CN103243223B - Method for removing tin from crude copper - Google Patents
Method for removing tin from crude copper Download PDFInfo
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- CN103243223B CN103243223B CN201310193419.9A CN201310193419A CN103243223B CN 103243223 B CN103243223 B CN 103243223B CN 201310193419 A CN201310193419 A CN 201310193419A CN 103243223 B CN103243223 B CN 103243223B
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- copper
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- blister copper
- crude copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 title claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002893 slag Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 15
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 13
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 13
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 6
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 229940001516 sodium nitrate Drugs 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- MAZPIOPHRNWBNG-UHFFFAOYSA-N [Cl-].Cl[NH3+].[Na] Chemical group [Cl-].Cl[NH3+].[Na] MAZPIOPHRNWBNG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- 239000000843 powder Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052785 arsenic Inorganic materials 0.000 description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229940079864 sodium stannate Drugs 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Abstract
The invention relates to a method for removing tin from crude copper. The method comprises the following steps: heating and fusing the crude copper; adding silicon dioxide the weight of which is twice that of the iron content; introducing compressed air; slagging; separating and oxidizing the floating slags; cooling the fused crude copper to the temperature of 1100 to 1150 DEG C; adding caustic soda which serves as a slag former and accounts for 5% to 10% of the weight of the crude copper and stirring; adding sodium nitrate or potassium nitrate which serves as an oxidant and accounts for 2% to 6% of the weight of the crude copper and stirring for 10 to 30 minutes; heating to the temperature of 1130 to 1200 DEG C; respectively adding the caustic soda serving as the slag former and accounting for 10% to 20% of the weight of the crude copper, the sodium nitrate or the potassium nitrate serving as the oxidant and accounting for 2% to 5% of the weight of the crude copper and an additive accounting for 2% to 3% of the weight of the crude copper; stirring for 20 to 60 minutes and standing for 30 to 180 minutes; then cooling to 900 to 1080 DEG C; removing alkali slag at the upper layer; heating and fusing the copper after removing the alkali slag; adding carbon powder or coal powder serving as a reducing agent and accounting for 2% to 15% of the weight of the crude copper; and stirring, preserving the heat and standing, thereby obtaining the copper with tin removed. As the method is used, the high-content tin in the crude copper can be removed; and the high copper recovery rate is achieved. The method is simple, easy to operate and easy in engineered realization.
Description
Technical field
The present invention relates to a kind of detinning method of blister copper.
Background technology
Copper is a kind of strategy metal, is also a kind of people's livelihood metal, is indispensable essential industry starting material, and Application Areas is wide, and interrelationship between industries is high.At present, taking copper secondary resource material and copper primary mineral as raw material, the blister copper that adopts various pyrometallurgical smelting process to obtain, all contains a certain amount of impurity element respectively, and the stanniferous blister copper higher than 3% is high tin blister copper.Blister copper, except stanniferous, generally also has the impurity metallic elementses such as iron, nickel, zinc, antimony, lead, sulphur, arsenic, and content of impurities is generally less than 8%, and wherein taking copper secondary resource material as raw material gained blister copper, content of impurities sometimes can be up to 15%.Blister copper need to first pass through pyrorefining, and then electrorefining could obtain the more than 99.99% commercial metal copper of purity.Traditional blister copper pyrorefining impurity-removing method is under high temperature fused state, air is blasted to melt and carry out chemical reaction, utilizes impurity phase than copper and the strong principle of affinity for oxygen, is the oxide compound that is insoluble to copper by oxidation of impurities, and final impurity removes with scum silica frost form.When oxidation refining, when adopting Red copper oxide supersaturation operating method in melt, easily remove the impurity such as zinc, nickel, sulphur, arsenic, antimony, but be difficult for removing completely the Impurity Sn of high-content in blister copper.
CN101292388 " a kind of electrolysis process of polymetallic blister copper " discloses a kind of nitric acid system blister copper electrolytic smelting method, compares traditional sulfuric acid system electrolysis, and operational condition complexity, cost are higher.CN101654744 " the reverberatory furnace pyrorefining method of high arsenic, antimony blister copper " discloses a kind of by fusing, the redox pyrorefining method combining with compound basic flux slag making of volatilizing, and this invention is the pyrorefining method that specific aim is processed high arsenic, antimony blister copper.
Summary of the invention
The object of this invention is to provide a kind of method of blister copper detin, method of the present invention can remove the tin of high-content, and copper recovery is high, and method is simple, easy to operate, easily realizes through engineering approaches.
For achieving the above object, method of the present invention is made up of following steps:
1. by blister copper heating and melting, remain in 1150 ~ 1250 DEG C, according to iron level in the blister copper of measuring in advance, in molten raw, add the silicon-dioxide of iron level double weight, in molten raw, pass into after pressurized air slag making separation of oxygenated scum silica frost simultaneously.
