CN104762476B - Method of selectively extracting and separating molybdenum from high-phosphorus tungsten- and molybdenum-containing mixed solution - Google Patents
Method of selectively extracting and separating molybdenum from high-phosphorus tungsten- and molybdenum-containing mixed solution Download PDFInfo
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Abstract
The invention relates to a method of selectively extracting and separating molybdenum from a high-phosphorus tungsten- and molybdenum-containing mixed solution. In the prior art, according to the process of extraction and separation of tungsten and molybdenum through complexation of hydrogen peroxide, when the content of phosphorus in the solution is higher than 0.005 mol/L, the extraction efficiency of the tungsten and the molybdenum is greatly reduced, so that the conventional process of extraction and separation of the tungsten and the molybdenum through complexation of the hydrogen peroxide cannot be used for directly treating the tungsten- and molybdenum-containing mixed solution being higher than 0.005 mol/L in the content of the phosphorus. According to the invention, by means of adjustment and control of the content of acid in the high-phosprous mixed solution, the tungsten and the molybdenum in the mixed solution can be reacted with the phosphorus completely to form tungstomolybdophosphate acid. By means of addition of a proper amount of the hydrogen peroxide, the phosphor-tungstic heteropoly acid and phospho-molybdic heteropoly acid are depolymerized to generate peroxy phosphotungstic acid and peroxy phospho-molybdic acid. By means of TBP as an extraction agent, the peroxy phospho-molybdic acid is extracted into an organic phase and then the loaded organic phase is subjected to reverse-extraction by an alkaline reverse-extraction agent. The method can treat the high-phosphorus tungsten- and molybdenum-containing mixed solution, is low in co-extraction of tungsten, can reach 70% in molybdenum extraction rate in a single stage, is low in the cost of the employed extraction agent and is easy to industrialize.
Description
Technical field
The invention belongs to tungsten field of metallurgy is and in particular to one kind selective extraction from high phosphorus mixed solution containing tungsten divides
Method from molybdenum.
Background technology
Tungsten is the indispensable strategic metal of national defence, in occupation of critical role in national military strategy deposit.
In view of current resources situation, it is inexorable trend that white tungsten replaces black tungsten, is the strategic choice of China's tungsten industry sustainable development.However, China
White tungsten resource natural endowment poor, be associated with the impurity such as more molybdenum phosphorus.Tungsten belongs to the vib race in the periodic table of elements together, due to group of the lanthanides
The impact shunk, tungsten property is very much like, molybdenum be separated into key issue urgently to be resolved hurrily in tungsten metallurgy.
The property of the many molybdenum parent sulfur according to tungsten oxyphie of industrial tungsten separation method at present, first by alkaline sodium tungstate solution
It is adjusted to neutrality or alkalescence with acid, add s2-Or hs-, make the molybdenum acid ion preferential conversion in solution be thiomolybdate
Ion, then utilizes thiomolybdate and the qualitative significant difference of tungstate radicle using handss such as precipitation, extraction, ion exchange absorption
Duan Shixian tungsten separates.These methods are all based on the tungsten separation method of Thiomolybdate generation, enable low molybdenum content
Tungstate solution (mo/wo3< 2%) in deeply removing molybdenum.But (the mo/wo when molybdenum content is higher3> 2%), said method is except molybdenum deeply
Degree, still have problems it is difficult to meet industrial needs except the aspect such as molybdenum cost and environmental conservation.
