CN106148695A - A kind of method producing high-grade germanium concentrate - Google Patents
A kind of method producing high-grade germanium concentrate Download PDFInfo
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- CN106148695A CN106148695A CN201610545333.1A CN201610545333A CN106148695A CN 106148695 A CN106148695 A CN 106148695A CN 201610545333 A CN201610545333 A CN 201610545333A CN 106148695 A CN106148695 A CN 106148695A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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Abstract
The present invention relates to technical field of wet metallurgy, a kind of method producing high-grade germanium concentrate, after to using N235 kerosene system extractant extracted germanium from germanic acid solution, the organic facies of load germanium is carried out cleaning mixture washing, used sodium hydroxide solution back extraction again, and after carrying out supplementing to anti-stripping agent, recycle, make germanic reach more than 15g/L after, hydrolyzed again, washing, dry, calcining, the grade making germanium concentrate reaches more than 20%, make germanium production cost be reduced to 400 500 yuan/kg germanium from original 800 1000 yuan/kg germanium simultaneously, the consuming cost making sodium hydroxide solution reduces more than 30%.
Description
Technical field
The present invention relates to technical field of wet metallurgy, a kind of method producing high-grade germanium concentrate.
Background technology
At present, on market, the grade for germanium concentrate requires more than for Pyatyi (JGe-5), needs germanic amount to exist the most exactly
More than 15%.In prior art, use tannin sink germanium or Lix63,7815, P204The extractants such as-W100 carry out extraction and produce germanium essence
Ore deposit, its not only cost high, and for germanic low raw material, it is extremely difficult to the requirement of above-mentioned grade;Also there is researcher
N235 extractant is used to carry out the extraction of germanium and produce germanium concentrate, although its cost has obtained significantly reducing, but its
The grade of germanium concentrate is the most relatively low, only between 5-15% so that the quality of germanium concentrate is difficult to meet the demand in market.
And in the technical scheme of N235 extracted germanium, it causes relatively low main reason is that of grade of germanium concentrate: extraction
After need to use alkali to carry out back extraction, and be that strip liquor is reused so that impurity content therein also obtain by
Increasing of step, promotees to form it into precipitation so that anti-stripping agent is during carrying out back extraction enriched germanium, and it is difficult to repeatedly
Enrichment so that after the Ge content in anti-stripping agent reaches 5-10g/L, it is difficult to again raise so that the germanium concentrate that hydrolysis obtains
Grade relatively low.
And in prior art, the extractant for N235-kerosene system does in terms of carrying out germanium extraction and producing germanium concentrate
Further research, by using two sections of neutralizing hydrolysis methods, first controls relatively low pH value so that carry out once when pH=7-8
Hydrolysis, then it is added thereto to settling agent, after controlling pH=9-10, carry out secondary hydrolysis.Enable to germanium concentrate although it is so
Grade makes moderate progress, but, in a hydrolytic process, its percent hydrolysis is the highest, the most only 50-70%, and is carrying out two
During secondary hydrolysis, need to add settling agent and the percent hydrolysis of germanium just can be made to reach 90% so that the germanium of secondary hydrolysis residue contains
Measure relatively low, and measure relatively big, cause needs return with once hydrolyze carry out being co-precipitated or with a hydrolysis residue mixed calcining, make
The grade becoming germanium concentrate is relatively low, it is difficult to reach more than 15%.
Then, there is again researcher to use dilute sulfuric acid to dissolve before calcination the slag after said hydrolyzed, obtain germanic higher
Solution, then be hydrolyzed, reach to improve the grade of germanium concentrate, although the grade enabling to germanium concentrate is necessarily carried
Height, but the settling agent that secondary hydrolysis is added yet suffers from, and affect the grade of germanium concentrate;And repeatedly hydrolysis makes raw
The technological process produced is longer, and the direct yield of germanium is relatively low, relatively costly.
In consideration of it, this researcher is by improving the technique of extracted germanium from germanic acid solution so that germanium essence
The grade in ore deposit reaches more than 20%, makes the production cost of germanium concentrate be reduced to 400-from original 800-1000 unit/kg simultaneously
500 yuan/kg.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of high-grade germanium concentrate that produces
Method.
