CN100340682C - Germanium recovering method - Google Patents
Germanium recovering method Download PDFInfo
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- CN100340682C CN100340682C CNB031583164A CN03158316A CN100340682C CN 100340682 C CN100340682 C CN 100340682C CN B031583164 A CNB031583164 A CN B031583164A CN 03158316 A CN03158316 A CN 03158316A CN 100340682 C CN100340682 C CN 100340682C
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- germanium
- low
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- added
- anthracite
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000428 dust Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002023 wood Substances 0.000 claims abstract description 12
- 239000000571 coke Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 8
- 239000004571 lime Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 31
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 20
- 239000003830 anthracite Substances 0.000 claims description 20
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 239000003500 flue dust Substances 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000003245 coal Substances 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract 3
- 238000007605 air drying Methods 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000013307 optical fiber Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Abstract
The present invention discloses a germanium recovering method which belongs to the technical field of metallurgy. The germanium recovering method is characterized in that firstly, low-grade germanium materials with subacidity are neutralized and transformed, white coal powder, lime milk, wood dust and water are added to the lower-grade germanium materials with subacidity during transformation, the PH is adjusted to 8 to 9, and bulk materials are made after drying or air drying once more; the bulk materials are put into a baker, coke and white coal blocks are added to the baker to calcine, and a compound of germanium become smoke dust containing germanium by temperature decrease in a flue after the compound of germanium is volatilized and reduced; the smoke dust containing germanium enters a dust collector then, and the dust collected by the dust collector is the needed compound with high germanium content. Germanium can be recovered from low-grade germanium materials with subacidity by using the germanium revering method, the germanium content of the low-grade germanium materials is less than 0.5%, and the content of germanium in collected smoke dust can be increased to 15 to 20%.
Description
Technical field
The present invention relates to a kind of recovery method of germanium, belong to metallurgical technology field.
Background technology
At present, can produce a kind of germanic in the fiber optic cables course of processing, the corner abrasive material of silicon etc., be called optical fiber germanium material, its germanic amount is generally 5%～10%, because germanium is more valuable, so having to recycle, the germanium in the optical fiber germanium material is worth, utilize optical fiber germanium material to reclaim the method for germanium in the prior art, what it adopted is that wet process acid leaches, traditional processing technology with tannin sinking germanium adsorbs again, earlier optical fiber germanium material is soaked with hydrofluoric acid and sulfuric acid during production, heat, soaked 2～4 hours to 85～95 ℃, after being cooled to 40 ℃ again, filter out impurity, get the tannic acid absorption after with the boiling water dissolving of solution after the filtration and reclaim germanium, the throw out in the solution can be obtained the higher throw out of germanic amount more after filtration, this method can make the content of germanium improve 3～4 times, because optical fiber germanium material mostly is commodity position germanium oxide greatly, of high grade because of raw material, more easily obtain germanium with the wet process acid leaching; But it is thorough inadequately that this method reclaims germanium because contain material such as silica gel in the raw material, part be wrapped in wherein germanium can't with acid-respons, make it can not be dissolved in the acid, so it is thorough inadequately to reclaim germanium with this method, in the remaining residue after the recovery, the content of germanium is still 0.15%～0.4%; On the other hand, for the low raw material of grade, its germanic amount adopts prior art to be difficult to reclaim below 0.5%, and its productive rate is low, has high input, and is profitless.
Adopt wet process acid to leach the germanic throw out that reclaims, its germanic amount can be to more than 20%, can further purify with the hydrochloric acid distillation method, this mixture is dropped into hydrochloric acid, distillation in the time of 110 ℃, can obtain purity at the germanium more than 70%, the compound of part germanium residues in the residue because of being insoluble to hydrochloric acid.
Residue after above-mentioned two kinds of methods reclaim is called low-grade slightly acidic germanium material, and its germanic amount is lower than 0.5%; Because the compound of germanium is insoluble to acid, can't from low-grade slightly acidic germanium material, obtain germanium, can't reclaim with prior art, so can only abandon reclaiming; This can cause the available stock waste.
Summary of the invention
The purpose of this invention is to provide a kind of method that reclaims germanium, utilize this technical scheme from low-grade slightly acidic germanium material, to reclaim germanium.
