CN104962743B - Method for selectively extracting and recycling gallium, germanium and indium from sulfuric acid leach liquid of zinc displacement residues - Google Patents
Method for selectively extracting and recycling gallium, germanium and indium from sulfuric acid leach liquid of zinc displacement residues Download PDFInfo
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Abstract
The invention discloses a method for selectively extracting and recycling gallium, germanium and indium from sulfuric acid leach liquid of zinc displacement residues. The method includes selectively extracting the germanium from the sulfuric acid leach liquid of the zinc displacement residues by the aid of synergistic extraction systems comprising hydroxamic chelate extraction agents and acidic phosphorus type extraction agents; recycling acid from germanium extraction raffinate by the aid of a diffusion dialysis process and finely adjusting the germanium extraction raffinate until a pH (potential of hydrogen) value of the germanium extraction raffinate is appropriate; selectively extracting the gallium and the indium from the germanium extraction raffinate by the aid of synergistic extraction systems comprising hydroxamic chelate extraction agents and carboxylic acid extraction agents. The method has the advantages that the germanium, the gallium and the indium can be effectively separated from foreign metal ions of iron, zinc, cadmium, nickel, cobalt and the like; the germanium, the gallium and the indium are high in recycling rate, good germanium, gallium, indium and foreign matter separation effects can be realized, technological processes are short, the extraction agents are long in service life and low in loss, and the method is low in cost and easy to industrialize.
Description
Technical field
The present invention relates to a kind of method that selective extraction reclaims gallium germanium indium in replacement slag sulphuric leachate from zinc, belongs to wet
Method metallurgical technology field.
Background technology
Germanium and gallium indium are important strategic dissipated metals, have extensive use in fields such as information electronics.Zinc factory smelted
The gallium germanium slag obtained using zinc dust precipitation in journey is the important source material that germanium is extracted with gallium indium.Gallium germanium indium is extracted from zinc replacement slag
Wet processing usually first use sulfuric acid leaching, then using solvent extraction from leachate extraction and recovery gallium germanium indium.Both at home and abroad
Numerous studies were carried out in terms of gallium germanium indium is reclaimed in solvent extraction, for example, LIX63 has from extracted germanium in high-concentration sulfuric acid solution
Good selectivity, but alkali concn required during load organic oppositing back-extraction is high, it is big to the extractant extent of damage, cause extractant to make
Use short life；Kelex100 extracts gallium from Alkaline Sodium Aluminate Solution, and extracted germanium in sulfuric acid solution is applied to later.Above two
Extractant all has a synthesis, and difficulty is big, expensive, the deficiency such as larger is lost in extraction process.China synthesis YW100 and
G315 hydroxamic acid kind of extractants also can from germanic sulfuric acid medium optionally extracted germanium, but exist it is water-soluble it is big, extracted
There are the drawbacks such as third phase in Cheng Yi.And from selective extraction gallium indium in the sulfuric acid solution containing impurity such as a large amount of zinc, iron, nickel, cobalt, cadmiums
It is rarely reported.
The content of the invention
For reclaiming the defect that gallium germanium indium technology is present in the existing replacement slag sulphuric leachate from zinc, the purpose of the present invention is
Be provide it is a kind of reclaim gallium germanium indium from selective extraction in zinc replacement slag sulphuric leachate, realize gallium germanium indium and iron, zinc, nickel,
The method that the plurality of impurities such as cobalt, cadmium are efficiently separated, the method technological process is short, service life of extractant length, little, the cost of consumption
It is low, it is easy to accomplish industrialized production.
In order to realize the technical purpose of the present invention, the invention provides one kind is selective from zinc replacement slag sulphuric leachate
The method of extraction and recovery gallium germanium indium, the method is adopted by the hydroxyl oxime chelating extractant with the structure of formula 1 and the acid with the structure of formula 2
Property organophosphorus extractant composition synergistic system I from selective extraction germanium in zinc replacement slag sulphuric leachate；Extraction germanium extraction raffinate is led to
Cross diffusive dialysis method recovery acid, and adjust after pH to 3.0～3.5, then using by the hydroxyl oxime chelating extractant with the structure of formula 1 and
The synergistic system II selective extractions gallium and indium of the composition of the carboxylic acid extractant with the structure of formula 3；
Wherein,
R1、R2、R3、R4And R5It is each independently selected from C6～C10Alkyl.
