CN102876906B - Method for extraction and separation of tungsten and molybdenum from tungsten and molybdenum mixed solution - Google Patents
Method for extraction and separation of tungsten and molybdenum from tungsten and molybdenum mixed solution Download PDFInfo
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Abstract
The invention provides a method for extraction and separation of tungsten and molybdenum. Hydrogen peroxide is filled in the tungsten and molybdenum mixed solution, the pH value is regulated to be acidic, and the acid tungsten mixed solution is taken as a water phase feed liquid to carry out extraction and separation with an organic phase. The organic phase comprises trialkylphosphine oxide, tributyl phosphate and a diluting agent; the organic phase conducts the multi-stage extraction with the water phase feed liquid, molybdenum is extracted into the organic phase, and tungsten is left in a raffinate, so that the separation of tungsten and molybdenum is achieved. The load-bearing organic phase adopts an alkaline back-extraction agent to carry out back-extraction to obtain a molybdenum-contained solution, and the organic phase subjected to the back-extraction returns to the extraction process. Tungsten and molybdenum are extracted and separated in the tungsten and molybdenum mixed solution containing H2O2 by adopting a novel binary mixture extracting agent, the method has the advantages that extraction and the back-extraction are high in split-phase speed, the separation effect of tungsten and molybdenum is good, the tungsten co-extraction loss is low, the loss of the organic phase as well as the environmental pollution is low, the industrialization is easy to realize, and the method is especially suitable for separating tungsten and molybdenum in the tungstate solution with high molybdenum content.
Description
Technical field
The present invention relates to a kind of method from tungsten mixing solutions extracting and separating tungsten.Belong to chemical extraction technical field.
Background technology
Tungsten and molybdenum are important strategic rare metals, at industrial tool, have been widely used.Tungsten belongs to the group vib in the periodic table of elements together, and due to lanthanide contraction, tungsten character is very similar, is difficult to separate.The frequent association of molybdenum, in tungsten minerals, also contains tungsten and molybdenum in addition in many secondary resources (as Spent hydrogenation catalyst, hard alloy scraps) simultaneously.But molybdenum is in tungsten metallurgy, to need the strict impurity element of controlling, for example, in 0 grade of ammonium paratungstate of China's GB GB10116-2007 regulation, containing molybdenum, be not more than 0.002%.Along with the minimizing of high-quality tungsten resource, the tungsten ore that molybdenum content is high or secondary resource become the important source material of extracting tungsten, and how from the tungsten raw material of high molybdenum content, to separate tungsten becomes key issue urgently to be resolved hurrily in tungsten metallurgy.
Industry at present adopts MoS
3the precipitator method (Zhang Qixiu, Zhao Qinsheng writes, tungsten metallurgy, metallurgical industry press, 2005:120-121), QUATERNARY AMMONIUM SALT method (U.S.Pat.No.3,969,478), ion exchange method (CN 88105712.6, CN93111497.7, CN 98122929.8) with selective precipitation (CN 97108113.1) etc. from containing the Fen Lis molybdenum that removes the tungstate solution of molybdenum.The essence of aforesaid method is to add S in solution
2-make the molybdenum acid ion in solution preferentially be converted into thiomolybdate ion under certain condition, then utilize the qualitative significant difference of thiomolybdate and wolframate radical to adopt the means such as precipitation, extraction, ion-exchange absorption to realize tungsten separation, these methods are referred to as the tungsten separation method generating based on Thiomolybdate.Aforesaid method can be realized the tungstate solution (Mo/WO of low molybdenum content
3<2%) in, the degree of depth is except molybdenum, but when molybdenum content is higher (Mo/WO
3>2%), aforesaid method exists except the molybdenum degree of depth, except the problem of the aspects such as molybdenum cost and environment protection, is difficult to meet industrial needs.