Raw materials for production of the present invention comprise low-grade slightly acidic germanium material, anthracite powder, anthracite piece, lime white, wood chip, coke and water, for realizing purpose of the present invention, can produce according to the following steps:
(1) neutralization of low-grade slightly acidic germanium material transforms:
With weight proportion be: low-grade slightly acidic germanium material: anthracite powder: the raw materials for production of wood chip=100: 50: 20, in stirrer, stir, add low-grade slightly acidic germanium material and proper amount of clear water furnishing pasty state during stirring earlier, add lime white again and transfer PH=8～9; Progressively add wood chip and anthracite powder again, and stir; With mixed drying materials or air-dry, make block raw material;
(2) baking operation:
Block raw material is added stoving oven carry out roasting, when reinforced, furnace temperature remains on 400～500 ℃, the charge weight proportioning is: block raw material: the anthracite piece: coke=100: 50: 100, drop into anthracite piece and coke earlier and make the fire in a stove before fuel is added, after treating that the fire in a stove before fuel is added is firing, block raw material is covered on the fire in a stove before fuel is added, seal fire door, open the gas blower roasting, enable the collection of flue dust collecting device simultaneously and contain germanium oxide dust, furnace temperature heats up and keeps 1100～1200 ℃ during roasting, until perfect combustion, gets final product blowing out, when treating that furnace temperature is reduced to 400～500 ℃, slag tap.
In and in the conversion process, the consumption of lime white can change because of the variation of the acid content of low-grade slightly acidic germanium material, mixes the anthracite powder and is for can roasting more abundant, mixes wood chip and is in order to make block raw material short texture when the roasting, is beneficial to the germanium volatilization; At high temperature, oxide compound, the muriate of germanium in the low-grade slightly acidic germanium material, and the compound of the germanium in the parcel silica gel volatilizees more than 75% and be reduced into germanium by CO after, become flue gas, and collected by the flue dust collecting device, collect flue dust and can adopt some cloth bags to gather dust, the temperature of gathering dust is controlled at 90～130 ℃, with whole flue dust collectings, ge content can reach 15%～20% in the collected flue dust, and the present invention can be effectively reclaims germanium from germanic amount is lower than 0.5% raw materials for production; Aid in distillation method of the prior art, can further obtain more highly purified germanium.
To carry out in advance baker during for the black furnace roasting earlier 3～5 days, and make furnace temperature rise to 1100～1200 ℃, after being cooled to 400～500 ℃, carry out baking operation again by normal temperature is slow.Its purpose is to make stoving oven to be heated evenly, to prevent the burner hearth cracking; For hot stove, can be directly the back of slagging tap drop into raw material not between section produce.
Embodiment
Embodiment one:
Production unit is one of 500 liters of mortar mixer, one of stoving oven, be connected with some cloth bags on the smoke-uptake of stoving oven, other raw material of getting 500 kilograms in low-grade slightly acidic germanium material about PH=2 and meeting producting proportion reclaims production, and its production stage is as follows:
One, hang down in the acid sludge and conversion operation
(1) according to the weight batching ratio, get low-grade slightly acidic germanium material: the anthracite powder: the raw material of wood chip=100: 50: 20, in 500 liters mortar mixer, add low-grade slightly acidic germanium material and proper amount of clear water earlier and stir into pasty state, add a certain amount of lime white again, transfer PH=8～9;
(2) stir after, progressively add wood chip and coal dust again;
(3) stirring stopped after half an hour;
(4) mix material after the neutralization, higher, about 50～60% because of water content, need spread oven dry out, make the cake piece raw material about thick 80mm, treat that moisture content does to about 10%, can throw stove and carry out baking operation;
Two, baking operation
(1) baker
Baker in advance before stoving oven comes into operation when black furnace, the baker operation is incremental to high temperature by low temperature; Use the firewood baker; Firewood is dispersed evenly in the burner hearth, prevents to concentrate a pile to cause the temperature inequality, cause local cracks, the baker operation amounts to needs 3～5 day time, makes furnace temperature rise to 1100～1200 ℃ by normal temperature is slow, is incubated and finishes baker after 10 hours, then the operation of feeding in raw material is again cleaned out on the stove side;
(2) reinforced operation
