CN1101380A - Extraction of germanium from lignite - Google Patents
Extraction of germanium from lignite Download PDFInfo
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- CN1101380A CN1101380A CN 93121175 CN93121175A CN1101380A CN 1101380 A CN1101380 A CN 1101380A CN 93121175 CN93121175 CN 93121175 CN 93121175 A CN93121175 A CN 93121175A CN 1101380 A CN1101380 A CN 1101380A
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- germanium
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Abstract
The process for extracting Ge from lignite includes fire and wet steps. The fire step for obtaining Ge concentrate includes sieving, making coal rod or briquette, smelting in chain furnace, and recovering Ge-containing fume. The wet step for extracting Ge includes chloridizing distillation and hydrolysis. The process features low requirement on raw material, high concentrating effect and recovery rate of Ge, low cost and good quality.
Description
The present invention relates to the Metal smelting technology, specifically from brown coal, extract the method for germanium.
At present, the method of extracting germanium from brown coal generally is: the powdery or the block fluidizing furnace high-temp combustion that drops into that adopt raw coal, make the interior temperature of stove remain on 850～950 ℃, under this temperature, germanium metal oxide in the brown coal and germanium metallic sulfide continue volatilization, enrichment.With flue dust and the thin grey mixture of furnace bottom and the lime poach stacking in proportion of enrichment,, it is compressed to nodulizing then, after nodulizing is air-dry, drops into blast furnace smelting according to a certain ratio with coke and Wingdale with nodulizer once fermentation.Again germanium concentrate is carried out wet processes at last.Its deficiency is thermal value and the reductibility that does not make full use of coal itself, need with a large amount of coke, Wingdale, so cost is higher.
The object of the present invention is to provide a kind of brown coal that make by pyrotic smelting, improve accumulation rate, reduce technological process, the method for from brown coal, extracting germanium that reduces cost.
Technical scheme of the present invention is: the smelting process that combines with wet method with pyrogenic process, the process of pyrogenic process is through screening, system coal rod or coal briquette with germanic raw coal, adding chain furnace then smelts, the germanium oxide dust that contains that produces in the stove is reclaimed by whirlwind smoke collector, bagroom and foam deduster, and the gained germanium concentrate extracts germanium through wet method once more.Wet method comprises chlorinated distillation and two processes of hydrolysis.
The grade of raw material is more than 0.1 ‰, and calorific value is the above germanic brown coal of non-powdery of 2800 kcal/kg.Temperature can reach 1100～1300 ℃ in the stove of chain furnace, and under this temperature condition, germanium metal oxide and the metallic sulfide in the brown coal volatilizees rapidly, enrichment.The germanium oxide dust that contains that chain furnace produces is reclaimed by whirlwind smoke collector, bagroom and foam deduster.Germanium concentrate after the recovery extracts germanium through wet processing again.
The present invention has following characteristics: 1) less demanding to raw material grade and calorific value; 2) furnace temperature height makes the volatilization of germanium, concentration effect better, and the bag dust grade can reach 2～5%, and concentration ratio can reach 80～100 times, and the germanium metal recovery rate can reach 60～65%, adds foam collection, makes that the germanium recovery system is more perfect, and the rate of recovery is improved naturally; 3) the compacting nodulizing has been saved in bag dust direct sending wet method operation processing, and the human and material resources that pyrogenic process processing is required have reduced production cost of products, and product impurity is few, and quality is good.4) be applicable to modern large-scale commercial production.
Fig. 1 is a process flow sheet of the present invention
Embodiment 1, with grade is 0.1 ‰, calorific value is 100 tons in the germanic brown coal of the non-powdery of 2800 kcal/kg, through sieving, make coal rod or coal briquette, adding chain furnace then smelts, temperature is 1100 ℃ in the stove, the smelting through 0.5 o'clock, and the germanium oxide dust that contains that produces in the stove is reclaimed by whirlwind smoke collector, bagroom and foam deduster.The germanium concentrate that gets that is reclaimed is carried out the wet method refinement, and carry out in two steps: 1) chlorinated distillation, compound concentration are 8.5～9.5 equivalents, 5～8 times to the hydrochloric acid of germanium concentrate weight, earlier 1/3rd of hydrochloric acid is injected reactor, drop into germanium concentrate then, all the other hydrochloric acid are injected mix thoroughly again.Add weight and be 8～15% Manganse Dioxide of germanium concentrate weight, feeding pressure is the steam of 20000～50000 handkerchiefs, and when kettle temperature reached more than 83 ℃, germanium was steamed with the form of germanium tetrachloride.The steam state germanium tetrachloride gets liquid four germanium oxides through condensation.2) hydrolysis is hydrolyzed germanium tetrachloride and the water volume ratio by 1: 6.5, stirs, stir finish after, with its standing separation two hours, through diafiltration, dry thick germanium dioxide product, its grade 〉=65%.Sulfur-bearing and water＜1% wherein, arsenic＜0.8%, wet method germanium metal recovery rate can reach more than 88%, and total yield is 53%.
