CN106337139A - Method for recovering germanium from germanium-containing material - Google Patents
Method for recovering germanium from germanium-containing material Download PDFInfo
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- CN106337139A CN106337139A CN201610715681.9A CN201610715681A CN106337139A CN 106337139 A CN106337139 A CN 106337139A CN 201610715681 A CN201610715681 A CN 201610715681A CN 106337139 A CN106337139 A CN 106337139A
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- germanium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for recovering germanium from a germanium-containing material. According to the method, a resin adsorption principle is adopted in the germanium separation process so as to thoroughly adsorb germanium into resin and let silicon enter a solvent in the form of sodium silicate. Therefore, germanium is separated thoroughly, recovery rate of germanium reaches about 95%, and the problem that lots of germanium is brought into silica precipitate in the silicon precipitation process of electrolyte produced by the electrolyte separation method of germanium is avoided. After resin adsorption, part of water is evaporated from a sodium silicate solution and then the product can be used as a soluble glass product for sale. Thus, sewage treatment problem is avoided, and production cost is reduced. Defects of a hydrofluoric acid method for processing a germanium-containing material, such as high production cost, severe equipment corrosion and environmental pollution, are eliminated; and the problem of low recovery rate in an alkali dissolution precipitation method is avoided. By the method of the invention, equipment corrosion, environmental pollution and other problems are not caused in the germanium-containing waste material dissolving process.
Description
Technical field
The present invention relates to technical field of wet metallurgy and in particular to a kind of recovery contain germanium waste material in germanium method.
Background technology
Germanium is a kind of dissipated metal, and nature reserves are less, the copper mine in brown coal, Pb-Zn deposits and South Africa for the main association it
In.8600 tons of the explored germanium reserves in the whole world, by the consumption calculating only enough more than 40 years of current germanium；Germanium is a kind of important
Strategic resource, suffer from replacing in high-technology fields such as Aero-Space, fiber optic communication, infrared optics, new energy technologies
The application in generation, with the development of China's new and high technology, the continuous upgrading of the industrial structure, the level of consumption of germanium will keep increasing at a high speed
Long.
The raw materials for production of germanium include two aspects at present, and one is the side-product extraction germanium from Pb-Zn deposits and colliery, such raw material
The technological process of production long, alternately, the response rate is low for pyrogenic process wet method, high cost.Two is to produce from the course of processing of germanium
Containing extracting germanium in germanium waste material, such germanium-containing raw material is that germanium reclaims important regenerated resources, extracts germanium tool from such germanium-containing raw material
There are preferable economic benefit and social meaning, belong to country and support that resource reclaim recycles industry.
When germanium is used for producing optical fiber and glasses for infrared use, produce substantial amounts of germanium-containing material, at silicon and germanium in germanium-containing material
Same main group in the periodic table of chemical element, chemical property is similar with physical property, and the separation of the two is always an industry difficult problem.
Conventional method includes (1) and distills oxidizer direct chlorination after germanium-containing material pulverizing, and this technique can hardly be by raw material
Germanium extracts.(2) germanium-containing material is carried out after oxidizing roasting chlorinated distillation again, the parcel problem due to silicon dioxide makes
The response rate of germanium is relatively low, and secondly silicon dioxide forms silica gel in acid medium and makes filtration difficulty.(3) by germanium-containing material pulverizing
After carry out high temperature alkali dissolution, obtain sodium silicate and germanic acid sodium solution, add electrolyte and adjust ph value and carry out sinking silicon and heavy germanium operation,
Though this technique can be effectively by germanic separation, the heavy silicon time is long, has a large amount of germanium also with silicon coprecipitation, make during heavy silicon
The response rate obtaining germanium is less than 75%, does not make full use of germanium resource.(4) hydrofluoric acid dissolution, tannin are used by after germanium-containing material pulverizing
Heavy germanium, this technique productions high cost is serious to equipment corrosion, because the presence of fluorion is to environment.To sum up several
Conventional treatment germanium-containing material technique, have such problems as that the response rate is low, production cost is high, equipment corrosion, environmental pollution.
Substantial amounts of acid slag is produced, germanic amount is in 0.2%～1% acid slag during the production process chlorinated distillation of germanium
Although germanic taste is high, also contain substantial amounts of chloride and silicon dioxide so that germanium is wrapped in silicate simultaneously, even if
Obtain germanium in these slags under acid condition also will not be dissolved in solution.Each smeltery is all using pyrogenic attack acid slag at present,
But during pyrogenic attack acid slag, the volatilization temperature of germanium is higher than 1100 DEG C, produces a large amount of poison gas, company's environmental protection is produced very big
Pressure, and serious to equipment corrosion, and production cost is high.
