CN102628109A - Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof - Google Patents
Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof Download PDFInfo
- Publication number
- CN102628109A CN102628109A CN2012100899916A CN201210089991A CN102628109A CN 102628109 A CN102628109 A CN 102628109A CN 2012100899916 A CN2012100899916 A CN 2012100899916A CN 201210089991 A CN201210089991 A CN 201210089991A CN 102628109 A CN102628109 A CN 102628109A
- Authority
- CN
- China
- Prior art keywords
- germanium
- complexing
- agent
- heavy
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 69
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000000536 complexating effect Effects 0.000 title claims abstract description 27
- 238000000151 deposition Methods 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 235000006667 Aleurites moluccana Nutrition 0.000 claims abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 240000004957 Castanea mollissima Species 0.000 claims abstract description 8
- 235000018244 Castanea mollissima Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000012141 concentrate Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 9
- -1 EDTA diamines Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 235000012054 meals Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 235000018553 tannin Nutrition 0.000 abstract description 8
- 229920001864 tannin Polymers 0.000 abstract description 8
- 239000001648 tannin Substances 0.000 abstract description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract 2
- 239000013522 chelant Substances 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- 229960001484 edetic acid Drugs 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- YDCFOUBAMGLLKA-UHFFFAOYSA-N 2,6,7-trihydroxy-9-phenylxanthen-3-one Chemical compound C1=2C=C(O)C(O)=CC=2OC2=CC(=O)C(O)=CC2=C1C1=CC=CC=C1 YDCFOUBAMGLLKA-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
Landscapes
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention relates to a complexing germanium depositing agent used for enriching rear metal germanium, which uses natural gallnut flowers and Chinese chestnut bracts as the mixed raw materials. After the raw materials are smashed, deionized water is added for extracting tannin liquid, then the complexing agent ammonium chloride or ethylene diamine tetraacetic acid(EDTA) diamine and powdered activated carbon are added for reaction at the temperature of 50-70 DEG C with stirring, then the activated carbon is filtered out, and the filter liquid is evaporated and dried in vacuum mode to obtain powdered complexing germanium depositing agent. The complexing germanium depositing agent is added in germanium-containing ore solution and can lead germanium to generate complex fast in acidity condition so as to generate and deposit out polydentate chelate with a complex structure, and germanium depositing rate can reach 99%, and germanium concentrate with germanium concentration 15% larger than before can be generated.
Description
Technical field
The present invention relates to be used for the heavy germanium agent of a kind of complexing of enrichment rare metal germanium and in the application of germanic ore deposit liquid enriched germanium.
Background technology
Germanium is a kind of rare metal, has a wide range of applications with fields such as electronic industry, infrared optics equipment, photoconductive fiber, medical science, metallurgy, the energy, has become a kind of very important strategic resource.Germanium is typical dispersed elements, and the enrichment extractive technique is most important.Element Ge obtains from germanic higher nonferrous metals ore mostly, in smelting the non-ferrous metal process, reclaims the enriched substance of germanium simultaneously.For example in zinc hydrometallurgy is produced, when handling the zinc sulfide concentrates of germanic higher (germanic 100-150g/ ton), at first germanium is enriched in the leached mud; Handle with fuming furnace, germanic 0.1% in the flue dust, go out with acidleach; Add the heavy germanium of Chinese gallotanninic acid behind the solution purification, germanic 3-5% in the throw out, germanium is enriched to 15-20% in the germanium ash that oven dry, calcining obtain;, further extract as germanium concentrate with this.
Along with expanding economy; The increase of the demand of germanium; Resource and output as the Chinese gallotanninic acid of the heavy germanium agent of typical case can not be met the need of market far away; Just there is nearly 3000 tons demand in domestic only southwestern market, causes the price of Weibull to be doubled and redoubled, thereby has improved the extraction cost of germanium metal.
Summary of the invention
The objective of the invention is to prepare the heavy germanium agent of a kind of complexing, improve the extraction yield of germanium, reduce the manufacturing cost of heavy germanium agent.
The germanium agent is sunk in complexing of the present invention, is made by following method:
With the raw material dry product doubly flower and dry product Chinese chestnut bud mix and pulverize by weight 1:0.2～0.3, the back adds deionized water immersion 2h, filter cleaner; Get filtrating (be and mix tannin liquid), add complexing agent ammonium chloride or EDTA diamines, add powdered carbon; 50 ~ 70 ℃ of following stirring reactions at least 30 minutes, the filtering gac, filtrating is through vacuum-evaporation, drying; Get meal, be the heavy germanium agent of complexing.
Said complexing dosage is the 1%-2% of a times flower, the luxuriant material quantity of Chinese chestnut.
Said deionized water soaking temperature is 50～70 ℃.
The application of the heavy germanium agent enriched germanium in the liquid of germanic ore deposit of said complexing, the method for enriched germanium is following:
15～25 times of amounts by germanium weight in the liquid of ore deposit drop into the heavy germanium agent of complexing, regulate pH to 2～3,35～45 ℃ following stirring reaction, separate out fully until deposition, and cross and filter throw out, 450～500 ℃ of roasting 2h, cooling promptly gets germanium concentrate.
