CN102181653B - Method for recovering germanium from germanium-containing smoke dust - Google Patents
Method for recovering germanium from germanium-containing smoke dust Download PDFInfo
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Abstract
The invention relates to a method for recovering germanium from germanium-containing smoke dust, in particular to a method for leaching the germanium-containing smoke dust by using sulfuric acid and sodium hydroxide sequentially and recovering the germanium from the germanium-containing smoke dust by hydrochloric acid distillation, and relates to the technical field of wet-process metallurgy. The method is realized by processes of leaching by the sulfuric acid twice, leaching by the sodium hydroxide twice, neutralizing leachate, performing evaporating and concentrating, chloridizing and distilling, preparing germanium dioxide and the like. In the method for recovering the germanium, the recovery rate of the germanium is more than 93 percent, so the successful study of the method has a great positive significance for the solving of problems of low recovery rate, high recovery cost and low resource utilization rate of the germanium in the germanium-containing smoke dust, a problem that distillation residues are needed to be processed repeatedly and a problem that environmental pollution is serious and the like.
Description
Technical field
The present invention relates to technical field of wet metallurgy, specifically be a kind of germanium oxide dust that will contain after sulfuric acid leaching～sodium hydroxide leaches pre-treatment, adopt hydrochloric acid distillatory method to reclaim the method for germanium in the germanic flue dust again.
Background technology
Germanic brown coal adopt the pyrogenic process enrichment to carry in the germanium process, and when being higher than 710 ℃ of germanous oxide volatilization temperatures, germanium mainly enters into dust collecting system with the form volatilization of GeO, and at the lower stove tail of temperature, most GeO generates GeO again by dioxygen oxidation
2, temperature reduces postadhesion on coal smoke dirt particulate surface, and a spot of not oxidized GeO reduces along with temperature, also attached to the soot dust granule surface, also has part germanium then to be present in the germanium oxide dust with the oxide morphology volatilization.Therefore, in coal smoke dirt, germanium is except with GeO
2Form exist outside, also have a spot of with GeO, GeS, GeS
2, Ge
2S
3And GeO
2.SiO
2Deng form have and GeO wherein
2There are amorphous, six square crystal, three kinds of forms of cubic N-type waferN to exist again.
At present, the method for from contain germanium oxide dust, extracting germanium generally is to adopt the Manganse Dioxide oxidation, and the method for concentrated hydrochloric acid fractionation by distillation is carried out then.In the method; The fuming liquid arsenic boiling point that forms because of arsenic (III) and hydrochloric acid is low; When distillation, enter into germanium tetrachloride easily; Therefore needing with Manganse Dioxide arsenic oxide arsenoxide (III) is arsenic (V), so that arsenic together is not distilled out with germanium when distillation, the post-heating fractionation by distillation is accomplished in oxidation can obtain germanium tetrachloride.When chlorinated distillation, the GeO of unformed, six squares
2Very easily form GeCl with the hydrochloric acid effect
4, GeCl
4Separate with other impurity through distillation and after steaming rectification and purification again and obtain pure GeCl
4And the GeO of cubic type
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2Etc. the germanium of form but be difficult to with hydrochloric acid reaction, therefore remained in and carried in the germanium residue.If in containing germanium oxide dust, if the shared ratio of the germanium of this part form is big more, then cause the distillation recovery of germanium tetrachloride to reduce, the germanium that remains in the chlorinated distillation residue is just many more.So want to contain germanium oxide dust the higher recovery is arranged when chlorinated distillation, should control the volatilization condition when then coal combustion volatilizees as far as possible, make germanium generate the cubic type GeO of hydrochloric acid indissoluble less
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2Deng compound.
But owing to receive the influence of raw material, the type of furnace, operational condition etc.; Restive processing condition are kept away unavoidably and can be generated this compounds, so when chlorinated distillation; The distillation yield difference that contains germanium in the germanium oxide dust can be very big; The part contain the germanium oxide dust yield low about 50%, high reaches about 85%, mostly between 60 ~ 80%.Because the processing condition of each producer differ, the chlorinated distillation yield of the germanium oxide dust of some factory's output can reach about 85%, and the germanium oxide dust that contains of the factory's output that has has only the yield about 75%.The low like this recovery one is to cause limited germanium resource not make full use of, the 2nd, and the later stage is reclaimed the germanium difficulty from acid sludge, and acid sludge is stored up for a long time and has been caused environmental pollution.