Content of the invention
In order to solve above-mentioned technical barrier, improve the direct yield of germanium and reduce production cost, the invention provides a kind of return
Receive the high method containing germanium in germanium waste material.
What the present invention provided reclaims the high method containing germanium in germanium waste material, specifically comprises the following steps that
1) germanic waste material is pulverized and be milled to 80 mesh～300 mesh, be added in sodium hydroxide solution, be heated to 120 DEG C
～250 DEG C of insulation reaction 2～3 hours, are cooled to room temperature, obtain the alkaline solution of sodium silicate and sodium germanate；
2) by step 1) alkaline solution of the sodium silicate that obtains and sodium germanate adds equipped with the tank of resin, obtains containing germanium
The resin of acid ion and the alkaline solution of sodium silicate；
3) the diluted acid resin containing germanic acid radical ion for the addition is carried out the parsing of germanium, obtain germanic acid solution and parsing
Resin afterwards, in case the absorption of germanium next time after resin washes with water, cleaning mixture is incorporated to germanic desorbed solution, germanic to gained
Add iron salt to carry out the enrichment procedure of germanium in acid solution, adjusting its ph value is 7～8, then carries out filter operation, obtain germanium essence
Ore deposit；
4) by step 3) germanium concentrate that obtains carries out chlorinated distillation, and obtain germanium tetrachloride, germanium tetrachloride hydrolysis is obtained two
Germanium oxide.
Step 1) described in include the production process chlorinated distillation of germanium containing germanium waste material during the acid slag that produces and germanium use
The germanium-containing material producing when production optical fiber and glasses for infrared use.
Described sodium hydroxide and described germanium are used for producing the quality of the germanium-containing material producing when optical fiber and glasses for infrared use
It is 3～5:1 than the mass ratio of the acid slag for producing during 1.5～2.5:1, with the production process chlorinated distillation of described germanium.
Step 2) described in resin be alkalescence epoxy type anion exchange resin or styrene series anion exchange resin,
Resin is 2～3:1 with the mass ratio containing germanium in germanium waste material, and including d301 alkalescence epoxy type anion exchange resin, d201 is weak
Alkaline epoxy type anion exchange resin and 201 × 7mb weakly basic styrene type anion exchange resin.
Step 3) described in diluted acid be dilute sulfuric acid or dilute hydrochloric acid, concentration range be 0.5mol/l～1mol/l, described iron salt
For ferrum oxide, the mass ratio of the germanium in ferrum oxide and germanium-containing solution is 1～4:1.
The present invention also provides a kind of preparation method of waterglass: is used for produce optical fiber and infrared containing germanium waste material for germanium when described
The germanium-containing material producing during optical glass, by step 2) obtain sodium silicate alkaline solution heating evaporation remove account for solution gross mass
10%～30% moisture content, can obtain waterglass, when described containing germanium waste material for the production process chlorinated distillation of germanium during produce
In the alkaline solution of produced sodium silicate during acid slag, silicic acid sodium content is too low to for producing waterglass.
The present invention adopt in germanic separation process resin absorption principle by germanium thoroughly absorption in resin silicon then with silicon
Sour sodium enters in solution, so that germanic separation is thoroughly so that the response rate of germanium reaches 95%, it is to avoid electrolyte separates and contains
A large amount of germanium are had to be brought to the problem in the precipitation of silicon dioxide during the heavy silicon of electrolyte that germanium method produces.After resin absorption
Sodium silicate solution can sell as waterglass product after evaporating part water, it is to avoid sewage handling problem, reduce production
Cost.Sodium germanate parses through resin, and trivalent iron salt absorbing process can get the germanium concentrate that mass fraction is 10%～15%.
The production cost that hydrogen fluoride process germanium-containing material generation has been abandoned in this technology invention is high, equipment corrosion is serious, ring
The shortcoming of border pollution, it is to avoid the alkali soluble sedimentation method process the low problem of the response rate producing containing germanium waste material, are dissolving containing germanium waste material
During do not cause the problems such as equipment corrosion, environmental pollution.
