CN115679379A - White alloy treatment method - Google Patents
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- CN115679379A CN115679379A CN202211502971.7A CN202211502971A CN115679379A CN 115679379 A CN115679379 A CN 115679379A CN 202211502971 A CN202211502971 A CN 202211502971A CN 115679379 A CN115679379 A CN 115679379A
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Abstract
The invention relates to the technical field of white alloys, in particular to a white alloy treatment method. The white alloy treatment method comprises the following steps: dividing white alloy to be treated into n parts, wherein n is more than or equal to 3; preparing a first anode from a first part of white alloy; (b) placing the first anode in an electrolyte for electrolysis; when a large amount of bubbles appear in the first anode area, taking out the first anode, soaking the first anode by adopting a fluorine-containing acid solution, and then placing the first anode in an electrolyte to repeatedly perform the electrolysis operation to obtain a first defect anode; (c) And (c) mixing the first defective anode with the second part of white alloy and preparing a second anode, repeating the operation of the step (b) to obtain a second defective anode, and the like until the nth part of white alloy is prepared into the nth anode and the electrolysis is completed. The invention adopts a mixing method of mainly electrochemical dissolution and assisting acid dissolution to treat the white alloy, and has the advantages of less used equipment, simple and convenient process, low production cost and high efficiency.
Description
Technical Field
The invention relates to the technical field of white alloys, in particular to a white alloy treatment method.
Background
At present, the treatment methods of the high-silicon white alloy mainly comprise two methods: the first is a wet method, after crushing the white alloy, using strong acid to carry out normal pressure or high pressure decomposition under the participation of oxidant; the other is a pyrogenic process, which is to melt the white alloy, add an oxidant to separate cobalt and iron slagging from copper, and then carry out reduction acid decomposition on cobalt-iron slag to leach out cobalt.
Both of the above two methods have the characteristics of high intensity of technological process, high cost and waste time and waste power. The wet process firstly solves the crushing problem, and the white alloy is hard and wear-resistant, so that the cost of conventional crushing equipment is high, the conventional method is water quenching after melting, but the particle size after water quenching is large (in millimeter level), the influence on the later oxidation acid immersion is great, and the crushing cost is also high. The other method is to use a hard alloy ball mill, but the efficiency is low, the cost is higher, when the leaching is carried out under normal pressure, the leaching temperature is very high (above 90 ℃), a large amount of strong oxidant (such as sodium chlorate, sodium persulfate and the like) is also added, and the salt content of the obtained leachate is very high, so the process requirement is high, the leaching strength is high, and the cost is high. The technological process of the pyrogenic process is long, the leaching temperature (above 90 ℃) is very high when the cobalt and iron slag is leached, and a large amount of reducing agents (such as sodium sulfite, sodium pyrosulfite and the like) are added, so that the obtained leachate is also very high in salt content and high in cost.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for treating white alloy, which solves the problems of high crushing and leaching strength caused by adopting wet smelting and the problems of long process flow and high leaching strength of pyrometallurgy in the prior art.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method of treating a white alloy, comprising the steps of:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; preparing a first anode from a first part of white alloy;
(b) Placing the first anode in an electrolyte for electrolysis; when a large amount of bubbles appear in the first anode region, taking out the first anode, soaking the first anode by adopting a fluorine-containing acid solution, and then placing the first anode in the electrolyte to repeatedly perform the electrolysis operation to obtain a first defect anode, wherein the area of the first defect anode accounts for 80-90% of the original area of the first anode;
(c) Mixing the first defective anode with a second part of white alloy and preparing a second anode, repeating the operation of the step (b) to obtain a second defective anode, and so on until the nth part of white alloy is prepared into the nth anode and the electrolysis is completed;
during electrolysis, copper is evolved at the cathode.
In one embodiment, the white alloy comprises the following components in percentage by mass:
10-45% of Co, 5-30% of Cu, 15-35% of Fe and 5-30% of Si.
In one embodiment, the electrolyte comprises a sulfuric acid solution; the equivalent concentration of the sulfuric acid solution is 0.1-2N.
In one embodiment, the voltage is 4-10V and the current density is 100-300A/m during the electrolysis 2 。
In one embodiment, the fluorine-containing acid solution has equivalent concentrations of hydrogen ions and fluorine ions of 0.1 to 1N, respectively.