2. molten raw is cooled in 1100 ~ 1150 DEG C, add the slag former caustic soda of blister copper weight 5 ~ 10%, stir, add oxygenant SODIUMNITRATE or the saltpetre of blister copper weight 2 ~ 6%, churning time is 10 ~ 30 minutes.
3. be warming up to 1130 ~ 1200 DEG C, add respectively slag former caustic soda, 2 ~ 5% oxygenant SODIUMNITRATE or the additive of saltpetre and 2 ~ 3% of blister copper weight 10 ~ 20%, stir, the time is 20 ~ 60 minutes.
4. leave standstill after 30 ~ 180 minutes, be cooled to 900 ~ 1080 DEG C, remove upper strata alkaline residue.
5. remove after alkaline residue, then the melting copper that heats up, add carbon powder of reducing agent or the fine coal of blister copper weight 2 ~ 15%, stir, insulation obtains the copper after detin after leaving standstill.
Described additive is sodium-chlor, ammonium chloride, calcium carbonate or sodium carbonate.
Step 2 of the present invention is to utilize two property metallines of tin, and tin is oxidized and generates sodium stannate (potassium) under alkaline condition, and reaction formula is: 5Sn+6NaOH+4Na (K) NO
3=5Na
2snO
3+ N
2↑+3H
2o.Add the caustic soda in molten raw to form melting tectum, caustic soda is sub-inert reaction medium, is again reactant.First add caustic soda, then add SODIUMNITRATE (potassium) can make reaction temperature and carry out, ensure security reaction under high-temperature fusion environment, improved the utilization ratio of oxygenant.The sodium stannate alkaline residue generating by reaction, removes the tin in blister copper.
Step 3 of the present invention promotes molten raw temperature by a small margin, utilizes and again adds slag former and oxygenant, augmenting response thing duration of contact, fully ensures that Impurity Sn total overall reaction slag making residual in melt separates.Further imurity-removal tin.Additive can improve the flowing property of high temperature blister copper melt.
Compared with prior art, the present invention is taking the high tin blister copper of pyrometallurgical smelting gained as object, alkaline medium covers the sub-inert reaction medium of melt composition, continual and steady in order to maintain the oxidizing atmosphere in when reaction, realize efficient imurity-removal tin in blister copper by making sodium stannate (potassium) alkaline residue, the method technique is simple, and copper recovery is high, with low cost, can realize scale production.
Embodiment
Embodiment 1
Get the blast furnace smelting gained blister copper of cupric 87.9%, stanniferous 10.8%, iron content 2.6%, be placed in pyrorefining stove, be warmed up to 1210 DEG C, in molten raw, add the silicon-dioxide deironing of iron level double weight, logical compressed air oxidation slag making simultaneously, except impurity such as nickel, zinc, sulphur, arsenic; After separation of oxygenated scum silica frost, adjusting molten raw temperature is 1140 DEG C, drops into caustic soda in the ratio of blister copper weight 9%, after stirring, adds the SODIUMNITRATE of blister copper weight 5%, stirs 25 minutes; Be warming up to 1180 DEG C, add caustic soda, 5% SODIUMNITRATE and 3% the sodium-chlor of blister copper weight 18%, stir, react 30 minutes; Insulation leaves standstill 120 minutes, is cooled to 1050 DEG C, separates stanniferous alkaline residue; Be warming up to 1130 DEG C, add the carbon dust of molten raw weight 5%, stir, after insulation leaves standstill, the metal content of copper test liquid: copper 98.7%, tin 0.9%, iron 0.2%.
Embodiment 2
Get the converting furnace gained blister copper of cupric 96.31%, stanniferous 2.03%, iron content 0.8%, be placed in pyrorefining stove, be warmed up to 1190 DEG C, in molten raw, add the silicon-dioxide deironing of iron level double weight, logical compressed air oxidation slag making simultaneously, except impurity such as nickel, zinc, sulphur, arsenic; After separation of oxygenated scum silica frost, adjusting molten raw temperature is 1130 DEG C, drops into caustic soda in the ratio of blister copper weight 5%, after stirring, adds the SODIUMNITRATE of blister copper weight 3%, stirs 15 minutes; Be warming up to 1150 DEG C, add caustic soda, 3% SODIUMNITRATE and 2% the ammonium chloride of blister copper weight 10%, stir, react 20 minutes; Insulation leaves standstill 50 minutes, is cooled to 1000 DEG C, separates stanniferous alkaline residue; Be warming up to 1150 DEG C, add the fine coal of molten raw weight 7%, stir the metal content of copper test liquid: cupric 99.6%, stanniferous 0.15%, iron content 0.1%.
