CN109929997A - A method of germanium concentrate is produced with N235 extractant - Google Patents
A method of germanium concentrate is produced with N235 extractant Download PDFInfo
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Abstract
The present invention relates to dissipated metal Comprehensive Recovery Technology field, in particular to a kind of method with N235 extractant production germanium concentrate extracts organic germanic acid with N235 extractant first from germanic Acidic Liquid, obtains the organic phase of load germanium；Then again with corresponding organic acid dilute liquid wash load organic phase, it is stripped purification organic phase with sodium hydroxide, obtains germanic alkali strip liquor, and be recycled to and wherein germanic reach 20g/L or more；Then precipitating germanium concentrate is hydrolyzed in the strip liquor；Hydrolytic precipitation filtered fluid carries out causticization processing, obtains calcium of organic acid precipitating and sodium hydroxide regenerated liquid is returned and used, then use sulfuric acid leaching calcium of organic acid, obtain organic acid leaching liquor and return to use.Not only ensure the organic extraction rate of germanium, but also reduced the consumption of sodium hydroxide, and improve germanium concentrate grade, the also organic complexing agent of regeneration recycling sodium hydroxide and germanium, while reducing slag and effluent environmental improvement cost.
Description
Technical field
The present invention relates to dissipated metal Comprehensive Recovery Technology field, in particular to a kind of to produce germanium concentrate with N235 extractant
Method.
Background technique
Germanium is a kind of rare dissipated metal, and mineral resources are distributed mainly in Pb-Zn deposits and coal mine.It is mentioned from Pb-Zn deposits
Take separating Ge mainly with hydrometallurgical method.The hydrometallurgical recovery method of germanium is in the presently mainly tannin precipitation method and has
Solvent extraction.Tannin organic matter, which must be fallen, in 500 DEG C or more calcinings after tannin precipitation method acquisition tannin organic germanium can just obtain
Obtain the germanium dioxide concentrate of 5-20% grade.10% is improved since germanium concentrate grade is every, price increases by 200 yuan/kilogram or more, has
The calcining of machine object, tannin is unable to get recycling, and can generate combust, and the grade of germanium concentrate is difficult to reach 30% or more.
In order to improve the economic benefit of germanium concentrate chlorinated distillation, chlorinated distillation raffinate amount, therefore the recycling life of tannin method are reduced
Production germanium concentrate is at high cost, economic benefit is low.Organic solvent extractionprocess can overcome the shortcomings that tannin method, can produce 30% or more
Germanium concentrate is the main developmental research direction of the wet underwater welding of current germanium.
Organic solvent extractionprocess mainly has hydroxamic acid (such as LiX63, Klex100,7815,8315) kerosene extraction agent at present
With amine (such as N235, Trifatty amine, trioctylamine N263 commonly use N235) kerosene extraction agent, the former (hydroxamic acid class) can be direct
From Acidic Liquid in the form of chelating extracted germanium, back extraction using fluoride ion diluted acid or fluoride ion salt mixture into
Row, but since hydroxamic acid water solubility is very big, organic extractant consumption is big, and price is at high cost, and extraction stable condition is poor, operation
It is big to control difficulty, is still difficult to realize industrialized production in China.Amine extractant especially N235 kerosene extraction agent, due to its extraction
Taking form is zwitterion associated forms, is easy to be stripped out by extracted species with sodium hydroxide solution, easy to operate, Er Qieshui
Dissolubility is small, and loss is small, cheap, has been realized in industrialized production, but the agent of N235 kerosene extraction must be first acidified
Processing, i.e., first extraction acid radical anion forms R3N+H2SO4→[R3NH+]HSO4 -It is lower than HSO with charge density again afterwards4 -Germanium have
Machine complex anion swaps (such as organic germanium complex such as catechol germanium, tartaric acid germanium).Due to germanium content in the solution
It is lower, therefore N235 load organic phases not only contain organic germanium complex anion, yet contain a large amount of HSO4 -, can also extract part
Impurity anions group necessarily consumes a large amount of sodium hydroxide when being stripped with sodium hydroxide, thus using amine extractant from
In Acidic Liquid when extraction and recovery germanium, mainly has the shortcomings that add the organic complex of germanium and consume a large amount of sodium hydroxide.It is logical
Often, those skilled in the art wash before being stripped process, according to clear water, weak acid, weak caustic solution as detergent, although
Can elution fraction impurity and sulfuric acid, but also can the germanium that has been extracted of elution fraction, reduce germanium recovery rate；It is washed according to organic acid solution
It washs, although the elution amount for being extracted germanium can be reduced, organic reagent price, it is necessary to be recycled.