Embodiment 2, with grade is 0.2 ‰, calorific value is 100 tons in the germanic brown coal of the non-powdery of 2900 kcal/kg, through sieving, make coal rod or coal briquette, adding chain furnace then smelts, temperature is 1200 ℃ in the stove, the smelting through 0.8 hour, and the germanium oxide dust that contains that produces in the stove is reclaimed by whirlwind smoke collector, bagroom and foam deduster.The germanium concentrate that gets that is reclaimed is carried out the wet method refinement, and carry out in two steps: 1) chlorinated distillation, compound concentration are 8.5～9.5 equivalents, 5～8 times to the hydrochloric acid of germanium concentrate weight, earlier 1/3rd of hydrochloric acid is injected reactor, drop into germanium concentrate then, all the other hydrochloric acid are injected mix thoroughly again.Add weight and be 8～15% Manganse Dioxide of germanium concentrate weight, feeding pressure is the steam of 20000～50000 handkerchiefs, and when kettle temperature reached more than 83 ℃, germanium was steamed with the form of germanium tetrachloride.The steam state germanium tetrachloride gets liquid four germanium oxides through condensation.2) hydrolysis is hydrolyzed germanium tetrachloride and the water volume ratio by 1: 6.5, stirs, stir finish after, with its standing separation two hours, through diafiltration, dry thick germanium dioxide product, its grade 〉=65%.Sulfur-bearing and water＜1% wherein, arsenic＜0.8%, wet method germanium metal recovery rate can reach more than 89%, and total yield is 58%.
Embodiment 3, with grade is 4 ‰, calorific value is 100 tons in the germanic brown coal of the non-powdery of 3000 kcal/kg, through sieving, make coal rod or coal briquette, adding chain furnace then smelts, temperature is 1300 ℃ in the stove, the smelting through 1.2 hours, and the germanium oxide dust that contains that produces in the stove is reclaimed by whirlwind smoke collector, bagroom and foam deduster.The germanium concentrate that gets that is reclaimed is carried out the wet method refinement, and carry out in two steps: 1) chlorinated distillation, compound concentration are 8.5～9.5 equivalents, 5～8 times to the hydrochloric acid of germanium concentrate weight, earlier 1/3rd of hydrochloric acid is injected reactor, drop into germanium concentrate then, all the other hydrochloric acid are injected mix thoroughly again.Add weight and be 8～15% Manganse Dioxide of germanium concentrate weight, feeding pressure is the steam of 20000～50000 handkerchiefs, and when kettle temperature reached more than 83 ℃, germanium was steamed with the form of germanium tetrachloride.The steam state germanium tetrachloride gets liquid four germanium oxides through condensation.2) hydrolysis is hydrolyzed germanium tetrachloride and the water volume ratio by 1: 6.5, stirs, stir finish after, with its standing separation two hours, through diafiltration, dry thick germanium dioxide product, its grade 〉=65%.Sulfur-bearing and water＜1% wherein, arsenic＜0.8%, wet method germanium metal recovery rate can reach more than 90%, and total yield is 63%.
Claims (3)
1, a kind of method of from brown coal, extracting germanium, comprise pyrogenic process and wet smelting process, wherein wet method comprises chlorinated distillation and two processes of hydrolysis, the process that it is characterized in that pyrogenic process is through screening, system coal rod or coal briquette with germanic raw coal, adding chain furnace then smelts, the germanium oxide dust that contains that produces in the stove is reclaimed by whirlwind smoke collector, bagroom and foam deduster, and the gained germanium concentrate extracts germanium through wet method once more.
2, method according to claim 1, the grade that it is characterized in that raw material is more than 0.1 ‰, calorific value is the above germanic brown coal of non-powdery of 2800 kcal/kg.
