O/A ratio of 1/1, respectively. Oxidation of cobalt in aqueous solution prior to extraction is needed to minimize co-extraction of cobalt. Co-extracted cobalt can be decreased from 90.3% to 30.3% by mixing 1% (v/v) H2O22 in aqueous solution prior to the extraction stage. It was found that nickel and cobalt extractions by LIX 84-ICNS are endothermic processes with enthalpy changes of +171.03 and +7.64 kJ/mole, respectively. Based on constructed McCabe-Thiele Diagram, nickel extraction level of more than 99.9% can be obtained in 2 stages at O/A ratio of 0.5. The highest stripping percentages of nickel and cobalt of 98.82% and 3.16% respectively were obtained at 200 g/l H2SO4 stripping agent.

Recovery of Copper（II） and Nickel（II） from Plating Wastewater by Solvent Extraction

The solvent extraction technology, was applied to recover Cu^2＋ and Ni^2＋ from plating wastewater.Lix984N was chosen as the extractant due to-its gooff extraction performance. The influence parame-ters were examlned. The results show that the separation of Cu^2＋ and Ni＂ from sulphate medium can be realized by adjusting pH value with the help of Lix984N. For extracting Cu^2＋ and Ni^2＋, the optimal pH values are 4 and 10.5, and the maximal extraction percentages are 92.9% and 93.0%, respectively .With recovered Cu^2＋ and Ni^2＋ stripped in 170g.L^ -1 and 200 g.L^-1 H2SO4 medium, the stripping percentages of Cu^2＋ and Ni^2＋ are 92.9% and 93.0%, respectively. This method is simple and can be used to recover Cu^2＋ and Ni^2＋ from plating wastewater. And a flow sheet for separation of Cu^2＋ and Ni^2＋ is presented.

Phase separation in solvent extraction of cobalt from acidic sulfate solution using synergistic mixture containing dinonylnaphthalene sulfonic acid and 2-ethylhexyl 4-pyridinecarboxylate ester

Phase separation rate is a critical character in determining the usefulness of a solvent extraction system in hydrometallurgy. A survey of the synergistic mixture containing dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexly 4-pyridinecarboxylate ester (4PC) for the extraction of cobalt from acidic single metal sulfate solution was carried out to suggest how the physicochemical properties and the morphology of the reverse micelles in the loaded organic phase affect the phase separation. The results show that effective parameters affecting the phase separation are the viscosity and the excess water uptake of the loaded organic phase. It is obvious that the specific settling rate (SSR) decreases with the apparent increase of these two parameters. The measurement of small angle X-ray scattering (SAXS) proves that the morphology of the reversed micelles in the loaded organic phase changes evidently with the change of the specific settling rate (SSR).

Extraction studies of cobalt (Ⅱ) and nickel (Ⅱ) from chloride solution using PC88A

Solvent extraction study of cobalt and nickel were carried out from a chloride solution with a high ratio of Co to Ni using the sodium salt of PC88A as extractant diluted in kerosene. The solution was generated in batches by leaching a tungsten super alloy scraps. The results show that extraction rate of metal ions increases with increase of aqueous phase pH value. The pH0.5 value difference of 1.40 with PC88A indicates the possible separation of cobalt and nickel. Increase of the concentration of the solvent can enhance the percentage extraction of both metal ions. Improvement of temperature is beneficial to extraction separation of cobalt and nickel. Extraction and stripping processes were also studied in a cross-current solvent extraction unit and the results were also given.

Separation of Copper and Nickel by Solvent Extraction Using LIX 664N

Separation of copper and nickel by liquid-liquid extraction from aqueous solutions was studied using LIX 664N in kerosene as solvent. Both metals were taken in their sulfate form and ratio of copper to nickel in feed solutions was maintained as 10:1. LIX 664N concentration in kerosene was varied from 10% to 40% (v/v) and its effect was studied on percent extraction of copper and nickel for organic to aqueous (O:A) phase ratio of 2:1 at pH 2. Experimental results showed that at pH 2, copper was selectively extracted from its mixture with nickel. Selectivity for copper extraction was as high as 6000 with 40% LIX 664N. Calculations using extraction isotherm indicate almost complete recovery of copper in two stages with O:A ratio of 1:1 and in one stage with O:A ratio of 2:1. After extraction of copper, the pH of raffinate containing nickel was adjusted to a value of 9 by addition of ammonia solution. The effect of LIX 664N concentration on extraction of nickel was studied. Up to 80% nickel could be extracted with 30% LIX 664N at O:A phase ratio of 2:1. Stripping of copper from the organic phase with 180 g/l sulfuric acid at O:A phase ratio of 1:1 gave 98.5% copper recovery in a two-stage operation.