The present invention uses the title complex generation method of coordination chemistry, in natural tannin extract, adds the chemical complexing agent and processes the unique compound tannin of proportioning as heavy germanium agent.The heavy germanium agent of this complexing adds in the liquid of germanic ore deposit, can under acidic conditions, with metals ion germanium (central ion) complex compound take place, and gradual reaction generates multiple tooth inner complex and be precipitated out rapidly, and heavy germanium rate reaches 99.0%, and throw out is through roasting acquisition germanium concentrate.Substitute in the ore deposit liquid that Chinese gallotanninic acid adds zinc metallurgy with this heavy germanium agent, when obtaining qualified zinc carbonate product, can obtain germanic amount greater than 15% germanium concentrate.Preparing this heavy germanium agent is raw material so that the wildwood product is doubly colored, Chinese chestnut is luxuriant, aboundresources, and low price can reduce heavy germanium agent production cost greatly, and economic benefit is considerable.
Specific embodiments
Embodiment 1:
One. the preparation of the heavy germanium agent of complexing
(1) by doubly a flower dry powder 100g, Chinese chestnut bud dry powder 30g proportioning, add deionized water 0.85L, 60 ℃ are stirred and soaked 2 hours, filter cleaner, receive tannin liquid.
(2) in tannin liquid, add EDTA diamines (YD 30 diamines) 0.90g, powdered carbon 0.6g, 60 ℃ of stirring reaction 0.5h go out gac through isolated by vacuum filtration, and the vacuum-evaporation of will filtrating is dry, gets the heavy germanium agent of product complexing.
Two. the germanium in the liquid of the heavy germanic ore deposit of germanium agent enrichment of complexing
Be respectively through detecting the content that obtains metals ion in the liquid of ore deposit: Ge
4+50mg/L, Zn
2+150g/L, Fe
2+3g/L.In the liquid of 0.5L ore deposit, add the heavy germanium agent dry product 0.55g of complexing, regulate PH ≈ and stir 45min down for 2.5,40 ℃, filter, multiple tooth inner complex deposition, cross the throw out of germanium that filtered enrichment, filtrating is used for detecting.Use the phenylfluorone development process, under the 510nm Visible Light Characteristics, absorb, measure the germanic amount of ore deposit liquid and above-mentioned filtrating respectively, calculating heavy germanium rate is 99.05%.
Embodiment 2
(1) take by weighing raw material and doubly spend dry powder 110g, Chinese chestnut bud dry powder 25g, add deionized water 0.75L, 60 ℃ are stirred extracting 2h, filter cleaner, receive tannin liquid.
(2) in tannin liquid, add ammonium chloride 1.2g, powdered carbon 0.5g, 60 ℃ of stirring reaction 0.5h remove gac through vacuum filtration, get the heavy germanium agent of product complexing after the filtrating vacuum-evaporation drying.
(3) application of the heavy germanium agent of complexing:
Record and contain germanium, iron, zinc element amount in the liquid of ore deposit and be followed successively by: Ge
4+50mg/L, Zn
2+150g/L, Fe
2+3g/L.In the liquid of the ore deposit of 0.5L, add the heavy germanium agent dry product 0.60g of complexing, regulate PH ≈ and stir 45min down for 2.0,40 ℃, filter, multiple tooth inner complex throw out.Filtrating is used the phenylfluorone development process, under the 510nm Visible Light Characteristics, absorbs, and measures the germanic amount of ore deposit liquid and filtered liq respectively, and calculating heavy germanium rate is 99.14%.
Claims (4)
1. heavy germanium agent of complexing is characterized in that being made by following method:
With the raw material dry product doubly flower and dry product Chinese chestnut bud mix and pulverize by weight 1:0.2～0.3, the back adds deionized water immersion 2h, filter cleaner; Get filtrating, add complexing agent ammonium chloride or EDTA diamines, add powdered carbon; 50 ~ 70 ℃ of following stirring reactions at least 30 minutes, the filtering gac, filtrating is through vacuum-evaporation, drying; Get meal, be the heavy germanium agent of complexing.
2. the germanium agent is sunk in complexing according to claim 1, it is characterized in that complexing dosage is the 1%-2% of flower, the luxuriant material quantity of Chinese chestnut doubly.
3. the germanium agent is sunk in complexing according to claim 1 and 2, it is characterized in that said deionized water soaking temperature is 50～70 ℃.
