CN105400969A - Method for extracting germanium from raw coal through roasting method - Google Patents
Method for extracting germanium from raw coal through roasting method Download PDFInfo
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- CN105400969A CN105400969A CN201510710782.2A CN201510710782A CN105400969A CN 105400969 A CN105400969 A CN 105400969A CN 201510710782 A CN201510710782 A CN 201510710782A CN 105400969 A CN105400969 A CN 105400969A
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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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Abstract
The invention discloses a method for extracting germanium from raw coal through a roasting method. The method comprises the following steps that the raw coal is crushed and screened, the crushed and screened raw coal and potassium permanganate are mixed uniformly and put into first processing equipment, the temperature of the first processing equipment and the contents inside the first processing equipment is increased gradually at a certain speed, heat preservation is conducted, then the temperature continues to be increased, and a material A and smoke B are obtained through temperature preservation; the temperature of the first processing equipment and the contents inside the first processing equipment continues to be increased gradually at a certain speed, heat preservation is conducted till the material A is burnt, and waste materials and smoke C in the first processing equipment are taken out; the smoke B and the smoke C are introduced into second processing equipment, and a material D is obtained through chloridizing leaching, extraction, rectification and washing; and the material D is subjected to rectification, drying and hydrogen reduction, and the metal germanium is obtained. The method is low in cost, high in germanium extraction rate and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to germanium extractive technique field, particularly relate to a kind of method that roasting method extracts germanium from raw coal.
Background technology
Germanium metal is mainly present in texture of coal seam with ADSORPTION STATE and monomineralic form, is widely used in the high-tech area such as aerospace, military project with the performance of its excellence.The method of the extraction of germanium is common is hydrometallurgy and fire smelting method.Hydrometallurgy is mainly broken by raw coal and immerse in specific solution, leaches or extraction obtains germanium metal, but this mode is high to equipment requirements, complex process and with high costs, is not suitable for large-scale commercial production.Fire smelting method mainly extracts germanium from the products of combustion of raw coal, technique is simple, advantage of lower cost, but in traditional burning extracting method, the extraction yield of germanium is low and consumption hydrochloric acid content is huge, temperature of combustion does not add control easily makes the germanium dioxide generated change into insoluble from solubility especially, thus increases waste.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of method that roasting method extracts germanium from raw coal, cost of the present invention is low, the extraction yield of germanium is high, be applicable to large-scale commercial production.
A kind of roasting method that the present invention proposes extracts the method for germanium from raw coal, comprises the following steps:
S1, by weight by broken for 150-180 part raw coal, sieve after, mix input first processing units with 8-12 part potassium permanganate;
S2, to raise the first processing units and contents temperature thereof with the speed of 50-60 DEG C/min to 250-300 DEG C and be incubated 10-15min, then raise the first processing units and contents temperature thereof to 500-550 DEG C with the speed of 20-40 DEG C/min and be incubated 1.5-2h and obtain material A and flue dust B;
S3, to raise containing the first processing units temperature of material A to 600-650 DEG C with the speed of 20-30 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C;
S4, S3 being obtained flue dust C that flue dust B and S4 obtain, to import containing massfraction be, after soaking 10-15min in the second processing units of 32-35wt% hydrochloric acid, pass into chlorine 3-5min, then extract, rectifying with the air quantity of 22-25L/min, and washing obtains material D;
S5, material D to be hydrolyzed, to insert after oven dry in the 3rd processing units, raise the 3rd processing units temperature after passing into hydrogen to 650-670 DEG C, and be incubated 24-25h and obtain germanium metal.
Raw coal refers to that the run-of-mine coal (ROM coal) excavated from ground or underground mining removes the coal after spoil, pyrite etc. through screening processing.
Preferably, what raw coal was selected is high germanium coal.
Preferably, in S1 Feedstock treating, the order number sieved is 4-6 order.
Preferably, in S3, with 3-5m
3/ min air quantity inputs filtered air in the first processing units.
Preferably, in S4, with 1-2m
3/ min air quantity inputs filtered air in the first processing units.