Recovery of cobalt and nickel in the presence of magnesium and calcium from sulfate solutions by Versatic 10 and mixtures of Versatic 10 and Cyanex 301

The extraction and stripping characteristics of Versatic 10 and its mixtures with Cyanex 301 were investigated for the recovery of cobalt and nickel from sulfate solutions containing magnesium and calcium. The optimum extraction factors of Versatic 10 were initial pH of 2.5, O/A ratio of 1/3, and saponification rate of 60%. The loaded Versatic 10 was stripped by using 2 mol/L H2SO4 at O/A ratio of 1/1. The optimum volume ratio of Versatic 10 to Cyanex301 was 7/3 in the mixtures, which could effectively reduce the equilibrium pH to 3.50. And the loaded mixtures were stripped by using 2 mol/L H2SO4at O/A ratio of 1/2. The reaction principle of Versatic10 and metal ions is an ion exchange reaction. However, in the extraction reaction of and metal ions, besides the ion exchange reaction, the strong coordination effect between Cyanex 301 and metal ions also exists, which is much weakened in the extraction reaction of the mixtures and metal ions.

Extraction of nickel from molybdenum leaching residue of metalliferous black shale by segregation roasting and acid leaching

The recovery of nickel from molybdenum leach residue by the process of segregation roasting-sulfuric acid leaching-solvent extraction was investigated. The residue was characterized by microscopic investigations, using X-ray fluorescence spectrometry （XRF） and X-ray diffractometry （XRD） techniques and the residue after segregation roasting was characterized by chemical phase analysis method. A series of experiments were conducted to examine the mass ratio of activated carbon （AC） to the residue, segregation roasting time and temperature, sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, addition amount of 30% H2O2, stirring speed （a constant） on the leaching efficiency of nickel. A maximum nickel leaching efficiency of 90.5% is achieved with the mass ratio of AC to the residue of 1：2.5, segregation roasting time of 2 h, segregation roasting temperature of 850 ℃, sulfuric acid concentration of 4.5 mol/L, liquid-to-solid ratio of 6：1, leaching time of 5 h, leaching temperature of 80 ℃, addition of 30% H202 of 0.6 mL for 1 g dry residue. Under these optimized conditions, the average leaching efficiency of nickel is 89.3%. The nickel extraction efficiency in the examined conditions is about 99.6%, and the nickel stripping efficiency in the examined conditions is about 99.2%.

Nickel solvent extraction from cold purification filter cakes of Angouran mine concentrate using LIX984N

Cold purification filter cakes generated in the hydrometallurgical processing of Angouran mine zinc concentrate commonly contain significant amounts of Zn, Cd, and Ni ions and thus are valuable resources for metal recovery. In this research, a nickel containing solution that was obtained from sulfuric acid leaching of the filter cake following cadmium and zinc removal was subjected to solvent extraction experiments using 10vol%LIX984N diluted in kerosene. Under optimum experimental conditions （pH 5.3, volume ratio of organic/aqueous （O：A） = 2：1, and contact time -5 min）, more than 97.1% of nickel was extracted. Nickel was stripped from the loaded organic by contacting with a 200 g/L sulfuric acid solution, from which 77.7% of nickel was recovered in a single contact at the optimum conditions （pH 1-1.5, O：A =5：1, and contact time =15 min）.