Patent No. CN201610339560.9 provides one kind using metal oxide as neutralization precipitation agent, using two sections of neutralization water
Solution precipitates the processing method of Ti recovery from germanic feed liquid, uses metal oxide as neutralization precipitation agent and in two sections
With liquid before the heavy germanium of method for hydrolysis processing, easy to operate, slag strainability preferably, auxiliary material additional amount germanium concentrate product that are few, but obtaining
Position is 6%-8% or so.
Patent No. CN201711330085.X provides a kind of side of recovery indium germanium in the chlorinated distillation raffinate from the germanium containing indium
Method, in the presence of distillation Liquid Residue is passed through tartaric acid, so that obtaining the (Ge containing InCl4- or InCl63- winestone germanium acid radical anion
(A) 32-, A are tartaric acid) mixed liquor, and using the indium germanium extraction simultaneously of N235- kerosene system extractant, then using dilute sulfuric acid or
Dilute hydrochloric acid be stripped indium, sodium hydroxide solution be stripped germanium, the patented technology be from the chlorination liquid system of high concentration simultaneously extraction of indium,
Germanium, load indium germanium organic phase are cannot to use clear water or sig water or organic, dilute mineral acid washing, purifying.Because using any
Dilution washing can all become the strip liquor of indium, and indium dispersion can be made to be unfavorable for recycling.Simultaneously using organic acid dilute liquid washing or
Back extraction can make zinc displacement sponge indium generate difficult and increase metallic zinc consumption due to the complexing of organic acid, masking action.If advanced
The alkali of row germanium is stripped, then indium can also be entered in alkali strip liquor by back extraction, and precipitate and cannot be separated simultaneously with germanium when neutralizing hydrolysis.
The segmentation back extraction of the technology can only be first acid back extraction indium, and rear alkali is stripped germanium.Therefore the patented technology be cannot be arranged load it is organic
The washing of phase and cleaning procedure.If but not only having a large amount of sulfuric acid when alkali is stripped without using organic acid work washing exchange liquid
Sodium and impurity enter strip liquor, and when hydrolysis carries secretly more, and calcining cannot remove sodium sulphate ingredient, will affect mentioning for germanium concentrate grade
It is high.
Patent No. CN201610545333.1 provides a kind of method for producing high-grade germanium concentrate, especially by from containing
It is after using N235- kerosene system extractant extracted germanium in germanium acid solution, the organic phase clear water or sodium carbonate that load germanium is dilute
It releases liquid or organic and inorganic dilution is washed, then used sodium hydroxide solution to be stripped, and mend to anti-stripping agent
After filling, be recycled so that it is germanic reach 15g/L or more after, then hydrolyzed, washed, dried, calcined, but according to non-right
The germanium being extracted also is washed and is handed over although the impurity and sulfuric acid for being swapped out and being extracted can be washed by the organic acid dilute liquid answered
Swap-in enters cleaning solution, although the germanium being washed off can re-form organic germanium complex anion, due in cleaning solution containing there are two types of with
On organic complexing agent, the complex reaction of germanium can all generate, and generate competitive extraction, reduce extraction yield.It is stripped simultaneously in alkali
There is also the organic complexing agents of two kinds of germanium in filtered fluid after hydrolytic precipitation germanium, when so that subsequent handling recycling organic acid, product
It is impure, use can not be returned, can not also be sold, so that the recycling of organic complexing agent is not worth.