This type of contains the GeO of cubic type
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2Flue dust burning etc. the germanium of form is insufficient, and volatile matter is higher, and sour indissoluble part is higher; The germanium grade is lower, and when the method for employing Manganse Dioxide oxidation～hydrochloric acid fractionation by distillation was extracted germanium, the germanium recovery was low, acid consumption is excessive; The spent acid treatment capacity is big, and processing costs is higher.
Summary of the invention
The present invention is directed to the GeO that contains cubic type
2With GeO, GeS, GeS
2, Ge
2S
3, GeO
2.SiO
2When adopting the method for Manganse Dioxide oxidation-hydrochloric acid fractionation by distillation to extract germanium etc. the flue dust of the germanium of form, the problem that the germanium recovery is low has proposed the cheap treatment process of a kind of ten minutes cost-effectively.
A kind of method that from contain germanium oxide dust, reclaims germanium of the present invention, its characteristic are to realize through following step in this method:
The first step, sulfuric acid leaches for the 1st time:
Adding weight is that the water and the weight of 0.5～1 times of flue dust weight are the industrial sulphuric acid of flue dust weight 3/20 ~ 1/4 in containing germanium oxide dust, is heated with stirring to 60～70 ℃, places and makes flue dust slaking reaction 1～2h; Adding weight then is the water of 3～5 times of flue dust weight, be heated with stirring to 80～85 ℃ after, agitation leach 1～3h; After leaching finishes; Filter, filter residue uses weight to wash as the hot water of flue dust weight 1/5～2/5, leaches moisture after clean; This moisture and filtering filtrating are merged into after the leach liquor for use, and filter residue changes over to and carries out the 2nd sulfoxylic acid and leach;
In second step, sulfuric acid leaches for the 2nd time:
In the first step, adding weight in the filter residue of gained is the industrial sulphuric acid of flue dust weight 3/20～1/4, is heated with stirring to 60～70 ℃, places to make flue dust slaking reaction 1～2h; Adding weight then is the water of 3～5 times of flue dust weight, behind heat temperature raising to 80～85 ℃, and agitation leach 1～3h; After leaching finishes; Filter, filter residue uses weight to wash as the hot water of 1/2～3/5 times of flue dust weight, leaches moisture after clean; This moisture and filtering filtrating are merged into after the leach liquor for use, and filter residue changes over to and carries out the 1st sodium hydroxide and leach;
In the 3rd step, sodium hydroxide leaches for the 1st time:
In the filter residue of the second step gained, adding weight is the former industrial sodium hydroxide that contains germanium oxide dust weight 1/10～1/5, and adding weight then is the water of 3～4 times of flue dust weight, behind heat temperature raising to 85～90 ℃; Leaching 1～3h after leaching finishes, filters; To filter residue weight is that the hot water of flue dust weight 1/5～2/5 washs; Leach moisture after cleaning, the filtrating of this moisture and filtration is merged into after the leachate for use, and filter residue then changes over to and carries out the 2nd NaOH leaching;
In the 4th step, sodium hydroxide leaches for the 2nd time:
In the filter residue of the 3rd step gained, adding weight is the industrial sodium hydroxide of former flue dust weight 1/10～1/5, and adding weight then is the water of 3～4 times of flue dust weight, behind heat temperature raising to 85～90 ℃; Leaching 1～3h after leaching finishes, filters; To filter residue weight be the hot water of flue dust weight 1/2～3/5 wash to the pH value of wash water be 6.5～7.0; Leach moisture, the filtrating of this moisture and filtration is merged into after the leachate for use, and filter residue is then done subsequent treatment;
The 5th step, the leach liquor neutralization:
The sulphuric leachate of gained in the first step and the sodium hydroxide leach liquor of the 3rd step gained are mixed, and the pH value of regulating mixed solution is 5.0～5.5;
The 6th step, evaporation concentration:
Mixed solution in the 5th step is heated to boiling, carry out evaporation concentration to mixeding liquid volume and be original volume 1/10 o'clock, stops evaporation;
The 7th step, chlorinated distillation:
After the liquid cooling that evaporation concentration is good in the 6th step, adding volume is the hydrochloric acid of 5～7 times of this liquid volumes, carries out chlorinated distillation, obtains germanium tetrachloride, and distillation speed is PM 10～15mL, about 40～60 minutes of distillation time;
The 8th step, the germanium dioxide preparation:
Germanium tetrachloride is made high-purity germanium dioxide through multiple steaming, rectifying, hydrolysis and oven dry.
