CN104862482A - Method of selective recovery of valuable metals from mixed metal oxides - Google Patents
Method of selective recovery of valuable metals from mixed metal oxides Download PDFInfo
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- CN104862482A CN104862482A CN201510076991.6A CN201510076991A CN104862482A CN 104862482 A CN104862482 A CN 104862482A CN 201510076991 A CN201510076991 A CN 201510076991A CN 104862482 A CN104862482 A CN 104862482A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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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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Abstract
The present invention relates to a process for recovering metals from indium tin oxide (ITO) scrap. It allows the selective recovery of indium and tin from waste ITO by means of a simple and environmentally benign dissolution-deposition method, with no requirement of using strong corrosive acid/alkaline chemicals (e.g. hydrochloric acid, nitric acid, sulfuric acid and sodium hydroxide) for dissolution and complicated procedures/operation. The dissolution baths can be reused without observable recovery deterioration. It significantly reduces the cost requirement in the recovery process.
Description
The cross reference of related application
This application claims the right of priority of the U.S. Provisional Patent Application sequence number 61/966,180 submitted on February 18th, 2014, the mode that the disclosure of described U.S. Provisional Patent Application is quoted in full is incorporated to herein.
Technical field
The present invention relates to a kind of by continuous-dissolution and the deposition method from ITO refuse selective recovery indium and tin, it relates to and optionally dissolves indium and tin and how from method and the bath preparations of solution collection indium and tin from ITO refuse.
Background technology
Indium is the important element in electronics and energy related industries.Its compound oxidation indium (In
2o
3) play an important role in transparent conductive oxide (TCO), TCO is the basic material for flat-panel monitor, solar cell and other device.Be difficult to extraction due to its increase in demand, therefore estimate in the shortage of following indium and price increase.Therefore set up and to be used for from the safety of indium-containing waste recovery indium and the method for low cost is very important.
There are many study group to be devoted to ITO Waste recovery, but use present invention from ITO refuse optionally recovery indium and tin without any study group.The people such as Park (Xin Luo university (SillaUniversity)) report a kind of method from ITO waste recovery indium metal, high purity 99%.But, described technique needs at 140 DEG C, in indium settling bath, use high-corrosion medium (i.e. 50% sodium hydroxide) 4 hours, and this is usually not recommended for scale operation object (Bull.KoreanChem.Soc., 2011,32,3796).The people such as Li (Central South University (Central South University)) propose a kind of use H
2sO
4leach ITO with HCl from refuse, and remove the method for tin from infusion solution by sulfuration.But, employ hydrogen sulfide (H
2s) gas is as vulcanizing agent, and this is very high, the flammable gas (Hydrometallurgy, 2011,105,207) of toxicity.The people such as Benedetto (Cidade Universitaria (City University)) propose the extraction agent (such as D2EHPA) of use based on organic phosphoric acid from selective extraction indium the infusion solution containing ITO.But the material cost of these proprietary extraction agents is relatively high (Minerals Eng., 1998,11,447).In above report, they all use highly corrosive chemical or proprietary extraction agent to implement its research, and often produce a large amount of refuses in the process.
Therefore, also need in described industry for from containing the low cost of ITO Waste recovery indium and tin, low toxicity and reusable preparation.
Summary of the invention
The present invention allows by simple and environment amenable technique selective recovery indium and tin from ITO refuse, and without the need to using corrosive bronsted lowry acids and bases bronsted lowry (such as hydrochloric acid, nitric acid, sulfuric acid and sodium hydroxide) and complicated program/operation.Therefore, present invention significantly reduces the cost in recovery process and horsepower requirements.Because the inventive method employs the renewable solution of more environmental protection, therefore it also reduces the impact on environment.
Therefore, a first aspect of the present invention relates to a kind of dissolution-deposition technique for optionally recovery indium and tin from ITO refuse.In order to recovery indium, technique of the present invention comprises the following steps:
A) by shredding and crush the size that reduces containing ITO material to form fine particle;
B) pre-treatment is carried out to described fine particle, to avoid the interference in dissolving step by chemistry and physics cleaning;
C) will dissolve in bath to first of the first bath preparation that comprises be under 60 DEG C to 120 DEG C scope bath temperature through pretreated transfer of granules, continuously stirring 30-180 minute simultaneously described through pretreated particle to dissolve;
D) water of 50-300 volume % is joined containing to form the first mixture in the solution of dissolved particles from step (c), and filter described first mixture so that collection is rich in the filtrate of indium and is rich in the filter residue (filtrand) of tin;
E) indium plate is put into described in be rich in filtrate 1-10 hour of indium to remove tin resistates by replacement(metathesis)reaction;
F) reclaim from described filtrate of being rich in indium the indium that purity is not less than 99.9% by the first depositing operation;
G) after vaporize water, the dissolving bath in step (c) is used further to next recovery and circulates.