Additionally, the peroxo-complex difference in nature based on tungsten, molybdenum, zelikman et al. proposes a kind of tungsten and divides
From method, to acid adding in the aqueous solution containing tungsten, solution ph is adjusted to 0.5-4.3 (optimal ph value scope is 0.5-2.5),
It is subsequently adding hydrogen peroxide, with the Neutral-neutral Extractants such as tributyl phosphate (tbp) or trialkyl phosphine (trpo) from above-mentioned solution
(when containing impurity silicon in feed liquid, adding a small amount of microcosmic salt in solution can it is achieved that the depth of tungsten separates for selective extraction molybdenum
Increase effect of extracting, but addition need to control between 0.002-0.005mol/l, exceed or deficiency all can reduce tungsten and divide
From efficiency).The Chinese patent (102876906a) developed on this basis is thought, tbp or trpo is used as tungsten extraction point
From reagent, have such problems as that tungsten common extraction is big, split-phase is undesirable, thus the volume ratio pressing 1%-5% adds trpo to tbp to form two
First mixed extractant is from containing h2o2Tungsten mixed solution in extract and separate tungsten, it is said that extraction compared with the work of zelikman
Take effect to improve, but best effort ph value (1.0-2.5) is still in zelikeman the scope of the claims.And the U.S. is special
Sharp (us4275039), in order to improve the split-phase problem in extraction process, uses three constituent element mixed extractants instead and replaces the extraction of single group unit
Agent, is mixed by a certain percentage by tri- kinds of extractants of d2ehpa, tbp, tbpo and forms three constituent element mixed extractants, feed liquid ph value is
0.65-2.75, efficiently solves problem of phase separation, but the common extraction amount of tungsten is larger, and organic phase composition is excessively complicated, unfavorable
In realization of industrialization.
Li Weixuan etc. also reports the similar research of entitled " slective extraction separates w, mo from acid solution ", from trpo
(trialkyl phosphine) mibk kerosene system have studied the condition of extract and separate tungsten under hydrogen peroxide Complexation conditions, adopts
Sodium tungstate, sodium molybdate configuration feed liquid, ph value is 0.9-1.8.And especially have studied the impact to extraction for the phosphorus addition, find that phosphorus contains
Amount is more than 9.2 × 10-4Mol/l will make selectivity decline.It is taken as that different with zelikman: " even if there is no phosphorus
In the case of, separating effect is also good, and a large amount of presence of phosphorus can only make selectivity decline.”
In fact, zelikman is for the feed liquid containing impurity element silicon.They find that peroxide phosphorus tungsta is many
Acid does not have peroxide silicotungstic heteropolyacid to be easily extracted, so adding a small amount of water-soluble phosphoruses in the presence of having impurity silicon, makes peroxide silicon
Heteropoly tungstic acid switchs to peroxide phosphorus heteropoly tungstic acid.And the experimental technique from Li Weixuan etc., their artificial solution used are not
Specially allocate silicon into.Zelikman is also considered as the addition slightly larger (more than 0.005mol/l) of phosphorus and is just harmful on the contrary in fact.
So at first glance, though the view of Li Weixuan and zelikman have different, essence is still the same.And they are
Find that phosphorus excessively will make the selectivity of tungsten extract and separate decline.
However, under many circumstances, such as: the leaching during the secondary resource of tungsten reclaims and using phosphate decomposition scheelite
In technique, phosphorus inevitably enters in leachate, obtains phosphorous tungsten mixed liquor.These feed liquid phosphorus contents are generally individually
More than 0.1mol/l, the method using above-mentioned hydrogen peroxide complexometric extraction separation tungsten cannot directly be processed.Therefore, this height
The direct extract and separate problem of phosphorus tungsten feed liquid is in addition it is also necessary to carry out system in-depth study, more properly effective to finding
Method.
Content of the invention
It is an object of the invention to provide a kind of mixed solution containing tungsten from high phosphorus selective extraction Separation of Molybdenum method.Should
Method first using controlling acid concentration and processing high phosphorus mixed solution containing tungsten by the way of adding hydrogen peroxide, then extract so that
Molybdenum in high phosphorus mixed solution containing tungsten is efficiently separated, and solves prior art and can not directly process high phosphorus containing tungsten mixing
The problem of solution extract and separate molybdenum, also provides new thinking for high phosphorus mixed solution containing tungsten extract and separate molybdenum.
The purpose of the present invention is accomplished by:
A kind of method of selective extraction Separation of Molybdenum mixed solution containing tungsten from high phosphorus, described high phosphorus contains tungsten and mixes
In solution, phosphorus concentration is not less than 0.1mol/l, adds hydrogen peroxide, and adjustment controls total acid concentration to be not less than 0.5mol/l；By feed liquid and
Organic faciess hybrid extraction molybdenum.
In high phosphorus mixed solution containing tungsten in said method, phosphorus concentration is 0.1mol/l 4mol/l.
In said method, adjustment controls total acid concentration is 0.5mol/l 4mol/l, and preferably total acid concentration is 1mol/l
3mol/l.Adjustment controls the acid inclusion that total acid concentration uses: one of hydrochloric acid, sulphuric acid, nitric acid, acetic acid and phosphoric acid or several
Kind.