Zinc replacement slag sulphuric leachate mainly includes germanium, gallium, indium, iron, zinc, cadmium, nickel and cobalt in technical scheme
In interior metal ion, also do not realize that the impurity such as germanium, gallium and indium and iron, zinc, cadmium, nickel and cobalt are separated in prior art well
Method.Compounding extraction system initially with hydroxyl oxime chelating extractant and acidic organophosphorus extractant of the invention is first by germanium selectivity
Extract, the synergistic system for further being constituted using hydroxyl oxime chelating extractant and carboxylic acid extractant is selected gallium and indium
Property is extracted, it is possible to achieve the purpose of the present invention.
The method for reclaiming gallium germanium indium from selective extraction in zinc replacement slag sulphuric leachate of the present invention also includes following excellent
Select scheme.
Hydroxyl oxime chelating extractant has the structure of formula 4 in preferred scheme：
Acidic organophosphorus extractant has the structure of formula 5 in preferred scheme：
Carboxylic acid extractant has the structure of formula 6 in preferred scheme：
The alkane chain of suitable length makes extractant have more preferable dispersive property in currently preferred extractant, while also having
Beneficial to the synergistic function between various extractants during extractant compounding use.
Contacting the organic phase containing synergistic system I with zinc replacement slag sulphuric leachate in preferred scheme carries out single-stage
Or multi-stage counter current extraction, germanium ion enters organic phase, including the metal ion including gallium, indium, iron, zinc, cadmium, nickel and cobalt extraction stayed in
In germanium extraction raffinate；After the organic phase of load germanium is scrubbed, using OH-Aqueous slkali of the concentration between 0.5～1.0mol/L is used as anti-
Extraction agent carries out single-stage or multi-stage countercurrent back extraction, obtains germanium-containing solution.By the aqueous slkali of low concentration in the preferred version
Back extraction is carried out, the service life of hydroxyl oxime chelating extractant and acidic organophosphorus extractant is substantially prolongs, loss is little, and can circulate makes
With.
More preferably the mol ratio of hydroxyl oxime chelating extractant and acidic organophosphorus extractant is in synergistic system I in scheme
4:1～1:1.
More preferably the organic phase containing synergistic system I includes TBP or at least one phase in sec-octyl alcohol in scheme
Conditioning agent, and sulfonated kerosene, No. 260 solvent naphthas, aviation kerosine, Escaid110, C8～13Higher alcohols at least one have
Machine diluent.Organic diluent is most preferably at least one in sulfonated kerosene, No. 260 solvent naphthas, aviation kerosines.Diluent with
The volume ratio of extractant is 70～85:15～30；Optimal proportion is 80:20.
Aqueous slkali is at least one in sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor in preferred scheme.Most preferably
Aqueous slkali be NaOH.
Contacting the organic phase containing synergistic system II with extraction germanium extraction raffinate in preferred scheme carries out single-stage or multistage
Counter-current extraction, gallium ion and indium ion enter organic phase, including the metal ion including iron, zinc, cadmium, nickel and cobalt stay in extraction gallium and
In indium extraction raffinate；After the organic phase of negative gallium and indium is scrubbed, using H+Acid solution of the concentration between 0.1～1.0mol/L is used as anti-
Extraction agent carries out single-stage or multi-stage countercurrent back extraction, obtains the solution containing gallium and indium.By the sour molten of low concentration in the preferred version
Liquid can carry out back extraction, substantially prolongs the service life of hydroxyl oxime chelating extractant, and loss is little, can recycle.
More preferably in the synergistic system II described in scheme hydroxyl oxime chelating extractant and carboxylic acid extractant mole
Than for 2:1～1:1.
More preferably the organic phase containing synergistic system II in scheme includes sulfonated kerosene, No. 260 solvent naphthas, boats
Empty kerosene, Escaid110, C8～13Higher alcohols at least one organic diluent.Most preferably liquid hydrocarbon diluent is
At least one in sulfonated kerosene, No. 260 solvent naphthas, aviation kerosines.Diluent is 70～85 with the volume ratio of extractant:15～
30；Optimal proportion is 80:20.
Acid solution described in preferred scheme is sulfuric acid solution and/or hydrochloric acid solution.Most preferably acid solution is sulfuric acid.
Sulfuric acid concentration is more than 30g/L in zinc replacement slag sulphuric leachate in preferred scheme；Most preferably in 80～120g/
L。
Hydroxyl oxime chelating extractant (such as HBL101) of the present invention, acidic organophosphorus extractant (P507), carboxylic acid extractant is (such as
Versatic 10) etc. be commercially available conventional dose, or can be obtained according to the simply synthesis of existing maturation method.
