CN102628109B - 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
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- CN102628109B CN102628109B CN2012100899916A CN201210089991A CN102628109B CN 102628109 B CN102628109 B CN 102628109B CN 2012100899916 A CN2012100899916 A CN 2012100899916A CN 201210089991 A CN201210089991 A CN 201210089991A CN 102628109 B CN102628109 B CN 102628109B
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- germanium
- complexing
- agent
- heavy
- liquid
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- 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 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 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
- 239000000047 product Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- -1 EDTA diamines Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration 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
- 235000018553 tannin Nutrition 0.000 abstract description 8
- 229920001864 tannin Polymers 0.000 abstract description 8
- 239000001648 tannin Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 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 description 4
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract 1
- 229960001484 edetic acid Drugs 0.000 abstract 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 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
- 238000001514 detection method 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
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification 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
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- 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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- 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 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, with fields such as electronic industry, infrared optics equipment, photoconductive fiber, medical science, metallurgy, the energy, has a wide range of applications, and 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 mostly from germanic higher nonferrous metals ore, reclaim simultaneously the enriched substance of germanium in the smelting non-ferrous metal process.For example in zinc hydrometallurgy is produced, while processing the zinc sulfide concentrates of germanic higher (germanic 100-150g/ ton), at first germanium is enriched in leached mud, with fuming furnace, processes, in flue dust germanic 0.1%, use Ore Leaching, add the heavy germanium of Chinese gallotanninic acid after solution purification, germanic 3-5% in throw out, in the germanium ash that drying, calcining obtain, germanium is enriched to 15-20%, use this as germanium concentrate, further extract.
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 the demand of nearly 3000 tons in domestic only southwestern market, cause the price of Weibull to be doubled and redoubled, thereby improved the extraction cost of germanium metal.
Summary of the invention
The object 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, by following methods, is made:
The raw material dry product is doubly mixed and pulverizes in luxuriant 1:0.2～0.3 by weight of colored and dry product Chinese chestnut, after add deionized water to soak 2h, filter cleaner, get filtrate (be and mix tannin liquid), adds complexing agent ammonium chloride or EDTA diamines, add powdered carbon, 50 ~ 70 ℃ of lower stirring reactions at least 30 minutes, the filtering gac, filtrate is through vacuum-evaporation, drying, obtain meal, be the heavy germanium agent of complexing.
Described complexing dosage is the 1%-2% of times flower and Chinese chestnut bud material quantity.
Described deionized water soaking temperature is 50～70 ℃.
The application of the heavy germanium agent enriched germanium in the liquid of germanic ore deposit of described complexing, the method for enriched germanium is as follows:
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 ℃ lower stirring reaction,, until precipitation is separated out fully, filter to obtain throw out, and 450～500 ℃ of roasting 2h are cooling, obtain germanium concentrate.
The present invention uses the title complex generation method of coordination chemistry, adds the chemical complexing agent and make the compound tannin of proportioning uniqueness as heavy germanium agent in natural tannin extract.The heavy germanium agent of this complexing adds in the liquid of germanic ore deposit, can with metal ion germanium (central ion), complex compound occur under acidic conditions, and gradual reaction generates multiple tooth inner complex and be precipitated out rapidly, and heavy germanium rate reaches 99.0%, and throw out obtains germanium concentrate by roasting.Substitute Chinese gallotanninic acid with this heavy germanium agent and add in the ore deposit liquid of zinc metallurgy, when obtaining qualified zinc carbonate product, can obtain germanic amount greater than 15% germanium concentrate.Prepare this heavy germanium agent take the wildwood product doubly flower, Chinese chestnut is luxuriant as raw material, aboundresources, low price, can reduce heavy germanium agent production cost, economic benefits greatly.
Specific embodiments
Embodiment 1:
One. the preparation of the heavy germanium agent of complexing
(1), by doubly spending dry powder 100g, Chinese chestnut bud dry powder 30g proportioning, add deionized water 0.85L, 60 ℃ of stirrings were soaked 2 hours, and filter cleaner, receive to obtain tannin liquid.
(2) add EDTA diamines (ethylenediamine tetraacetic acid (EDTA) diamines) 0.90g in tannin liquid, powdered carbon 0.6g, 60 ℃ of stirring reaction 0.5h, go out gac through isolated by vacuum filtration, and filtrate vacuum-evaporation is dry, obtains 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
The content that obtains after testing metal ion in the liquid of ore deposit is respectively: Ge
4+50mg/L, Zn
2+150g/L, Fe
2+3g/L.In the liquid of 0.5L ore deposit, add complexing to sink germanium agent dry product 0.55g, regulate under 2.5,40 ℃ of PH ≈ and stir 45min, filter, obtain multiple tooth inner complex precipitation, filter enrichment the throw out of germanium, filtrate for detection of.Use the phenylfluorone development process, absorb under the 510nm Visible Light Characteristics, measure respectively the germanic amount of ore deposit liquid and above-mentioned filtrate, calculating heavy germanium rate is 99.05%.
Embodiment 2
(1) take raw material and doubly spend dry powder 110g, Chinese chestnut bud dry powder 25g, add deionized water 0.75L, 60 ℃ are stirred extracting 2h, and filter cleaner, receive to obtain tannin liquid.
(2) add ammonium chloride 1.2g in tannin liquid, powdered carbon 0.5g, 60 ℃ of stirring reaction 0.5h,, except gac, obtain the heavy germanium agent of product complexing through vacuum filtration after filtrate vacuum-evaporation drying.
(3) application of the heavy germanium agent of complexing:
Record in the liquid of ore deposit and contain germanium, zinc, ferro element amount 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 complexing to sink germanium agent dry product 0.60g, regulate under 2.0,40 ℃ of PH ≈ and stir 45min, filter, obtain multiple tooth inner complex throw out.Filtrate is used the phenylfluorone development process, absorbs under the 510nm Visible Light Characteristics, measures respectively the germanic amount of ore deposit liquid and filtered liquid, and calculating heavy germanium rate is 99.14%.
Claims (4)
1. heavy germanium agent of complexing is characterized in that being made by following methods:
The raw material dry product is doubly mixed and pulverizes in luxuriant 1:0.2～0.3 by weight of colored and dry product Chinese chestnut, after add deionized water to soak 2h, filter cleaner, get filtrate, adds complexing agent ammonium chloride or EDTA diamines, add powdered carbon, 50 ~ 70 ℃ of lower stirring reactions at least 30 minutes, the filtering gac, filtrate is through vacuum-evaporation, drying, obtain meal, be the heavy germanium agent of complexing.
2. the heavy germanium agent of complexing according to claim 1, is characterized in that the 1%-2% of complexing dosage for times flower and Chinese chestnut bud material quantity.
3. the heavy germanium agent of complexing according to claim 1 and 2, is characterized in that described 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 complexing claimed in claim 1, it 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, regulate pH to 2～3,35～45 ℃ of lower stirring reactions,, until precipitation is separated out fully, filter to obtain throw out, 450～500 ℃ of roasting 2h, cooling, obtain germanium concentrate.
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| 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 |
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| 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 |
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| Publication Number | Publication Date |
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| CN102628109A CN102628109A (en) | 2012-08-08 |
| CN102628109B true CN102628109B (en) | 2013-11-13 |
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| 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 |
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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 (2)
| Title |
|---|
| 含锗锌精矿提取锗、锌工艺试验研究;王侃等;《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》;20031001;第93-96页 * |
| 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》.2003,第93-96页. |
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| CN102628109A (en) | 2012-08-08 |
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