CN101205572A - Technique for extracting germanium from germanium-containing material by pressure leaching - Google Patents
Technique for extracting germanium from germanium-containing material by pressure leaching Download PDFInfo
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- CN101205572A CN101205572A CNA2007100664110A CN200710066411A CN101205572A CN 101205572 A CN101205572 A CN 101205572A CN A2007100664110 A CNA2007100664110 A CN A2007100664110A CN 200710066411 A CN200710066411 A CN 200710066411A CN 101205572 A CN101205572 A CN 101205572A
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- germanium
- germanic
- obtains
- leaching
- zinc
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 157
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002386 leaching Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000002699 waste material Substances 0.000 claims abstract description 28
- 239000002893 slag Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims description 34
- 238000004070 electrodeposition Methods 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 12
- GDXUDZHLHOBFJH-UHFFFAOYSA-N germanium iron Chemical compound [Fe].[Ge] GDXUDZHLHOBFJH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 5
- 229910005839 GeS 2 Inorganic materials 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000012054 meals Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract 1
- 229960001763 zinc sulfate Drugs 0.000 abstract 1
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229910001656 zinc mineral Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a germanium-containing material leaching method and a germanium extracting technique. The method comprises the following steps of adding germanium-containing materials, zinc electro deposited waste liquid, oxygen with the purity of 70-90 percent or oxygen-enriched air into a pressure reactor, controlling leaching temperature and pressure, directly leaching the germanium in the germanium-containing materials, obtaining germanium-containing solution, adding neutralizing agent into the germanium-containing solution to precipitate germanium, controlling temperature and the final pH value, forming high polymer molecules of germanium and iron for coprecipitation, obtaining first-stage enriched slag of germanium, using electro deposited waste liquid containing zinc sulfate to leach the obtained the first-stage enriched slag of germanium, controlling leaching time and temperature to effectively dissolve germanium out, obtaining germanium-enriched leaching solution, having the obtained germanium-enriched leaching solution extracted and reextracted, and obtaining germanium-containing enriched products through enriching once again. The pressurized leaching treatment of germanium-containing materials is a novel smelting method with high efficiency, low consumption and low pollution.
Description
Technical field
The invention belongs to the metallurgy of rare metal field, in particular, relate to a kind of leaching method of germanic material and the refinement technique of germanium.
Background technology
Germanium belongs to rare diffusing precious metal, and independent mineral deposit is seldom arranged, and most of germanium are distributed in plumbous zinc mineral and the coal with isomorph or adsorbed state, and in polymetallic ore dressing process, germanium mainly is enriched in the concentrate.
Rotary kiln evaporation method or fuming furnace volatilization method are adopted in the extraction of conventional germanium usually, and germanium is enriched in the flue dust, contain germanium oxide dust and obtain germanic 12%~30% germanium concentrate by leaching, tannin sinking germanium, calcining process; The deficiency of above-mentioned technology is that direct leaching yield is low, and is economical unreasonable, and total direct yield of germanium (expecting the germanium product from former) is lower than 60%, and the longer equipment complexity of flow process, investment is big, production cost is higher; Flue gas causes environmental pollution easily.
Summary of the invention
The present invention has overcome the deficiency of existing method, provides that a kind of germanium rate of recovery height, flow process and equipment are simple, less investment, production cost be low.
Carrying out step of the present invention is: in (1), the oxygen or oxygen-rich air adding autoclave with germanic material, sulfur acid 130g/l~200g/l zinc electrodeposition waste liquid, purity 70%~90%, 100 ℃~150 ℃ of control extraction temperatures, under pressure 1.0MPa~1.4MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution;
(2), the above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent, controlled temperature is 60 ℃~90 ℃, in terminal point pH=5~5.4 o'clock, complex anion HGeO with ferric hydroxide colloid form non-selectivity ground absorption germanium is separated out in quantitative ferric iron hydrolysis
3 -And GeO
3 2-, form the high dimeric molecule of germanium iron and co-precipitation, obtain first section enrichment slag of germanium;
(3), with the above-mentioned germanium that obtains section enrichment just slag, with sulfur acid 130g/l~200g/l zinc electrodeposition waste liquid, the control extraction time is 2~4 hours, temperature is 60 ℃~80 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
(4), with above-mentioned obtain be rich in the germanium leach liquor by the extraction, back extraction, enrichment obtains germanic 35~40% germanium enriched substance once more;
The leaching reaction formula of germanium is in the germanic material:
GeS
2+2H
2SO
4+O
2=Ge(SO
4)
2+2H
2O+2S
0
GeS+H
2SO
4+0.50
2=GeSO
4+H
2O+S
0。
Wherein: germanic material can be germanic lead ore concentrate or germanic zinc ore concentrate; Germanic 30g/t~the 1000g/t of germanic material; Germanic raw meal particle size is that 300 orders~400 orders reach 50%~80%; Neutralizing agent can be roasted ore or rich zinc oxidized ore or zinc oxide fumes or lime carbonate etc.; The liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid is 3~5: 1.