Wo in high phosphorus mixed solution containing tungsten described in said method3/ mo mass ratio is between 1,/10 150/1.
In said method, the mole of addition hydrogen peroxide is 0.8 2 times of tungsten and molybdenum molal quantity sum.Preferably 1.1-1.6
Times.
Organic faciess described in said method include diluent and extractant.Diluent is sulfonated kerosene, aero oil, kerosene
One of with benzene, extractant is tributyl phosphate.The percent by volume that extractant accounts for organic faciess is 40% 90%.
In said method, load organic phases carry out back extraction using alkaline back washing agent.Described alkalescence back washing agent be sodium hydroxide,
One of sodium carbonate, sodium bicarbonate, ammonia, ammonium carbonate and ammonium hydrogen carbonate, concentration is 0.5mol/l 4mol/l.
The present invention is directed to the direct extract and separate problem of high phosphorus tungsten feed liquid, has carried out system in-depth study, specifically such as
Under:
First, any tungsten separation method must all is fulfilled for following two conditions: one, tungsten and molybdenum will respectively with individually from
Sub- form exists；2nd, the ion of tungsten and molybdenum will have larger difference in nature.
But the property of tungsten ion is more complicated with the change of solution acid-basicity: in the basic conditions, though tungsten and molybdenum point
Not with positive acid group (tungstate radicle and molybdenum acid ion) form individualism, but the two various chemical property are similar and cannot divide
From；And the decline with solution ph, under mildly acidic conditions, tungsten ion can occur polymerization, generates tungstenic molybda many
Acid, makes tungsten co-exist in formation " siamese twins " in same ion, nor separates；When solution ph declines further,
Tungsten ion has the trend of gradually depolymerization on the contrary again, and (under higher acidity, molybdenum even can be converted into moo2 2+Ion and solve completely
Poly-).But unfortunately under the conditions of strong acidity, jellied for shape wolframic acid is precipitated and makes the deterioration of solution situation (not phosphorous by tungsten
Under the conditions of).So while now tungsten and molybdenum can also more thoroughly depolymerization, but nobody has an optimistic view of under the conditions of strong acidity so far
Tungsten extraction separation process.
But things has a dual character: be previously noted when there is substantial amounts of phosphorus in solution, hydrogen peroxide complexometric extraction can be made to divide
Method from tungsten lost efficacy.But it is exactly the phosphorus in solution again, the great phosphorus heteropoly tungstic acid of dissolubility can be generated with tungsten, even if
Under higher acidity, also it is unlikely to generate wolframic acid precipitation.Under these conditions it is possible to avoid tungsten miscellaneous with " siamese twins "
Polyacid form exists, thus meeting detached first condition of tungsten, (certainly, extremely too high acidity condition is both uneconomical and not
Reality).Based on this, we have done different extraction systems, a series of experiment under the conditions of different feed liquid acidity, phosphorus concentration etc..
Extractant is done using tbp, handled solution contains wo3For 85.4g/l, it is 11.2g/l containing mo, phosphorus content is 1mol/
l.Add sulphuric acid to above-mentioned solution, make feed liquid sulfuric acid content be 1mol/l.The extraction yield of tungsten up to 99.7%, molybdenum when directly extracting
Extraction yield also have 70%, separating effect is very poor.Even if apparently tungsten and molybdenum do not have with " siamese twins " shape in such a situa-tion
Formula exists, and their chemical property difference still can not meet second condition efficiently separating.
Adding hydrogen peroxide is a kind of the simplest and the most direct and the method for the change tungsten ion existing forms of cleaning.We have found that with
The addition of hydrogen peroxide, in feed liquid, phosphotungstic acid and phosphomolybdic acid generate peroxide phosphotungstic acid and peroxide phosphomolybdic acid with hydrogen peroxide complexation,
The nature difference making tungsten and molybdenum in solution drastically expands.The extraction of tungsten is quickly restrained, and the extraction yield of molybdenum is basically unchanged, and makes
Obtain separating effect gradually to improve.As shown in figure 1, when addition is wo3, 1.1 times of mo mole of total amount when, tungsten extraction yield is down to
Less than 10%, and the extraction yield of molybdenum is still maintained at 70% about.Fig. 2 as a comparison, illustrates dioxygen water consumption to wo3、
The impact of mo extraction, feed liquid used contains wo3For 82.4g/l, it is 10.8g/l containing mo, phosphorus content is less than 3 × 10-4mol/l.With Fig. 1
The difference of experiment essentially consists in that solution is phosphorous, acidity low (ph value is 1.5).But in Fig. 2 the variation tendency of curve is not completely
With: when not containing hydrogen peroxide in solution, wo3, the extraction yield all very low (be below 30% in some instances it may even be possible to also less than 20%) of mo.