Specific embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art can be more preferable
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
Weigh 200kg germanium for producing the germanium-containing material producing when optical fiber and glasses for infrared use, Ge content is 0.6%,
Obtain the germanic silicon dioxide powder of 300 mesh after broken pulverizing, the sodium hydroxide that silicon dioxide powder addition mass concentration is 30%
In solution, sodium hydroxide solution quality is 1000kg；With pump, reactant liquor is extracted in autoclave, is heated to 150 DEG C, insulation
3 hours, obtain the sodium silicate alkaline solution containing sodium germanate；It is 1m that solution is added volume3The d301 equipped with quality for 2.4kg
In the tank of alkalescence epoxy type anion exchange resin, the sodium silicate solution obtaining is evaporated concentrating, evaporates mother solution matter
The water of amount 15%, output water glass product；By excessively above-mentioned for the dilute sulfuric acid 100l for 0.5mol/l for the concentration tank equipped with resin, obtain
Containing germanic solion；3kg ferrum oxide is added to containing in germanic solion, and adds sodium hydroxide to adjust ph
It is worth to 8, stir a hour and filtered, after drying, obtain germanium concentrate 12kg；Germanium concentrate is carried out conventional chlorinating distillation, hydrolysis
Technique obtains high-purity germanium dioxide 1.6kg, and the response rate of germanium is 95%.
Embodiment 2
Weigh 300kg germanium for producing the germanium-containing material producing when optical fiber and glasses for infrared use, Ge content is 0.8%,
Obtain the germanic silicon dioxide powder of 200 mesh after broken pulverizing, the sodium hydroxide solution that silicon dioxide powder addition concentration is 30%
In, sodium hydroxide solution quality is 1200kg；With pump, reactant liquor is extracted in autoclave, is heated to 180 DEG C, insulation 2 is little
When, obtain the sodium silicate alkaline solution containing sodium germanate；By solution through volume be 1m3The d201 equipped with quality for 3.6kg weak
In the tank of alkaline epoxy type anion exchange resin, the sodium silicate solution obtaining is evaporated concentrating, evaporates mother solution quality
25% water, output water glass product；By excessively above-mentioned for the dilute sulfuric acid 100l for 0.5mol/l for the concentration tank equipped with resin, contained
There is germanic solion；3kg ferrum oxide is added to containing in germanic solion, and adds sodium hydroxide to adjust ph value
To 7, stir a hour and filtered, after drying, obtain germanium concentrate 34kg；Germanium concentrate is carried out conventional chlorinating distillation, hydrolysis
Technique obtains high-purity germanium dioxide 3.4kg, and the response rate of germanium is 97%.
Embodiment 3
Weigh 500kg germanium for producing the germanium-containing material producing when optical fiber and glasses for infrared use, Ge content is 0.4%,
Obtain the germanic silicon dioxide powder of 200 mesh after broken pulverizing, the sodium hydroxide solution that silicon dioxide powder addition concentration is 30%
In, sodium hydroxide solution quality is 1400kg；With pump, reactant liquor is extracted in autoclave, is heated to 120 DEG C, insulation 2 is little
When, obtain the sodium silicate alkaline solution containing sodium germanate；By solution through volume be 1m3201 × 7mb equipped with quality for 3kg
In the tank of weakly basic styrene type anion exchange resin, the sodium silicate solution obtaining is evaporated concentrating, evaporates mother solution
The water of quality 30%, output water glass product；By excessively above-mentioned for the dilute sulfuric acid 100l for 0.5mol/l for the concentration tank equipped with resin, obtain
To containing germanic solion；2.5kg ferrum oxide is added to containing in germanic solion, and adds sodium hydroxide to adjust
Section ph value, to 8, stirs two hours and is filtered, obtain germanium concentrate 34kg after drying；By germanium concentrate carry out conventional chlorinating distillation,
Hydrolysis process obtains high-purity germanium dioxide 2.6kg, and the response rate of germanium is 92%.