It is achieved particular by techniques below scheme:
A kind of method producing high-grade germanium concentrate, uses N235-kerosene system extractant extracts from germanic acid solution
Take germanium, obtain loading germanium organic facies;Load germanium organic facies is used tartaric acid or oxalic acid or ammonium bicarbonate aqueous solution washing, then uses
Sodium hydroxide solution back extraction germanium processes, it is thus achieved that germanic strip liquor;And additional mass percent is 3-5%'s in germanic strip liquor
After sodium hydroxide, it is recycled back extraction germanium and processes so that after Ge content is at least up to 15g/L, use sulfuric acid solution, adjust pH value
For 9-10 so that germanium hydrolyzes, and after hydrolysis residue is filtered, use hot wash, dry, calcine, it is thus achieved that germanium concentrate.
Described N235-kerosene system extractant, wherein N235 volume basis accounting is 30%.
Described aqueous tartaric acid solution, its mass percentage concentration is 0.1-0.5%.
Described aqueous tartaric acid solution uses the one in clear water, ammonium bicarbonate soln, oxalic acid solution to substitute.
Described ammonium bicarbonate soln, its mass percentage concentration is 1-5%;Described oxalic acid solution, its percent mass is dense
Degree is 0.5-1%.
Described sodium hydroxide solution, its mass percentage concentration is 20-30%.
Described calcining, its temperature is 200-300 DEG C.
Described uses aqueous tartaric acid solution washing by load germanium organic facies, then is clarified or centrifuge separation,
Obtain washing after liquid with washing after load germanium organic facies;After after washing, liquid is used for circulating washing 5 times, return it into germanic
Acid solution mixes.
Described hydrolysis, temperature is 70-80 DEG C.
Described hot water, temperature is 60-80 DEG C.
Compared with prior art, the technique effect of the present invention is embodied in:
After to using N235-kerosene system extractant extracted germanium from germanic acid solution, the organic of germanium will be loaded
Carry out cleaning mixture washing mutually, then used sodium hydroxide solution back extraction, and anti-stripping agent is carried out supplement after, circulation makes
With so that germanic reach more than 15g/L after, then hydrolyzed, washed, dried, calcined so that the grade of germanium concentrate is reached 20%
Above, make germanium production cost be reduced to 400-500 unit/kg germanium from original 800-1000 unit/kg germanium so that hydroxide simultaneously
The consuming cost of sodium solution reduces more than 30%.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further limited, but claimed
Scope is not only limited to description.
Embodiment 1
Take germanic 2.28g/L, the acid solution of zinc 152g/L, used the extractant of N235-kerosene system to extract
Taking, wherein N235 volumetric concentration in extractant is 30%, obtains loading the organic facies of germanium, and is used clear water to wash,
The sodium hydroxide solution back extraction using mass percentage concentration to be 20% organic facies of the load germanium after washing again, obtains back extraction
Liquid;Supplement after accounting for the sodium hydroxide that strip liquor mass percent is 3% in strip liquor, bearing after next time washing
Carry germanium organic facies back extraction, circulation make in strip liquor germanic reach more than 15g/L after, use mass concentration be the sulphuric acid of 10%
It is 9 that solution adjusts pH value, and controlling temperature is 80 DEG C of hydrolysis, it is thus achieved that hydrolysis residue, and hydrolysis residue uses clear water wash at 80 DEG C,
To washed-residue, washed-residue dried at 250 DEG C and calcines, obtaining the germanium concentrate of germanic 27.44%.
Embodiment 2
Take germanic 2.28g/L, the acid solution of zinc 152g/L, used the extractant of N235-kerosene system to extract
Taking, wherein N235 volumetric concentration in extractant is 30%, obtains loading the organic facies of germanium, and is used tartaric acid solution
Washing, then clarify or centrifuge separate, it is thus achieved that after washing liquid with wash after load germanium organic facies;After washing, liquid is used
After circulation washing 5 times, return it into and mix with germanic acid solution.Again the organic facies of the load germanium after washing is used matter
Amount percentage concentration is the sodium hydroxide solution back extraction of 30%, obtains strip liquor;Supplement in strip liquor and account for strip liquor quality hundred
After proportion by subtraction is the sodium hydroxide of 5%, the organic facies back extraction of the load germanium after next time washing, circulation makes strip liquor
In germanic reach more than 15g/L after, use mass concentration be 10% sulfuric acid solution adjust pH value be 10, control temperature be 70 DEG C
Hydrolysis, it is thus achieved that hydrolysis residue, uses hydrolysis residue clear water to wash at 60 DEG C, obtains washed-residue, dried by washed-residue at 200 DEG C
And calcine, obtain the germanium concentrate of germanic 28.13%.Above-mentioned aqueous tartaric acid solution, its mass percentage concentration is 0.1-0.5%.