Described counter-current extraction O/A (volume ratio) is 1/5～10/1, and series is 1～3 grade.
It is 1/3～5/1 that described countercurrent reextraction takes O/A (volume ratio), and series is 1～3 grade.
The present invention more preferably from zinc replacement slag sulphuric leachate selective extraction reclaim gallium germanium indium method be：By sulphur
The zinc replacement slag sulphuric leachate of 80～120g/L of acid concentration is first and containing hydroxyl oxime chelating extractant (formula 4) HBL101+ acid phosphorus
The organic phase of type extractant P507 (formula 5) synergistic system carries out the extraction of 1～3 stage countercurrent with the contact of volume ratio 5/1～1/10；
Germanium ion in leachate is entered in organic phase, and stays in extraction including the metal ion including gallium, indium, iron, zinc, nickel, cobalt and cadmium
In remainder liquid, load organic phases and OH obtained by counter-current extraction-Concentration is connect for the aqueous slkali of 0.5mol/L with volume ratio 1/3～5/1
Touching carries out 1～3 stage countercurrent back extraction, obtains the germanic aqueous solution；Extraction germanium extraction raffinate is reclaimed after most of acid by diffusion dialysis, Jing
Fine setting pH value is adopted and contains hydroxyl oxime chelating extractant (formula 4) HBL101+ carboxylic acid extractants (formula 6) to 3.0～3.5
The organic phase of Versatci10 collaboration extraction systems carries out the extraction of 1～3 stage countercurrent, the extraction germanium with the contact of volume ratio 5/1～1/10
Gallium ion and indium ion in extraction raffinate enter organic phase in, including iron, zinc, nickel, cobalt and cadmium metal ionic impurity stay in extraction gallium and
In indium extraction raffinate, load organic phases and H obtained by counter-current extraction+Concentration is contacted for the acid solution of 0.1mol/L with volume ratio 1/3～5/1
1～3 stage countercurrent back extraction is carried out, the aqueous solution containing gallium and indium is obtained.
Hinge structure, beneficial effects of the present invention：
1st, the different compounding extractant system of first passage of the present invention is selective successively from zinc replacement slag sulphuric leachate
Extract and separate goes out germanium and gallium and indium, and germanium is high with the rate of recovery of gallium indium, and purity is high, effectively realize germanium, gallium, indium and impurity iron,
The separation of zinc, nickel, cobalt, cadmium etc..
2nd, have individually selective from the high acidic oils liquid containing gallium and germanium using hydroxyl oximes chelating extractant in prior art
The method of extracted germanium, but have at least to carry out back extraction in the alkali lye of more than 3.75mol using concentration could be by for the method
Out, hydroxyl oximes chelating extractant is easily hydrolyzed the complete back extraction of germanium in the aqueous slkali of the concentration, causes hydroxyl oximes chelate extraction
The loss of agent, it is relatively costly.In preferred embodiments of the present invention, made using hydroxyl oxime chelating extractant and acidic organophosphorus extractant compounding
With, the problem is efficiently solved, not only back extraction can be carried out with the aqueous slkali less than 1mol/L concentration, and equally can reach
To good back extraction effect.
3rd, yet there are no in prior art and the detached report of the impurity such as gallium and indium and iron, zinc, nickel, cobalt and cadmium is realized by extraction
Road.The present invention is realized by selecting hydroxyl oxime chelating extractant and carboxylic acid extractant compounding use, and the pH conditions that control is appropriate
The Selective Separation of the impurity such as gallium and indium and iron, zinc, nickel, cobalt and cadmium.
4th, hydroxyl oximes chelating extractant of the invention is also unstable under strongly acidic conditions, in preferred embodiments of the present invention,
By hydroxyl oxime chelating extractant and carboxylic acid extractant compounding use according to a certain percentage, the selectivity of gallium and indium can be not only realized
Extraction, while back extraction can also be carried out using weak acid, reduces the waste of hydroxyl oxime chelating extractant.
5th, technological process of the invention is short, low cost, it is easy to accomplish industrialization.
Specific embodiment
Embodiments of the present invention are illustrated below by embodiment, following examples are intended to illustrate rather than
Limitation of the invention further.
