CN101070563A - Method for treating cobalt-copper alloy by sulfuric acid - Google Patents
Method for treating cobalt-copper alloy by sulfuric acid Download PDFInfo
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Abstract
This invention has publicized a method of processing cobalt copper alloy using sulphuric acid, which include the following steps: (1) catalyzed oxidation leaching working procedure: Join the cobalt copper alloy powder to reactor, according to fluid solid ratio 3: 1-12: 1 to add water, according to the 75% -150% response theory quantity to add sulfuric acid and hydrochloric acid; Again add the catalyst, it heats up and stir under oxidant function, which make the cobalt, copper valuable metal in cobalt copper alloy leach to and enter solution; (2) magnetic separation parting: Using the different magnetism characteristic of cobalt copper alloy and the leaching dregs, separate the few unresponse remaining cobalt copper alloy with material liquid by weak magnetic separation, the magnetic separation cobalt copper alloy will return to the before working procedure; the flaw of using hydrometallurgical method to process cobalt copper alloy craft has been solvd; it has short technical process, low production cost, high cobalt copper leaching rate and high actual receipt rate, energy conservation, environmental protection, security, broad adaption and so on merits.
Description
Technical field
The present invention relates to a kind of method of handling cobalt-copper alloy, particularly a kind of method with treating cobalt-copper alloy by sulfuric acid.
Background technology
Cobalt-copper alloy is the important source material of producing cobalt metal and various cobalt products, is commonly called as cobalt white metal or cobalt red alloy or cobalt AB alloy or cobalt sulfonium, mainly originates from Africa.Cobalt-copper alloy makes by electric furnace reduction melting cupric oxide cobalt ore and the copper slag that contains cobalt, generally contains cobalt: 10%-40%, copper: 10%-50%, iron: 5%-50%, nickel: 0.1%-5%, manganese: 0.1%-5%.This alloy raw material intractability is bigger, and subject matter is that the yield of cobalt, copper is low, cost is high, technical process is long.
The method of handling cobalt-copper alloy at present mainly contains:
1, electro-dissolving: this method current efficiency is lower, power consumption is higher, and the rate of recovery of cobalt is lower.
2, sulfuration lixiviation process: this method production capacity is big, technical process is long, energy consumption is high, and the total recovery of cobalt, copper is lower.
3, High Temperature High Pressure lixiviation process: this method technical process is long, equipment is complicated, must solve the anticorrosion problem of equipment under high temperature, the condition of high voltage.
4, chlorine lixiviation process: the leaching yield of this method cobalt, copper, iron higher (mining and metallurgy, 1997, Vol6 (1): 67-69), but equipment complexity, equipment anticorrosion and environmental requirement height.
5, direct pickling process: this method is under normal pressure, and speed of response is slow, and leaching process efficient is not high, and technical process is long, the production cost height.
Problem at above-mentioned treatment process existence, we are by a large amount of research and development, invented a kind of catalyzed oxidation salt acid leaching process, and this method to State Intellectual Property Office patent application proposed, number of patent application is 2005100620166, and denomination of invention is a kind of method of handling cobalt-copper alloy; This method for economical, efficiently handle cobalt-copper alloy and lay a good foundation, advantage is very outstanding, leaching velocity is fast, technical process is short, yield is high, cost is low, and has obtained application in process of production.But yet there is weak point in this method: the one, and the adaptability of industrialization has limitation, and hydrochloric acid production region is strong, generally must transport for long-distance; The 2nd, hydrochloric acid is volatile, and protection against corrosion and environmental requirement height easily produce acid mist in the use, must set up the acid mist absorption unit.
In order to seek the method for better processing cobalt-copper alloy, we directly adopt sulfuric acid to replace salt acid treatment cobalt-copper alloy to research and develop, those of ordinary skill in the art knows employing vitriolic benefit: the one, and sulfuric acid is strong than hydrochloric acid adaptability, sulfuric acid is byproduct for most coloured smelting factory, than the easier acquisition of hydrochloric acid.The 2nd, the sulfuric acid leaching process does not have acid mist.The 3rd, the concentration of general industry hydrochloric acid is 20%～35%, the proportion of the hydrochloric acid of concentration 35% is 1.16, and the concentration of industrial sulphuric acid is 93%～98%, the vitriolic proportion of concentration 98% is 1.84, the sulfuric acid of one volume is equivalent to the hydrochloric acid of 3.5～4.5 volumes, adopts sulfuric acid process more to help leaching operation.The 4th, vitriolic is stored, the common carbon steel jar of transportation gets final product, and hydrochloric acid then must adopt heavy preservative tank.The 5th, utilize the vitriolic heat of dilution, initial reaction stage just to need not heating when adopting sulfuric acid to leach, thereby more energy-conservation.But many detours in the research and development process, have been passed by, also run into various difficult problems, most importantly the difficulty that adopts sulfuric acid to leach is big than hydrochloric acid, hydrometallurgy kinetics and production reality show that all the sulfuric acid reaction activity is poor than hydrochloric acid, speed of response is slower, again because sulfuric acid can make the cobalt-copper alloy surface passivation, directly influence the carrying out of leaching process, cause leaching process efficient low, valuable element yields such as cobalt, copper are low.The sulfuric acid extract technology does not have developedly all the time, does not see relevant research report at present as yet yet, and enterprise inside the circle all knows and captures the significance of sulfuric acid extract technology to the cobalt industry development.