Before reinforced, furnace temperature remains on 500 ℃, ignites earlier, drops into anthracite piece and coke again as the fire in a stove before fuel is added; Its proportioning is: raw material: the anthracite piece: coke=100: 50: 100; After treating that the fire in a stove before fuel is added is firing, the germanic cake piece piece material that makes is covered on the fire in a stove before fuel is added, seal fire door, open the gas blower roasting, enable whole cloth bags simultaneously and collect flue dust;
(3) warming temperature
The initial period of temperature-rise period is the evaporation stage of furnace charge moisture content, the furnace temperature in this stage is through slowly being warming up to more than 950 ℃ by 500 ℃ about one hour, along with self burning of the fire in a stove before fuel is added and cake piece raw material, the compound of germanium is become germanium by the CO gas reduction and volatilizees, furnace temperature is risen to 1100～1200 ℃ again, the germanium that is contained in the silica gel is reduced and volatilization gradually with the furnace temperature rising, forms flue dust with the temperature reduction in calcining kiln flue, and flue dust enters cloth bag in the time of 90 ℃; Keep furnace temperature between 1100～1200 ℃, until fire in a stove before fuel is added burning fully, furnace temperature descends, the flame deepening gets final product blowing out, and whole baking operation needs 4 hours approximately, promptly contain a large amount of germanium in the collected flue dust of flue dust collecting device, also contain other metal oxide of part and impurity simultaneously;
(4) slag tap
When furnace temperature was reduced to 400 ℃, blowing out was slagged tap.
Embodiment two:
Production unit is one of 500 liters of mortar mixer, one of stoving oven, and water distilling apparatus one cover is connected with some cloth bags that gather dust on the smoke-uptake of stoving oven, low-grade slightly acidic germanium material raw material is divided into about 500 kilograms some parts, by following production stage production:
One, in the low-grade acid germanium slag charge and conversion operation
(1) according to the weight batching ratio, with low-grade slightly acidic germanium material: the anthracite powder: the raw material of wood chip=100: 50: 20, in 500 liters mortar mixer, add low-grade slightly acidic germanium material and proper amount of clear water earlier and stir into pasty state, add a certain amount of lime white again, transfer PH=8～9 to get final product;
(2) stir after, progressively add wood chip and anthracite powder again;
(3) stirring stopped after half an hour;
(4) will mix material after the neutralization, pour out, and spread out and dry, make the block raw material about diameter 800mm, treat that moisture content does to about 10%, and can throw stove and carry out baking operation;
Two, baking operation
(1) baker uses stoving oven to carry out roasting, carries out in advance baker before the roasting earlier 5 days, with carbon fire baker, incremental by low temperature to high temperature, make furnace temperature rise to 1100～1200 ℃ by normal temperature is slow, be incubated 10 hours, after baker finishes, the operation of feeding in raw material is again cleaned out on the stove side;
(2) reinforced operation
Before reinforced, make furnace temperature reduce to 400 ℃ naturally, ignite again and drop into the anthracite piece and the coke fire in a stove before fuel is added; Its weight proportion is: block raw material: the anthracite powder: coke=100: 50: 100; After treating that fire in a stove before fuel is added coal is firing, the germanic block raw material that makes is covered on the fire in a stove before fuel is added, seal fire door, open the gas blower roasting, enable whole cloth bags simultaneously and collect flue dust;
(3) warming temperature
The initial period of temperature-rise period is the evaporation stage of furnace charge moisture content, the furnace temperature in this stage is through slowly being warming up to more than 950 ℃ by 500 ℃ about one hour, the compound of germanium is become germanium by the CO gas reduction and volatilizees, furnace temperature is risen between 1100～1200 ℃ again, the germanium that is contained in the silica gel is reduced and volatilization gradually with the furnace temperature rising, all germanium that evaporate form flue dust with the temperature reduction in the flue of stoving oven, flue dust enters cloth bag in the time of 130 ℃; Keep furnace temperature between 1100～1200 ℃, complete until carbon burning, furnace temperature descends, the flame deepening, get final product blowing out, whole baking operation needs 4 hours approximately, promptly contains a large amount of germanium in the collected flue dust of flue dust collecting device, also contain other metal oxide of part and impurity simultaneously, wherein ge content is about 15%;
(4) slag tap
When furnace temperature is reduced to 500 ℃, slag tap, and drop into the fire in a stove before fuel is added again by above-mentioned steps immediately and raw material is produced again.