Beneficial effect
It is under the state of pressurization that the pressurization of high germanium material is leached, extraction temperature is brought up to 100 ℃~150 ℃, directly leach germanium in the germanic material with zinc electrodeposition waste liquid, just section enriched germanium, extract technology leach a step by pressurization and finish with pyrogenic process, make work simplification, process is strengthened, germanium leaching yield 90%~93%, improved the direct yield of germanium, realized that the efficient of germanium directly leached in the germanic material.
In the pressurization leaching process, in germanium directly leached by (1) and (2) formula by sulfuric acid, the leaching yield of germanium is greater than 91%.
GeS
2+2H
2SO
4+O
2=Ge(SO
4)
2+2H
2O+2S
0(1)
GeS+H
2SO
4+0.5O
2=GeSO
4+H
2O+S
0 (2)
The pressurization leaching process satisfies the complex anion HGeO of ferric hydroxide colloid non-selectivity ground absorption germanium by ferric iron content in the control leach liquor
3 -And GeO
3 2-, form the high dimeric molecule of germanium iron and co-precipitation in the germanium scum, germanium is leached in solution germanium scum and zinc electrodeposition waste liquid again, enrichment obtains germanic 35~50% germanium intermediates once more, the germanium direct yield 83% of germanium product.
Specific embodiment
Embodiment one, granularity is accounted for 50% germanic lead ore concentrate (germanic 30g/t), sulfur acid 130g/l zinc electrodeposition waste liquid, oxygen-rich air and adds in the autoclave for-300,100 ℃ of control extraction temperatures, under the pressure 1.0MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution.The leaching yield 70% of germanium.
The above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent roasted ore, and controlled temperature is 60 ℃, when terminal point pH=5, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
With the above-mentioned germanium that obtains section enrichment just slag (liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid is 3: 1) sulfur acid 130g/l zinc electrodeposition waste liquid, the control extraction time is 2 hours, and temperature is 60 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
The above-mentioned germanium leach liquor that is rich in that obtains is passed through extraction, back extraction, and enrichment obtains germanic enriched substance once more.Germanium direct yield 61.3%.
Embodiment two, with granularity for-400 account for 80% germanic zinc ore concentrate (germanic 1000g/t), sulfur acid 200g/l zinc electrodeposition waste liquid, 90% oxygen adds in the autoclave, 150 ℃ of control extraction temperatures, under the pressure 1.4MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution.The leaching yield 91% of germanium.
The above-mentioned germanium-containing solution that obtains is added the heavy germanium of the rich zinc oxidized ore of neutralizing agent, and controlled temperature is 90 ℃, when terminal point pH=5.4, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
With the above-mentioned germanium that obtains section enrichment just slag (liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid is 5: 1) sulfur acid 200g/l zinc electrodeposition waste liquid, the control extraction time is 4 hours, and temperature is 80 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
The above-mentioned germanium leach liquor that is rich in that obtains is passed through extraction, back extraction, and enrichment obtains germanic enriched substance once more.Germanium direct yield 85.8%.
Embodiment three, with granularity for-350 orders account for 60% germanic zinc ore concentrate (germanic 800g/t), sulfur acid 170g/l zinc electrodeposition waste liquid, 80% oxygen adds in the autoclave, 120 ℃ of control extraction temperatures, under the pressure 1.2MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution.The leaching yield 80% of germanium.
The above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent zinc oxide fumes, and controlled temperature is 80 ℃, when terminal point pH=5.2, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
With the above-mentioned germanium that obtains section enrichment just slag (liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid is 4: 1) sulfur acid 180g/l zinc electrodeposition waste liquid, the control extraction time is 3 hours, and temperature is 70 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
The above-mentioned germanium leach liquor that is rich in that obtains is passed through extraction, back extraction, and enrichment obtains germanic enriched substance once more.Germanium direct yield 72%.
Embodiment four, with granularity for-320 account for 60% germanic lead ore concentrate (germanic 200g/t), sulfur acid 180g/l zinc electrodeposition waste liquid, 80% oxygen adds in the autoclave, 150 ℃ of control extraction temperatures, under the pressure 1.2MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution; The leaching yield 82% of germanium.
The above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent lime carbonate, and controlled temperature is 70 ℃, when terminal point pH=5.3, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
With the above-mentioned germanium that obtains section enrichment just slag (liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid is 3: 1) sulfur acid 190g/l zinc electrodeposition waste liquid, the control extraction time is 2 hours, and temperature is 65 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
The above-mentioned germanium leach liquor that is rich in that obtains is passed through extraction, back extraction, and enrichment obtains germanic enriched substance once more.Germanium direct yield 73%.