Summary of the invention
The present invention exists for the method for overcoming N235 kerosene extraction agent extraction and recovery germanium from Acidic Liquid to produce germanium concentrate
The problem that alkali consumption is big, energy consumption is big, while realizing the organic complexing agent recycling and reusing of germanium proposes a kind of N235 and extracts
The method for taking agent production germanium concentrate.
It is realized especially by following technical scheme:
A method of germanium concentrate being produced with N235 extractant, includes the following steps: that germanium 1) is added into germanic Acidic Liquid
Organic acid complexing agent, and N235 kerosene extraction agent extracts organic acid germanium complex, obtains negative containing organic acid germanium complex
Carry organic phase；Then it with organic acid dilute liquid washing, purifying corresponding with the organic acid germanium complex load organic phases, obtains
The load organic phases of the germanium complex containing organic acid of purification；2) with the load organic phases of sodium hydroxide back extraction purification, it is anti-to obtain alkali
Extraction liquid is recycled for multiple times, and reaches 20g/L or more until wherein germanic；3) after alkali strip liquor hydrolytic precipitation high-grade germanium concentrate,
Hydrolytic precipitation filtered fluid is handled with calcium hydroxide or calcium oxide causticization, obtains calcium of organic acid precipitating and sodium hydroxide regenerated liquid；4)
With sulfuric acid leaching calcium of organic acid, the organic acid complexing agent of Ti recovery, which returns, to be used.
Further, include the following steps:
(1) organic complexing agent is added into germanic Acidic Liquid, makes the mass ratio (3-5) of organic complexing agent and germanium: 1, so
Germanium extraction is carried out with the agent of N235 kerosene extraction afterwards, extraction series is 3-5 grades, obtains the load organic phases of the germanium containing organic complex；
(2) the organic acid dilute liquid corresponding with organic germanium complex for being 0.1-5% with mass fraction is to containing organic network
The load organic phases for closing germanium carry out 2-3 grades of washings, exchange the impurity and sulfuric acid being extracted, and obtain purification load organic phases；
(3) sodium hydroxide solution for being 20-30% with mass fraction carries out 3-4 grades of back extraction to purification load organic phases, obtains
It obtains after the germanic strip liquor of level-one supplements sodium hydroxide by 3-4% and comes back for being stripped again, be recycled until level-one strip liquor contains
Germanium reaches 20g/L or more；
(4) the alkali strip liquor of germanic 20g/L or more is neutralized with sulfuric acid to pH=9-11 and is hydrolyzed, obtained and contain hydroxide
The hydrolytic precipitation object of germanium and hydrolytic precipitation filtered fluid containing organic acid sodium salt and sodium sulphate；
(5) it after hydrolytic precipitation object is washed 1-2 times with the hot water that temperature is 60-80 DEG C, is calcined under the conditions of 200-300 DEG C de-
Water obtains the germanium dioxide concentrate of germanic grade 30-50%；Cleaning solution returns to washing and uses or merge with hydrolytic precipitation filtered fluid；
(6) by hydrolytic precipitation filtered fluid and cleaning solution calcium hydroxide or calcium oxide in 80-90 DEG C, calcium ion/(organic acid
+ sulfate ion) causticizing reaction 5-6h is carried out under=(1.1-1.5)/1 molar ratio, it obtains and contains Ca-deposit and hydroxide
Sodium regenerated liquid；
(7) sulfuric acid leaching containing Ca-deposit obtains sulphuric leachate and calcium sulfate precipitation slag containing organic acid, organic acid
Leachate condensing crystallizing recycling organic acid complexing agent is directly returned as the use of germanium complexing agent.
The organic complexing agent is catechol, tartaric acid, citric acid, any in humic acid；It is preferred that tartaric acid.