Described germanium dioxide obtains distinguishing molten germanium after reduction.
In the described the first step with in second step, the speed setting of stirring is that PM 115～120 changes.
Adopt the main chemical compositions that contains germanium oxide dust of art breading of the present invention to see table 1:
Table 1 unit: massfraction, %
| Numbering | 600 ℃ are burnt decrement | SiO 2 | FeO 3 | Al 2O 3 | CaO | MgO | S | Ge |
| B～01 | 15.50 | 60.24 | 1.90 | 8.60 | 0.84 | 1.08 | 0.58 | 1.33 |
| B～02 | 17.70 | 55.30 | 2.13 | 9.69 | 0.66 | 1.05 | 0.55 | 5.43 |
| B～03 | 16.88 | 56.65 | 2.72 | 18.95 | 0.91 | 1.08 | 0.74 | 9.17 |
Technological principle of the present invention is a method of before chlorinated distillation, taking wet oxidation to leach flue dust, leaches the germanium in the flue dust after with sulfuric acid dissolution, and then utilizes the GeO of tetragonal structure in the leached mud
2, silicon～germanium junction is fit, sulphided state germanium is prone to and the sodium hydroxide reaction, forms the character that the germanic acid root gets into solution, leaches with the sodium hydroxide solution dissolving, after the soluble substance on soot dust granule surface and the silicon dissolving, the germanium of parcel is also next by further leaching simultaneously.Mix acid leaching liquor and sodium hydroxide leach liquor then, utilize germanium in the mixed solution again at sulfuric acid medium, the nonvolatile characteristic of germanic acid root under the sodium hydroxide property condition, heating evaporation concentrates leach liquor, reaches the purpose of enriched germanium.Rich germanium liquid adds hydrochloric acid again and carries out chlorinated distillation, thereby obtains GeCl
4, GeCl
4Hydrolysis obtains GeO
2
The main chemical reactions that relates in this process method is following:
GeO
2(tetrahedron)+2NaOH=Na
2GeO
3+ H
2O
GeO
2.SiO
2+4?NaOH=Na
2GeO
3+Na
2SiO
3+2H
2O
GeS+?4NaOH=Na
2GeO
2+Na
2S+2H
2O
GeS
2+?4NaOH=Na
2GeO
3+Na
2S+2H
2O
Ge
2S
3+10NaOH=Na
2GeO
2+Na
2GeO
3+3Na
2S+5H
2O
Na
2GeO
3+H
2SO
4=Ge(SO
4)
2+Na
2SO
4+3H
2O
Ge(SO
4)
2+4HCl=GeCl
4↑+2H
2SO
4
GeCl
4+2H
2O=GeO
2+4HCl
The process method and the control condition of germanium in the hydrometallurgic recovery distillation residue have been gone out according to above principle tests; For ge content at this type of germanium oxide dust of 0.3 ~ 15.0%; Reclaim germanium with this process method, the recovery of germanium can reach more than 93%, and this proposes the research success of germanium method; Problems such as the recovery for solving germanium in this type of flue dust is low, cost recovery is high, resource utilization is low, distillation residue are wanted repeated treatments, and environmental pollution is serious have very positive meaning.