In order to reclaim tin, technique of the present invention is further comprising the steps of:
H) filter residue being rich in tin described in obtaining from step (d) being transferred to second of the second bath preparations that comprises being in 60 DEG C to 120 DEG C scopes bath temperature dissolves in bath, while continuously stirring 30-180 minute to be rich in the filter residue of tin described in dissolving;
I) water of 50-300 volume % is joined containing being rich in form the second mixture in the solution of the filter residue of tin of dissolving, and filter described second mixture to collect the filtrate and the undissolved matrix (substrates) that are rich in tin;
J) filtrate of being rich in tin obtained from step (i) by the second depositing operation reclaims tin;
K) after vaporize water, second in step (h) is dissolved bath and be used further to next recovery circulation.
A second aspect of the present invention relates to for the bath preparations according to dissolution-deposition technique difference recovery indium of the present invention and tin.Different from the conventional bath preparations of the sodium hydroxide containing highly corrosive, hydrochloric acid and sulfuric acid, the first and second bath preparations being respectively used to dissolve indium and tin comprise low cost and the more weak compound of corrodibility.In one embodiment, the mixture of Organohalogen compounds and dicarboxylic acid is comprised for the first bath preparation of dissolution-deposition technique of the present invention.In another embodiment, the mixture of Organohalogen compounds and carboxylic acid is comprised for the second bath preparations of dissolution-deposition technique of the present invention.
Compare with the common process of tin with from the salvage material indium containing ITO, whole technique of the present invention is carried out all at relatively low temperature, and this does not need a large amount of energy consumptions.Ion solvent in bath preparations of the present invention can also be reused after simple water evaporation, and does not have the observable rate of recovery to decline.
Accompanying drawing explanation
Fig. 1 is the schema describing dissolution-deposition technique of the present invention.
Embodiment
Now with detailed reference to preferred embodiment at present of the present invention, to explain principle of the present invention.Enough describe in detail these embodiments or embodiment, to make one of ordinary skill in the art to implement the present invention, and should be appreciated that and can also utilize other embodiment, and change can be made when not departing from spirit of the present invention.
Embodiment 1-is used for the composition of the bath preparations of recovery indium/tin
For mainly comprising following two kinds of components from the first bath preparation through the pretreated particle recovery indium containing ITO:
A) a kind of or more than the Organohalogen compounds salt of a type: the positively charged ion of these Organohalogen compounds salt can be but be not limited to tetra-allkylammonium, (dialkyl group, trialkyl and tetraalkyl) imidazoles, alkyl pyridine, dialkyl pyrrolidinium, dialkyl piperidine, four alkane base Phosphonium, tetraalkyl sulfonium, dialkyl group pyrazoles (dialkylpyrazolium) and N-alkyl thiazole.In this embodiment, use chlorination 2-hydroxy-n, N, N-trimethylammonium second ammonium (choline chloride 60) is as the described Organohalogen compounds salt in described first bath preparation;
B) dicarboxylic acid of 20-80mol%: described dicarboxylic acid can be but be not limited to oxalic acid, propanedioic acid, succinic acid, pentanedioic acid and hexanodioic acid.
In one embodiment, the described Organohalogen compounds salt in described first bath preparation and the mol ratio of described dicarboxylic acid are about 1:1.
The second bath preparations for reclaiming tin from the material (filter residue being rich in tin that such as dissolution-deposition technique according to the present invention obtains from the waste material containing ITO) being rich in tin comprises following two kinds of components:
A) a kind of or more than the Organohalogen compounds salt of a type: the positively charged ion of these Organohalogen compounds salt can be but be not limited to tetra-allkylammonium, (dialkyl group, trialkyl and tetraalkyl) imidazoles, alkyl pyridine, dialkyl pyrrolidinium, dialkyl piperidine, four alkane base Phosphonium, tetraalkyl sulfonium, dialkyl group pyrazoles and N-alkyl thiazole.In this embodiment, use chlorination 2-hydroxy-n, N, N-trimethylammonium second ammonium (choline chloride 60) is as the described Organohalogen compounds salt in described second bath preparations;
B) carboxylic acid of 20-80mol%: described carboxylic acid can be but be not limited to trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Mono Chloro Acetic Acid, propionic acid, butyric acid and valeric acid.