Summary of the invention
For overcoming existing treatment process above shortcomings, the method of a kind for the treatment of cobalt-copper alloy by sulfuric acid that the purpose of this invention is to provide that a kind of technical process is short, production cost is low, cobalt copper leaching rate and casting yield is high has solved a series of problems in the wet processing cobalt-copper alloy technology preferably.
The technical solution adopted for the present invention to solve the technical problems is, it may further comprise the steps: (1), catalyzed oxidation leach operation: the cobalt-copper alloy powder is added reactive tank, by liquid-solid ratio 3: 1-12: 1 adds entry, adds the mixing acid of sulfuric acid or sulfuric acid and hydrochloric acid by 75%～150% of reaction theory amount; Press 5g/l～300g/l again and add catalyzer, under the oxygenant effect, heat, stir then, make cobalt, copper valuable metal 90%-99% leaching in the cobalt-copper alloy enter solution;
(2), magnetic separation separation circuit: utilize the cobalt-copper alloy magnetic properties different with leached mud, to leach by low intensity magnetic separation that unreacted small portion of residual cobalt-copper alloy separates with slip in the slip, slip after the magnetic separation makes solid-liquid separation by filtering, and the cobalt-copper alloy that magneticly elects is back to last process.
Described cobalt-copper alloy powder median size is between 5 μ m-150 μ m.
When the mixing acid of employing sulfuric acid and hydrochloric acid leached, the mol ratio of sulfuric acid and hydrochloric acid was 2/8～8/2 in the mixing acid.
Described catalyzer is at least a in ammonium, fluorine, chlorine, the bromine inorganic salt of containing that has katalysis and anti-passivation simultaneously, and the add-on that plays katalysis is 0g/l～150g/l, and the add-on that plays anti-passivation is 5g/l～150g/l.
What described oxygenant was the chemical potential that metallic copper can be oxidized to bivalent cupric ion greater than the liquid state of Cu-Cu++ current potential or solid oxide agent or gaseous oxidizer is a kind of; When adopting liquid and solid oxide agent, its add-on is 10g/l～150g/l; When adopting gaseous oxidizer, its add-on is 0.2m
3/ m
3Slip～2.0m
3/ m
3Slip.
The preheating temperature that described catalyzed oxidation leaches operation is controlled between 35 ℃～65 ℃, and temperature of reaction is controlled between 55 ℃～95 ℃.
The pH value that described catalyzed oxidation leaches the operation reaction end is controlled between 1.0～4.5.
The reaction times that described catalyzed oxidation leaches operation is controlled between 200min～900min.
After adopting aforesaid method, not only have with hydrochloric acid and leach the advantage of handling the cobalt-copper alloy method: the one, technical process is short, under condition of normal pressure, can make the leaching yield of cobalt in the cobalt-copper alloy, copper reach 90%-99%; Be simple to operate, be easy to control; The 3rd, it is very fast to leach speed of response, and it is higher to leach operating efficiency; The 4th, cobalt and copper leaching rate, casting yield height; And solved with hydrochloric acid and leach to handle the volatile generation acid mist of hydrochloric acid in the cobalt-copper alloy production process, must set up acid mist absorption unit, corrosion protection of equipment and environmental protection treatment and require high and be subjected to problem such as hydrochloric acid production region restriction, have advantages such as energy-saving and environmental protection, safety, wide accommodation.