Recovery of Mn^(2+), Co^(2+) and Ni^(2+) from manganese nodules by redox leaching and solvent extraction

The recovery of Mn, Co and Ni from deep-sea manganese nodules was conducted by acid oxidative leaching and solvent extraction. The results indicate that pyrrhotite used during leaching can effectively facilitate the leaching out of manganese, cobalt and nickel. The leaching behaviors of Mn, Ni and Co were determined and the influences of temperature, leaching time and sulphuric acid concentration on leaching rate were also investigated. Co and Ni are precipitated from the leaching liquor by adding sodium sulfide into solution with agitation for 2 h at 50 ℃, and the manganese sulphate is obtained by concentrating the resulting solution. By re-dissolving the precipitates of cobalt and nickel, the separation of cobalt and nickel is performed using di(2-ethylhexyl) phosphoric acid (D2EHPA) for impurities elimination with 8 stages at organic-to-aqueous(O/A) volume ratio of 3:5, and 2- ethylhexyl phosphonic acid mono-2-ethylhexyl ester (known as PC88A or P507) for cobalt extraction with 3 stages counter-current operations at O/A volume ratio of 2:3 followed by their scrubbings and strippings, respectively. The final maximum recovery rates for manganese, cobalt and nickel are 85%, 75% and 78%, respectively.

PURIFICATION OF COBALT ANOLYTE USING THE NOVEL SOLVENT EXTRACTION SYSTEM

In present research, a novel extractant system (D2EHPA + naphthenic acid + pyridine- ester) was used to purify cobalt anolyte and a simulated industrial production were carried out. This novel extraction system can extract Cu and/or Ni against Co from chloride medium solutions at pH range of 2.5-4.5. About 2g/l nickel and 0.2g/l copper were removed from the cobalt chloride anolyte containing about 100g/l cobalt and 200g/l chloride ions respectively, the raffinate contains nickel and copper less than 0.03g/l and 0.0003g/l respectively and can be used to electrolyze high-purity cobalt. About 5.5t cobalt anolyte was purified in the simulation industrial experiment and kilogram quantities of cobalt of 99.98% purity and about 95% recovery have been produced.

Chemical forms of cobalt and nickel extracted by M1,M3 and CaCl_(2)-DTPA

Mehlich 1(M1), mehlich 3(M3) and CaCl 2 DTPA have been used to predict the available micronutrient in soil. However, the forms of micronutrient extractable by these extractants are not known. In the present study, ten soils, collected from five provinces and the capital of China, representing a wide range of chemical and physical properties, were analyzed by sequential extraction to isolate five forms of cobalt and nickel, they are exchangeable, carbonate bound, Fe Mn oxide bound, organically bound and residual forms. The chemical forms extracted by M1, M3 and CaCl 2 DTPA were also investigated. The results show strong correlation between the carbonate bound or organically bound forms of Co or Ni and the amounts of extractable by any of the above three extractants. The main forms extracted by these extractants are carbonate and organically bound forms. The ranking of these three extractants for extraction of Co and Ni are M1>M3=CaCl 2 DTPA and M1=M3>CaCl 2 DTPA, respectively.

Extraction of valuable metals from low-grade nickeliferous laterite ore by reduction roasting-ammonia leaching method

Nickel and cobalt were extracted from low-grade nickeliferous laterite ore using a reduction roasting-ammonia leaching method.The reduction roasting-ammonia leaching experimental tests were chiefly introduced,by which fine coal was used as a reductant.The results show that the optimum process conditions are confirmed as follows:in reduction roasting process,the mass fraction of reductant in the ore is 10%,roasting time is 120 min,roasting temperature is 1 023-1 073 K;in ammonia leaching process,the liquid-to-solid ratio is 4:1(mL/g),leaching temperature is 313 K,leaching time is 120 min,and concentration ratio of NH3 to CO2 is 90 g/L:60 g/L.Under the optimum conditions,leaching efficiencies of nickel and cobalt are 86.25% and 60.84%,respectively.Therefore,nickel and cobalt can be effectively reclaimed,and the leaching agent can be also recycled at room temperature and normal pressure.