In one embodiment, the described Organohalogen compounds salt in described second bath preparations and the mol ratio of described carboxylic acid are about 1:2.
Embodiment 2-is used for the electrodeposition condition collecting indium/tin from the bath preparations containing the indium dissolved and/or tin
In embodiment 1, by the grain dissolution through the pretreated refuse containing ITO in first bath preparation and after adding the water of 50-300 volume %, filtering solution is also separated and is rich in the filtrate of indium and is rich in the filter residue of tin.In order to from the described filtrate collection indium being rich in indium, indium plate is put into described filtrate to remove the tin of any remnants of described filtrate, carry out the first electrodeposition technology under the following conditions subsequently: pH is not higher than 1.5; Current density is 0.6mA/cm
2to 4mA/cm
2or voltage is 2V to 4V, more preferably voltage is about 2.6V; Electrodeposition time: 30-90 minute; Temperature is 60 DEG C to 120 DEG C.In electrochemical cell, indium metal is electrochemically-deposited on substrate from described being rich in the filtrate of tin.Described substrate can be but be not limited to titanium, stainless steel and graphite.To electrode can be but be not limited to titanium, platinum and graphite.
Then the filter residue being rich in tin that the filtration from the first mixture obtains is dissolved in the second bath preparations, adds the water of 50-300 volume % subsequently to form the second mixture.Filter described second mixture to obtain the filtrate of being rich in tin and the filter residue containing undissolved matrix.The filtrate of being rich in tin described in then making experiences the second electrodeposition technology under the following conditions: pH is not higher than 1; Current density is 0.8mA/cm
2to 5mA/cm
2or voltage is 2.2V to 4.5V, more preferably voltage is about 3.2V; Electrodeposition time: 30-90 minute; Temperature is 60 DEG C to 120 DEG C.In electrochemical cell, tin metal is electrochemically-deposited on substrate from described being rich in the filtrate of tin.Described substrate can be but be not limited to titanium, stainless steel and graphite.To electrode can be but be not limited to titanium, platinum and graphite.
Embodiment 3-uses bath preparations of the present invention and electrodeposition technology from the waste recovery indium and the tin that contain ITO
In FIG, the recovery approach of indium and tin is made up of 3 key steps.First, crush the waste material containing ITO that is collected and that manufacture to reduce refuse size, and carry out chemical washing to eliminate those organic residue (liquid crystal (LC) in such as liquid-crystal display (LCD)).Subsequently, in bathing to the dissolving containing corresponding ion solvent through pretreated powder transfer, such as, the first bath preparation for dissolving indium in embodiment 1.Dissolve in bath first, indium and tin dissolve from ITO (equation 1 and 2), and respectively with In (X)
2 -with Sn (X)
2form stable (equation 3 and 4).
In
2o
3+ 6H
+=2In
3++ 3H
2o ... (equation 1)
SnO
2+ 4H
+=Sn
4++ 2H
2o ... .. (equation 2)
In
3++ 2X
2-=In (X)
2 -.. (equation 3)
Sn
4++ 2X
2-=Sn (X)
2.. (equation 4)
X: dicarboxylic acid
Because the first ion solvent dissolved in bath represents for In (X)
2 -dissolving selectivity and for Sn (X)
2precipitation Potential, be rich in the filter residue of tin so can be separated from mixture by filtering with any suitable filtration unit (such as glass micro-fibers peacekeeping membrane filter).Then under specified conditions (corresponding conditions for recovery indium in such as embodiment 2), indium metal can be collected by electrodeposition technology from described bath.
As from inductively coupled plasma atomic emission spectrum test result (ICP-OES) (table 1) obviously, in original I TO waste material, the content of indium and tin is the ratio of about 85:15.By with first bath preparation (the such as chlorination 2-hydroxy-n in embodiment 1, N, N-trimethylammonium second ammonium (Organohalogen compounds salt) and oxalic acid (dicarboxylic acid) are with the mixture of 1:1 mol ratio) mix, its dissolving selectivity represented for indium is better than tin.In dissolution process, indium is dissolved in reaction medium fully, and most of tin-oxide is then precipitated out.After filtration, in filtrate, the ratio of indium and tin is increased to up to 96:4.If chlorination 2-hydroxy-n, the mol ratio of N, N-trimethylammonium second ammonium and oxalic acid becomes 2:1 or 1:2, and in the filter residue so obtained, the ratio of indium and tin does not have noticeable change; But, need higher temperature (about 120 DEG C) and longer time (about 180 minutes) to carry out dissolution process.Pass through, as in embodiment 1, in the second bath preparations, replace dicarboxylic acid with carboxylic acid (such as trichoroacetic acid(TCA)), indium and tin are both dissolved in reaction medium fully.It does not show dissolving selectivity, and the content of indium therefore after dissolution process and tin is still the ratio of about 85:15.
Table 1:
ICP sample | In:Sn ratio | Purity, % |
Original I TO waste material | 85:15 | 85% |
After dissolution process | 96:4 | 96% |
After replacement(metathesis)reaction | 99.95:0.05 | 99.95% |
In order to reduce the Theil indices in filtrate further, implement Galvanic displacement (galvanicdisplacement) technique to remove tin impurity with indium plate.By contrast, the reductibility of indium metal is higher.It can replace the tin in ion solvent and promote that tin deposits.After replacement(metathesis)reaction, indium metal is electrochemically-deposited on substrate (such as titanium, stainless steel and graphite), and indium purity can be increased to >99.9% further.
In order to Footwall drift tin from the filter residue being rich in tin, the filter residue being rich in tin is dissolved into again and comprises second of the second bath preparations (the second bath preparations for dissolving tin in such as embodiment 1) and dissolve in bath.Because show good solubility, so any suitable filtration unit (such as glass microfiber filter and membrane filter) can be passed through easily be separated resistates (such as glass and plastics) from mixture for the second bath preparations reclaiming tin for tin throw out.Then under specified conditions (corresponding conditions for reclaiming tin in such as embodiment 2), tin metal can be collected by electrodeposition technology from bath.
Because the chemical constitution of bath preparations does not substantially change after each dissolving step, therefore they can reuse and not have the observable rate of recovery to decline after single vaporization falls excessive water.
Industrial usability
Application claims protection for from containing to dissolve respectively in the refuse of ITO and in waste management that the method and formulation of recovery indium and tin can be used for containing ITO refuse (such as display panel) and processing plant.Comprise, compared with conventional formulation, there is the reusable for the invention formulation dissolving indium and tin of low-corrosiveness and hypotoxic material, and do not have the observable rate of recovery to decline, the composition of described preparation there is no change after water evaporation simultaneously, therefore becomes more better than conventional formulation alternative with regard to cost with to the pollution of environment.
Should be appreciated that, other step that easily can know with not mentioned herein but one of ordinary skill in the art of method/equipment/system as herein described with different order, while and/or common implementing to obtain method/equipment/system of the present invention.Without the need to elaborating further, believe that one of ordinary skill in the art can revise the present invention when not departing from spirit of the present invention based on description herein and maximally utilise the present invention.The mode that all publications quoted herein are quoted all is in full incorporated herein.
Claims (14)
1., for from the method containing continuously recovery indium and tin in the refuse of ITO, it comprises:
A) by shredding and crush the size that reduces containing ITO material to form fine particle;
B) pre-treatment is carried out to described fine particle, to avoid the interference in dissolving step by chemistry and physics cleaning;
C) will dissolve in bath to first of the first bath preparation that comprises be under 60 DEG C to 120 DEG C scope bath temperature through pretreated transfer of granules, continuously stirring 30-180 minute simultaneously described through pretreated particle to dissolve;
D) water of 50-300 volume % is joined containing to form the first mixture in the solution of dissolved particles from step (c), and filter described first mixture so that collection is rich in the filtrate of indium and is rich in the filter residue of tin;
E) indium plate is put into described in be rich in filtrate 1-10 hour of indium to remove tin resistates by replacement(metathesis)reaction;
F) reclaim from described filtrate of being rich in indium the indium that purity is not less than 99.9% by the first depositing operation;
G) after vaporize water, the described dissolving bath in step (c) is used further to next recovery and circulates.
2. method according to claim 1, it comprises further:
H) filter residue being rich in tin described in obtaining from step (d) being transferred to second of the second bath preparations that comprises being in 60 DEG C to 120 DEG C scopes bath temperature dissolves in bath, while continuously stirring 30-180 minute to be rich in the filter residue of tin described in dissolving;
I) water of 50-300 volume % is joined containing being rich in form the second mixture in the solution of the filter residue of tin of dissolving, and filter described second mixture so that the filtrate of tin and undissolved matrix are rich in collection;
J) obtained from step (i) by the second depositing operation described in be rich in tin filtrate reclaim tin;
K) after vaporize water, described second in step (h) is dissolved bath and be used further to next recovery circulation.
3. method according to claim 1, wherein said first bath preparation comprises following component:
Or more than the Organohalogen compounds salt of a type, the positively charged ion of wherein said Organohalogen compounds salt comprises tetra-allkylammonium, (dialkyl group, trialkyl and tetraalkyl) imidazoles, alkyl pyridine, dialkyl pyrrolidinium, dialkyl piperidine, four alkane base Phosphonium, tetraalkyl sulfonium, dialkyl group pyrazoles and N-alkyl thiazole; With
The dicarboxylic acid of 20-80mol%, described dicarboxylic acid comprises oxalic acid, propanedioic acid, succinic acid, pentanedioic acid and hexanodioic acid.
4. method according to claim 3, the positively charged ion of wherein said Organohalogen compounds salt is tetra-allkylammonium and described dicarboxylic acid is oxalic acid; The mol ratio of described Organohalogen compounds salt and dicarboxylic acid is 1:1.
5. method according to claim 1, wherein said first depositing operation is the electrodeposition technology of indium, and it comprises following operational condition and/or component:
PH is not higher than 1.5;
Current density is 0.6mA/cm
2to 4mA/cm
2or voltage is 2V to 4V;
Electrodeposition time is 10 minutes to 60 minutes;
Temperature is 20 DEG C to 70 DEG C;
For from the described substrate being rich in galvanic deposit indium in the filtrate of indium, described substrate comprises titanium, stainless steel and graphite; With
To electrode, described titanium, platinum and graphite are comprised to electrode.
6. method according to claim 2, wherein said second bath preparations comprises following component:
Or more than the Organohalogen compounds salt of a type, the positively charged ion of wherein said Organohalogen compounds salt comprises tetra-allkylammonium, (dialkyl group, trialkyl and tetraalkyl) imidazoles, alkyl pyridine, dialkyl pyrrolidinium, dialkyl piperidine, four alkane base Phosphonium, tetraalkyl sulfonium, dialkyl group pyrazoles and N-alkyl thiazole; With
The carboxylic acid of 20-80mol%, described carboxylic acid comprises trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Mono Chloro Acetic Acid, propionic acid, butyric acid and valeric acid.
7. method according to claim 6, the positively charged ion of wherein said Organohalogen compounds salt is tetra-allkylammonium and described carboxylic acid is trichoroacetic acid(TCA); The mol ratio of described Organohalogen compounds salt and carboxylic acid is 1:2.
8. method according to claim 2, wherein said second depositing operation is the electrodeposition technology of tin, and it comprises following operational condition and/or component:
PH is not higher than 1;
Current density is 0.8mA/cm
2to 5mA/cm
2or voltage is 2.2V to 4.5V;
Electrodeposition time is 10 minutes to 60 minutes;
Temperature is 20 DEG C to 70 DEG C;
For from the described substrate being rich in galvanic deposit tin in the filtrate of tin, described substrate comprises titanium, stainless steel and graphite; With
To electrode, described titanium, platinum and graphite are comprised to electrode.
9. method according to claim 1, wherein said replacement(metathesis)reaction comprises the Galvanic replacing process utilizing indium plate, for removing tin resistates from described being rich in the filtrate of indium after described first depositing operation.
10. method according to claim 1, the wherein said ITO material that contains comprises from the waste material containing ITO of display panel, solar battery panel or consumer electronics byproduct and the powder containing ITO.
11. 1 kinds are rich in the bath preparations of the solution of indium for dissolving indium to be formed, and described preparation comprises:
Or more than the Organohalogen compounds salt of a type, the positively charged ion of wherein said Organohalogen compounds salt comprises tetra-allkylammonium, (dialkyl group, trialkyl and tetraalkyl) imidazoles, alkyl pyridine, dialkyl pyrrolidinium, dialkyl piperidine, four alkane base Phosphonium, tetraalkyl sulfonium, dialkyl group pyrazoles and N-alkyl thiazole; With
The dicarboxylic acid of 20-80mol%, described dicarboxylic acid comprises oxalic acid, propanedioic acid, succinic acid, pentanedioic acid and hexanodioic acid.
