CN102181652A - Germanium leaching enrichment method for germanium-containing soot of power plant - Google Patents
Germanium leaching enrichment method for germanium-containing soot of power plant Download PDFInfo
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- CN102181652A CN102181652A CN2011101321010A CN201110132101A CN102181652A CN 102181652 A CN102181652 A CN 102181652A CN 2011101321010 A CN2011101321010 A CN 2011101321010A CN 201110132101 A CN201110132101 A CN 201110132101A CN 102181652 A CN102181652 A CN 102181652A
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- germanium
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- tannin
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Abstract
The invention discloses a leaching process for germanium-containing soot of a power plant. The leaching process comprises the following steps of: performing repeated acid leaching 5 to 10 times, wherein the initial acid is 0.2 to 0.3 N, and the final acid is 0.25 to 0.05N; performing alkaline leaching 2 to 3 times by using Na2CO3, in an amount which is 20 to 30 percent of the amount of the fed materials, till the pH value is 12 to 14; boiling, stirring for 0.5 hours, acidifying and then stirring for 15 to 20 minutes; performing precipitation with tannin: precipitating germanium by using the tannin in the acid leached and alkaline leached solution; performing pressure filtration: performing pressure filtration on the tannin precipitation solution to form filter cakes (namely tannin germanium) containing 60 to 70 percent of moisture by using an acid-resistant medium; and drying and roasting, wherein 60 to 70 percent of moisture of the filter cakes is removed in a drying furnace during drying, the drying temperature is less than or equal to 400 DEG C, the drying time is about 7 to 8 hours, and the filter cakes are gray when the moisture is dried to be less than 8 percent and then roasted. The germanium in the soot of the power plant can be enriched by 100 to 120 times by using acid and alkaline leaching methods.
Description
Technical field
The present invention relates to the leaching enriching method that a kind of power plant contains germanium oxide dust germanium.
Background technology
Rare and scatter element germanium is composed in North China, the geographic brown lignite in the Inner Mongol (brown), bituminous coal, mud coal and is contained trace germanium.In recent years part power plant adopts this kind coal power generation, and trace germanium volatilizees when power plant boiler in the coal, and flue dust is collected by electrostatic precipitator or bagroom, and flue dust germanium obtains enrichment, and content is at 60～200ug/g.Because smoke granularity is at 100～300um, the flue dust germanium grade after the enrichment does not have industrial value, also need carry out the secondary enrichment.
Summary of the invention
At the deficiencies in the prior art, the present invention is with acid, alkali leaching method (wet method), power plant can be contained in the flue dust germanium 100～120 times of enrichments again.
The technical solution used in the present invention is: power plant contains the leaching enriching method of germanium oxide dust germanium, it is characterized in that: step 1, and leaching method,
Acidleach is 5～10 times repeatedly: first acidleach H
2SO
4, beginning acid is 0.2～0.3N, the steam direct heating, and boiling was stirred 0.5 hour, and the acidity of acidleach should descend one by one, and the acidity of last acidleach is 0.25～0.05N;
It is to begin to carry out after reaching 20～25ug/ml in that acid dip solution is germanic that alkali soaks, and will use H after alkali soaks
2SO
4Acidifying makes leaching still be acid, PH=1.5～2, and according to the leach liquor situation, it is 2～3 times that alkali soaks number of times;
Alkali soaks uses Na
2CO
3, consumption is for throwing 20～30% of feeding, and seethe with excitement to stir after 0.5 hour and carry out acidifying in PH=12～14, and restir is 15～20 minutes after the acidifying;
Solution after acidleach and alkali soak precipitates germanium with tannin, and the total consumption of tannin is directly proportional with the gross weight of germanium during precipitation, and the concentration of total consumption of tannin and germanium is inversely proportional to;
Step 3, press filtration,
Do medium with the press filtration of tannin precipitated liquid with the acid proof canvas, perhaps do medium centrifuging with the acid proof canvas, becoming the filter cake of water content 60～70% is tannin germanium;
Step 4, oven dry, roasting,
Oven dry is that the moisture content of filter cake 60～70% is sloughed in stoving oven, and bake out temperature≤400 ℃ about 7～8 hours, treat that the moisture content baking to being grey shape below 8%, carries out roasting again.
Above-mentioned power plant contains the leaching enriching method of germanium oxide dust germanium, and it is further characterized in that: described step 1 leaching method, acidleach, alkali soak and all adopt the open steam heated and stirred to boiling, Gu: liquid=1:15～20; The effect that alkali soaks mainly is the GeO that makes indissoluble
2(tetragonal system), GeS, GeO, MeGeO
3Thereby change solution over to etc. the germanium of form and be able to enrichment; Solution after acidleach and alkali soak adds No. three flocculation agent, gelatin, allows the solution natural sedimentation.