The working principle of the invention:
N235 kerosene extraction agent is weakly-basic anion extractant, extracts sulfuric acid first in sulfuric acid solution and forms [R3NH+]
HSO4 -Ionic associate, then (ionic charge density=ionic charge/ion is swapped with the lower complex anion of charge density
The atomicity of group).Germanium is very low with the charge density for organic complex anion that organic complexing agent forms germanium, such as tartaric acid germanium yin
Ion is Ge (C4O6H4)2-, with [R3NH]+Hardness more match, and easily extracted by N235, while being swapped out HSO4 -,
Extract 2 [R of reaction equation3NH]+HSO4 -+H2 +Ge(C4O6H4)2-→[R3NH]2 +Ge(C4O6H4)2-+2H2SO4.And germanium is in acidleach
Content is low in liquid, so the only [R of part3NH]+HSO4 -Abjection sulfuric acid, remaining N235 are exchanged with tartaric acid germanium anionic reactive
Still contain a large amount of sulfuric acid.
The agent of N235 kerosene extraction can also be with AsO2 3-、AsO4 3-、SbO2 3-Be extracted etc. associated matter is formed, using with it is molten
In liquid the corresponding organic acid dilute liquid of the complex anion of germanium makees the cleaning solution of load organic phases, and washable be swapped out is extracted
AsO2 3-、AsO4 3-、SbO2 3-Equal impurity and HSO4 -, purify load organic phases.
The present invention makees cleaning solution using organic acid corresponding with germanium is extracted, and has both reached purification purpose and has in turn avoided extracting
The organic germanium loss taken.Also, the organic acid used is weak acid, acidity substantially reduces after load organic phases purification, and then reduces
Alkali consumption when alkali back extraction can repeatedly return to recycling, thus the germanium in strip liquor after alkali strip liquor supplement sodium hydroxide
Content increases, and is conducive to the hydrolysis of germanium and improves the germanium grade of hydrolysate.In conjunction with calcine technology, so that hydrolytic precipitation is carried secretly
Organic matter burn-up, further increase the grade of germanium.
The present invention is easy to Precipitation using organic calcium salt and is easy to by the reaction mechanism of sulfuric acid leaching, using calcium hydroxide
Or calcium oxide carries out causticizing reaction to the organic acid sodium in hydrolytic precipitation filtrate, obtains organic acid calcium salt and regeneration sodium hydroxide.
Organic acid calcium salt sulfuric acid leaching obtains organic acid and calcium sulfate precipitation again and the organic complexing agent of Ti recovery is returned and is used.
The utility model has the advantages that
The present invention had not only ensured the organic extraction rate of germanium, but also greatly reduced the consumption of sodium hydroxide, improved germanium essence
Mine grade, also regeneration have recycled the organic complexing agent of sodium hydroxide and germanium, while reducing slag and effluent environmental improvement cost, have
There are good economic benefit and environmental benefit；Specifically: 1) the organic acid dilute liquid used in washing process and complex reaction institute
Kinds of organic acids is consistent, has not only purified the organic phase of load germanium, but also ensure that the extraction yield of germanium does not reduce；2) increase
The recycling number of alkali strip liquor while the consumption of lower sodium hydroxide so that improve containing for germanium in alkali strip liquor
Amount is conducive to improve Ge content in sodium germanate hydrolytic precipitation object, can get high-grade germanium concentrate；3) organic complex of germanium has been recycled
Agent and sodium hydroxide, which return, to be used, and is reduced the usage amount and sodium hydroxide concentration of complexing agent, is conducive to the water from alkali strip liquor
Solution precipitating high-grade germanium concentrate and from hydrolytic precipitation filtered fluid causticization Ti recovery organic acid complexing agent and regeneration sodium hydroxide,
Reduce slag and effluent environmental improvement cost, with good economic efficiency and environmental benefit.
The present invention is in the organic phase washing of load germanium using organic acid dilute liquid corresponding with the complexing organic acid of germanium
Technical matters and from after germanic alkali strip liquor hydrolytic precipitation in liquid recycle organic acid technical matters, not only reduce alkali
Consumption, has recycled organic acid and sodium hydroxide, has also improved the grade of hydrolytic precipitation germanium concentrate, greatly reduce and produce germanium concentrate
Cost.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited to these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Embodiment 1
Germanic 0.85g/L is taken, tartaric acid is added as germanium by tartaric acid/germanium=5 in the zinc sulfate pickle liquor of zinc 125g/L
Organic complexing agent, with 20% N235,80% kerosene carries out 3 grades of extractions as organic germanium extractant, obtains level-one containing organic
The load organic phases of germanium；Then it is carried out two-stage containing 0.5% tartaric acid dilution with pH=1.5 and washed, obtain first class purification
Load organic germanium organic phase and germanic 5.3mg/L, the tartaric acid cleaning solution of pH=0.8；Then by the load of first class purification
The organic phase of organic germanium carries out three-level back extraction, the hydrogen of the level-one alkali strip liquor supplement 3% of acquisition with 30% sodium hydroxide solution
It returns and is recycled after sodium oxide molybdena, after 8 times are recycled, the germanic 16.3g/L of level-one alkali strip liquor；Then neutralize with sulfuric acid to
PH=10 carries out the hydrolytic precipitation of germanium, hydrolytic precipitation object germanic 13.8% is obtained, after hot water washing, by the hydroxide germanium 200
DEG C calcining, obtain germanium concentrate grade 31.2%, hydrolytic precipitation filtered fluid with calcium oxide powder by calcium/(tartaric acid+sulfate radical)=
1.3, causticization processing in 5 hours is carried out at 80 DEG C, filtered fluid is 230mg/L containing tartrate anion, and sulfate radical is micro, sodium hydroxide 52g/
L；Filtering calcium slag is leached with the concentrated sulfuric acid, obtains the germanic 1250mg/L of leachate, 10.2g/L containing tartaric acid.
Embodiment 2
Germanic 2.28g/L is taken, adjacent benzene two is added by catechol/germanium=3 in the solution of zinc sulfate of zinc 104g/L, pH=2.5
For phenol as germanium complexing agent, then with 30% N235,70% kerosene carries out three-level extraction, level-one load as organic extractant
Organic phase carries out two-stage with 1% catechol dilution and washs, and cleaning solution is germanic micro；First class purification load organic phases are with 25%
Sodium hydroxide solution carries out three-level back extraction, and the sodium hydroxide of level-one strip liquor supplement 4%, which returns, to be used, and alkali strip liquor is recycled
After 12 times, then the germanic 23.7g/L of level-one strip liquor carries out neutralizing hydrolysis and precipitates hydroxide germanium, precipitates pH=9, the water of acquisition
It is calcined 1.5 hours after solving the washing of sediment hot water at 300 DEG C, obtains germanium concentrate grade germanic 42.37%；Hydrolytic precipitation filtered fluid
Causticization is carried out at 90 DEG C with calcium hydroxide to handle 6 hours, obtains liquid 93.5g/L containing sodium hydroxide after causticization, and causticization slag is with 30%
Sulfuric acid dissolution leaches, and leachate is 15.6g/L containing catechol.
Embodiment 3
The organic phase of the load tartaric acid germanium of example 1 is used into clear water respectively, 5% ammonium hydrogen carbonate weak solution carries out second level and washes
It washs, it is respectively 530mg/L, 895mg/L that liquid is germanic after the washing of acquisition.Purify back loading organic phase 30-40% sodium hydroxide
Three-level back extraction is carried out, returns and is recycled 5 times after the sodium hydroxide of level-one strip liquor supplement 3%, strip liquor thickens, and has big
The sulfate crystal of amount carries out back extraction difficult.Chemically examine the germanic 7.3g/L of level-one strip liquor, hydrolytic precipitation hydroxide germanium hot water wash
It is calcined after washing at 300 DEG C, obtains germanium concentrate grade 10.5%.