Extraction and stripping of Cu and Ni from synthetic and industrial solutions of Sarcheshmeh Copper Mine containing Cu, Ni, Fe and Zn ions

The extraction and stripping of Cu and Ni ions from synthetic and industrial solutions of Sarcheshmeh Copper Mine containing Cu(770 mg/L),Ni(3200 mg/L),Fe(800 mg/L)and Zn(200 mg/L)were comprehensively investigated using D2 EHPA,LIX 984,Cyanex 302,Chemorex CP 150 and Acorga 5774 diluted in kerosene.The influential parameters such as mixing speed and time,concentration of extractant,p H and temperature were considered in extraction stage.Furthermore,stripping of Cu and Ni was examined using different inorganic and organic acids(sulfuric,hydrochloric,nitric and citric acids)with different concentrations.The results indicated that the highest extractions of Cu and Ni occurred within 3 min,with the mixing speed of 500 r/min,28℃and A/O ratio of 1:1.Moreover,Cu was extracted by LIX 984 at the concentration of 10%(v/v),whereas Ni was extracted by Cyanex 302 at the concentration of 30%(v/v),efficiently.The optimal p H for Cu and Ni extraction is in ranges of 2-3 and 4-5,respectively.Cu and Ni were selectively extracted with the recoveries of 85%,93%and 77%,82%from synthetic and industrial solutions containing Ni,Cu,Zn and Fe ions,respectively.The results of optimal condition showed that 96%of Ni and 93%of Cu were stripped from the synthetic and industrial solutions.Finally,four elements Zn,Fe,Cu and Ni were extracted in three stages with D2 EHPA,LIX 984 and Cyanex 302 extractants respectively with the least impurities.

Efficient and selective recovery of Ni, Cu, and Co from low-nickel matte via a hydrometallurgical process

Low-nickel matte was intensively characterized, and Ni, Cu, and Co were determined to exist mainly as (Fe,Ni)9S8and FeNi3, Cu5FeS4, and (Fe,Ni)9S8and Fe3O4(in isomorphic form), respectively. The efficient and selective extraction of Ni, Cu, and Co from the low-nickel matte in an (NH4)2S2O8/NH3·H2O solution system was studied. The effects of (NH4)2S2O8and NH3·H2O concentrations, leaching time, and leaching temperature on the metal extraction efficiency were systematically investigated. During the oxidative ammonia leaching process, the metal extraction efficiencies of Ni 81.07%, Cu 93.81%, and Co 71.74% were obtained under the optimal conditions. The relatively low leaching efficiency of Ni was mainly ascribed to NiFe alloy deactivation in ammonia solution. By introducing an acid pre-leaching process into the oxidative ammonia leaching process, we achieved the high extraction efficiencies of 98.03%, 99.13%, and 85.60% for the valuable metals Ni, Cu, and Co, respectively, from the low-nickel matte. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

The Property of Alkylthiophosphoric Cobalt and Separation of Co(Ⅱ) and Ni(Ⅱ)

The effect of sulfuric acid solution on the behavior of extracting Co(Ⅱ) and Ni(Ⅱ) with di (2 ethylhexyl) monothiophosphoric acid (D 2EHMTPA) was studied and compared with HEH(EH)P. The reaction equilibrium of extraction can be determined by slope method, equimolar series method and saturation method. The extracting equilibrium constant ( K ex ) and the thermodynamic functions (Δ H 0, Δ S 0, Δ G 0) were evaluated through the determination of the distribution ratio at different temperatures (5～30℃). The solid complex of alklythiophosphate cobalt was synthesized and its thermal stability was studied by TG DTA analysis.

Dialkyl phosphinic acids:Synthesis and applications as extractant for nickel and cobalt separation

Three kinds of dialkylphosphinic acids(DAPAs),i.e.dihexylphophinic acid(DHPA),di-(2,4,4-trimethylpentyl) phosphinic acid(DTMPPA)and didecylphophinic acid(DDPA),were synthesized through free radical addition reaction.The influence of the types of initiator,reation time and reaction temperature on the yield of DAPAs were investigated.The products were characterized by NMR and MS.By using DHPA,DTMPPA and DDPA(10%in kerosene)as extractants,the extraction of Co2 +and Ni2 +in sulphate medium at different equilibrium pH values were measured.The results show that the maximum yield of DHPA, DTMPPA and DDPA can all be achieved at about 130℃under the initiation of di-tert-butyl peroxide(DTBP).All the extraction of cobalt with respect to DHPA,DDPA and DTMPPA precedes that of nickel.The difference in pH1/2 value(defined as the pH at which 50%metal extraction occurs)between cobalt and nickel increases in the following sequence from large to small:DHPA,DDPA and DTMPPA,which indicates that the separation ability for cobalt and nickel ascends from DHPA,DDPA to DTMPPA.