4. the application of the heavy germanium agent enriched germanium in the liquid of germanic ore deposit of the described complexing of claim 1 is characterized in that dropping into the heavy germanium agent of complexing by 15～25 times of amounts of germanium weight in the liquid of ore deposit, regulates pH to 2～3; 35～45 ℃ of following stirring reactions; Separate out fully until deposition, cross and filter throw out, 450～500 ℃ of roasting 2h; Cooling promptly gets germanium concentrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100899916A CN102628109B (en) | 2012-03-30 | 2012-03-30 | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100899916A CN102628109B (en) | 2012-03-30 | 2012-03-30 | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102628109A true CN102628109A (en) | 2012-08-08 |
| CN102628109B CN102628109B (en) | 2013-11-13 |
Family
ID=46586500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100899916A Expired - Fee Related CN102628109B (en) | 2012-03-30 | 2012-03-30 | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102628109B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179472A (en) * | 1996-11-25 | 1998-04-22 | 云南会泽铅锌矿 | Method for treating high-germanium alum precipitation liquid |
| FI116730B (en) * | 2003-07-31 | 2006-02-15 | Outokumpu Oy | Method and apparatus for controlling demetallization |
| CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
| CN102127125A (en) * | 2011-01-05 | 2011-07-20 | 中国林业科学研究院林产化学工业研究所 | Multielement combined purification preparation process of refined tannic acid serie and combined preparation of products |
| CN102181652A (en) * | 2011-05-21 | 2011-09-14 | 南京中锗科技股份有限公司 | Germanium leaching enrichment method for germanium-containing soot of power plant |
-
2012
- 2012-03-30 CN CN2012100899916A patent/CN102628109B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179472A (en) * | 1996-11-25 | 1998-04-22 | 云南会泽铅锌矿 | Method for treating high-germanium alum precipitation liquid |
| FI116730B (en) * | 2003-07-31 | 2006-02-15 | Outokumpu Oy | Method and apparatus for controlling demetallization |
| CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
| CN102127125A (en) * | 2011-01-05 | 2011-07-20 | 中国林业科学研究院林产化学工业研究所 | Multielement combined purification preparation process of refined tannic acid serie and combined preparation of products |
| CN102181652A (en) * | 2011-05-21 | 2011-09-14 | 南京中锗科技股份有限公司 | Germanium leaching enrichment method for germanium-containing soot of power plant |
Non-Patent Citations (1)
| Title |
|---|
| 王侃等: "含锗锌精矿提取锗、锌工艺试验研究", 《中国重有色金属工业发展战略研讨会暨重冶学委会第四届学术年会论文集》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102628109B (en) | 2013-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Recovery of bismuth and arsenic from copper smelter flue dusts after copper and zinc extraction | |
| Nayl et al. | Selective extraction and separation of metal values from leach liquor of mixed spent Li-ion batteries | |
| CN104046800B (en) | A kind of from containing the technique extracting white tungsten fine ore ferberite or tungstenic waste residue | |
| CN103343234B (en) | Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation | |
| CN101914695B (en) | Method for recycling vanadium from vanadium ore containing high silicon and high carbon via wet process | |
| CN101538651A (en) | Method for recycling metal | |
| CN102101699A (en) | Method for extracting pyrolusite and producing manganese sulfate by utilizing by-product in production of titanium white | |
| CN103773967A (en) | Method for recycling silver, copper and zinc from sintered ash in iron and steel plant | |
| CN105087949A (en) | Method for selectively leaching cobalt, nickel and copper in converting slag of converter | |
| CN104131157A (en) | Hydrometallurgical method for refining tungsten from tungsten oxide limonite | |
| CN101157548A (en) | Method for preparing high-performance manganese-zinc ferrite material | |
| CN102703694A (en) | Method for treating low-grade zinc oxide ores by wet method | |
| CN106732432A (en) | A kind of shitosan/persimmon tannin composite and preparation method thereof and the application in Ti recovery | |
| CN102876904B (en) | Method for leaching beryllium from beryllium minerals of bertrandite | |
| CN104556205B (en) | A kind of processing method utilizing the environmental protection of electrolytic zinc waste residue to produce feed level zinc sulfate | |
| CN103395825B (en) | A kind of method utilizing steel-smelting electric furnace flue dust to produce nano zine oxide | |
| CN103264997B (en) | Method for extracting tellurium from low-concentration tellurium solution | |
| RU2721731C1 (en) | Method of leaching and extraction of gold and silver from pyrite cinder | |
| CN103194767B (en) | High ferro high-phosphorus manganese is utilized to prepare the method for manganese sulfate electrolyte | |
| CN106282571B (en) | A kind of comprehensive recycling process of tin copper gold and silver waste material | |
| CN102628109B (en) | Complexing germanium depositing agent and application in germanium enriching in germanium-containing ore solution thereof | |
| CN108251638B (en) | A method of extracting lithium beryllium from the chrysoberyl type beryllium containing lithium | |
| CN110508286A (en) | (Ni, Mg, Cu) Fe is prepared with nickel sulfide concentrate2O4Out-phase type Fenton catalyst and application method | |
| CN102703711B (en) | Method for extracting rhenium from rhenium-containing waste liquor | |
| CN108043587A (en) | Extraction process containing ferrous sulfide in golden cyaniding tailing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131113 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |