CN101812585A - Microbubble oxidization and acid dissolution method for copper-cobalt alloy - Google Patents
Microbubble oxidization and acid dissolution method for copper-cobalt alloy Download PDFInfo
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- CN101812585A CN101812585A CN200910101977A CN200910101977A CN101812585A CN 101812585 A CN101812585 A CN 101812585A CN 200910101977 A CN200910101977 A CN 200910101977A CN 200910101977 A CN200910101977 A CN 200910101977A CN 101812585 A CN101812585 A CN 101812585A
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Abstract
The invention discloses a microbubble oxidization and acid dissolution method for copper-cobalt alloy. The current commonly used copper-cobalt alloy wet-process treatment method has the defects of low reaction speed, low efficiency, high cost, large equipment investment and the like. The technical scheme adopted by the invention is that dilute sulfuric acid is used as solvent and air is used as oxidant under normal temperature and normal pressure, a reaction device is formed by a centrifugal pump, a liquid-air injection pump and an acid dissolution reactor, the dilute sulfuric acid enters the acid dissolution reactor from the centrifugal pump through the injection pump, air is sucked in by using negative pressure generated when the injection pump injects high-speed liquid flow, the air is dispersed in the dilute sulfuric acid to form emulsion and to generate a large amount of oxygen-enriched microbubbles, and the microbubbles participate in the oxidization and acid dissolution reaction of the copper-cobalt alloy and the dilute sulfuric acid. The microbubble oxidization and acid dissolution method has the advantages that the dissolution speed is high, the dissolution rate is high, the fine grinding is not required for the alloy water quenching particles, the energy consumption is low, the dissolution cost is low, the air utilization ratio is high, no environmental pollution is caused and the like.
Description
Technical field
The present invention relates to a kind of microbubble oxidization and acid dissolution method of copper-cobalt alloy.
Background technology
The main component of copper-cobalt alloy is cobalt, copper and iron, because of the difference of copper content, the branch of red alloy and white metal is arranged.Red alloy is meant the copper-cobalt alloy that copper content is higher, and the ratio of copper, cobalt, iron is roughly 1: 1: 1 or in the fluctuation of this scope in the white metal.
The treatment process of copper-cobalt alloy generally has two kinds at present, and a kind of is that pyrogenic process adds wet method junction reason, and another kind is full wet processing.According to the difference of copper content, the treatment process of selection is also different.The alloy that copper content is high generally is to adopt the pyrogenic process pre-treatment to blow into anode copper, and electrolysis obtains electrolytic copper then, and cobalt adopts wet processing to reclaim cobalt from the blowing slag.The alloy (as white metal) that copper content is relatively low, normally the initial oxidation roasting obtains the cobalt copper oxide, and then carries out wet processing and reclaim cobalt copper, also has the dissolving of the nitration mixture of employing or oxidation reinforced dose of acid molten.
The full wet processing of copper-cobalt alloy generally is to carry out the molten leaching of oxidizing acid earlier, and the solution of leaching is produced electrolytic copper through extraction-electrodeposition, and raffinate is produced cobalt salt or cobalt compound through iron purification-P204 abstraction impurity removal-P507 extracting and separating nickel cobalt.
Full wet processing copper-cobalt alloy extracts the copper cobalt, and gordian technique is the dissolving liquid making of alloy, and the pertinent literature report is quite a few.Because cobalt copper iron is with the alloy form combination, it is bigger that such alloy difficulty is leached in full wet method dissolving, and when air was made oxygenant at normal temperatures and pressures, general speed of response was slower, improved speed of response and generally need use heavy dose of strong oxidizer (chlorine, sodium chlorate); If the molten employing high-temperature and high-pressure conditions of oxidizing acid is just quite strict for the requirement of equipment, and has the problem of operating with device security.
