CN1070430A - A kind of technology of from germanic coal, extracting germanium - Google Patents
A kind of technology of from germanic coal, extracting germanium Download PDFInfo
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- CN1070430A CN1070430A CN92105988A CN92105988A CN1070430A CN 1070430 A CN1070430 A CN 1070430A CN 92105988 A CN92105988 A CN 92105988A CN 92105988 A CN92105988 A CN 92105988A CN 1070430 A CN1070430 A CN 1070430A
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Abstract
A kind of novel process of carrying germanium from germanic coal belongs to field of metallurgy and chemical engineering.The present invention utilizes temperature and the atmosphere that germanic coal when burning itself produce, and germanium is fully volatilized in combustion processes and obtains highly enriched technology in the cooled flue gas after secondary combustion.The present invention compares with prior art, and raw materials consumption descends significantly, and flow process is greatly simplified, and the germanium rate of recovery increases substantially.For the coal that contains Ge＞0.02%, evaporation rate of germanium＞90%, germanium dirt contains Ge＞6%, and this technology is adapted to carry germanium from containing Ge＞0.005% in the coal of thermal value＞12000KJ/kg.
Description
The present invention relates to a kind of technology of from germanic coal, extracting germanium, belong to field of metallurgy and chemical engineering.
From germanic coal, extract germanium, two kinds of approach are arranged usually, the one, carry germanium the flying dust behind fire coal; The one, from the tar water that process of coking produced, extract germanium.The former is as United States Patent (USP) 4678647,4643110; The latter such as United States Patent (USP) 2786750.In addition, No. 110688 patents of the former Soviet Union have been invented a kind of processing method of carrying germanium in liquid medium from coal.The domestic somewhere sixties begin to test from coal carries germanium, and method is to adopt thin layer coal low-temperature burning, makes in the coal ash after germanium enters burning, will go into blast furnace secondary volatilizing and enriching germanium behind the germanic coal ash nodulizing then; About 1980, the this area uses the smeltery boiling furnace combustion germanic coal, blast furnace secondary volatilizing and enriching germanium will be gone into then behind germanic coal dust and the coal ash nodulizing, from rich germanium dirt, further carry germanium with traditional chlorinated distillation technology at last, the common weak point of prior art is to fail directly to carry from coal cost-effectively germanium, thus cause long flow path, yield is low, energy consumption is big, with high costs.Smeltery, somewhere for example, the grade of germanium is low in the coal dust of germanic coal burning back gained and the coal ash, particularly all the more so for the germanic brown coal of ash-rich, usually only 4～5 times of enrichments, grade only reaches 0.1～0.7%, can not adopt traditional chlorinated distillation technology further to carry germanium, must behind nodulizing, go into blast furnace secondary volatilizing and enriching germanium.After the secondary enrichment, germanium dirt is germanic to be 5～8%, compares more than 100 times of common enrichment with raw coal.The blast furnace operation, the metal direct yield is low, and usually only 60%, and running cost is very high, it is also high to consume energy, and only is adapted to handle the germanium coal of germanic＞0.03%.
The object of the present invention is to provide a kind of technology that can overcome the prior art common drawback.Use rational combustion system, utilize the temperature and the atmosphere that are produced when containing Ge coal self burning, Ge is fully volatilized and highly enriched, thereby save the secondary enrichment operation that yield is low, cost is high, reach from coal the purpose that germanium is carried in directly enrichment.
Purpose of the present invention reaches by following measure:
Burning of coal adopts the lump coal of the higher bed of material or coal briquette or the two to be mixed into the stove combustion system, lumpiness 10～120mm, coal seam height 300～2000mm, the temperature of burning volatilization germanium is 1000～1500 ℃, the germanic coal gas that has fugitive constituents such as tar that combustion processes produced carries out secondary combustion, the temperature of secondary combustion is only required tar is burnouted, and then the germanic flue gas cooling after the secondary combustion is entered dust-precipitator and gathers dust.