Embodiment 4
The acid slag producing during weighing the production process chlorinated distillation of 500kg germanium, Ge content is 0.8%, drying
To 80 mesh after broken pulverizing, gained powder addition concentration is in 1% sodium hydroxide solution, sodium hydroxide solution quality is
1200kg；With pump, reactant liquor is extracted in autoclave, is heated to 130 DEG C, be incubated 2.5 hours, obtain the silicon containing sodium germanate
Sour sodium alkaline solution；By solution through volume be 1m3Equipped with 201 × 7mb weakly basic styrene type anion exchange resin's
In tank, the sodium silicate solution obtaining acid adding is carried out acid-base neutralization process；The dilute sulfuric acid 120l for 0.5mol/l for the concentration is gone up excessively
State the tank equipped with resin, obtain containing germanic solion；15kg ferrum oxide is added to containing germanic solion
In, and add sodium hydroxide to adjust ph value to 8, stir two hours and filtered, after drying, obtain germanium concentrate 40kg；By germanium essence
Ore deposit carries out conventional chlorinating distillation, hydrolysis process obtains high-purity germanium dioxide 5.5kg, and the response rate of germanium is 95%.
Embodiment 5
The acid slag producing during weighing the production process chlorinated distillation of 400kg germanium, Ge content is 0.5%, through broken
To 100 mesh after pulverizing, gained powder addition concentration is in 1% sodium hydroxide solution, sodium hydroxide solution quality is
800kg；With pump, reactant liquor is extracted in autoclave, is heated to 140 DEG C, be incubated 3 hours, obtain the sodium silicate containing sodium germanate
Alkaline solution；By solution through volume be 1m3The tank equipped with 201 × 7mb weakly basic styrene type anion exchange resin in,
The sodium silicate solution obtaining acid adding is carried out acid-base neutralization process；By excessively above-mentioned for the dilute sulfuric acid 100l for 0.5mol/l for the concentration equipped with
The tank of resin, obtains containing germanic solion；6kg ferrum oxide is added to containing in germanic solion, and adds
Sodium hydroxide adjusts ph value to 8, stirs two hours and is filtered, obtains germanium concentrate 13kg after drying；Germanium concentrate is carried out often
Rule chlorinated distillation, hydrolysis process obtain high-purity germanium dioxide 2.8kg, and the response rate of germanium is 96%.
Ultimate principle, principal character and the advantages of the present invention of the present invention have been shown and described above.The technology of the industry
, it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and description is originally for personnel
Invention principle, without departing from the spirit and scope of the present invention the present invention also have various changes and modifications, these change
Change and improvement both falls within scope of the claimed invention.
Claims (7)
1. a kind of method reclaiming germanium in germanium-containing material is it is characterised in that specifically comprise the following steps that
1) germanic waste material is pulverized and be milled to 80 mesh～300 mesh, be added in sodium hydroxide solution, be heated to 120 DEG C～250
DEG C insulation reaction 2～3 hours, is cooled to room temperature, obtains the alkaline solution of sodium silicate and sodium germanate；
2) by step 1) alkaline solution of the sodium silicate that obtains and sodium germanate adds equipped with the tank of resin, obtaining containing germanic acid root
The resin of ion and the alkaline solution of sodium silicate；
3) the diluted acid resin containing germanic acid radical ion for the addition is carried out the parsing of germanium, after obtaining germanic acid solution and parsing
Resin, in case the absorption of germanium next time after resin washes with water, cleaning mixture is incorporated to germanic desorbed solution, to the germanic acidity of gained
Iron salt is added to carry out the enrichment procedure of germanium in solution, adjusting its ph value is 7～8, then carries out filter operation, obtains germanium concentrate；
4) by step 3) germanium concentrate that obtains carries out chlorinated distillation, and obtain germanium tetrachloride, germanium tetrachloride hydrolysis is obtained titanium dioxide
Germanium.
2. the method reclaiming germanium in germanium-containing material according to claim 1 is it is characterised in that step 1) described in germanic useless
When the acid slag producing during expecting to include the production process chlorinated distillation of germanium and germanium are used for producing optical fiber and glasses for infrared use
The germanium-containing material producing.
3. according to claim 2 reclaim germanium-containing material in germanium method it is characterised in that described sodium hydroxide with described
The mass ratio that germanium is used for producing the germanium-containing material producing when optical fiber and glasses for infrared use is 1.5～2.5:1, the life with described germanium
The mass ratio of the acid slag producing during producing operation chlorinated distillation is 3～5:1.
4. the method reclaiming germanium in germanium-containing material according to claim 1 is it is characterised in that step 2) described in resin be
Alkalescence epoxy type anion exchange resin or styrene series anion exchange resin, resin and the mass ratio containing germanium in germanium waste material
For 2～3:1.