Embodiment 3
Take germanic 2.28g/L, the acid solution of zinc 152g/L, used the extractant of N235-kerosene system to extract
Taking, wherein N235 volumetric concentration in extractant is 30%, obtains loading the organic facies of germanium, and is used ammonium hydrogen carbonate molten
Liquid washs, during washing, and A/O=1, then use mass percentage concentration to be the hydroxide of 25% organic facies of the load germanium after washing
Sodium solution back extraction, obtains strip liquor;Supplement in strip liquor after accounting for the sodium hydroxide that strip liquor mass percent is 4%, use
After washing next time load germanium organic facies back extraction, circulation make in strip liquor germanic reach more than 15g/L after, adopt
Adjusting pH value with the sulfuric acid solution that mass concentration is 10% is 9.5, and controlling temperature is 75 DEG C of hydrolysis, it is thus achieved that hydrolysis residue, will hydrolysis
Slag uses clear water to wash at 70 DEG C, obtains washed-residue, is dried by washed-residue and calcine, obtain germanic at 300 DEG C
22.93%, containing the germanium concentrate of zinc 35.74%.Above-mentioned ammonium bicarbonate soln, its mass percentage concentration is 1-5%.
Embodiment 4
Take germanic 2.28g/L, the acid solution of zinc 152g/L, used the extractant of N235-kerosene system to extract
Taking, wherein N235 volumetric concentration in extractant is 30%, obtains loading the organic facies of germanium, and is used oxalic acid solution to wash
Wash, during washing, A/O=1, then the sodium hydroxide using mass percentage concentration to be 20% organic facies of the load germanium after washing is molten
Liquid back extraction, obtains strip liquor;Supplement in strip liquor after accounting for the sodium hydroxide that strip liquor mass percent is 3.5%, be used for
After washing next time load germanium organic facies back extraction, circulation make in strip liquor germanic reach more than 15g/L after, use
Mass concentration be 10% sulfuric acid solution adjust pH value be 9.8, control temperature be 78 DEG C of hydrolysis, it is thus achieved that hydrolysis residue, by hydrolysis residue
Use clear water to wash at 75 DEG C, obtain washed-residue, washed-residue dried at 280 DEG C and calcines, obtaining germanic 38.69%
Germanium concentrate.Above-mentioned oxalic acid solution, its mass percentage concentration is 0.5-1%.
Embodiment 5
Take germanic 2.28g/L, the acid solution of zinc 152g/L, used the extractant of N235-kerosene system to extract
Taking, wherein N235 volumetric concentration in extractant is 30%, obtains loading the organic facies of germanium, and is used tartaric acid solution
Washing, then the sodium hydroxide solution back extraction using mass percentage concentration to be 28% organic facies of the load germanium after washing,
To strip liquor;Supplement after accounting for the sodium hydroxide that strip liquor mass percent is 4.5% in strip liquor, for washing next time
After washing load germanium organic facies back extraction, circulation make in strip liquor germanic reach more than 15g/L after, use mass concentration be
It is 9 that the sulfuric acid solution of 10% adjusts pH value, and controlling temperature is 76 DEG C of hydrolysis, it is thus achieved that hydrolysis residue, and hydrolysis residue uses clear water 68
Wash at DEG C, obtain washed-residue, washed-residue dried at 230 DEG C and calcines, obtaining the germanium concentrate of germanic 42.37%.Above-mentioned
Aqueous tartaric acid solution, its mass percentage concentration is 0.3%.
Test example:
Test 1:
To embodiment 1-5 using clear water, ammonium bicarbonate soln, oxalic acid solution, tartaric acid solution to N235-kerosene system
After the organic facies of the load germanium after extracted germanium is washed, to after washing each time in liquid in zinc, sulphuric acid, the changes of contents of germanium
Situation is added up and is analyzed, and its result is as follows:
When using clear water or ammonium bicarbonate soln to wash, it is possible to after making washing, the zinc in liquid raises 3-6g/ every time
L, sulphuric acid raise 2-5g/L, germanium every time and raise 20-50mg/L every time;And to it along with the increase of washing times, it is substantially in line
Property rise, it is seen then that when using clear water or ammonium bicarbonate soln to carry out carrying out washing treatment, it enables to load in the organic facies of germanium
The impurity such as zinc, sulphuric acid significantly reduces and reduces, and the content of germanium also can be made to reduce simultaneously, but the minimizing width of zinc, sulphuric acid
Spend for relative germanium very fast so that during germanium follow-up back extraction germanium, it can be ensured that germanium grade improves;
When using oxalic acid solution or tartaric acid solution to wash, after washing, in liquid, only zinc and sulfuric acid content are linearly gone up
Rising, the content in germanium liquid after washing maintains 30-50mg/L.Visible, use oxalic acid solution to wash with tartaric acid solution
During process, it is possible to avoid the washing of recycled for multiple times cleaning mixture to take away the defect of germanium so that germanium substantial amounts of can stay load germanium
Organic facies in, simultaneously can be through repeatedly circulating washing so that the impurity such as zinc, sulphuric acid is removed, effectively raise germanium essence
The grade in ore deposit.