Peroxo-complex based on tungsten, molybdenum is in qualitative difference, United States Patent (USP) U.S.Pat.No.3, and 969,478 have proposed another tungsten separation method.The method is to add H in acid tungsten mixing solutions
2o
2make tungsten, molybdenum forms respectively tungsten, the peroxo-complex of molybdenum, then use respectively phosphoric acid fat (as tbp TBP) or trialkyl phosphine (as tributylphosphine oxide TBPO, trioctyl phosphine oxide TOPO) or the extraction agent such as tertiary amine (as trioctylamine TOA) or quaternary ammonium salt (as four octyl group ammonium sulfate) preferentially extract the peroxo-complex of molybdenum under certain condition and separation with tungsten, the method can effectively be removed the molybdenum in tungstate, but the coextraction amount of tungsten is larger, and above-mentioned extraction agent needs higher extractant concentration could obtain good separating effect, and higher extractant concentration causes difficulty (the United States Patent (USP) U.S.Pat.No.4 that in particularly reextraction process of extraction process, existence is separated, 275, 039).United States Patent (USP) U.S.Pat.No.4,275,039 in order to improve the phase-splitting problem in extraction process, uses three constituent element mixed extractants instead and replace single constituent element extraction agent, by D
2eHPA, TBP, tri-kinds of extraction agents of TBPO mix composition three constituent element mixed extractants by a certain percentage, have effectively solved problem of phase separation, and have reduced the H of process
2o
2consumption, but still do not solve the larger problem of common extraction amount of tungsten, and make organic phase composition too complicated, be unfavorable for realization of industrialization.Li Weixuan etc. have reported " slective extraction separates W, Mo from acidic solution " at < < rare metal > > (the 3rd phase: 3-4 in 1989), this article is selected TRPO(trialkyl phosphine)-MIBK-kerosene system studied extracting and separating tungsten under hydrogen peroxide complexing condition, tungsten good separation, it is less that tungsten extracts loss altogether, but MIBK(methyl iso-butyl ketone (MIBK)) water-soluble larger, organic phase runs off larger, subsequent disposal complexity.The research object of aforesaid method is the tungstate solution (Mo/WO of high molybdenum content
3>2%), but aforesaid method all exists such as the tungsten problems such as to extract altogether that loss is large, phase-splitting is difficult, organic phase runs off serious, therefore the report of industrial applications rarely.
Summary of the invention
The object of the present invention is to provide that a kind of method flow is short, cost is low, tungsten good separating effect, it is little that tungsten extracts loss altogether, and organic phase runs off few, the method for extracting and separating tungsten from tungsten mixing solutions that environmental pollution is little.Tungsten mixing solutions can obtain highly purified tungstate solution or highly purified molybdate solution after method provided by the invention is processed.A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, comprises the steps:
The first step: organic phase is contacted and extracted with aqueous phase liquid, and molybdenum extracts into organic phase, and tungsten is stayed in raffinate; Described aqueous phase liquid refers to the acid tungsten mixed aqueous solution that contains hydrogen peroxide; Described organic phase is the mixture of extraction agent and thinner; Described extraction agent is the mixture of trialkyl phosphorus and tbp;
Second step: load organic phases adopts alkaline reverse-extraction agent to strip, obtains containing molybdenum solution; Organic phase after back extraction is returned to the first step recycling.
A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, the volume percent that described extraction agent accounts for organic phase is 40 ~ 85%, surplus is thinner; In described extraction agent, the volume ratio of trialkyl phosphorus and tbp is between 1/8 ~ 1/80; Described thinner is liquefied hydrocarbon organism, specifically the one in sulfonated kerosene, No. 260 solvent oils, aviation kerosene.
A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, described trialkyl phosphorus is for mixing trialkyl phosphorus, and wherein the carbonatoms in each alkyl is 6 ~ 8.
A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, described in contain hydrogen peroxide acid tungsten mixed aqueous solution for containing tungsten, molybdenum and H
2o
2sodium salt or ammonium salt solution, pH value between 1.0 ~ 2.5, wherein Mo/WO
3mass ratio between 1/50 ~ 50/1, H
2o
2mole number be tungsten and molybdenum mole number sum 1.0 ~ 2.5 times.
A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, described alkaline reverse-extraction agent is the alkali lye of pH value between 7.5 ~ 14 or the salts solution of alkalescence, is selected from the mixing solutions of one or more solution in sodium hydroxide solution, sodium carbonate solution, sodium hydrogen carbonate solution, ammoniacal liquor, sal volatile or ammonium bicarbonate soln.
A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, described extraction is multi-stage counter current extraction process, the stream of extraction process is than between 1/10 ~ 10/1, and extraction progression is 3 ~ 15 grades, and described stream is than referring to the ratio of organic phase with the volumetric flow rate of aqueous phase liquid.