5. the method reclaiming germanium in germanium-containing material according to claim 4 is it is characterised in that include d301 alkalescence epoxy
Series anion exchange resin, d201 alkalescence epoxy type anion exchange resin and 201 × 7mb alkalescence styrene series anion
Exchanger resin.
6. the method reclaiming germanium in germanium-containing material according to claim 1 is it is characterised in that step 3) described in diluted acid be
Dilute sulfuric acid or dilute hydrochloric acid, concentration range is 0.5mol/l～1mol/l, and described iron salt is ferrum oxide, in ferrum oxide and germanium-containing solution
Germanium mass ratio be 1～4:1.
7. a kind of preparation method of waterglass it is characterised in that include claim 1 step 1) and step 2), wherein said
It is used for producing the germanium-containing material producing when optical fiber and glasses for infrared use, now, step 2 for germanium containing germanium waste material) also obtain silicic acid
The alkaline solution of sodium, the alkaline solution heating evaporation of the sodium silicate obtaining is removed the water accounting for solution gross mass 10%～30%
Part, obtain waterglass.
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| CN201610715681.9A CN106337139A (en) | 2016-08-23 | 2016-08-23 | Method for recovering germanium from germanium-containing material |
| CN201710234873.2A CN107010655B (en) | 2016-08-23 | 2017-04-12 | Method for recovering germanium from germanium-containing material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610715681.9A CN106337139A (en) | 2016-08-23 | 2016-08-23 | Method for recovering germanium from germanium-containing material |
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| CN201710234873.2A Active CN107010655B (en) | 2016-08-23 | 2017-04-12 | Method for recovering germanium from germanium-containing material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111118293A (en) * | 2020-01-14 | 2020-05-08 | 华中科技大学 | Method for recovering germanium from germanium-containing solution and application thereof |
| CN111647760A (en) * | 2020-06-16 | 2020-09-11 | 中南大学 | Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber |
| CN112593083A (en) * | 2020-11-26 | 2021-04-02 | 胡冲丽 | Process for recovering germanium from germanium-containing luminescent glass microcrystalline material |
| CN116555596A (en) * | 2023-03-31 | 2023-08-08 | 云南驰宏国际锗业有限公司 | Method for comprehensively recovering germanium from germanium tetrachloride hydrolysis mother solution and washing water |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115504502B (en) * | 2022-06-17 | 2023-11-03 | 灵宝市民生高新材料有限公司 | Method for recycling and preparing high-purity germanium dioxide from abandoned germanium-containing glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552923A (en) * | 2003-06-03 | 2004-12-08 | 贵州工业大学 | Method for enrichment recovering germanium from acid solution |
| CN102618721A (en) * | 2012-02-24 | 2012-08-01 | 云南五鑫实业有限公司 | Method for extracting germanium, indium and zinc from high iron, silicon and manganese materials containing germanium, indium and zinc |
| CN103388086B (en) * | 2012-05-09 | 2014-12-10 | 深圳市格林美高新技术股份有限公司 | Method for extracting germanium from germanium-containing abandoned element |
| CN104357688B (en) * | 2014-11-19 | 2016-06-22 | 辽宁大学 | The method of Levextrel Resin separating Ge |
-
2016
- 2016-08-23 CN CN201610715681.9A patent/CN106337139A/en active Pending
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2017
- 2017-04-12 CN CN201710234873.2A patent/CN107010655B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111118293A (en) * | 2020-01-14 | 2020-05-08 | 华中科技大学 | Method for recovering germanium from germanium-containing solution and application thereof |
| CN111118293B (en) * | 2020-01-14 | 2021-01-22 | 华中科技大学 | Method for recovering germanium from germanium-containing solution and application thereof |
| CN111647760A (en) * | 2020-06-16 | 2020-09-11 | 中南大学 | Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber |
| CN111647760B (en) * | 2020-06-16 | 2021-03-23 | 中南大学 | Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber |
| CN112593083A (en) * | 2020-11-26 | 2021-04-02 | 胡冲丽 | Process for recovering germanium from germanium-containing luminescent glass microcrystalline material |
| CN116555596A (en) * | 2023-03-31 | 2023-08-08 | 云南驰宏国际锗业有限公司 | Method for comprehensively recovering germanium from germanium tetrachloride hydrolysis mother solution and washing water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107010655A (en) | 2017-08-04 |
| CN107010655B (en) | 2020-06-05 |
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Application publication date: 20170118 |