In addition, this researcher also further in above-mentioned cleaning mixture, ammonium bicarbonate soln, oxalic acid solution, wine
The research that the mass concentration of stone acid solution is tested, its result shows, the mass percentage concentration at ammonium bicarbonate soln is
1-5%, the mass percentage concentration of oxalic acid solution are 0.5-1%, when the mass percentage concentration of tartaric acid solution is 0.1-0.5%,
The removing of the impurity such as the zinc in the organic facies of load germanium, sulphuric acid is linearly risen by it, and invariable to the eluting of germanium, it is possible to
The impurity such as eluting zinc, sulphuric acid, reduces the loss of germanium to greatest extent;And use the quality hundred beyond above-mentioned mass percentage concentration
Point concentration, as to use the mass percentage concentration of ammonium bicarbonate soln be 0.9%, the mass percentage concentration of oxalic acid solution is 0.4%,
When the mass percentage concentration of tartaric acid solution is 0.09%, carrying out loading the washing of the organic facies of germanium, it enables to germanium composition
Substantial amounts of loss so that the Ge content in the organic facies of load germanium reduces, and presents the trend of linear decline;In like manner use
The mass percentage concentration of ammonium bicarbonate soln is 6%, the mass percentage concentration of oxalic acid solution is 1.2%, the matter of tartaric acid solution
When amount percentage concentration is 0.6%, carrying out loading the washing of the organic facies of germanium, it enables to the substantial amounts of loss of germanium composition.To sum up,
Choosing so that the germanium component loss rate in washing process significantly reduces of the concentration of above-mentioned cleaning mixture, and can be effective
Removing zinc therein, the impurity such as sulphuric acid, effectively guarantee that the grade of follow-up germanium concentrate improves.
Test 2:
This researcher, by the operational approach in embodiment 1 is tracked process, in the volumetric concentration using N235 is
After the N235-kerosene system extractant of 30% carries out three grades of extracted germaniums, the organic facies of load germanium being used clear water washing, clear water is
After circulation washing about 5 times, it is mixed with germanic acid solution;And the organic facies of the load germanium after washing is used quality hundred
Point concentration is the sodium hydroxide solution back extraction of 20%, and after carrying out cycling extraction 5 times, by liquid mixing more than the extractions of 5 times;And examine
Germanium in liquid, strip liquor, Zn content situation after the remaining liquid of survey extraction, washing, result is: the germanic 0.084g/L of liquid more than extraction, washing
The germanic 0.179g/L of rear liquid, zinc 15.6g/L, the germanic 23.4g/L of strip liquor, zinc 8.56g/L.According still further in embodiment 1 by back extraction
Liquid is hydrolyzed, and after processing hydrolysis residue, germanic 0.586g/L in liquid after being hydrolyzed, hydrolysis residue is germanic 16.37%,
Zinc 18.12%;Hydrolysis residue is used the hot wash of 80 DEG C, the germanic 0.72g/L of liquid, zinc 0.47g/L after washing again;And will washing
Slag is dried at 250 DEG C and calcines, and obtains germanium concentrate, containing zinc 32.38% in this germanium concentrate, and germanic 27.44%;Visible effectively
The grade making germanium concentrate is improved.
Test 3
The process of the germanium that embodiment 2-5 is carried out is tracked, and the onium hydroxide solution used is being produced 1kg germanium
Time consumption add up, and by sodium hydroxide solution according to 3000 yuan/t calculate, the quantity of alkali consumption of embodiment 3 is 70kg,
Cost is about 210 yuan;The quantity of alkali consumption of embodiment 4 is 50kg, and cost is about 150 yuan;The alkali consumption of embodiment 2 and embodiment 5
Amount is for 50kg, and cost is about 150 yuan, but germanic in its germanium concentrate has reached more than 40%.