Above-mentioned power plant contains the leaching enriching method of germanium oxide dust germanium, described step 4 oven dry, roasting, and the purpose of roasting is to remove volatility detrimental impurity such as As, S, 550～600 ℃ of temperature, the time is divided volatilization phase and soak, 5～6 hours total times.
Beneficial effect: the present invention is with acid, alkali leaching method (wet method), power plant can be contained in the flue dust germanium 100～120 times of enrichments again.
Description of drawings
Fig. 1 contains germanium concentration and the multiple figure that adds tannin for the leach liquor of the inventive method.
Fig. 2 contains germanium oxide dust extract technology schema for the power plant of the inventive method.
Embodiment
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.The drawings and specific embodiments do not limit the scope of protection of present invention.
The production technique of leaching enriching method that power plant of the present invention contains germanium oxide dust germanium is as follows.
1) leaching method:
Acidleach is 5～10 times repeatedly.First acidleach H
2SO
4, beginning acid is 0.2～0.3N, the steam direct heating, and boiling was stirred 0.5 hour.The acidity of acidleach should descend one by one, and the acidity of last acidleach is 0.25～0.05N.
It is to begin to carry out after reaching 20～25ug/ml in that acid dip solution is germanic that alkali soaks.After soaking, alkali to use H
2SO
4Acidifying makes leaching still be acid (PH=1.5～2).According to the leach liquor situation, it is 2～3 times that alkali soaks number of times.
Alkali soaks uses Na
2CO
3, consumption is for throwing 20～30% of feeding, and seethe with excitement to stir after 0.5 hour and carry out acidifying in PH=12～14, and restir is 15～20 minutes after the acidifying.
The effect that alkali soaks mainly is the GeO that makes indissoluble
2(tetragonal system), GeS, GeO, MeGeO
3Thereby change solution over to etc. the germanium of form and be able to enrichment.
Solution after acidleach and alkali soak adds No. three flocculation agent, gelatin, allows the solution natural sedimentation.
2) tannin tannine(or be translated into tannin) precipitation
With tannin precipitation germanium is optimised process, and the total consumption of tannin is directly proportional with the gross weight of germanium during precipitation, and the concentration of total consumption of tannin and germanium is inversely proportional to.Leach liquor contains germanium concentration and sees Fig. 1 with the amount that adds tannin.
3) press filtration
Doing medium with the acid proof canvas, tannin precipitated liquid press filtration (or same acid proof canvas do medium centrifuging) is become the filter cake of water content 60～70% is tannin germanium.
4) oven dry, roasting
Oven dry is that the moisture content of filter cake 60～70% is sloughed in stoving oven, bake out temperature≤400 ℃, about 7～8 hours.Treat that moisture content dries by the fire to being grey shape below 8%, carries out roasting again.
The purpose of roasting is to remove volatility detrimental impurity such as As, S.550～600 ℃ of temperature, the time is divided volatilization phase and soak, 5～6 hours total times.
The major equipment that the invention is used has: leaching vat, neutralization precipitation groove, stainless steel whizzer, acid proof pump, pressure filter, stoving oven, stoving oven etc.
Though the invention with preferred embodiment openly as above; but embodiment and accompanying drawing are not to be used for limiting the invention; anyly be familiar with this skill person; in the spirit and scope that do not break away from the invention; can do various variations or retouching from working as, but same within the protection domain of the invention.Therefore the protection domain of the invention should with the application claim was defined is as the criterion.
Claims (6)
1. power plant contains the leaching enriching method of germanium oxide dust germanium, it is characterized in that:
Step 1, leaching method,
Acidleach is 5～10 times repeatedly: first acidleach H
2SO
4, beginning acid is 0.2～0.3N, the steam direct heating, and boiling was stirred 0.5 hour, and the acidity of acidleach should descend one by one, and the acidity of last acidleach is 0.25～0.05N;
It is to begin to carry out after reaching 20～25ug/ml in that acid dip solution is germanic that alkali soaks, and will use H after alkali soaks
2SO
4Acidifying makes leaching still be acid, PH=1.5～2, and according to the leach liquor situation, it is 2～3 times that alkali soaks number of times;
Alkali soaks uses Na
2CO
3, consumption is for throwing 20～30% of feeding, and seethe with excitement to stir after 0.5 hour and carry out acidifying in PH=12～14, and restir is 15～20 minutes after the acidifying;
Step 2, the tannin precipitation,
Solution after acidleach and alkali soak precipitates germanium with tannin, and the total consumption of tannin is directly proportional with the gross weight of germanium during precipitation, and the concentration of total consumption of tannin and germanium is inversely proportional to;
Step 3, press filtration,
With the press filtration of tannin precipitated liquid, perhaps do centrifuging with the acid proof medium with the acid proof medium, becoming the filter cake of water content 60～70% is tannin germanium;
Step 4, oven dry, roasting,
Oven dry is that the moisture content of filter cake 60～70% is sloughed in stoving oven, and bake out temperature≤400 ℃ about 7～8 hours, treat that the moisture content baking to being grey shape below 8%, carries out roasting again.