Three, the purification of germanium
With hydrochloric acid distillating method of the prior art flue dust is purified, pour flue dust collected in the cloth bag into hydrochloric acid, distill, distillation temperature is 110 ℃, can obtain purity at the germanium more than 70% after distillation.
Claims (2)
1, a kind of method that reclaims germanium is characterized in that: raw materials for production comprise low-grade slightly acidic germanium material, anthracite powder, anthracite piece, lime white, wood chip, coke and water, and its production method may further comprise the steps:
(1) neutralization of low-grade slightly acidic germanium material transforms:
With weight proportion be: low-grade slightly acidic germanium material: anthracite powder: the raw materials for production of wood chip=100: 50: 20, in stirrer, stir, add low-grade slightly acidic germanium material and proper amount of clear water furnishing pasty state during stirring earlier, add lime white again and transfer PH=8～9; Progressively add wood chip and anthracite powder again, and stir; With mixed drying materials or air-dry, make block raw material;
(2) baking operation:
Block raw material is added stoving oven carry out roasting, when reinforced, furnace temperature remains on 400～500 ℃, the charge weight proportioning is: block raw material: the anthracite piece: coke=100: 50: 100, drop into anthracite piece and coke earlier and make the fire in a stove before fuel is added, after treating that the fire in a stove before fuel is added is firing, block raw material is covered on the fire in a stove before fuel is added, seal fire door, open the gas blower roasting, enable the collection of flue dust collecting device simultaneously and contain germanium oxide dust, furnace temperature heats up and keeps 1100～1200 ℃ during roasting, until perfect combustion, gets final product blowing out, when treating that furnace temperature is reduced to 400～500 ℃, slag tap.
2, a kind of method that reclaims germanium according to claim 1 is characterized in that: carried out in advance baker during roasting earlier 3～5 days, and made furnace temperature rise to 1100～1200 ℃ by normal temperature is slow, carry out baking operation again after being cooled to 400～500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031583164A CN100340682C (en) | 2003-09-20 | 2003-09-20 | Germanium recovering method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031583164A CN100340682C (en) | 2003-09-20 | 2003-09-20 | Germanium recovering method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1526840A CN1526840A (en) | 2004-09-08 |
| CN100340682C true CN100340682C (en) | 2007-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB031583164A Expired - Lifetime CN100340682C (en) | 2003-09-20 | 2003-09-20 | Germanium recovering method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476042B (en) * | 2009-01-06 | 2013-07-10 | 扬州宁达贵金属有限公司 | Method for recycling indium and germanium from alkali slag |
| CN103334011B (en) * | 2013-07-22 | 2015-01-21 | 云南临沧鑫圆锗业股份有限公司 | Process for secondary recovery of germanium from germanium refining coal cinder and germanium refining acid sludge |
| CN104805316A (en) * | 2015-05-07 | 2015-07-29 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium by thermally reducing and volatilizing germanium ores |
| CN108504874B (en) * | 2018-05-03 | 2019-10-18 | 广东省稀有金属研究所 | A method of the separating Ge gallium from zinc oxygen pressure wet process replacement slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070430A (en) * | 1992-07-15 | 1993-03-31 | 广州有色金属研究院 | A kind of technology of from germanic coal, extracting germanium |
| CN1101380A (en) * | 1993-12-31 | 1995-04-12 | 云南省临仓地区冶炼厂 | Extraction of germanium from lignite |
| WO2002099145A1 (en) * | 2001-06-07 | 2002-12-12 | Elcogas, S.A. | Method for recovering metals from the flying ashes generated in an integrated gasification combined cycle-type (igcc) thermal station |
-
2003
- 2003-09-20 CN CNB031583164A patent/CN100340682C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070430A (en) * | 1992-07-15 | 1993-03-31 | 广州有色金属研究院 | A kind of technology of from germanic coal, extracting germanium |
| CN1101380A (en) * | 1993-12-31 | 1995-04-12 | 云南省临仓地区冶炼厂 | Extraction of germanium from lignite |
| WO2002099145A1 (en) * | 2001-06-07 | 2002-12-12 | Elcogas, S.A. | Method for recovering metals from the flying ashes generated in an integrated gasification combined cycle-type (igcc) thermal station |
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| CN1526840A (en) | 2004-09-08 |
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