In a word, the shortcoming that copper-cobalt alloy wet treatment method at present commonly used exists has: speed of response is slow, and efficient is low, and cost height, equipment have high input etc.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming that the molten wet processing copper-cobalt alloy of existing oxidizing acid exists, a kind of microbubble oxidization and acid dissolution method of copper-cobalt alloy is provided, it produces a large amount of oxygen enrichment microbubbles by squirt pump in lysate, microbubble is adsorbed on the particle surface of copper-cobalt alloy, promote the oxidation and the dissolving of copper, cobalt, iron, thereby accelerate the dissolution rate of copper-cobalt alloy greatly.
For this reason, the technical solution used in the present invention is as follows: the microbubble oxidization and acid dissolution method of copper-cobalt alloy, at normal temperatures and pressures, with the dilute sulphuric acid is solvent, air is an oxygenant, form reaction unit by impeller pump, liquid-gas jetting pump and sour molten reactor, dilute sulphuric acid is entered in the sour molten reactor through squirt pump by impeller pump, the negative pressure that produces when utilizing squirt pump to spray high velocity liquid stream sucks air, and air dispersion formed milk sap in dilute sulphuric acid, produce a large amount of oxygen enrichment microbubbles, microbubble participates in the oxidation dissolution reaction of copper-cobalt alloy and dilute sulphuric acid.The liquid that air content is few flows out from the bottom of the molten reactor of acid, reenters in the sour molten reactor by impeller pump, until the copper-cobalt alloy dissolving fully.
The standard reducing electrode potential data of copper, cobalt, iron is as follows:
Cu
2++ 2e=Cu E
00.344 volt
O
2+ 4H
++ 4e=2H
2O E
01.23 volt
Fe
2++ 2e=Fe E
0-0.441 volt
Co
2++ 2e=Co E
0-0.277 volt
2H
++2e＝H
2?????????E
0??????0
From standard reducing electrode potential data, the Fe in the alloy, Co can be by sulfuric acid dissolutions, and the copper employing air oxidant in the alloy also can be by the sulfuric acid stripping, and this is a theoretical basis of the present invention.
The present invention has effectively utilized the liquid-gas jetting pump to carry out oxygenation, in lysate, introduce a large amount of oxygen enrichment microbubbles, microbubble contacts with copper-cobalt alloy in lysate, and be adsorbed on the alloying pellet surface, oxidation and the dissolving of copper, cobalt, iron have been promoted, thereby accelerated the dissolution rate of copper-cobalt alloy greatly, also increased substantially the utilization ratio of oxygen in the air simultaneously.In general, the bubble tower air utilization ratio only is about 15%, and is approximately 40-45% with the air utilization ratio of squirt pump generation negative pressure suction air generation microbubble.Microbubble oxidization and acid dissolution method of the present invention has advantages such as dissolution rate is fast, solubility rate is high, alloy shrend particle does not need fine grinding, energy consumption is low, the stripping cost is low, air utilization ratio is high, non-environmental-pollution.
The copper-cobalt alloy composition range that the present invention relates to handle is wide, and the alloy mass percentage composition is: Co (5-40%), Cu (10-80%), Fe (10-70%).Use sulfuric acid concentration in 1mol/L～5mol/L fluctuation.
Beneficial effect of the present invention is as follows:
1) the alloy stripping is complete, and copper, cobalt, iron solubility rate are nearly 100%, usually greater than 99.5%;
2) need not independent apparatus of oxygen supply, air is sucked by the negative pressure that squirt pump produces, and is dispersed in the liquid, and noiselessness pollutes;
3) waste gas qualified discharge: H
2SO
4Acid mist＜50mg/NM
3
4) the air utilization ratio height is roughly 40～45%;
5) energy consumption is low, about 1 ton of about 500kwh of alloy power consumption;
6) dissolution rate is fast, the labour productivity height;
7) low equipment investment.
The present invention is further illustrated below in conjunction with specification drawings and specific embodiments.
Description of drawings
Fig. 1 is for realizing the structural representation of the reaction unit that microbubble oxidization and acid dissolution method of the present invention is used.