2. power plant according to claim 1 contains the leaching enriching method of germanium oxide dust germanium, it is characterized in that: described step 1 leaching method, acidleach, alkali soak and all adopt the open steam heated and stirred to boiling, Gu: liquid=1:15～20.
3. power plant according to claim 2 contains the leaching enriching method of germanium oxide dust germanium, it is characterized in that: described step 1 leaching method, the effect that alkali soaks mainly are the GeO that makes indissoluble
2(tetragonal system), GeS, GeO, MeGeO
3Thereby change solution over to etc. the germanium of form and be able to enrichment.
4. power plant according to claim 3 contains the leaching enriching method of germanium oxide dust germanium, it is characterized in that: described step 1 leaching method, solution after acidleach and alkali soak add No. three flocculation agent, gelatin, allow the solution natural sedimentation.
5. contain the leaching enriching method of germanium oxide dust germanium according to the described power plant of one of claim 1 to 4, it is characterized in that: described step 3 press filtration, the acid proof medium is selected the acid proof canvas for use.
6. the leaching enriching method that contains germanium oxide dust germanium according to the described power plant of one of claim 1 to 4, it is characterized in that: described step 4 oven dry, roasting, the purpose of roasting is to remove volatility detrimental impurity such as As, S, 550～600 ℃ of temperature, time is divided volatilization phase and soak, 5～6 hours total times.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345021A (en) * | 2011-10-08 | 2012-02-08 | 昆明理工大学 | Method for recovering germanium from germanium smoke dust by microwave pretreatment |
| CN102628109A (en) * | 2012-03-30 | 2012-08-08 | 中国林业科学研究院林产化学工业研究所 | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof |
| CN104593611A (en) * | 2014-12-30 | 2015-05-06 | 郴州丰越环保科技有限公司 | Method for efficiently recovering germanium |
| CN108715938A (en) * | 2018-07-16 | 2018-10-30 | 四环锌锗科技股份有限公司 | A kind of technique improving the electric Zn system germanium rate of recovery |
| CN110819828A (en) * | 2019-11-18 | 2020-02-21 | 扬州宁达贵金属有限公司 | Method for recovering germanium dioxide from germanium-containing smoke dust |
| CN110922006A (en) * | 2019-12-18 | 2020-03-27 | 云南驰宏国际锗业有限公司 | Germanium mud pretreatment method |
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| CN101638725A (en) * | 2009-08-14 | 2010-02-03 | 扬州宁达贵金属有限公司 | Method for enriching germanium concentrates from low-germanium coal dust |
| CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
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- 2011-05-21 CN CN2011101321010A patent/CN102181652B/en not_active Expired - Fee Related
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| CN101638725A (en) * | 2009-08-14 | 2010-02-03 | 扬州宁达贵金属有限公司 | Method for enriching germanium concentrates from low-germanium coal dust |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345021A (en) * | 2011-10-08 | 2012-02-08 | 昆明理工大学 | Method for recovering germanium from germanium smoke dust by microwave pretreatment |
| CN102345021B (en) * | 2011-10-08 | 2014-02-12 | 昆明理工大学 | Method for recovering germanium from germanium smoke dust by microwave pretreatment |
| CN102628109A (en) * | 2012-03-30 | 2012-08-08 | 中国林业科学研究院林产化学工业研究所 | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof |
| CN102628109B (en) * | 2012-03-30 | 2013-11-13 | 中国林业科学研究院林产化学工业研究所 | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof |
| CN104593611A (en) * | 2014-12-30 | 2015-05-06 | 郴州丰越环保科技有限公司 | Method for efficiently recovering germanium |
| CN108715938A (en) * | 2018-07-16 | 2018-10-30 | 四环锌锗科技股份有限公司 | A kind of technique improving the electric Zn system germanium rate of recovery |
| CN110819828A (en) * | 2019-11-18 | 2020-02-21 | 扬州宁达贵金属有限公司 | Method for recovering germanium dioxide from germanium-containing smoke dust |
| CN110819828B (en) * | 2019-11-18 | 2021-07-16 | 扬州宁达贵金属有限公司 | Method for recovering germanium dioxide from germanium-containing smoke dust |
| CN110922006A (en) * | 2019-12-18 | 2020-03-27 | 云南驰宏国际锗业有限公司 | Germanium mud pretreatment method |
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| CN102181652B (en) | 2012-12-26 |
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Owner name: NANJING CHINA GERMANIUM TECHNOLOGY CO., LTD. Free format text: FORMER NAME: NANJING GERMANIUM TECHNOLOGY CO., LTD. |
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Address after: 211165 general road, Jiangning Development Zone, Jiangsu, Nanjing, China, No. 718 Patentee after: CHINA GERMANIUM CO., LTD. Address before: 211165 general road, Jiangning Development Zone, Jiangsu, Nanjing, China, No. 718 Patentee before: Nanjing Germanium Technology Co., Ltd. |
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