Purpose of the present invention can also reach by following measure:
1. lump coal or coal briquette adopt gasification or semi-coal gas burning, and the coal seam height is 400～1800mm preferably, and combustion high temperature district optimum temps is 1100～1350 ℃.
2. secondary combustion is carried out on the top of primary combustion stove or is independently carried out in the roasting kiln at another.
3. the flue gas of secondary combustion is cooled to 80～170 ℃ and enters the cloth bag chamber and gather dust.
4. with germanic fine coal system ball or when making honeycomb briquette, tackiness agent adopts clay, and its add-on press 15～25% addings of fine coal weight, specifically can allocate into by final coal briquette ash 35～40%.
Fig. 1 is seen in technical process of the present invention.Below concrete processing method of the present invention is further described:
1. with germanic coal screening, lumpiness＞10mm directly into stove, the coal cinder of＞120mm needs broken a little.Undersized fine coal send the system coal briquette, and compacting coal briquette adhesive therefor can be a lime, paper waste, but most economical be to use clay, the amount of allocating into is 15～25% of a raw coal, specifically decide on original coal ash part, be 30～45% with the coal briquette ash of making.But be preferably 35～40%.The coal briquette size be 20～100 the gram/.Also fine coal can be pressed into honeycomb briquette.
2. contain Ge lump coal and coal briquette and can go into stove separately, also can be mixed into stove by arbitrary proportion.Thickness of coal seam＞300mm, but best 400～1800mm, blast intensity is by 50～250 kilograms/meter of bed abilities
2Hour meter, 1000～1500 ℃ of the temperature of burning volatilization Ge, best 1100～1400 ℃.Lump coal and coal briquette thermal value＞12000KJ/kg, but best lump coal＞13000KJ/kg, coal briquette＞14000KJ/kg.
3. the germanic coal gas that has fugitive constituent such as tar that is produced during with lump coal and coal briquette burning volatilization germanium carries out secondary combustion, and secondary combustion can be carried out on the top of lump coal and coal briquette roasting kiln, also can introduce another and independently carry out in the after-burning stove.The secondary combustion temperature is not done strict restriction, as long as satisfy the naked light burning, can totally get final product the tar burning.
4. the germanic flue gas after secondary combustion is cooled to 80～170 ℃ through water cooler, enters the cloth bag chamber and gathers dust, and also can adopt other mode of gathering dust.
5. germanium dirt is further carried germanium with traditional chlorinated distillation technology.
6. the slag that is produced behind lump coal and the coal briquette burning volatilization germanium sieves out the rich germanium thin slag of a small amount of granularity less than 1mm, is back to further recovery germanium wherein of fine coal system ball operation.Thick slag is germanic extremely low on the sieve, can discard.
The present invention compared with prior art has following advantage:
1. adopt high bed of material operation, make air progressively obtain preheating, thereby improved temperature of combustion, help the volatilization of germanium, also reduced the requirement to the germanium calorific value of coal, the burning of the high bed of material can form on a certain aspect and can satisfy germanium evaporable weak reducing atmosphere.Therefore, the temperature that is reached when utilizing germanic coal self burning with the atmosphere that is produced germanium is fully volatilized and enrichment need not to increase energy consumption and subsidiary material, and production cost is reduced significantly.
2. adopt the burning of lump coal or coal briquette, increased ventilation property, make the air-flow uniform distribution, temperature is even, helps comprehensive volatilization of germanium in the whole furnace charge; Simultaneously, reduced the coal dust amount significantly, thereby the dirt rate is low, the germanium concentration ratio is up to 50～700 times, and germanium dirt is germanic to reach the effect that the volatilization of 6～10%, one step can reach the secondary enrichment, and technical process is greatly simplified.
3. high bed of material burning, essence have become coal gas or semi-coal gas burning, and process has the coal gas that contains fugitive constituents such as tar in a large number to produce (germanic brown coal are all the more so), introduce secondary combustion, the tar composition that burnouts has further improved the concentration ratio of germanium, and dust collecting system is normally moved.