Embodiment
Below in conjunction with specific embodiments main processes of the present invention is sketched: it may further comprise the steps:
(1), catalyzed oxidation leaches operation: the cobalt-copper alloy powder is added reactive tank, described cobalt-copper alloy powder median size is between 5 μ m-150 μ m, by liquid-solid ratio 3: 1-12: 1 adds entry, adds the mixing acid of sulfuric acid or sulfuric acid and hydrochloric acid by 75%～150% of reaction theory amount; When the mixing acid of employing sulfuric acid and hydrochloric acid leached, the mol ratio of sulfuric acid and hydrochloric acid was 2/8～8/2 in the mixing acid; Add catalyzer again, the add-on that wherein plays katalysis is that 0g/l～150g/l, the add-on that plays anti-passivation are 5g/l～150g/l, under the oxygenant effect, heat, stir then, mixing speed is controlled between 80 rev/mins to 350 rev/mins, makes cobalt, copper valuable metal 90%-99% leaching in the cobalt-copper alloy enter solution.Described catalyzer is at least a in ammonium, fluorine, chlorine, the bromine inorganic salt of containing that has katalysis and anti-passivation simultaneously, also can be several combinations.What described oxygenant was the chemical potential that metallic copper can be oxidized to bivalent cupric ion greater than the liquid state of Cu-Cu++ current potential or solid oxide agent or gaseous oxidizer is a kind of; When adopting liquid and solid oxide agent, its add-on is 10g/l～150g/l; When adopting gaseous oxidizer, its add-on is 0.2m
3/ m
3Slip～2.0m
3/ m
3Slip.The preheating temperature that described catalyzed oxidation leaches operation is controlled between 35 ℃～65 ℃, and temperature of reaction is controlled between 55 ℃～95 ℃.By the relative quantity or the adding neutralizing agent of control reactive tank internal reaction material, the pH value of control reaction end is controlled between 1.0～4.5; The reaction times that described catalyzed oxidation leaches operation is controlled between 200min～900min.
In the catalyzed oxidation leaching process, the mixing acid of cobalt-copper alloy, sulfuric acid or sulfuric acid and hydrochloric acid, catalyzer and oxygenant (for liquid state or solid oxide agent) can also can add in batches in disposable adding.When adopting gaseous oxidizer, its add-on can be different in initial reaction stage, mid-term and later stage.
(2), magnetic separation separation circuit: magnetic separation is the important means of simplifying leaching operation, accelerating leaching velocity and assurance cobalt copper casting yield, utilize the cobalt-copper alloy magnetic properties different with leached mud, to leach by low intensity magnetic separation that unreacted small portion of residual cobalt-copper alloy separates with slip in the slip, slip after the magnetic separation is by filtering, make solid-liquid separation, the cobalt-copper alloy that magneticly elects is back to last process.
Be that the cobalt-copper alloy of cobalt 29.1%, copper 21.1%, iron 33.3%, nickel 1.1%, manganese 0.9% is illustrated with major ingredient below.
Example one cobalt-copper alloy 1000g put into the ball mill mill 90 minutes, and then shakes mill 120 minutes, and median size is 47 microns.Weigh this alloy 80g, NH4Cl 50g, NH4F 10g, FeCl2 20g, 80 milliliters in 98% sulfuric acid adds 500 milliliters in water, and 82 ℃ of temperature are pressed the speed bubbling air that flow 1.2l/ divides, and reaction is 8 hours under agitation condition.Reaction end PH=2.5.Earlier slip is filtered.The leaching filtrate that obtains contains cobalt 37.9g/l, copper 26.3g/l, iron 43.4g/l.Leached mud is carried out magnetic separation, magneticly elect the remaining cobalt-copper alloy 3.3g of unreacted, the leached mud of process magnetic separation contains cobalt 0.52g, copper 0.60g.The leaching yield of cobalt is 93.6%, and the leaching yield of copper is 92.3%.The casting yield of cobalt is 97.8%, and the casting yield of copper is 96.4%.
Example two cobalt-copper alloy 1000g put into the ball mill mill 90 minutes, and then shake mill 120 minutes, and median size is 47 microns.Weigh this alloy 80g, NH4Cl 50g, NH4F 10g, FeCl2 20g, 40 milliliters in 98% sulfuric acid, 66 milliliters of 35% hydrochloric acid add 500 milliliters in water, and 84 ℃ of temperature are pressed the speed bubbling air that flow 1.3l/ divides, and add NaClO3 25g and react 8 hours under agitation condition.Reaction end PH=2.5.Earlier slip is filtered.The leaching filtrate that obtains contains cobalt 3 8.1g/l, copper 25.6g/l, iron 41.3g/l.Leached mud is carried out magnetic separation, magneticly elect the remaining cobalt-copper alloy 3.1g of unreacted, the leached mud of process magnetic separation contains cobalt 0.40g, copper 0.45g.The leaching yield of cobalt is 94.0%, and the leaching yield of copper is 91.9%.The casting yield of cobalt is 98.1%, and the casting yield of copper is 97.2%.