Embodiment 1
Aqueous phase liquid：Zinc replacement slag sulphuric leachate, wherein germanic 0.254g/L, gallium 0.311g/L, indium 0.06g/L, iron
1.07g/L, zinc 16.55g/L, nickel 0.58g/L, cobalt 0.87g/L, cadmium 4.6g/L, feed liquid sulfuric acid concentration 100g/L；
Extraction germanium organic phase：Extractant is 0.2mol/L HBL101+0.1mol/L P507, and diluent is sulfonated kerosene.
Extract and separate：Organic phase carries out single-stage extraction under conditions of feed liquid is 1/1 compared with, and the extraction equilibrium time is
10min, 25 DEG C of temperature.Experimental result is as shown in table 1.
The extraction yield (%) of metal ion in table 1HBL101+P507 synergistic extractant system extracting zinc replacement slag sulphuric leachates
As it can be seen from table 1 HBL101+P507 synergistic extractant systems have excellent extraction to the germanium in zinc replacement slag sulphuric leachate
Take selection performance, Jing single-stage extractions, germanium extraction yield i.e. up to more than 94%, indium, iron, the extraction yield of zinc less than 2%, other metals
Ion is not extracted substantially.The extraction process split-phase time is less than 3 minutes.
Embodiment 2
Aqueous phase liquid be embodiment 1 in extraction germanium extraction raffinate, sulfur acid about 100g/L, Jing after diffusion dialysis, dialysate sulfuric acid
Concentration is only 5g/L, plus pH value is adjusted to 3.0 as extraction gallium, the material liquid of indium for concentrated NaOH solution, and concentration of metal ions is basic
Keep constant；
Extraction gallium indium organic phase：Extractant is 0.1mol/L HBL101+0.1mol/L Versatic 10, and diluent is 260
Number solvent naphtha.
Extract and separate：Organic phase carries out single-stage extraction under conditions of feed liquid is 1/1 compared with, and the extraction equilibrium time is
10min, 25 DEG C of temperature.Experimental result is as shown in table 2.
The extraction yield (%) of metal ion in table 2HBL101+Ver.10 synergistic extractant systems extraction extraction germanium extraction raffinate
From table 2 it can be seen that HBL101+Ver.10 synergistic extractant systems respectively reach 92% and to the single-stage extraction rate of gallium, indium
More than 86%, the extraction yield of other metal ions is less less than 10%.The synergistic extractant system can realize gallium, indium and impurity iron, zinc,
Nickel, cobalt, cadmium are efficiently separated.The extraction process split-phase time is less than 5 minutes.
Embodiment 3
Aqueous phase liquid is in the same manner as in Example 1；
It is 0.2mol/L HBL101+0.2mol/L P507 that organic phase is extractant, and diluent is aviation kerosine.
Back washing agent：0.5mol/L NaOH solutions.
Extract and separate：Above-mentioned organic phase carries out 3 stage countercurrent extractions under conditions of aqueous phase liquid is 1/5 compared with, is loaded with
Machine back washing agent carries out single-stage back extraction under conditions of comparing 1/1.Extraction and back extraction incorporation time are 10min, temperature
Spend for 25 DEG C.Table 3 is that extraction-back extraction reaches the experimental result after balance.
Table 3HBL101+P507 multi-stage countercurrent cascade extraction analog reslts
Note：-- do not detect
From table 3 it can be seen that through the extraction of 3 stage countercurrents, the Ge content of raffinate is only 0.003g/L, and extraction yield is up to
98.8%.Respectively up to more than 91%, the removal rate of impurity reaches or close 100% the single-stage back extraction ratio of load organic phases germanium.
Embodiment 4
Aqueous phase liquid is identical in embodiment 2.
Organic phase is 0.12mol/L HBL101+0.12mol/L Versatic 10, and diluent is Escaid110.
Back washing agent：0.05mol/L H2SO4Solution
Extract and separate：Above-mentioned organic phase carries out 3 stage countercurrent extractions under conditions of aqueous phase liquid is 1/5 compared with, is loaded with
Machine back washing agent carries out 3 stage countercurrent back extraction under conditions of comparing 5/1.Extraction and back extraction incorporation time are 10min,
Temperature is 25 DEG C.Table 4 is that extraction-back extraction reaches the experimental result after balance.