A kind of method from tungsten mixing solutions extracting and separating tungsten of the present invention, described back extraction is taken as single-stage or multi-stage counter current extraction process, the stream of reextraction process is than between 1/1～10/1, reextraction progression is 1 ~ 4 grade, and described stream is than referring to the ratio of load organic phases with the volumetric flow rate of alkaline reverse-extraction agent solution.
Described aqueous phase liquid is that tungsten mixed sodium salts solution or tungsten mixed-ammonium salt solution are through overregulating pH value and adding H
2o
2obtain.
Organic phase and water are in contact with one another and carry out multi-stage counter current extraction, organic phase selective extraction molybdenum, and tungsten is stayed in raffinate, realizes tungsten and separates, Mo/WO in raffinate
3much smaller than aqueous phase liquid.In multi-stage counter current extraction process, stream than be the ratio of volumetric flow rate of organic phase and water between 1/10 ~ 10/1, extracting progression is 3 ~ 15 grades.
Reextraction adopts single-stage back extraction or multistage back extraction depending on reverse-extraction agent kind is different with concentration, strips and obtains the solution that is rich in molybdenum, Mo/WO in strip liquor
3much larger than aqueous phase liquid.Organic phase after back extraction is returned to extraction.
In above-mentioned binary mixed extractant, the ability of TRPO extraction molybdenum is strong, but its molybdenum tungsten separation factor is not high while using separately, more seriously the extracted species of TRPO and molybdenum easily forms third phase (solid precipitation) at inert diluent in as sulfonated kerosene, has a strong impact on normal extracting operation; In organic phase, add TBP composition mixed extractant, the solubleness of the extracted species that can significantly improve on the one hand TRPO and molybdenum in organic phase, elimination third phase, can improve the extracting power of molybdenum on the other hand, what is more important TBP adds the extraction that can suppress tungsten, significantly improves tungsten separating effect.
Method provided by the invention can not only overcome United States Patent (USP) U.S.Pat.No.3,969, the phase-splitting difficult problem existing in 478, and can overcome United States Patent (USP) U.S.Pat.No.3,969,478 and U.S.Pat.No.4,275, the tungsten all existing in 039 extracts the large problem of loss altogether, does not also have the organic phase of (rare metal, the 3rd phase: 3-4 in 1989) in the TRPO-MIBK system large problem that runs off simultaneously.In addition, the binary hybrid extraction system that the present invention adopts is compared with United States Patent (USP) U.S.Pat.No.4, and 275, the 039 ternary hybrid extraction systems that adopt are more simple.
The present invention adopts a kind of new binary mixed extractant from containing H
2o
2tungsten mixing solutions in extracting and separating tungsten, the method tungsten good separating effect, it is little that tungsten extracts loss altogether, organic phase runs off few, environmental pollution is little, is easy to realize industrialization, is particularly suitable for separating tungsten in the tungstate solution of high molybdenum content.
Embodiment
Below by embodiment, illustrate embodiments of the present invention, following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Organic phase composition (volume percent): 3%TRPO+60%TBP+37% sulfonated kerosene, the mixing trialkyl phosphine that the trade mark that wherein TRPO provides for Canadian Cytec company is Cynex923.
Aqueous phase liquid: preparation containing molybdenum sodium tungstate solution, pH value 10.3, use nitre acid for adjusting pH value is to pH 3.5, adds wherein concentration and be 30% H
2o
2the aqueous solution, H
2o
2addition is 1.0 times of mole number total amount of tungsten, then with salpeter solution, regulates pH value to 1.5, obtains and extracts feed liquid, wherein WO
3140.5g/L, Mo 16.3g/L, Mo/WO
3=0.116.
Extracting and separating: above-mentioned organic phase and aqueous phase liquid compared with carry out 8 stage countercurrent extractions under 2/1 condition, load organic phases is carried out single-stage reextraction with the 0.1mol/L NaOH aqueous solution under the condition of comparing 1/1, after back extraction, organic phase is returned to extraction.Until extracting-back extraction, get circulation and reach after balance, sampling analysis.
Result: raffinate WO
3138.0g/L, Mo 0.01g/L, Mo/WO
3<1 × 10
-4; Strip liquor WO
31.25g/L, Mo8.14g/L, Mo/WO
3=6.51.