Example three cobalt-copper alloy 1000g adopt mechanical atomizing to make powder behind the hot melt, median size is 87 microns.Weigh this alloy 160g, NH4Cl 10g, NH4F 10g, FeCL2 10g, 160 milliliters in 98% sulfuric acid adds 500 milliliters in water, and 87 ℃ of temperature are pressed 1.41/ minute speed bubbling air of flow, add NaClO3 35g, reaction is 8 hours under agitation condition, reaction end PH=2.5.Earlier slip is filtered.The leaching filtrate that obtains contains cobalt 69.2g/l, copper 50.0g/l, iron 69.8g/l.Leached mud is carried out magnetic separation, magneticly elect the remaining cobalt-copper alloy 5.1g of unreacted, the leached mud of process magnetic separation contains cobalt 0.41g, copper 0.67g.The leaching yield of cobalt is 95.7%, and the leaching yield of copper is 94.8%.The casting yield of cobalt is 98..9%, and the casting yield of copper is 97.7%.
Example four cobalt-copper alloy 1000g adopt mechanical atomizing to make powder behind the hot melt, median size is 87 microns.Weigh this alloy 160g, NH4Cl 10g, NH4F 10g, FeCL2 10g, 80 milliliters of 98% hydrochloric acid, 135 milliliters of 35% hydrochloric acid add 500 milliliters in water, 87 ℃ of temperature, press the speed bubbling air that flow 1.5l/ divides, under agitation condition, react after 8 hours reaction end PH=2.5.Earlier slip is filtered.The leaching filtrate that obtains contains cobalt 66.2g/l, copper 51.0g/l, iron 66.8g/l.Leached mud is carried out magnetic separation, magneticly elect the remaining cobalt-copper alloy 5.8g of unreacted, the leached mud of process magnetic separation contains cobalt 0.43g, copper 0.60g.The leaching yield of cobalt is 95.1%, and the leaching yield of copper is 95.0%.The casting yield of cobalt is 98.7%, and the casting yield of copper is 97.9%.
Claims (8)
1, a kind of method for the treatment of cobalt-copper alloy by sulfuric acid is characterized in that: may further comprise the steps:
(1), catalyzed oxidation leaches operation: the cobalt-copper alloy powder is added reactive tank, and by liquid-solid ratio 3: 1-12: 1 adds entry, by 75%～150% adding sulfuric acid of reaction theory amount or the mixing acid of sulfuric acid and hydrochloric acid; Press 5g/l～300g/l again and add catalyzer, under the oxygenant effect, heat, stir then, make cobalt, copper valuable metal 90%-99% leaching in the cobalt-copper alloy enter solution;
(2), magnetic separation separation circuit: utilize the cobalt-copper alloy magnetic properties different with leached mud, to leach by low intensity magnetic separation that unreacted small portion of residual cobalt-copper alloy separates with slip in the slip, slip after the magnetic separation makes solid-liquid separation by filtering, and the cobalt-copper alloy that magneticly elects is back to last process.
2, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1 is characterized in that: described cobalt-copper alloy powder median size is between 5 μ m-150 μ m.
3, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1 is characterized in that: when the mixing acid of employing sulfuric acid and hydrochloric acid leached, the mol ratio of sulfuric acid and hydrochloric acid was 2/8～8/2 in the mixing acid.
4, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1, it is characterized in that: described catalyzer is at least a in ammonium, fluorine, chlorine, the bromine inorganic salt of containing that has katalysis and anti-passivation simultaneously, the add-on that plays katalysis is 0g/l～150g/l, and the add-on that plays anti-passivation is 5g/l～150g/l.
5, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1 is characterized in that: what described oxygenant was the chemical potential that metallic copper can be oxidized to bivalent cupric ion greater than the liquid state of Cu-Cu++ current potential or solid oxide agent or gaseous oxidizer is a kind of; When adopting liquid and solid oxide agent, its add-on is 10g/l～150g/l; When adopting gaseous oxidizer, its add-on is 0.2m
3/ m
3Slip～2.0m
3/ m
3Slip.
6, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1 is characterized in that: the preheating temperature that described catalyzed oxidation leaches operation is controlled between 35 ℃～65 ℃, and temperature of reaction is controlled between 55 ℃～95 ℃.
7, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1 is characterized in that: the pH value that described catalyzed oxidation leaches the operation reaction end is controlled between 1.0～4.5.
8, the method for a kind for the treatment of cobalt-copper alloy by sulfuric acid according to claim 1 is characterized in that: the reaction times that described catalyzed oxidation leaches operation is controlled between 200min～900min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925695A (en) * | 2012-10-20 | 2013-02-13 | 贵研铂业股份有限公司 | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material |
| CN112609090A (en) * | 2020-11-19 | 2021-04-06 | 中国恩菲工程技术有限公司 | Separation method of copper-cobalt oxide ore |
-
2007
- 2007-06-08 CN CNA2007100690685A patent/CN101070563A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925695A (en) * | 2012-10-20 | 2013-02-13 | 贵研铂业股份有限公司 | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material |
| CN112609090A (en) * | 2020-11-19 | 2021-04-06 | 中国恩菲工程技术有限公司 | Separation method of copper-cobalt oxide ore |
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