With the increase of dioxygen water consumption, the extraction yield of tungsten slowly reduces, and molybdenum then raises rapidly.When addition is wo3, mo mole total
Amount more than 0.6 times when, the change of molybdenum extraction yield tends towards stability.
As can be seen that because whether phosphorous the difference () of two solution system compositions and the change of solution state be (acid
Strong and weak), lead to its Extraction behavior and extraction mechanism far from each other.Under the conditions of these differences just become high phosphorus of the present invention, tungsten separates
Theory and Process ba- sis.
In a word, the inventive method is passed through to add hydrogen peroxide and adjust the total acid concentration controlling in high phosphorus tungsten feed liquid system,
Then just can realize the extract and separate of tungsten under the conditions of high phosphorus using tributyl phosphate (tbp) as extractant well, be work
In industry, the phosphorous high tungsten of tungsten ore deposit leaches the extraction new method that feed liquid provides a method that easy realization simple, with low cost.
Brief description
Fig. 1 is that in phosphoric acid and the tungsten feed liquid of each 1mol/l of sulfuric acid concentration, dioxygen water consumption is to wo3, the shadow of mo extraction yield
Ring；
Fig. 2 is that tungsten feed liquid is phosphorous, ph value is under the conditions of 1.5, dioxygen water consumption is to wo3, the impact of mo extraction yield.
Specific embodiment
Illustrate embodiments of the present invention below by embodiment, following examples are intended to illustrate rather than
Limitation of the invention further.
Embodiment 1
Organic phase composition (percent by volume): 90%tbp+10% sulfonated kerosene.
Original liquid: certain company processes, using mixture of sulfuric phosphoric acid, the leachate that high seyrigite obtains, containing wo3120.5g/l,
Mo 12.05g/l, phosphoric acid concentration 1.3mol/l, sulfuric acid concentration 1.1mol/l.
Feed adjustment: be added to the h that concentration is 30%2o2Solution, h2o2Addition is the molal quantity total amount of tungsten
1.4 again.Obtain containing wo3114.1g/l, mo 11.41g/l, wo3/ mo=10/1, phosphoric acid concentration 1.2mol/l, sulfuric acid concentration
The feed liquid containing hydrogen peroxide of 1mol/l.
Extract and separate: above-mentioned organic faciess and aqueous phase liquid compared with carry out 5 stage countercurrent extractions under conditions of 1/1, be loaded with
Machine carries out back extraction with 4mol/l ammonia aqueous solution under conditions of comparing 1/1, returns extraction after organic faciess pickling after back extraction.
Result: raffinate wo3112.8g/l, mo 0.1g/l；Strip liquor wo31.2g/l, mo11.3g/l.
Embodiment 2
Organic phase composition (percent by volume): 80%tbp+20% sulfonated kerosene.
Original liquid: the leaching that certain company is obtained using the method for the high seyrigite of phosphate decomposition in the basic conditions
Liquid, containing wo3105.3g/l, mo 5.27g/l, phosphorus concentration 0.82mol/l, naoh concentration is 0.4mol/l.
Feed adjustment: be added thereto to sulphuric acid, final feed liquid sulfur-bearing acid concentration is 1.4mol/l；And add concentration for 30%
H2o2Solution, h2o2Addition is 0.8 times of the molal quantity total amount of tungsten.Finally give containing wo390.5g/l, mo 4.53g/
L, wo3/ mo=20/1, phosphorus concentration 0.7mol/l, the feed liquid containing hydrogen peroxide of sulfuric acid concentration 1.4mol/l.