12. bath preparations according to claim 11, the positively charged ion of wherein said Organohalogen compounds salt is tetra-allkylammonium and described dicarboxylic acid is oxalic acid; The mol ratio of described Organohalogen compounds salt and dicarboxylic acid is 1:1.
13. 1 kinds are rich in the bath preparations of the solution of tin for dissolving tin to be formed, and described preparation comprises:
Or more than the Organohalogen compounds salt of a type, the positively charged ion of wherein said Organohalogen compounds salt comprises tetra-allkylammonium, (dialkyl group, trialkyl and tetraalkyl) imidazoles, alkyl pyridine, dialkyl pyrrolidinium, dialkyl piperidine, four alkane base Phosphonium, tetraalkyl sulfonium, dialkyl group pyrazoles and N-alkyl thiazole; With
The carboxylic acid of 20-80mol%, described carboxylic acid comprises trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Mono Chloro Acetic Acid, propionic acid, butyric acid and valeric acid.
14. bath preparations according to claim 13, the positively charged ion of wherein said Organohalogen compounds salt is tetra-allkylammonium and described carboxylic acid is trichoroacetic acid(TCA); The mol ratio of described Organohalogen compounds salt and carboxylic acid is 1:2.
Applications Claiming Priority (4)
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US201461966180P | 2014-02-18 | 2014-02-18 | |
US61/966,180 | 2014-02-18 | ||
US14/601,189 | 2015-01-20 | ||
US14/601,189 US20150233004A1 (en) | 2014-02-18 | 2015-01-20 | Method of selective recovery of valuable metals from mixed metal oxides |
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CN104862482A true CN104862482A (en) | 2015-08-26 |
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Cited By (5)
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CN105483389A (en) * | 2016-01-13 | 2016-04-13 | 云南大学 | Leaching method for indium in waste liquid crystal panel and leaching agent |
CN106757157A (en) * | 2016-12-12 | 2017-05-31 | 贵州宏达环保科技有限公司 | One kind reclaims thick indium method from indium purification slag |
CN108277354A (en) * | 2018-03-26 | 2018-07-13 | 华南理工大学 | A kind of method that oxalic acid leaches indium in ito glass substrate |
CN112534071A (en) * | 2018-08-03 | 2021-03-19 | 帝国科学、技术与医学学院 | Recovery of lead and tin materials |
CN115491494A (en) * | 2022-09-19 | 2022-12-20 | 安徽工业大学 | Method for treating ITO waste target and efficiently recovering metal indium and tin oxide by eutectic solvent system |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CZ2016281A3 (en) * | 2016-05-13 | 2017-01-18 | DEKONTA, a.s. | A method of selective regeneration of rare earth elements and/or toxic metals harmful to the environment from e-waste, particularly from cathode-ray tubes and CRT monitors |
FR3133789A1 (en) * | 2022-03-24 | 2023-09-29 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR RECOVERING INDIUM FROM A SUBTRATE COMPRISING INDIUM-TIN OXIDE AND A METAL LAYER USING GREEN CHEMISTRY |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1420184A (en) * | 2002-11-07 | 2003-05-28 | 长沙矿冶研究院 | Method for extracting refined indium from indium tin oxide waste material |
JP2011073964A (en) * | 2009-09-29 | 2011-04-14 | Torecom Corp | Method for manufacturing tin oxide powder by recycling indium-tin oxide scrap |
CN102159662A (en) * | 2008-09-19 | 2011-08-17 | 卡伯特微电子公司 | Barrier slurry for low-k dielectrics |
CN103103356A (en) * | 2012-11-09 | 2013-05-15 | 柳州百韧特先进材料有限公司 | Process for recovering crude indium and tin from ITO (indium tin oxide) waste target |
WO2014058312A1 (en) * | 2012-10-08 | 2014-04-17 | Stichting Wetsus Centre Of Excellence For Sustainable Water Technology | Desalination of aqueous media using ionic liquids |
-
2015
- 2015-01-20 US US14/601,189 patent/US20150233004A1/en not_active Abandoned
- 2015-02-12 CN CN201510076991.6A patent/CN104862482A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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