Table 4HBL101+Ver.10 multi-stage countercurrent cascade extraction analog reslts
From table 4, it can be seen that the organic phase of load gallium indium is through 3 stage countercurrent back extraction, back extraction ratio can respectively reach 98%
With more than 99%, gallium, indium concentration respectively reach 7g/L and 1.34g/L in strip liquor, and than the gallium in material liquid, indium 20 are enriched
As many as times.
Claims (10)
1. in a kind of replacement slag sulphuric leachate from zinc selective extraction reclaim gallium germanium indium method, it is characterised in that using by
Hydroxyl oxime chelating extractant with the structure of formula 1 and the acidic organophosphorus extractant with the structure of formula 2 composition synergistic system I from
Selective extraction germanium in zinc replacement slag sulphuric leachate；Extraction germanium extraction raffinate by diffusive dialysis method recovery acid, and adjust pH to 3.0～
After 3.5, then using the collaboration being made up of the hydroxyl oxime chelating extractant with the structure of formula 1 and the carboxylic acid extractant with the structure of formula 3
Extraction system II selective extraction gallium and indium；
Wherein,
R1、R2、R3、R4And R5It is each independently selected from C6～C10Alkyl.
2. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 1, its
It is characterised by,
Described hydroxyl oxime chelating extractant has the structure of formula 4：
Described acidic organophosphorus extractant has the structure of formula 5：
Described carboxylic acid extractant has the structure of formula 6：
3. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 1, its
It is characterised by, the organic phase containing synergistic system I is contacted with zinc replacement slag sulphuric leachate carries out single-stage or multi-stage countercurrent
Extraction, germanium ion enters organic phase, stays in extraction germanium extraction raffinate including the metal ion including gallium, indium, iron, zinc, cadmium, nickel and cobalt；
After the organic phase of load germanium is scrubbed, using OH-Aqueous slkali of the concentration between 0.5～1.0mol/L carries out list as back washing agent
Level or multi-stage countercurrent back extraction, obtain germanium-containing solution.
4. gallium germanium indium is reclaimed from selective extraction in zinc replacement slag sulphuric leachate according to any one of claims 1 to 3
Method, it is characterised in that the mol ratio of hydroxyl oxime chelating extractant and acidic organophosphorus extractant in described synergistic system I
For 4:1～1:1.
5. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 3, its
It is characterised by, the described organic phase containing synergistic system I includes at least one phase modifier in TBP and sec-octyl alcohol,
And sulfonated kerosene, No. 260 solvent naphthas, aviation kerosine, Escaid110, C8～13Higher alcohols at least one organic dilution
Agent.
6. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 3, its
It is characterised by, described aqueous slkali is at least one in sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor.
7. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 1, its
It is characterised by, the organic phase containing synergistic system II is contacted with extraction germanium extraction raffinate carries out single-stage or multi-stage counter current extraction, gallium
Ion and indium ion enter organic phase, stay in extraction gallium and indium extraction raffinate including the metal ion including iron, zinc, cadmium, nickel and cobalt；It is negative
After the organic phase of gallium and indium is scrubbed, using H+Acid solution of the concentration between 0.1～1.0mol/L carries out list as back washing agent
Level or multi-stage countercurrent back extraction, obtain the solution containing gallium and indium.
8. according to claim 1,2 or 7 from zinc replacement slag sulphuric leachate selective extraction reclaim gallium germanium indium side
Method, it is characterised in that the mol ratio of hydroxyl oxime chelating extractant and carboxylic acid extractant is 2 in described synergistic system II:1～
1:1。
9. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 7, its
Be characterised by, the described organic phase containing synergistic system II include sulfonated kerosene, No. 260 solvent naphthas, aviation kerosine,
Escaid110、C8～13Higher alcohols at least one organic diluent；Described acid solution is sulfuric acid solution and/or hydrochloric acid
Solution.
10. the method that selective extraction reclaims gallium germanium indium in the replacement slag sulphuric leachate from zinc according to claim 1, its
It is characterised by, sulfuric acid concentration is more than 30g/L in described zinc replacement slag sulphuric leachate.
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| CN108977657B (en) * | 2017-06-01 | 2019-10-08 | 中南大学 | A method of the recovery indium from the methanesulfonic acid solution containing indium |
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| CN108300876A (en) * | 2018-01-31 | 2018-07-20 | 广东省稀有金属研究所 | A method of leaching gallium and germanium from zinc replacement slag |
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| CN103320611B (en) * | 2013-06-09 | 2014-09-17 | 中南大学 | Method for selectively extracting gallium and germanium from peracid lixivium containing gallium and germanium |
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