Extract and separate: above-mentioned organic faciess and aqueous phase liquid compared with carry out 5 stage countercurrent extractions under conditions of 1/1, be loaded with
Machine carries out back extraction with 0.5mol/l sodium hydrate aqueous solution under conditions of comparing 1/1, and after back extraction, organic faciess are with 1mol/l's
Sulphuric acid returns extraction after washing.
Result: raffinate wo388.2g/l, mo 0.2g/l；Strip liquor wo31.9g/l, mo4.3g/l.
Embodiment 3
Organic phase composition (percent by volume): 70%tbp+30% benzene.
Original liquid: feed liquid contains wo310.2g/l, mo 102.9g/l, phosphorus concentration 4.5mol/l, concentration of nitric acid 2.6mol/
L, concentration of hydrochloric acid 1.9mol/l.
Feed adjustment: be added to the h that concentration is 30%2o2Solution, h2o2Addition is the molal quantity total amount of tungsten
1.2 again.Obtain containing wo39g/l, mo 90.8g/l, wo3/ mo=1/10, phosphorus concentration 4mol/l, concentration of nitric acid 2.3mol/l, salt
The feed liquid containing hydrogen peroxide of acid concentration 1.7mol/l.
Extract and separate: above-mentioned organic faciess and aqueous phase liquid compared with carry out 7 stage countercurrent extractions under conditions of 2/1, be loaded with
Machine carries out back extraction with 1mol/l ammonium carbonate solution under conditions of comparing 2/1, returns extraction after organic faciess pickling after back extraction.
Result: raffinate wo38.4g/l, mo 0.1g/l；Strip liquor wo30.5g/l, mo 90.7g/l.
Embodiment 4
Organic phase composition (percent by volume): 60%tbp+40% aero oil.
Original liquid: feed liquid contains wo3122.9g/l, mo 4.1g/l, phosphorus concentration 2mol/l, naoh concentration 0.2mol/
l.
Feed adjustment: be added thereto to sulphuric acid, final feed liquid sulfur-bearing acid concentration is 1.5mol/l；And add concentration for 30%
H2o2Solution, h2o2Addition is 1.5 times of the molal quantity total amount of tungsten.Obtain containing wo3102.9g/l, mo 3.43g/l,
wo3/ mo=30/1, phosphorus concentration 1.8mol/l, the feed liquid containing hydrogen peroxide of sulfuric acid concentration 1.5mol/l.
Extract and separate: above-mentioned organic faciess and aqueous phase liquid compared with carry out 5 stage countercurrent extractions under conditions of 1/1, be loaded with
Machine carries out back extraction with 2mol/l ammonium bicarbonate aqueous solution under conditions of comparing 1/1, returns extraction after organic faciess pickling after back extraction
Take.
Result: raffinate wo3100.8g/l, mo 0.05g/l；Strip liquor wo31.9g/l, mo 3.37g/l.
Embodiment 5
Organic phase composition (percent by volume): 50%tbp+50% kerosene.
Original liquid: feed liquid contains wo322.9g/l, mo 68.7g/l, phosphorus concentration 0.11mol/l, acetic acid concentration 0.3mol/
L, sulfuric acid concentration 1.2mol/l.
Feed adjustment: be added to the h that concentration is 30%2o2Solution, h2o2Addition is the molal quantity total amount of tungsten
2 times.Obtain containing wo319.8g/l, mo 59.4g/l, wo3/ mo=1/3, phosphorus concentration 0.1mol/l, acetic acid concentration 0.26mol/
L, the feed liquid containing hydrogen peroxide of sulfuric acid concentration 1.01mol/l.
Extract and separate: above-mentioned organic faciess and aqueous phase liquid compared with carry out 5 stage countercurrent extractions under conditions of 2/1, be loaded with
Machine carries out back extraction with 3mol/l aqueous sodium carbonate under conditions of comparing 2/1, returns extraction after organic faciess pickling after back extraction.
Result: raffinate wo318.6g/l, mo 0.3g/l；Strip liquor wo30.9g/l, mo58.9g/l.
Embodiment 6
Organic phase composition (percent by volume): 40%tbp+60% sulfonated kerosene.
Original liquid: feed liquid contains wo390g/l, mo 0.6g/l, phosphorus concentration 3mol/l.