Embodiment
Embodiment 1:
The first step: get 250g and contain germanium oxide dust in the 3000ml beaker, flue dust is germanic to be 1.33%, and flue dust germanium metal 3.325g adds 125mL water, adds the industrial sulphuric acid of 37.5g, stirs into a paste, and is heated to 65 ℃, places and makes flue dust slaking reaction 1h.The water that adds 750mL then places on the temperature control electric furnace, starts mechanical stirrer, and stirring velocity is set in PM 115 changes, heat temperature raising to 85 ℃, agitation leach 1.5h.Soak after rolling, vacuum filtration is washed the boiling water of filter residue with 50mL, and washings and filtrating and be leach liquor obtain leach liquor 860mL, and filter residue is transferred in the former beaker.
Second step: add the industrial sulphuric acid of 37.5g in the first step gained filter residue, stir into a paste, be heated to 65 ℃, place and make flue dust slaking reaction 1h.The water that adds 750mL then places on the electric furnace, starts mechanical stirrer, and stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 1.5h.Soak after rolling, vacuum filtration is fully cleaned sulfuric acid to filter residue with the boiling water of 125mL, and washings and filtrating and be leach liquor obtain leach liquor 870mL.
The 3rd step: the second step gained filter residue is changed in the former beaker, add 25g sodium hydroxide, add 750mL water.Place on the electric furnace, start mechanical stirrer, stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 1.5h.After leaching finishes, vacuum filtration, to filter residue with the washing of the boiling water of 50mL,, washings and filtrating and be leach liquor obtain leach liquor 810mL.
The 4th step: the 3rd step gained filter residue is changed in the former beaker, add the sodium hydroxide of 25g, add 750mL water, place on the electric furnace; Start mechanical stirrer, stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 1.5h; After leaching finishes, vacuum filtration, extremely neutral to filter residue with the boiling water thorough washing of 125mL, with pH detection paper wash water; The pH value is 6.8, and washings and filtrating and be leach liquor obtain leach liquor 835mL.
The 5th step: the 1st sulfoxylic acid leach liquor 860mL and the 1st sodium hydroxide leach liquor 810mL are mixed in the Erlenmeyer flask of 5000mL; The pH value of using the 2nd sulfoxylic acid leach liquor to regulate mixed solution again is 5.0; The consume sulfur acid leaching liquor is 50mL, and total mixeding liquid volume is 1720mL.
The 6th step: mixed solution is heated to boiling, carries out evaporation concentration, when the volume of evaporation concentration to solution is 172mL, stop heating.
The 7th step: will evaporate the back liquid cooling after room temperature, and add the 860mL technical hydrochloric acid, behind the connection water distilling apparatus; Distill; Distillation speed is controlled at PM 10～12mL, distills after 45 minutes, stops distillation; Obtain germanium tetrachloride metal 3.163g, the recovery from the germanium oxide dust to the germanium tetrachloride is 95.12%.
The 8th step: with germanium tetrachloride by the multiple steaming of conventional germanium-extracting technology, rectification and purification after, be hydrolyzed, make high-purity germanium dioxide.
The 9th step: described germanium dioxide obtains distinguishing molten germanium after reduction.
Embodiment 2:
The first step: get 250g and contain germanium oxide dust in the 3000ml beaker, flue dust is germanic to be 5.43%, and flue dust germanium metal 13.575g adds 125mL water, adds the industrial sulphuric acid of 50.0g, stirs into a paste, and is heated to 65 ℃, places and makes flue dust slaking reaction 1.5h.The water that adds 1000mL then places on the temperature control electric furnace, starts mechanical stirrer, and stirring velocity is set in PM 115 changes, heat temperature raising to 85 ℃, agitation leach 2.0h.Soak after rolling, vacuum filtration is washed the boiling water of filter residue with 50mL, and washings and filtrating and be leach liquor obtain leach liquor 1040mL, and filter residue is transferred in the former beaker.
In second step, the industrial sulphuric acid of adding 50.0g stirs into a paste in the filter residue of the first step gained, is heated to 65 ℃, places and makes flue dust slaking reaction 1.5h.The water that adds 1000mL then places on the electric furnace, starts mechanical stirrer, and stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 2h.Soak after rolling, vacuum filtration is fully cleaned sulfuric acid to filter residue with the boiling water of 125mL, and washings and filtrating and be leach liquor obtain leach liquor 1100mL.Filter residue changes in the former beaker.