Embodiment 4
The Resource regeneration for extracting production germanium concentrate to embodiment 1,2,3 carries out tracking statistics, with having for every 1 kilogram of germanium of production
Machine complexing agent and sodium hydroxide consumption are made comparisons；The net dosage of organic complexing agent=complexing germanium dosage+washing dosage-yield
(80% rate of recovery), the first dosage+supplemental amount-yield (50% rate of recovery) of the net dosage=strip liquor of sodium hydroxide；
Embodiment 1: 5 kg/kg germanium of the net dosage=complexing of tartaric acid complexing agent+12 kg/kg germanium of washing-have
Imitate 15.3 kg/kg germanium of yield=3.4 kg/kg germanium.The net dosage of sodium hydroxide=(300 kilograms/m3Initial content+
240 kilograms/m3- 270 kilograms of supplemental amount/m3Yield) 14.6 kilograms of germanium/m of ÷3It (is recycled by 8 returns of strip liquor, instead
Extract germanic 16.3g/L=16.3 kilograms/m of liquid3, the calculating of hydrolytic precipitation 90%) and=18-19 kg/kg germanium
Embodiment 2: 3 kg/kg germanium of the net dosage of catechol complexing agent=complexing dosage+13.5 kilograms of washing dosage/
Kilogram germanium-effectively 13.2 kg/kg germanium of yield=3.3 kg/kg germanium.The net dosage of sodium hydroxide=(250 kilograms/m3+
480 kilograms/m3- 360 kilograms/m3) 21.33 kilograms of germanium/m of ÷3=17-18 kg/kg germanium
Embodiment 3: the net dosage=complexing of tartaric acid complexing agent 5 kg/kg germanium -2.5 kg/kg germanium of yield
(due to containing a large amount of sodium sulphate, recycling tartaric acid is up to 50%)=2.5 kg/kg germanium.The net dosage of sodium hydroxide=
(300 kilograms/m3+ 150 kilograms/m3- 225 kilograms/m3) 7.3 kilograms of germanium/m of ÷3=34-35 kg/kg germanium.
Embodiment 5
The calculating economic indicator evaluation that example 1,2,3 is carried out with the data of embodiment 4, by current market for industrial goods price,
20 yuan/kilogram of tartaric acid, 40 yuan/kilogram of catechol, 4 yuan/kilogram of sodium hydroxide calculate, then:
Embodiment 1: tartaric acid pure cost is 68 yuan/kilogram germanium, and it is 72 yuan/kilogram germanium that alkali consumes cost only, 140 yuan total/
Kilogram germanium；
Embodiment 2: catechol pure cost is 132 yuan/kilogram germanium, and alkali cost is 68 yuan/kilogram germanium, adds up to 200 yuan/public affairs
Jin germanium；
Embodiment 3: tartaric acid pure cost is 50 yuan/kilogram germanium, and alkali cost is 140 yuan/kilogram germanium, adds up to 190 yuan/kilogram
Germanium.And the every increase by 10% of gained germanium concentrate quality, price raising 150-200 member/kilogram；
Therefore embodiment 1 and embodiment 2 compared to the increased economic benefit of embodiment 3 be respectively 300-400 member/kilogram
Germanium, 450-600 member/kilogram germanium；The consuming cost of complexing agent and alkali is subtracted, then embodiment 1 and embodiment 2 have a net increase of compared with embodiment 3
Adding economic benefit is respectively 160-260 member/kilogram germanium, 250-400 member/kilogram germanium.