Feed adjustment: be added thereto to 98% sulphuric acid, and add the h that concentration is 30%2o2Solution, h2o2Addition is
1 times of the molal quantity total amount of tungsten, final feed liquid sulfur-bearing acid concentration is 1mol/l.Obtain containing wo375g/l, mo 0.5g/l,
wo3/ mo=150/1, phosphorus concentration 2.7mol/l, the feed liquid containing hydrogen peroxide of sulfuric acid concentration 1mol/l.
Extract and separate: above-mentioned organic faciess and aqueous phase liquid compared with carry out 6 stage countercurrent extractions under conditions of 5/3, be loaded with
Machine carries out back extraction with 2mol/l sodium bicarbonate aqueous solution under conditions of comparing 5/3, returns extraction after organic faciess pickling after back extraction
Take.
Result: raffinate wo373.1g/l, mo 0.05g/l；Strip liquor wo31.8g/l, mo 0.45g/l.
Claims (11)
1. a kind of mixed solution containing tungsten from high phosphorus the method for selective extraction Separation of Molybdenum it is characterised in that described high phosphorus
In mixed solution containing tungsten, phosphorus concentration is not less than 0.1mol/l, adds hydrogen peroxide, and adjustment controls total acid concentration to be not less than 0.5mol/
l；By feed liquid and organic faciess hybrid extraction molybdenum；Described organic faciess include diluent and extractant；Extractant is tributyl phosphate,
Diluent is one of sulfonated kerosene, aero oil, kerosene and benzene.
2. method according to claim 1 it is characterised in that in described high phosphorus mixed solution containing tungsten phosphorus concentration be
0.1mol/l—4mol/l.
3. method according to claim 1 is it is characterised in that it is 0.5mol/l 4mol/l that adjustment controls total acid concentration.
4. method according to claim 3 is it is characterised in that it is 1mol/l 3mol/l that adjustment controls total acid concentration.
5. the method according to claim 1 or 2 or 3 or 4 is it is characterised in that adjustment controls the acid that total acid concentration uses to wrap
Include: one or more of hydrochloric acid, sulphuric acid, nitric acid, acetic acid and phosphoric acid.
6. method according to claim 1 is it is characterised in that wo in described high phosphorus mixed solution containing tungsten3/ mo mass
Than between 1,/10 150/1.
7. the method according to claim 1 or 2 or 3 or 4 or 6 it is characterised in that add hydrogen peroxide mole be tungsten and
0.8 2 times of molybdenum molal quantity sum.
8. method according to claim 7 is it is characterised in that add the mole of hydrogen peroxide to be tungsten and molybdenum molal quantity sum
1.1-1.6 times.
9. method according to claim 1 is it is characterised in that the percent by volume that extractant accounts for organic faciess is 40%
90%.
10. method according to claim 1 is it is characterised in that load organic phases carry out back extraction using alkaline back washing agent.
11. methods according to claim 10 are it is characterised in that described alkalescence back washing agent is sodium hydroxide, sodium carbonate, carbon
One of sour hydrogen sodium, ammonia, ammonium carbonate and ammonium hydrogen carbonate, concentration is 0.5mol/l 4mol/l.
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| CN105349803B (en) * | 2015-10-22 | 2018-05-25 | 中南大学 | A kind of method from the phosphotungstic acid containing molybdenum/phosphotungstate solution separation tungsten |
| CN105271413B (en) * | 2015-10-22 | 2017-03-15 | 中南大学 | A kind of method for extracting tungsten from phosphotungstic acid/phosphotungstate solution |
| CN109295322A (en) * | 2018-11-05 | 2019-02-01 | 中南大学 | A method of removing tungsten from the molybdate solution of tungstenic |
| CN110376148B (en) * | 2019-09-02 | 2021-11-23 | 赣州有色冶金研究所有限公司 | Method for measuring content of tungsten trioxide in high-phosphorus scheelite |
| CN110904350B (en) * | 2019-12-12 | 2021-07-20 | 中国地质科学院郑州矿产综合利用研究所 | Method for separating tungsten and molybdenum |
| CN113621835A (en) * | 2021-07-23 | 2021-11-09 | 福建金鑫钨业股份有限公司 | Method for efficiently removing molybdenum based on extraction-precipitation combination |
| CN114369718B (en) * | 2021-12-17 | 2023-12-15 | 中核沽源铀业有限责任公司 | System and method for separating organic phase entrained in molybdenum qualified liquid by hydrogen peroxide |
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