The 3rd step added 37.5g sodium hydroxide in the filter residue of the second step gained, added 1000mL water.Place on the electric furnace, start mechanical stirrer, stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 2h.After leaching finishes, vacuum filtration, with the washing of the boiling water of 50mL, washings and filtrating and be leach liquor obtain leach liquor 1060mL to filter residue.Filter residue is changed in the former beaker.
The 4th step: in the filter residue of the 3rd step gained, add the sodium hydroxide of 37.5g, add 1000mL water, place on the electric furnace, start mechanical stirrer; Stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, agitation leach 2h, leach finish after; Vacuum filtration, extremely neutral to filter residue with the boiling water thorough washing of 125mL, with pH detection paper wash water; The pH value is 6.8, and washings and filtrating and be leach liquor obtain leach liquor 1150mL.
The 5th step: the 1st sulfoxylic acid leach liquor 1040mL and the 1st sodium hydroxide leach liquor 1060mL are mixed in the Erlenmeyer flask of 5000mL; The pH value of using the 2nd sulfoxylic acid leach liquor to regulate mixed solution again is 5.25; The consume sulfur acid leaching liquor is 70mL, and total mixeding liquid volume is 2170mL.
The 6th step: mixed solution is heated to boiling, carries out evaporation concentration, when the volume of evaporation concentration to solution is 217mL, stop heating.
The 7th step: will evaporate the back liquid cooling after room temperature, and add the 1250mL technical hydrochloric acid, behind the connection water distilling apparatus; Distill; Distillation speed is controlled at PM 12～15mL, distills after 40 minutes, stops distillation; Obtain germanium tetrachloride metal 13.123g, the recovery from the germanium oxide dust to the germanium tetrachloride is 96.67%.
The 8th step: with germanium tetrachloride by the multiple steaming of conventional germanium-extracting technology, rectification and purification after, be hydrolyzed, make high-purity germanium dioxide.
The 9th step: described germanium dioxide obtains distinguishing molten germanium after reduction.
Embodiment 3:
The first step: get 250g and contain germanium oxide dust in the 3000ml beaker, flue dust is germanic to be 9.17%, and flue dust germanium metal 22.925g adds 125mL water, adds the industrial sulphuric acid of 62.5g, stirs into a paste, and is heated to 70 ℃, places and makes flue dust slaking reaction 2h.The water that adds 1250mL then places on the temperature control electric furnace, starts mechanical stirrer, and stirring velocity is set in PM 115 changes, heat temperature raising to 85 ℃, agitation leach 2.5h.Soak after rolling, vacuum filtration is washed the boiling water of filter residue with 50mL, and washings and filtrating and be leach liquor obtain leach liquor 1260mL, and filter residue is transferred in the former beaker.
Second step: in the filter residue of the first step gained, add the industrial sulphuric acid of 62.5g, stir into a paste, be heated to 70 ℃, place and make flue dust slaking reaction 2h.The water that adds 1250mL then places on the electric furnace, starts mechanical stirrer, and stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 2.5h.Soak after rolling, vacuum filtration is fully cleaned sulfuric acid to filter residue with the boiling water of 125mL, and washings and filtrating and be leach liquor obtain leach liquor 1280mL.Filter residue changes in the former beaker.
The 3rd step: in the filter residue of the second step gained, add 50g sodium hydroxide, add 1250mL water.Place on the electric furnace, start mechanical stirrer, stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, and agitation leach 2.5h.After leaching finishes, vacuum filtration, with the washing of the boiling water of 50mL, washings and filtrating and be leach liquor obtain leach liquor 1255mL to filter residue.Filter residue is changed in the former beaker.
The 4th step: in the filter residue of the 3rd step gained, add the sodium hydroxide of 50g, add 1250mL water, place on the electric furnace, start mechanical stirrer; Stirring velocity is set in PM 115 changes, behind the heat temperature raising to 85 ℃, agitation leach 2.5h, leach finish after; Vacuum filtration, extremely neutral to filter residue with the boiling water thorough washing of 125mL, with pH detection paper wash water; The pH value is 6.8, and washings and filtrating and be leach liquor obtain leach liquor 1270mL.