Preferably, the weight sum of flue dust B and flue dust C is x, and the weight of hydrochloric acid is y, then x:y=1-2:8-15.
Preferably, in S4, the wind speed passing into chlorine is 0.1-0.3m/s.
Preferably, in S5, the wind speed passing into hydrogen is 0.5-1m/s.
Preferably, in S2, raise the first processing units and contents temperature thereof to 260-270 DEG C with the speed of 55-58 DEG C/min and be incubated 12-14min, then raise the first processing units and contents temperature thereof to 520-530 DEG C with the speed of 25-35 DEG C/min and be incubated 1.6-1.8h and obtain material A and flue dust B.
Preferably, in S3, contain the first processing units temperature of material A to 620-630 DEG C with the rising of the speed of 22-25 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C.
In the invention process process, raw coal is broken also crosses 4-6 mesh sieve, raw coal can be made fully to contact oxygen thus sufficient combustion, make the germanium in raw coal be oxidized to the germanium dioxide of solubility and depend on flue dust C; And in S2, S3, with specific speed raised temperature, ensure that raw coal abundant, burn equably, thus make the germanium in raw coal stably generate germanium dioxide and be attached on flue dust C; Wherein, the first processing units is incubated 10-15min when 250-300 DEG C, the potassium permanganate of interpolation can be made stably to decompose and produce oxygen and be full of raw coal inside, impel raw coal Thorough combustion, prevents from generating excess carbon monoxide; Potassium permanganate decomposes the Manganse Dioxide produced and can produce oxygen by last decomposition in ensuing temperature-rise period, thus ensures raw coal Thorough combustion further; And in S4, adopt chlorine to coordinate chlorination of hydrochloric acid to leach, improve the leaching yield of germanium on the one hand, make hydrochloric acid be easy to reclaim on the other hand, reduce cost, passing into chlorine with the wind speed of 0.1-0.3m/s then ensure that chlorine is fully dissolved in hydrochloric acid; In S5, the contact surface that hydrogen can strengthen hydrogen and reactant is passed into the wind speed of 0.5-1m/s, the temperature of charge simultaneously preventing the quickening along with wind speed from causing reduces rapidly, the specific temperature of reaction adopted can make reactant fully contact with hydrogen, react with the reaction times, thus improves the purity of germanium metal.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of roasting method that the present invention proposes extracts the method for germanium from raw coal, comprises the following steps:
S1, by weight by broken for the raw coal of 150 parts high germanium coals, cross 6 mesh sieves after, mix input first processing units with 8 parts of potassium permanganate;
S2, to raise the first processing units and contents temperature to 250 thereof DEG C with the speed of 60 DEG C/min and be incubated 15min, then raising the first processing units and contents temperature to 550 thereof DEG C with the speed of 20 DEG C/min and be incubated 1.5h and obtain material A and flue dust B;
S3, to raise containing the first processing units temperature to 600 DEG C of material A with the speed of 30 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C; In the course of processing, with 5m
3/ min air quantity inputs filtered air in the first processing units;
S4, S3 being obtained flue dust C that flue dust B and S4 obtain, to import containing massfraction be, after soaking 15min in the second processing units of 32wt% hydrochloric acid, pass into chlorine 5min, then extract, rectifying with the air quantity of 22L/min, and washing obtains material D; In the course of processing, with 1m
3/ min air quantity inputs filtered air in the first processing units; Wherein, the weight sum of flue dust B and flue dust C is x, and the weight of hydrochloric acid is y, then x:y=1:4; The wind speed passing into chlorine is 0.3m/s;
S5, material D to be hydrolyzed, to insert after oven dry in the 3rd processing units, after passing into hydrogen, raise the 3rd processing units temperature to 650 DEG C, and be incubated 25h and obtain germanium metal; Wherein, the wind speed passing into hydrogen is 0.5m/s.