According still further to following processing mode as a control group:
According to the processing mode in above-described embodiment 2-5, the extractant using N235-kerosene system is molten from germanic acidity
Extracted germanium in liquid, by the organic facies of load germanium without washing, the sodium hydroxide solution directly using mass concentration to be 30% is anti-
Extraction, does not carries out supplementing of sodium hydroxide in anti-stripping agent, result shows: a back extraction has a small amount of white precipitate to produce;
Repeating secondary counter extraction, white precipitate increases, and split-phase slows;Back extraction for the third time, split-phase difficulty, back extraction
Liquid-based originally presents precipitated form, and pH is reduced to 7, germanic 8.93g/L in strip liquor, then after being hydrolyzed, washing, calcine,
The germanium concentrate germanic 10.79% arrived, and the yield of every kilogram of germanium, alkali consumption is about 109kg, and cost is 328 yuan so that germanium
Total cost of production has reached 800-1000 unit/kg germanium.
As fully visible, the invention can effectively reduce germanium concentrate production cost so that it is compared tradition and reduces about
300-600 unit/kg germanium, but also the grade enabling to germanium concentrate improves more than at least 10%.
Above example and test are only intended merely to the further explanation to technical scheme and explanation, with
It is easy to those skilled in the art's understanding to technical solution of the present invention, therefore, the protection domain of the invention is not carried out
Limiting, on this basis, that makes does not has prominent essential characteristics and the improvement of non-significant progress to those skilled in the art,
Belong to the protection category of the present invention.
Claims (10)
1. the method producing high-grade germanium concentrate, it is characterised in that use N235-kerosene system extractant is from germanic acid
Property solution in extracted germanium, obtain load germanium organic facies;Load germanium organic facies is used aqueous tartaric acid solution washing, then uses hydroxide
Sodium solution back extraction germanium processes, it is thus achieved that germanic strip liquor;And additional mass percent is the hydroxide of 3-5% in germanic strip liquor
After sodium, being recycled back extraction germanium and process so that after Ge content is at least up to 15g/L, use sulfuric acid solution, adjustment pH value is 9-
10 so that germanium hydrolyzes, and after hydrolysis residue is filtered, use hot wash, dry, calcine, it is thus achieved that germanium concentrate.
2. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described N235-kerosene system extracts
Taking agent, wherein N235 volume basis accounting is 30%.
3. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described aqueous tartaric acid solution,
Its mass percentage concentration is 0.1-0.5%.
4. the method for the production high-grade germanium concentrate as described in claim 1 or 3, it is characterised in that described tartaric acid is water-soluble
Liquid uses the one in clear water, ammonium bicarbonate soln, oxalic acid solution to substitute.
5. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described ammonium bicarbonate soln,
Its mass percentage concentration is 1-5%;Described oxalic acid solution, its mass percentage concentration is 0.5-1%.
6. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described sodium hydroxide solution,
Its mass percentage concentration is 20-30%.
7. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described calcining, its temperature is
200-300℃。
8. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described will load germanium organic facies
Employing aqueous tartaric acid solution wash, then clarify or centrifuge separate, it is thus achieved that after washing liquid with wash after load germanium
Organic facies;After liquid is used for circulating washing 5 times after washing, returns it into and mix with germanic acid solution.
9. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described hydrolysis, temperature is 70-
80℃。
10. the method producing high-grade germanium concentrate as claimed in claim 1, it is characterised in that described hot water, temperature is
60-80℃。
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CN108060305A (en) * | 2017-12-13 | 2018-05-22 | 贵州宏达环保科技有限公司 | A kind of method of recovery indium germanium in chlorinated distillation raffinate from the germanium containing indium |
CN109929997A (en) * | 2019-03-14 | 2019-06-25 | 贵州宏达环保科技有限公司 | A method of germanium concentrate is produced with N235 extractant |
CN111206149A (en) * | 2020-03-04 | 2020-05-29 | 北京高能时代环境技术股份有限公司 | Method for centrifugal extraction of germanium |
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CN108060305A (en) * | 2017-12-13 | 2018-05-22 | 贵州宏达环保科技有限公司 | A kind of method of recovery indium germanium in chlorinated distillation raffinate from the germanium containing indium |
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CN111206149A (en) * | 2020-03-04 | 2020-05-29 | 北京高能时代环境技术股份有限公司 | Method for centrifugal extraction of germanium |
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