The 5th step: the 1st sulfoxylic acid leach liquor 1260mL and the 1st sodium hydroxide leach liquor 1255mL are mixed in the Erlenmeyer flask of 5000mL; The pH value of using the 2nd sulfoxylic acid leach liquor to regulate mixed solution again is 5.5; The consume sulfur acid leaching liquor is 80mL, and always leaching mixeding liquid volume is 2595mL.
The 5th step: mixed solution is heated to boiling, carries out evaporation concentration, when the volume of evaporation concentration to solution is 260mL, stop heating.
The 6th step: will evaporate the back liquid cooling after room temperature, and add the 1750mL technical hydrochloric acid, behind the connection water distilling apparatus; Distill; Distillation speed is controlled at PM 12～15mL, distills after 45 minutes, stops distillation; Obtain germanium tetrachloride metal 22.405g, the recovery from the germanium oxide dust to the germanium tetrachloride is 97.73%.
The 8th step: with germanium tetrachloride by the multiple steaming of conventional germanium-extracting technology, rectification and purification after, be hydrolyzed, make high-purity germanium dioxide.
The 9th step: described germanium dioxide obtains distinguishing molten germanium after reduction.
Test control condition among the embodiment 1,2,3 and result are listed in the table below in 2.
Subordinate list test control condition and result
| Test | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Contain the germanium oxide dust consumption, g | 250 | 250 | 250 |
| The bag dust grade, % | 1.33 | 5.43 | 9.17 |
| Amount of metal, g | 3.325 | 13.575 | 22.925 |
| Leach for 1 time and add H 2SO 4Quality, g | 37.5 | 50.0 | 62.5 |
| The slaking reaction time, h | 1.0 | 1.5 | 2.0 |
| 1 sulfoxylic acid leach liquor volume, mL | 860 | 1040 | 1260 |
| Leach for 2 times and add H 2SO 4Quality, g | 37.5 | 50.0 | 62.5 |
| 2 sulfoxylic acid leach liquor volumes, mL | 870 | 1100 | 1280 |
| Leach the quality that adds NaOH, g 1 time | 25 | 37.5 | 50 |
| 1 NaOH leach liquor volume, mL | 810 | 1060 | 1255 |
| Leach the quality that adds NaOH, g 2 times | 25 | 37.5 | 50 |
| 2 NaOH leach liquor volumes, mL | 835 | 1150 | 1270 |
| The single extraction time, h | 1.5 | 2.0 | 2.5 |
| The neutralizer volume, mL | 1720 | 2210 | 2595 |
| The liquid concentrator volume, mL | 170 | 220 | 260 |
| The pH value of mixed solution | 5.02 | 5.25 | 5.54 |
| 10mol/L technical hydrochloric acid add-on, g | 860 | 1250 | 1500 |
| The germanium tetrachloride distillation speed, mL/min | 10～12 | 12～15 | 12～15 |
| Steam the germanium tetrachloride amount of metal, g | 3.163 | 13.123 | 22.405 |
| The germanium recovery, % | 95.12 | 96.67 | 97.73 |
Claims (3)
1. method that from contain germanium oxide dust, reclaims germanium is characterized in that this method is to realize through following step:
The first step, sulfuric acid leaches for the 1st time:
Adding weight is that the water and the weight of 0.5～1 times of flue dust weight are the industrial sulphuric acid of flue dust weight 3/20 ~ 1/4 in containing germanium oxide dust, is heated with stirring to 60～70 ℃, places and makes flue dust slaking reaction 1～2h; Adding weight then is the water of 3～5 times of flue dust weight, be heated with stirring to 80～85 ℃ after, agitation leach 1～3h; After leaching finishes; Filter, filter residue uses weight to wash as the hot water of flue dust weight 1/5～2/5, leaches moisture after clean; This moisture and filtering filtrating are merged into after the leach liquor for use, and filter residue changes over to and carries out the 2nd sulfoxylic acid and leach;
In second step, sulfuric acid leaches for the 2nd time:
In the first step, adding weight in the filter residue of gained is the industrial sulphuric acid of flue dust weight 3/20～1/4, is heated with stirring to 60～70 ℃, places to make flue dust slaking reaction 1～2h; Adding weight then is the water of 3～5 times of flue dust weight, behind heat temperature raising to 80～85 ℃, and agitation leach 1～3h; After leaching finishes; Filter, filter residue uses weight to wash as the hot water of 1/2～3/5 times of flue dust weight, leaches moisture after clean; This moisture and filtering filtrating are merged into after the leach liquor for use, and filter residue changes over to and carries out the 1st sodium hydroxide and leach;