Embodiment five, with granularity for-300 account for 60% germanic lead ore concentrate (germanic 500g/t), sulfur acid 130g/l zinc electrodeposition waste liquid, 70% oxygen adds in the autoclave, 100 ℃ of control extraction temperatures, under the pressure 1.2MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution.The leaching yield 83% of germanium.
The above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent lime carbonate, and controlled temperature is 75 ℃, when terminal point pH=5.2, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
With the above-mentioned germanium that obtains section enrichment just slag (liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid is 4: 1) sulfur acid 190g/l zinc electrodeposition waste liquid, the control extraction time is 3 hours, and temperature is 75 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
The above-mentioned germanium leach liquor that is rich in that obtains is passed through extraction, back extraction, and enrichment obtains germanic enriched substance once more.Germanium direct yield 75%.
Embodiment six, with granularity for-400 account for 80% germanic lead ore concentrate (germanic 100g/t), sulfur acid 170g/l zinc electrodeposition waste liquid, 90% oxygen adds in the autoclave, 120 ℃ of control extraction temperatures, under the pressure 1.2MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution; The leaching yield 85% of germanium.
The above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent lime carbonate, and controlled temperature is 70 ℃, when terminal point pH=5.2, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
With the above-mentioned germanium that obtains section enrichment just slag (liquid-solid ratio of germanium first section enrichment slag and zinc electrodeposition waste liquid 5: 1) sulfur acid 190g/l zinc electrodeposition waste liquid, the control extraction time is 2.5 hours, and temperature is 70 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
The above-mentioned germanium leach liquor that is rich in that obtains is passed through extraction, back extraction, and enrichment obtains germanic enriched substance once more.Germanium direct yield 76%.
Analyze, from finding out, it is a kind of efficient, low consumption, oligosaprobic novel smelting process that germanic material leach is handled in pressurization, can improve the leaching yield of germanium in the raw material, more conventional germanium-extracting technology, the leaching yield of germanium can be brought up to 90%-93% by 70%-80%, and whole technology germanium product direct yield can reach 83%.
Claims (6)
1. the processing method of an extracting germanium from germanium-containing material by pressure leaching the steps include:
(1), oxygen or the oxygen-rich air with germanic material, sulfur acid 130g/l~200g/l zinc electrodeposition waste liquid, purity 70%~90% adds in the autoclave, 100 ℃~150 ℃ of control extraction temperatures, under pressure 1.0MPa~1.4MPa condition, directly leach the germanium in the germanic material, obtain germanium-containing solution;
(2), the above-mentioned germanium-containing solution that obtains is added the heavy germanium of neutralizing agent, controlled temperature is 60 ℃~90 ℃, in terminal point pH=5~5.4 o'clock, forms the high dimeric molecule of germanium iron and co-precipitation, obtains first section enrichment slag of germanium;
(3), with the above-mentioned germanium that obtains section enrichment just slag, with sulfur acid 130g/l~200g/l zinc electrodeposition waste liquid, the control extraction time is 2~4 hours, temperature is 60 ℃~80 ℃, makes the effective stripping of germanium, obtains being rich in the germanium leach liquor;
(4), with above-mentioned obtain be rich in the germanium leach liquor by the extraction, back extraction, enrichment obtains germanic enriched substance once more
The leaching reaction formula of germanium is in the germanic material:
GeS
2+2H
2SO
4+O
2=Ge(SO
4)
2+2H
2O+2S
0
GeS+H
2SO
4+0.5O
2=GeSO
4+H
2O+S
0。
2. the process for extracting of germanium and germanium is leached in the pressurization of germanic material according to claim 1, and it is characterized in that: described germanic material comprises germanic lead ore concentrate or germanic zinc ore concentrate.
3. the process for extracting of germanium and germanium is leached in the pressurization of germanic material according to claim 1 and 2, it is characterized in that: the germanic 30g/t~1000g/t of described germanic material.
4. the process for extracting of germanium and germanium is leached in the pressurization of germanic material according to claim 1, and it is characterized in that: described germanic raw meal particle size reaches 50%~80% for-300 orders~-400 orders.
5. the process for extracting of germanium and germanium is leached in the pressurization of germanic material according to claim 1, and it is characterized in that: described neutralizing agent is roasted ore or rich zinc oxidized ore or zinc oxide fumes or lime carbonate.
6. the process for extracting of germanium and germanium is leached in the pressurization of germanic material according to claim 1, it is characterized in that: the liquid-solid ratio of described germanium first section enrichment slag and zinc electrodeposition waste liquid is 3~5: 1.
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