4. concentration ratio is higher during low-grade germanium coal combustion volatilization germanium, thus make low-grade germanic coal utilization economically with the technical possibility that all becomes.
5. the volatilization rate of recovery of germanium improves greatly, for the coal of germanic＞0.015%, and the rate of recovery＞80%; For the coal of germanic＞0.02%, the rate of recovery＞90% is compared with prior art, and the rate of recovery improves 20% at least.
Embodiment 1
Contain Ge0.153%, thermal value 12540KJ/kg, size is the lump coal 410kg of 10～120mm, Ge volatilizees in producer gas generator.Adopt progressively to add the thick seam operating method, the combustion processes coal seam changes between 400～1600, and intensity of combustion is 80kg/hm
2, 1100～1300 ℃ of high-temperature zone burning volatilization temperatures.The coal gas of the fugitive constituents such as band tar that contain Ge that produce is introduced one and is independently carried out secondary combustion in the roasting kiln, and flue gas is gone into the cloth bag chamber and gathered dust after being cooled to 80～120 ℃, obtain the Ge dirt 5.1kg that contains Ge11.44%.The Ge rate of recovery 93.01%.Ge dirt contains Ge and has compared enrichment 74.8 times with raw coal.
Embodiment 2
Contain Ge0.0237%, thermal value 13790KJ/kg, size is the lump coal 500kg of 10～120mm, and the Ge that volatilizees in producer gas generator adopts the operating method that progressively adds thick seam, and the combustion processes coal seam changes between 400～1600, and intensity of combustion is 85kg/hm
21200～1400 ℃ of high-temperature zone burning volatilization temperatures, the coal gas of the fugitive constituents such as band tar that contain Ge that produce is introduced and is carried out secondary combustion in the independent burning stove, flue gas is through being cooled to 80～120 ℃, going into the cloth bag chamber gathers dust, obtain the Ge dirt 1.78kg that contains Ge6.23, the rate of recovery 93.58% of Ge, Ge dirt contains Ge and has compared enrichment 262.9 times with raw coal.
Embodiment 3
Contain Ge0.0457%, thermal value 13590KJ/kg, size is the lump coal 500kg of 10～120mm, and the Ge that volatilizees in producer gas generator adopts the operating method that progressively adds thick seam, and the combustion processes coal seam changes between 400～1600mm, and intensity of combustion is 130kg/hm
2, 1300～1500 ℃ of high-temperature zone temperature of combustion, the coal gas that has fugitive constituents such as tar that contains Ge is introduced one and is independently carried out secondary combustion in the combustion chamber, contains the Ge flue gas and goes into the cloth bag chamber and gather dust through being cooled to 80～140 ℃.Obtain the Ge dirt 5kg that contains Ge4.37%, the Ge rate of recovery 95.62%, Ge dirt contains Ge and has compared enrichment 95.6 times with raw coal.
Embodiment 4
Contain Ge fine coal and allocate 20% clay into, be pressed into～20 grams/coal briquette, coal briquette contains Ge0.044%, thermal value 15350KJ/kg, in the disposable adding producer gas generator of 200kg, coal seam beginning height 1800mm, intensity of combustion 75kg/hm
2, high-temperature zone temperature of combustion 1200～1350mm, the coal gas that contains the fugitive constituents such as band tar of Ge is introduced one and is independently carried out secondary combustion in the combustion chamber, and flue gas is gone into the cloth bag chamber and is gathered dust through being cooled to 80～120 ℃.Obtain the Ge dirt 1.28kg that contains Ge6.28, the Ge rate of recovery 91.34%, Ge dirt contains Ge and has compared enrichment 142.7 times with raw coal.