Embodiment 2
A kind of roasting method that the present invention proposes extracts the method for germanium from raw coal, comprises the following steps:
S1, by weight by broken for the raw coal of 180 parts high germanium coals, cross 4 mesh sieves after, mix input first processing units with 12 parts of potassium permanganate;
S2, to raise the first processing units and contents temperature to 300 thereof DEG C with the speed of 50 DEG C/min and be incubated 10min, then raising the first processing units and contents temperature to 500 thereof DEG C with the speed of 40 DEG C/min and be incubated 2h and obtain material A and flue dust B;
S3, to raise containing the first processing units temperature to 650 DEG C of material A with the speed of 20 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C; In the course of processing, with 3m
3/ min air quantity inputs filtered air in the first processing units;
S4, S3 being obtained flue dust C that flue dust B and S4 obtain, to import containing massfraction be, after soaking 10min in the second processing units of 35wt% hydrochloric acid, pass into chlorine 3min, then extract, rectifying with the air quantity of 25L/min, and washing obtains material D; In the course of processing, with 2m
3/ min air quantity inputs filtered air in the first processing units; Wherein, the weight sum of flue dust B and flue dust C is x, and the weight of hydrochloric acid is y, then x:y=1:15; The wind speed passing into chlorine is 0.1m/s;
S5, material D to be hydrolyzed, to insert after oven dry in the 3rd processing units, after passing into hydrogen, raise the 3rd processing units temperature to 670 DEG C, and be incubated 24h and obtain germanium metal; Wherein, the wind speed passing into hydrogen is 1m/s.
Embodiment 3
A kind of roasting method that the present invention proposes extracts the method for germanium from raw coal, comprises the following steps:
S1, by weight 160 parts high germanium coal raw coal are broken, sieve after, mix input first processing units with 9 parts of potassium permanganate;
S2, to raise the first processing units and contents temperature to 260 thereof DEG C with the speed of 58 DEG C/min and be incubated 14min, then raising the first processing units and contents temperature to 530 thereof DEG C with the speed of 25 DEG C/min and be incubated 1.6h and obtain material A and flue dust B;
S3, to raise containing the first processing units temperature to 620 DEG C of material A with the speed of 25 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C;
S4, S3 being obtained flue dust C that flue dust B and S4 obtain, to import containing massfraction be, after soaking 12min in the second processing units of 33wt% hydrochloric acid, pass into chlorine 3.5min, then extract, rectifying with the air quantity of 23L/min, and washing obtains material D; In the course of processing, with 1.5m
3/ min air quantity inputs filtered air in the first processing units; Wherein, the weight sum of flue dust B and flue dust C is x, and the weight of hydrochloric acid is y, then x:y=1.5:10; The wind speed passing into chlorine is 0.2m/s;
S5, material D to be hydrolyzed, to insert after oven dry in the 3rd processing units, after passing into hydrogen, raise the 3rd processing units temperature to 665 DEG C, and be incubated 24.5h and obtain germanium metal; Wherein, the wind speed passing into hydrogen is 0.6m/s.
Embodiment 4
A kind of roasting method that the present invention proposes extracts the method for germanium from raw coal, comprises the following steps:
S1, by weight 170 parts high germanium coal raw coal are broken, sieve after, mix input first processing units with 10 parts of potassium permanganate;
S2, to raise the first processing units and contents temperature to 270 thereof DEG C with the speed of 55 DEG C/min and be incubated 12min, then raising the first processing units and contents temperature to 520 thereof DEG C with the speed of 35 DEG C/min and be incubated 1.8h and obtain material A and flue dust B;
S3, to raise containing the first processing units temperature to 630 DEG C of material A with the speed of 2 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C;
S4, S3 being obtained flue dust C that flue dust B and S4 obtain, to import containing massfraction be, after soaking 14min in the second processing units of 34wt% hydrochloric acid, pass into chlorine 4min, then extract, rectifying with the air quantity of 24L/min, and washing obtains material D; In the course of processing, with 1.8m
3/ min air quantity inputs filtered air in the first processing units; Wherein, the weight sum of flue dust B and flue dust C is x, and the weight of hydrochloric acid is y, then x:y=1.8:12; The wind speed passing into chlorine is 0.3m/s;
S5, material D to be hydrolyzed, to insert after oven dry in the 3rd processing units, after passing into hydrogen, raise the 3rd processing units temperature to 668 DEG C, and be incubated 24.8h and obtain germanium metal; Wherein, the wind speed passing into hydrogen is 0.7m/s.