Embodiment 2
Organic phase composition (volume percent): 1%TRPO+40%TBP+59% aviation kerosene, the mixing trialkyl phosphine that the trade mark that wherein TRPO provides for Cytec company is Cynex923.
Aqueous phase liquid: the industry that certain company adopts ion exchange process to produce is actual in molybdenum ammonium tungstate solution, and pH value 9.5, with salt acid for adjusting pH value to 3.5, adds 30%H wherein
2o
2, H
2o
2addition is 1.5 times of mole number sum of tungsten, mixes, and then with ammonia soln, regulates pH value to 2.5, acquisition aqueous phase extracted complexing feed liquid, wherein WO
3180.2g/L, Mo 3.60g/L, Mo/WO
3=0.020.
Extracting and separating: above-mentioned organic phase and aqueous phase liquid compared with carry out 3 stage countercurrent extractions under 4/3 condition, load organic phases is carried out single-stage reextraction under the condition of comparing 10/1 with 0.5mol/L ammoniacal liquor, after back extraction, organic phase is returned to extraction.Extraction and back-extraction is got and is reached after balance, and sampling analysis detects.
Result: raffinate WO
3179.2g/L, Mo 0.015g/L, Mo/WO
3<1 × 10
-4; Strip liquor WO
37.6g/L, Mo27.0g/L, Mo/WO
3=3.56.
Embodiment 3
Organic phase composition (volume percent): 5%TRPO+80%TBP+15% sulfonated kerosene, the mixing trialkyl phosphine that the trade mark that wherein TRPO provides for Cytec company is Cynex923.
Aqueous phase liquid: the industry that certain company adopts quaternary ammonium salt alkalescence medium extraction process to produce is actual in molybdenum ammonium tungstate solution, and pH value 9.5, to pH 3.0, adds 30%H with sulphur acid for adjusting pH value wherein
2o
2, H
2o
2addition is 1.8 times of tungsten mole number sum, and pH value is 1.30, then with ammonia soln, regulates pH value to 1.8, obtains extraction feed liquid, wherein WO
3140.2g/L, Mo17.5g/L, Mo/WO
3=0.125.
Extracting and separating: above-mentioned organic phase and aqueous phase liquid compared with carry out 15 stage countercurrent extractions under 3/2 condition, load organic phases is carried out 3 stage countercurrent reextraction under the condition of comparing 7/1 with 1.0mol/L ammonium bicarbonate aqueous solution, after back extraction, organic phase is returned to extraction.Extraction and back-extraction is got and is reached after balance, and sampling analysis detects.
Result: raffinate WO
3138.5g/L, Mo 0.008g/L, Mo/WO
3<1 × 10
-4; Strip liquor WO
37.92g/L, Mo81.6g/L, Mo/WO
3=10.30.
Embodiment 4
Organic phase composition (volume percent): 1%TRPO+80%TBP+19% sulfonated kerosene, the mixing trialkyl phosphine that the trade mark that wherein TRPO provides for Cytec company is Cynex923.
Aqueous phase liquid: the tungstenic ammonium molybdate solution of preparation, pH value 7.2, to pH 4.0, adds 30%H with nitre acid for adjusting pH value wherein
2o
2, H in water
2o
2amount is 2.5 times of tungsten mole number sum, mix, and then to regulate pH value is 1.0, obtains and extracts feed liquid, wherein WO
31.60g/L, Mo 80.2g/L, Mo/WO
3=50.125.
Extracting and separating: above-mentioned organic phase and aqueous phase liquid compared with carry out 8 stage countercurrent extractions under 10/1 condition, load organic phases is carried out single-stage reextraction under the condition of comparing 8/1 with 0.6mol/L ammonium carbonate solution, after back extraction, organic phase is returned to extraction.Extraction and back-extraction is got and is reached after balance, and sampling analysis detects.
Result: raffinate WO
31.58g/L, Mo 1.2g/L, Mo/WO
3=0.76; Strip liquor WO
30.015g/L, Mo 63.1g/L, Mo/WO
3=4206.7.
Embodiment 5
Organic phase and aqueous phase liquid are with embodiment 1
Extracting and separating: above-mentioned organic phase and aqueous phase liquid compared with carry out 8 stage countercurrent extractions, load organic phases 1.0mol/L NaHCO under 2/1 condition
3the aqueous solution carries out 4 grades of reextraction under the condition of comparing 5/1, and after back extraction, organic phase is returned to extraction, gets circulation and reaches after balance, sampling analysis until extracting-back extraction.