Embodiment 5
Contain Ge0.015%, thermal value 15470KJ/kg, size is the lump coal of 15～70mm, goes into semi-coal gas stove burning volatilization Ge, coal seam height 400mm, intensity of combustion is 120kg/hm
2, 1200～1300 ℃ of high-temperature zone temperature of combustion, the coal gas that contains the fugitive constituents such as band tar of Ge carries out secondary combustion on the top of semi-coal gas stove.The volatilization rate of recovery of Ge is 86.1%.
Claims (5)
1, a kind of technology of from germanic coal, extracting germanium, it comprises burning of coal, flue gas cools off, gathers dust, the chlorinated distillation operation, it is characterized in that adopting the lump coal of the higher bed of material or coal briquette that fine coal is made or the two to be mixed into the stove combustion system, lumpiness 10～120mm, coal seam height 300～2000mm, the temperature of burning volatilization germanium is 1000～1500 ℃, the germanic coal gas that has fugitive constituents such as tar that combustion processes produced carries out secondary combustion, the temperature of secondary combustion is only required tar is burnouted, and then the germanic flue gas cooling after the secondary combustion is entered dust-precipitator and gathers dust.
2, technology as claimed in claim 1 is characterized in that: lump coal or coal briquette adopt gasification or semi-coal gas burning, and the coal seam height is 400～1800mm preferably, and combustion high temperature district optimum temps is 1100～1350 ℃.
3, technology as claimed in claim 1 is characterized in that: secondary combustion is carried out on the top of primary combustion stove or is independently carried out in the roasting kiln at another.
4, as claim 1 or 3 described technologies, it is characterized in that: the flue gas of secondary combustion is cooled to 80～170 ℃ and enters the cloth bag chamber and gather dust.
5, technology as claimed in claim 1 is characterized in that: with germanic fine coal system ball or when making honeycomb briquette, tackiness agent adopts clay, and its add-on press 15～25% addings of fine coal weight, specifically can allocate into by final coal briquette ash 35～40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92105988A CN1025223C (en) | 1992-07-15 | 1992-07-15 | Process for extracting germanium from germanic coal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92105988A CN1025223C (en) | 1992-07-15 | 1992-07-15 | Process for extracting germanium from germanic coal |
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| Publication Number | Publication Date |
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| CN1070430A true CN1070430A (en) | 1993-03-31 |
| CN1025223C CN1025223C (en) | 1994-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN92105988A Expired - Fee Related CN1025223C (en) | 1992-07-15 | 1992-07-15 | Process for extracting germanium from germanic coal |
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Cited By (6)
| 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 |
| CN101476052B (en) * | 2009-01-06 | 2013-06-19 | 扬州宁达贵金属有限公司 | Germanium volatilization oxidation oven |
| CN103334011A (en) * | 2013-07-22 | 2013-10-02 | 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 |
| CN103361496A (en) * | 2012-12-14 | 2013-10-23 | 锡林郭勒通力锗业有限责任公司 | Method for volatilizing, enriching and extracting germanium concentrate from low-quality low-grade germanium-containing powdery brown coal in chain grate furnace |
-
1992
- 1992-07-15 CN CN92105988A patent/CN1025223C/en not_active Expired - Fee Related
Cited By (7)
| 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 |
| CN101476052B (en) * | 2009-01-06 | 2013-06-19 | 扬州宁达贵金属有限公司 | Germanium volatilization oxidation oven |
| 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 |
| CN103361496A (en) * | 2012-12-14 | 2013-10-23 | 锡林郭勒通力锗业有限责任公司 | Method for volatilizing, enriching and extracting germanium concentrate from low-quality low-grade germanium-containing powdery brown coal in chain grate furnace |
| CN103361496B (en) * | 2012-12-14 | 2015-02-18 | 锡林郭勒通力锗业有限责任公司 | Method for volatilizing, enriching and extracting germanium concentrate from low-quality low-grade germanium-containing powdery brown coal in chain grate furnace |
| CN103334011A (en) * | 2013-07-22 | 2013-10-02 | 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 |
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| Publication number | Publication date |
|---|---|
| CN1025223C (en) | 1994-06-29 |
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