Embodiment 3
Get cupric 92.91%, oxygen-enriched bottom-blowing smelting furnace stanniferous 5.33%, iron content 2.1% is smelted gained blister copper, be placed in pyrorefining stove, be warmed up to 1230 DEG C, in molten raw, add the silicon-dioxide deironing of iron level double weight, logical compressed air oxidation slag making simultaneously, except impurity such as nickel, zinc, sulphur, arsenic; After separation of oxygenated scum silica frost, adjusting molten raw temperature is 1150 DEG C, drops into caustic soda in the ratio of blister copper weight 8%, after stirring, adds the SODIUMNITRATE of blister copper weight 4%, stirs 25 minutes; Be warming up to 1170 DEG C, the caustic soda of overstriking weight of copper 15%, 5% SODIUMNITRATE and 2% sodium carbonate, stir, and reacts 50 minutes; Insulation leaves standstill 150 minutes, is cooled to 950 DEG C, separates stanniferous alkaline residue; Be warming up to 1150 DEG C, add the carbon dust of molten raw weight 9%, stir the metal content of copper test liquid: copper 98.2%, tin 0.9%, iron 0.3%.
Claims (2)
1. a method for detin in blister copper, is characterized in that being made up of following steps:
1) by blister copper heating and melting, remain in 1150 ~ 1250 DEG C, according to iron level in the blister copper of measuring in advance, in molten raw, add the silicon-dioxide of iron level double weight, in molten raw, pass into after pressurized air slag making separation of oxygenated scum silica frost simultaneously;
2) molten raw is cooled in 1100 ~ 1150 DEG C, add the slag former caustic soda of blister copper weight 5 ~ 10%, stir, add oxygenant SODIUMNITRATE or the saltpetre of blister copper weight 2 ~ 6%, churning time is 10 ~ 30 minutes;
3) be warming up to 1130 ~ 1200 DEG C, add respectively slag former caustic soda, 2 ~ 5% oxygenant SODIUMNITRATE or the additive of saltpetre and 2 ~ 3% of blister copper weight 10 ~ 20%, stir, the time is 20 ~ 60 minutes;
4) leave standstill after 30 ~ 180 minutes, be cooled to 900 ~ 1080 DEG C, remove upper strata alkaline residue;
5) remove after alkaline residue, then the melting copper that heats up, add carbon powder of reducing agent or the fine coal of blister copper weight 2 ~ 15%, stir, insulation obtains the copper after detin after leaving standstill.
2. the method for detin in blister copper according to claim 1, is characterized in that described additive is sodium-chlor, ammonium chloride, calcium carbonate or sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310193419.9A CN103243223B (en) | 2013-05-23 | 2013-05-23 | Method for removing tin from crude copper |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310193419.9A CN103243223B (en) | 2013-05-23 | 2013-05-23 | Method for removing tin from crude copper |
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| CN103243223A CN103243223A (en) | 2013-08-14 |
| CN103243223B true CN103243223B (en) | 2014-07-09 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102014008987A1 (en) * | 2014-06-13 | 2015-12-17 | Aurubis Ag | Process for the recovery of metals from secondary and other organic materials |
| CN106400052A (en) * | 2016-12-14 | 2017-02-15 | 江西自立环保科技有限公司 | Method for purification tin removing for copper electrolyte |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275186A (en) * | 2008-04-16 | 2008-10-01 | 倪如宝 | Production method for high-purity copper and low-oxygen bright copper rod |
| CN101532091B (en) * | 2009-04-17 | 2010-12-29 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology of extracting and separating valuable metals such as Pb, In, Sb, Cu and Sn from lead smelting converter slags |
| CN101705372B (en) * | 2009-11-25 | 2011-09-21 | 郴州市金贵银业股份有限公司 | Process for extracting tin from wet lead with high tin content |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4505843B2 (en) * | 2006-03-31 | 2010-07-21 | 日鉱金属株式会社 | Copper dry refining method |
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2013
- 2013-05-23 CN CN201310193419.9A patent/CN103243223B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275186A (en) * | 2008-04-16 | 2008-10-01 | 倪如宝 | Production method for high-purity copper and low-oxygen bright copper rod |
| CN101532091B (en) * | 2009-04-17 | 2010-12-29 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology of extracting and separating valuable metals such as Pb, In, Sb, Cu and Sn from lead smelting converter slags |
| CN101705372B (en) * | 2009-11-25 | 2011-09-21 | 郴州市金贵银业股份有限公司 | Process for extracting tin from wet lead with high tin content |
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Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of rare metals, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: GUANGDONG INSTITUTE OF RARE METALS |
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Effective date of registration: 20230331 Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: Institute of rare metals, Guangdong Academy of Sciences |
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Application publication date: 20130814 Assignee: Guangdong Yinghua Electronic Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980049297 Denomination of invention: A method for removing tin from crude copper Granted publication date: 20140709 License type: Common License Record date: 20231204 |