Embodiment
As shown in Figure 1, the top of sour molten reactor 8 has dog-house 7, and the false end 2 is equipped with in the bottom, has a plurality of small through hole at false the end 2.The liquid feeding end of impeller pump 1 is connected by the bottom of pipeline with sour molten reactor 8, and outlet end is connected with liquid-gas jetting pump 3 by pipeline.The top of liquid-gas jetting pump 3 is positioned at outside the sour molten reactor 8 and has a blast inlet 4, and the bottom is positioned at sour molten reactor 8, and outlet at bottom is positioned at below, the false ends 2.Acid mist resorber 6 is equipped with on the top of the molten reactor 8 of acid.
In reaction unit when work,, particle diameter is that the copper-cobalt alloy of 0.1～5.0mm is packed in the sour molten reactor 8 by dog-house 7, places at false the end 2.Add dilute sulphuric acid in the molten reactor 8 of acid, start impeller pump 1, acid solution sprays into and forms a negative pressuren zone through pipeline at a high speed by the nozzle 5 of liquid-gas jetting pump 3, air is inhaled into by inlet mouth 4, and be dispersed in the high velocity liquid stream and form milk sap, produce a large amount of oxygen enrichment microbubbles, participate in copper-cobalt alloy and sour oxidation dissolution reaction.The liquid that air content is few flows out from the molten reactor bottom of acid, reenters in the sour molten reactor by impeller pump, and the circulation above-mentioned steps, up to the alloy dissolving fully.
The present invention can handle the copper-cobalt alloy of multiple different components, sees Table 1.
The composition of table 1 copper-cobalt alloy and granularity
| Form | Cobalt | Copper | Iron | Granularity |
| Mass percent | ??5-40％ | ??10-80％ | ??10-70％ | Powdery or 0.5-5mm's is granular |
Initial vitriolic concentration is: 1～5mol/L, terminal point sulfuric acid concentration are 0.1～0.5mol/L.Temperature in the process is 40～80 ℃, self-heating.
Below for using the related data of copper-cobalt alloy that the present invention handles two kinds of different components:
1) copper-cobalt alloy, Cu: Co: Fe=1: 1: 1
| The device specification | Beginning acid concentration mol/L | Whole acid concentration mol/L | Process temperature ℃ | Production capacity | Acid consumption t/t alloy | Power consumption Kwh |
| ??2.0t | ??～2 | ??～0.2 | ??60-80 | ??2.0t | ??～2.2 | ??～550 |
2) copper-cobalt alloy, Cu: Co: Fe=75: (5-7): (15-20)
| The device specification | Beginning acid concentration mol/L | Whole acid concentration mol/L | Process temperature ℃ | Production capacity | Acid consumption t/t alloy | Power consumption Kwh |
| ??2.0t | ??～2.5 | ??～0.4 | ??60-80 | ??2.0t | ??～2.0 | ??～500 |
Claims (4)
1. the microbubble oxidization and acid dissolution method of copper-cobalt alloy, at normal temperatures and pressures, with the dilute sulphuric acid is solvent, air is an oxygenant, form reaction unit by impeller pump, liquid-gas jetting pump and sour molten reactor, dilute sulphuric acid is entered in the sour molten reactor through squirt pump by impeller pump, the negative pressure that produces when utilizing squirt pump to spray high velocity liquid stream sucks air, and air dispersion formed milk sap in dilute sulphuric acid, produce a large amount of oxygen enrichment microbubbles, microbubble participates in the oxidation dissolution reaction of copper-cobalt alloy in the sour molten reactor and dilute sulphuric acid.
2. microbubble oxidization and acid dissolution method according to claim 1, it is characterized in that the few liquid of air content flows out from the bottom of the molten reactor of acid, reenter participation reaction in the sour molten reactor by impeller pump and liquid-gas jetting pump, fully until the copper-cobalt alloy dissolving.
3. microbubble oxidization and acid dissolution method according to claim 1 and 2, it is characterized in that the quality percentage composition in the described copper-cobalt alloy is: Co is 5-40%, and Cu is 10-80%, and Fe is 10-70%.