In the 3rd step, sodium hydroxide leaches for the 1st time:
In the filter residue of the second step gained, adding weight is the industrial sodium hydroxide of flue dust weight 1/10～1/5, and adding weight then is the water of 3～4 times of flue dust weight, behind heat temperature raising to 85～90 ℃; Leaching 1～3h after leaching finishes, filters; To filter residue weight is that the hot water of flue dust weight 1/5～2/5 washs; Leach moisture after cleaning, the filtrating of this moisture and filtration is merged into after the leachate for use, and filter residue then changes over to and carries out the 2nd NaOH leaching;
In the 4th step, sodium hydroxide leaches for the 2nd time:
In the filter residue of the 3rd step gained, adding weight is the industrial sodium hydroxide of flue dust weight 1/10～1/5, and adding weight then is the water of 3～4 times of flue dust weight, behind heat temperature raising to 85～90 ℃; Leaching 1～3h after leaching finishes, filters; To filter residue weight be the hot water of flue dust weight 1/2～3/5 wash to the pH value of wash water be 6.5～7.0; Leach moisture, the filtrating of this moisture and filtration is merged into after the leachate for use, and filter residue is then done subsequent treatment;
The 5th step, the leach liquor neutralization:
The sulphuric leachate of gained in the first step and the sodium hydroxide leach liquor of the 3rd step gained are mixed, and the pH value of regulating mixed solution is 5.0～5.5;
The 6th step, evaporation concentration:
Mixed solution in the 5th step is heated to boiling, carry out evaporation concentration to mixeding liquid volume and be original volume 1/10 o'clock, stops evaporation;
The 7th step, chlorinated distillation:
After the liquid cooling that evaporation concentration is good in the 6th step, adding volume is the hydrochloric acid of 5～7 times of this liquid volumes, carries out chlorinated distillation, obtains germanium tetrachloride, and distillation speed is PM 10～15mL, distillation time 40～60 minutes;
The 8th step, the germanium dioxide preparation:
Germanium tetrachloride is made high-purity germanium dioxide through multiple steaming, rectifying, hydrolysis and oven dry.
2. a kind of method that from contain germanium oxide dust, reclaims germanium as claimed in claim 1 is characterized in that described germanium dioxide obtains distinguishing molten germanium after reduction.
3. a kind of method that from contain germanium oxide dust, reclaims germanium as claimed in claim 1 is characterized in that the described the first step and in second step, the speed setting of stirring is that PM 115～120 changes.
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| 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 |
| CN102392138B (en) * | 2011-11-07 | 2013-04-03 | 云南东昌金属加工有限公司 | Technological method for comprehensively recovering valued metal such as indium and germanium from lead-zinc smoke |
| CN104789785B (en) * | 2015-05-19 | 2017-01-25 | 河北工程大学 | Method for extracting germanium from germanium-containing smoke dust |
| CN109321764A (en) * | 2018-11-22 | 2019-02-12 | 衡阳恒荣高纯半导体材料有限公司 | A method of the Ti recovery from germanic zinc oxide fumes |
| 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 |
| CN111560529A (en) * | 2020-06-24 | 2020-08-21 | 深圳思创环保科技有限公司 | Method for recovering germanium from germanium-containing material |
| CN113584319B (en) * | 2021-08-04 | 2022-05-24 | 云南大学 | Method for extracting germanium from smoke dust |
| CN116875826B (en) * | 2023-09-07 | 2023-11-14 | 昆明理工大学 | Method for extracting germanium by zinc oxide smoke depth and short process |
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