Claims (9)
1. a kind of method with N235 extractant production germanium concentrate, which comprises the steps of: 1) to germanic Acidic Liquid
The middle organic acid complexing agent that germanium is added, and N235 kerosene extraction agent extracts organic acid germanium complex, obtains and contains organic acid germanium network
Close the load organic phases of object；Then with organic acid dilute liquid washing, purifying corresponding with organic acid germanium complex, the load is organic
Phase obtains the load organic phases of the germanium complex containing organic acid of purification；2) it with the load organic phases of sodium hydroxide back extraction purification, obtains
It obtains alkali strip liquor to be recycled for multiple times, reaches 20g/L or more until wherein germanic；3) alkali strip liquor hydrolytic precipitation high-grade germanium essence
After mine, hydrolytic precipitation filtered fluid is handled with calcium hydroxide or calcium oxide causticization, obtains calcium of organic acid precipitating and sodium hydroxide regeneration
Liquid；4) sulfuric acid leaching calcium of organic acid is used, the organic acid complexing agent of Ti recovery, which returns, to be used.
2. a kind of method with N235 extractant production germanium concentrate as described in claim 1, which is characterized in that including following step
It is rapid:
(1) after adding organic complexing agent mixing into germanic Acidic Liquid, the agent of N235 kerosene extraction is added and carries out germanium extraction, is contained
The load organic phases of organic germanium complex；
(2) it is washed using organic acid weak solution, purification and impurity removal, obtains purification load organic phases；
(3) load organic phases are purified using sodium hydroxide solution back extraction, obtain alkali strip liquor and repeatedly returns to recycling and is anti-to alkali
Until Ge content reaches 20g/L or more in extraction liquid；
(4) the alkali strip liquor of germanic 20g/L or more is hydrolyzed, obtains hydrolytic precipitation object and hydrolytic precipitation filtered fluid；Hydrolysis
It after sediment is washed with hot water, is placed under 200-300 DEG C of environment and calcines, obtain high-grade germanium concentrate；
(5) causticization processing is carried out to hydrolytic precipitation filtered fluid using calcium hydroxide or calcium oxide, obtains and contains Ca-deposit and hydrogen-oxygen
Change the return of sodium regenerated liquid and is used with alkali using or for waste water neutralizer；
(6) it is leached containing Ca-deposit with sulfuric acid dissolution, obtains organic acid leaching liquor and calcium sulfate slag；Organic acid leaching liquor concentration knot
Crystalline substance recycling organic acid complexing agent is directly returned as the use of germanium complexing agent.
3. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that the organic complex
Agent is catechol, tartaric acid, citric acid, any in humic acid.
4. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that organic complexing agent is used
Amount be that the mass ratio of organic complexing agent and germanium is (3-5): 1.
5. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that the organic acid is dilute
Solution is organic acid dilute liquid corresponding with organic germanium complex.
6. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that the organic acid is dilute
The mass percentage concentration of solution is 0.1-5%.
7. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that the high-quality germanium
Concentrate is the germanium dioxide concentrate that germanic mass percent is 30-50%.
8. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that the causticizing reaction
Process conditions are as follows: 80-90 DEG C of temperature, time 5-6h.
9. a kind of method with N235 extractant production germanium concentrate as claimed in claim 2, which is characterized in that the calcium hydroxide
Or the dosage of calcium oxide is calcium ion: (organic acid ion+sulfate ion)=(1.1-1.5): 1.
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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 |
| CN112410584A (en) * | 2020-11-10 | 2021-02-26 | 广东先导稀材股份有限公司 | Method for recovering germanium from zinc leaching residues |
| CN112695212A (en) * | 2020-12-10 | 2021-04-23 | 衢州华友钴新材料有限公司 | Method for separating germanium from high-iron high-arsenic sulfate solution through ternary co-extraction |
| CN114921665A (en) * | 2022-06-01 | 2022-08-19 | 朝阳金美镓业有限公司 | Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method |
| CN115505762A (en) * | 2022-09-22 | 2022-12-23 | 湖南锐异资环科技有限公司 | Indium extraction method of indium-containing multi-metal smelting slag |
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