3, method according to claim 1 is characterized in that the interior temperature of stove of chain furnace can reach 1100～1300 ℃, and be 0.5～1.2 hour tap to tap time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93121175 CN1035630C (en) | 1993-12-31 | 1993-12-31 | Extraction of germanium from lignite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93121175 CN1035630C (en) | 1993-12-31 | 1993-12-31 | Extraction of germanium from lignite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101380A true CN1101380A (en) | 1995-04-12 |
| CN1035630C CN1035630C (en) | 1997-08-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93121175 Expired - Lifetime CN1035630C (en) | 1993-12-31 | 1993-12-31 | Extraction of germanium from lignite |
Country Status (1)
| Country | Link |
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| CN (1) | CN1035630C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340682C (en) * | 2003-09-20 | 2007-10-03 | 樊红杰 | Germanium recovering method |
| CN100408654C (en) * | 2006-01-27 | 2008-08-06 | 云南冶金集团总公司技术中心 | Method for preparing carbocoal and extracting germanium-contained matter from brown coal destructive ditillation |
| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN104480328A (en) * | 2014-12-01 | 2015-04-01 | 云南临沧鑫圆锗业股份有限公司 | Method for recycling germanium in low-grade brown coal germanium concentrate by using vacuum enrichment |
| CN105170311A (en) * | 2015-10-23 | 2015-12-23 | 云南临沧鑫圆锗业股份有限公司 | Germanium ore washing method capable of improving pyrometallurgy recovery rate |
| CN107058728A (en) * | 2017-05-25 | 2017-08-18 | 江苏省冶金设计院有限公司 | A kind of system and method for comprehensively utilizing ferrous material and germanic lignite |
| US9963761B2 (en) | 2014-12-01 | 2018-05-08 | Yunnan Lincang Xinyuan Germanium Industry Co., Ltd. | Method and apparatus for secondary enrichment and recovery of germanium from low-grade lignite germanium concentrates with by microwave heating in vacuum |
| CN109439909A (en) * | 2018-12-15 | 2019-03-08 | 六盘水中联工贸实业有限公司 | A method of the Ti recovery from high siliceous optical fiber production waste material |
| CN110453097A (en) * | 2019-09-17 | 2019-11-15 | 广东先导稀材股份有限公司 | A method of germanium is extracted in distillation from fluorine-containing germanium concentrate |
-
1993
- 1993-12-31 CN CN 93121175 patent/CN1035630C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340682C (en) * | 2003-09-20 | 2007-10-03 | 樊红杰 | Germanium recovering method |
| CN100408654C (en) * | 2006-01-27 | 2008-08-06 | 云南冶金集团总公司技术中心 | Method for preparing carbocoal and extracting germanium-contained matter from brown coal destructive ditillation |
| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN104480328A (en) * | 2014-12-01 | 2015-04-01 | 云南临沧鑫圆锗业股份有限公司 | Method for recycling germanium in low-grade brown coal germanium concentrate by using vacuum enrichment |
| CN104480328B (en) * | 2014-12-01 | 2016-01-20 | 云南临沧鑫圆锗业股份有限公司 | The method of germanium in the low-grade brown coal germanium concentrate of vacuum enriching and recovering |
| US9963761B2 (en) | 2014-12-01 | 2018-05-08 | Yunnan Lincang Xinyuan Germanium Industry Co., Ltd. | Method and apparatus for secondary enrichment and recovery of germanium from low-grade lignite germanium concentrates with by microwave heating in vacuum |
| CN105170311B (en) * | 2015-10-23 | 2018-05-11 | 云南临沧鑫圆锗业股份有限公司 | Improve the washing germanium ore deposit method of the pyrometallurgical smelting rate of recovery |
| CN105170311A (en) * | 2015-10-23 | 2015-12-23 | 云南临沧鑫圆锗业股份有限公司 | Germanium ore washing method capable of improving pyrometallurgy recovery rate |
| CN107058728A (en) * | 2017-05-25 | 2017-08-18 | 江苏省冶金设计院有限公司 | A kind of system and method for comprehensively utilizing ferrous material and germanic lignite |
| CN109439909A (en) * | 2018-12-15 | 2019-03-08 | 六盘水中联工贸实业有限公司 | A method of the Ti recovery from high siliceous optical fiber production waste material |
| CN109439909B (en) * | 2018-12-15 | 2023-09-05 | 六盘水中联工贸实业有限公司 | Method for recycling germanium from high-silicon-content optical fiber production waste |
| CN110453097A (en) * | 2019-09-17 | 2019-11-15 | 广东先导稀材股份有限公司 | A method of germanium is extracted in distillation from fluorine-containing germanium concentrate |
| CN110453097B (en) * | 2019-09-17 | 2021-12-17 | 广东先导稀材股份有限公司 | Method for distilling and extracting germanium from fluorine-containing germanium concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1035630C (en) | 1997-08-13 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: Yunnan Lincang Smelting Plant Applicant after: Guangzhou Research Institute of Non-ferrous Metals Applicant before: Yunnan Lincang Smelting Plant |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: YUNNAN LINCANG DISTRICT SMELTER TO: GUANGZHOU NON-FERROUS METAL INSTISTUTE YUNNAN LINCANG DISTRICT SMELTER |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: YUNNAN LINCANG XINYUAN GERMANI CO., LTD. Free format text: FORMER OWNER: SMELTER, LINCANG DISTRICT, YUNNAN PROVINCE; GUANGZHOU RESEARCH INSTITUTE OF NONFERROUS METALS Effective date: 20071221 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20071221 Address after: Lincang City, Yunnan Province Industrial Park East Area Patentee after: Yunnan Lincang Xinyuan Germanium Co., Ltd. Patentee after: Guangzhou Research Institute of Non-ferrous Metals Address before: No. 125, Nanjing depression, Cang County, Yunnan Province Patentee before: Lincang Prefecture Smeltery, Yunnan Prov. |
|
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20131231 Granted publication date: 19970813 |