Carry out performance test to embodiment 1-4, choose the flue dust of common fire smelting method in contrast, detect the content of germanium in flue dust, result is as follows:
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. roasting method extracts a method for germanium from raw coal, it is characterized in that, comprises the following steps:
S1, by weight by broken for 150-180 part raw coal, sieve after, mix input first processing units with 8-12 part potassium permanganate;
S2, to raise the first processing units and contents temperature thereof with the speed of 50-60 DEG C/min to 250-300 DEG C and be incubated 10-15min, then raise the first processing units and contents temperature thereof to 500-550 DEG C with the speed of 20-40 DEG C/min and be incubated 1.5-2h and obtain material A and flue dust B;
S3, to raise containing the first processing units temperature of material A to 600-650 DEG C with the speed of 20-30 DEG C/min, be incubated to material A all burnt, take out the waste material in the first processing units and flue dust C;
S4, S3 being obtained flue dust C that flue dust B and S4 obtain, to import containing massfraction be, after soaking 10-15min in the second processing units of 32-35wt% hydrochloric acid, pass into chlorine 3-5min, then extract, rectifying with the air quantity of 22-25L/min, and washing obtains material D;
S5, material D to be hydrolyzed, to insert after oven dry in the 3rd processing units, raise the 3rd processing units temperature after passing into hydrogen to 650-670 DEG C, and be incubated 24-25h and obtain germanium metal.
2. roasting method extracts the method for germanium from raw coal according to claim 1, it is characterized in that, in S1 Feedstock treating, what raw coal was selected is high germanium coal.
3. according to claim 1 or 2, roasting method extracts the method for germanium from raw coal, it is characterized in that, the order number sieved is 4-6 order.
4. according to any one of claim 1-3, roasting method extracts the method for germanium from raw coal, it is characterized in that, in S3, with 3-5m
3/ min air quantity inputs filtered air in the first processing units.
5. according to any one of claim 1-4, roasting method extracts the method for germanium from raw coal, it is characterized in that, in S4, with 1-2m
3/ min air quantity inputs filtered air in the first processing units.
6. according to any one of claim 1-5, roasting method extracts the method for germanium from raw coal, it is characterized in that, the weight sum of flue dust B and flue dust C is x, and the weight of hydrochloric acid is y, then x:y=1-2:8-15.
7. according to any one of claim 1-6, roasting method extracts the method for germanium from raw coal, it is characterized in that, in S4, the wind speed passing into chlorine is 0.1-0.3m/s.
8. according to any one of claim 1-7, roasting method extracts the method for germanium from raw coal, it is characterized in that, in S5, the wind speed passing into hydrogen is 0.5-1m/s.
9. according to any one of claim 1-8, roasting method extracts the method for germanium from raw coal, it is characterized in that, in S2, raise the first processing units and contents temperature thereof to 260-270 DEG C with the speed of 55-58 DEG C/min and be incubated 12-14min, then raise the first processing units and contents temperature thereof to 520-530 DEG C with the speed of 25-35 DEG C/min and be incubated 1.6-1.8h and obtain material A and flue dust B.
10. according to any one of claim 1-9, roasting method extracts the method for germanium from raw coal, it is characterized in that, in S3, the first processing units temperature of material A is contained to 620-630 DEG C with the rising of the speed of 22-25 DEG C/min, insulation, to material A all burnt, takes out the waste material in the first processing units and flue dust C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678647A (en) * | 1986-05-12 | 1987-07-07 | Enron Corp. | Process for the recovery of gallium and germanium from coal fly ash |
| CN104818397A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Method for extracting germanium from coal |
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2015
- 2015-10-27 CN CN201510710782.2A patent/CN105400969A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678647A (en) * | 1986-05-12 | 1987-07-07 | Enron Corp. | Process for the recovery of gallium and germanium from coal fly ash |
| CN104818397A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Method for extracting germanium from coal |
Non-Patent Citations (1)
| Title |
|---|
| 李存国等: "火法提取煤中锗燃烧条件的实验研究", 《煤炭转化》 * |
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