4. microbubble oxidization and acid dissolution method according to claim 3 is characterized in that in the dissolution process that the initial concentration of dilute sulphuric acid is controlled at 1～5mol/L, and terminal point concentration is controlled at 0.1～0.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910101977A CN101812585A (en) | 2009-08-27 | 2009-08-27 | Microbubble oxidization and acid dissolution method for copper-cobalt alloy |
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|---|---|---|---|
| CN200910101977A CN101812585A (en) | 2009-08-27 | 2009-08-27 | Microbubble oxidization and acid dissolution method for copper-cobalt alloy |
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|---|---|
| CN101812585A true CN101812585A (en) | 2010-08-25 |
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105695737A (en) * | 2016-04-08 | 2016-06-22 | 金川集团股份有限公司 | Concentrated acid leaching reactor |
| CN106086420A (en) * | 2016-07-29 | 2016-11-09 | 广东先导稀材股份有限公司 | The method extracting valuable metal from germanium-containing alloy |
| CN108220594A (en) * | 2016-12-14 | 2018-06-29 | 北京有色金属研究总院 | A kind of method for improving gold mine gold leaching rate in the golden system of alkaline thiourea leaching |
| CN109608327A (en) * | 2019-01-04 | 2019-04-12 | 武汉稀源汇冶金科技有限公司 | A kind of method and microbubble oxidation trough of microbubble oxidation production copper acetate |
| CN109971953A (en) * | 2019-03-18 | 2019-07-05 | 中国科学院过程工程研究所 | A method of enhanced oxidation extracts valuable metal from the sulfide mineral containing non-ferrous metal |
| CN113145057A (en) * | 2021-05-28 | 2021-07-23 | 金川镍钴研究设计院有限责任公司 | Acid dissolution reactor, equipment and method for preparing nickel sulfate |
| CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
| CN113441066A (en) * | 2021-06-01 | 2021-09-28 | 常州大学 | Method for quickly dissolving copper in electrolytic copper foil manufacturing process |
| CN115109927A (en) * | 2021-03-17 | 2022-09-27 | 中国科学院过程工程研究所 | Method for removing manganese and magnesium from laterite-nickel ore hydrochloric acid leaching solution |
-
2009
- 2009-08-27 CN CN200910101977A patent/CN101812585A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105695737A (en) * | 2016-04-08 | 2016-06-22 | 金川集团股份有限公司 | Concentrated acid leaching reactor |
| CN105695737B (en) * | 2016-04-08 | 2018-02-13 | 金川集团股份有限公司 | A kind of Leaching by strong acid curing reactor |
| CN106086420A (en) * | 2016-07-29 | 2016-11-09 | 广东先导稀材股份有限公司 | The method extracting valuable metal from germanium-containing alloy |
| CN108220594A (en) * | 2016-12-14 | 2018-06-29 | 北京有色金属研究总院 | A kind of method for improving gold mine gold leaching rate in the golden system of alkaline thiourea leaching |
| CN109608327A (en) * | 2019-01-04 | 2019-04-12 | 武汉稀源汇冶金科技有限公司 | A kind of method and microbubble oxidation trough of microbubble oxidation production copper acetate |
| CN109971953A (en) * | 2019-03-18 | 2019-07-05 | 中国科学院过程工程研究所 | A method of enhanced oxidation extracts valuable metal from the sulfide mineral containing non-ferrous metal |
| CN115109927A (en) * | 2021-03-17 | 2022-09-27 | 中国科学院过程工程研究所 | Method for removing manganese and magnesium from laterite-nickel ore hydrochloric acid leaching solution |
| CN113145057A (en) * | 2021-05-28 | 2021-07-23 | 金川镍钴研究设计院有限责任公司 | Acid dissolution reactor, equipment and method for preparing nickel sulfate |
| CN113441066A (en) * | 2021-06-01 | 2021-09-28 | 常州大学 | Method for quickly dissolving copper in electrolytic copper foil manufacturing process |
| CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
| CN113416855B (en) * | 2021-06-18 | 2022-10-18 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
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Open date: 20100825 |