Result: raffinate WO
3138.5g/L, Mo 0.012g/L, Mo/WO
3<1 × 10
-4; Strip liquor WO
35.01g/L, Mo40.7g/L, Mo/WO
3=8.12.
Embodiment 6
Organic phase composition (volume percent): 5%TRPO+40%TBP+55% sulfonated kerosene, the mixing trialkyl phosphine that the trade mark that wherein TRPO provides for Cytec company is Cynex923.
Aqueous phase liquid: preparation containing molybdenum sodium tungstate solution, pH value 9.5, use sulphur acid for adjusting pH value, to pH 3.5, adds 30%H wherein
2o
2, H
2o
2addition is 1.8 times of mole number of tungsten, mixes, and pH value is 1.4, obtains extraction feed liquid, wherein WO
347.1g/L, Mo 0.97g/L, Mo/WO
3=0.021.
Extracting and separating: above-mentioned organic phase and aqueous phase liquid compared with carry out 5 stage countercurrent extractions, load organic phases 0.5mol/LNa under 1/10 condition
2cO
3under the condition of comparing 7/1, carry out single-stage reextraction, after back extraction, organic phase is returned to extraction.
Result: extraction and back-extraction is got and reached after balance, sampling analysis detects.Raffinate WO
346.8g/L, Mo 0.004g/L, Mo/WO
3<1 × 10
-4; Strip liquor WO
320.8g/L, Mo 67.8g/L, Mo/WO
3=3.26.
Claims (5)
1. from a method for tungsten mixing solutions extracting and separating tungsten, comprise the steps:
The first step: organic phase is contacted and extracted with aqueous phase liquid, and molybdenum extracts into organic phase, and tungsten is stayed in raffinate; Described aqueous phase liquid refers to the acid tungsten mixed aqueous solution that contains hydrogen peroxide; Described organic phase is the mixture of extraction agent and thinner; Described extraction agent is the mixture of trialkyl phosphorus and tbp;
Second step: load organic phases adopts alkaline reverse-extraction agent to strip, obtains containing molybdenum solution; Organic phase after back extraction is returned to the first step recycling;
The volume percent that described extraction agent accounts for organic phase is 40～85%, and surplus is thinner; In described extraction agent, the volume ratio of trialkyl phosphorus and tbp is between 1/8～1/80; Described thinner is liquefied hydrocarbon organism, specifically the one in sulfonated kerosene, No. 260 solvent oils, aviation kerosene; The described acid tungsten mixed aqueous solution that contains hydrogen peroxide is for containing tungsten, molybdenum and H
2o
2sodium salt or ammonium salt solution, wherein Mo/WO
3mass ratio between 1/50～50/1, H
2o
2mole number be tungsten and molybdenum mole number sum 1.0～2.5 times, pH value is between 1.0～2.5.
2. a kind of method from tungsten mixing solutions extracting and separating tungsten according to claim 1, is characterized in that: described trialkyl phosphorus is for mixing trialkyl phosphorus, and wherein the carbonatoms in each alkyl is 6～8.
3. a kind of method from tungsten mixing solutions extracting and separating tungsten according to claim 1, it is characterized in that: described alkaline reverse-extraction agent is the alkali lye of pH value between 7.5～14 or the salts solution of alkalescence, be selected from the mixing solutions of one or more solution in sodium hydroxide solution, sodium carbonate solution, sodium hydrogen carbonate solution, ammoniacal liquor, sal volatile or ammonium bicarbonate soln.
4. a kind of method from tungsten mixing solutions extracting and separating tungsten according to claim 3, it is characterized in that: described extraction is multi-stage counter current extraction process, the stream of extraction process is than between 1/10～10/1, extraction progression is 3～15 grades, and described stream is than referring to the ratio of organic phase with the volumetric flow rate of aqueous phase liquid.
5. a kind of method from tungsten mixing solutions extracting and separating tungsten according to claim 3, it is characterized in that: described back extraction is taken as single-stage or multi-stage counter current extraction process, the stream of reextraction process is than between 1/1～10/1, reextraction progression is 1～4 grade, and described stream is than referring to the ratio of load organic phases with the volumetric flow rate of alkaline reverse-extraction agent solution.
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