In one embodiment, the fluorine-containing acid solution comprises a hydrofluoric acid solution.
In one embodiment, the soaking treatment is performed for 0.5 to 1.5 hours.
In one embodiment, the anodes are washed after each soaking treatment during electrolysis.
In one embodiment, the method further comprises: and washing the n-th defective anode.
In one embodiment, when the concentration of copper ions in the electrolyte is 20g/L or more, the copper is precipitated at the cathode.
In one embodiment, the material of the cathode comprises stainless steel.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a mixing method of mainly electrochemical dissolution and assisting acid dissolution to treat the white alloy, and has the advantages of less used equipment, simple and convenient process, low production cost and high efficiency.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The white alloy is an intermediate product containing cobalt, copper, iron and silicon obtained by converting slag obtained in the process of converter blowing in the copper smelting process and then carrying out electric furnace matte making and reduction smelting enrichment, and is an important secondary resource. In one embodiment, the white alloy of the present invention comprises the following components in mass percent: 10% -45% of Co, 5% -30% of Cu, 15% -35% of Fe and 5% -30% of Si. The white alloy has complex distribution of metal elements and high silicon content, so that the phenomena of mutual wrapping among metal phases and wrapping between silicon dioxide and the metal phases are common, particularly iron silicate phases, so that the white alloy is hard, wear-resistant, corrosion-resistant and insoluble, and valuable elements such as copper, cobalt and the like are difficult to leach. In one embodiment, the Co is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc., and the Cu is 5%, 10%, 15%, 20%, 25%, 30%, etc., in mass percent; 15%, 20%, 25%, 30%, 35% and the like of Fe; si is 5%, 10%, 25%, 30%, etc.
The invention provides a white alloy treatment method aiming at the characteristics of the white alloy, which comprises the following steps:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; preparing a first anode from a first part of white alloy;
(b) Placing the first anode in an electrolyte for electrolysis; when a large amount of bubbles appear in the first anode region, taking out the first anode, soaking the first anode by adopting a fluorine-containing acid solution, and then placing the first anode in the electrolyte to repeatedly perform the electrolysis operation to obtain a first defect anode, wherein the area of the first defect anode accounts for 80-90% of the original area of the first anode;
(c) Mixing the first defective anode with a second part of white alloy and preparing a second anode, repeating the operation of the step (b) to obtain a second defective anode, and repeating the operation in the same way until the nth part of white alloy is prepared into an nth anode and electrolysis is completed;
during electrolysis, copper is evolved at the cathode.
The invention uses a mixing method of electrochemical dissolution as the main method and acid dissolution as the auxiliary method to treat the white alloy; from the structure of the white alloy, it can be known that cobalt, copper and iron can quickly enter a solution during electrolytic dissolution, but the dissolution of silicon is very small, and after the cobalt, copper and iron on the surface of an anode plate are dissolved out, silicon and silicon oxides are left on the surface, which can prevent the continuous electrolytic dissolution and cause the surface passivation phenomenon of the anode plate; therefore, the fluorine-containing acid solution is used to dissolve silicon, so that new cobalt-copper-iron surface is exposed to achieve the purpose of activation.
The method does not need to crush the white alloy and add oxidant (or reducing agent), so that the salinity of the solution is increased, the used equipment is few, the process is simple and convenient, the production cost is low, and the efficiency is high; in addition, in the process of dissolving the white alloy, copper can be directly electrodeposited to obtain a cathode copper product, and the production efficiency is greatly improved.
In one embodiment, the present invention accomplishes the decomposition of the white alloy using three conventional devices: (1) an electric furnace for melting a white alloy to cast an anode plate; (2) an electrolytic bath for electrodissolution of the white alloy anode plate; (3) And the silicon washing tank is used for dissolving silicon during the surface passivation of the anode plate so as to reactivate the surface.
When bubbles are generated in the anode area, the dissolution speed of the anode is reduced. The larger the bubble, the smaller the dissolution rate of the anode. When a large amount of bubbles are generated, it is indicated that the anode is substantially insoluble, but oxygen is generated in the electrolyzed water.
In one embodiment, the area of the first defective anode accounts for 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%, etc. of the original area of the first anode. If the proportion is too high, the production efficiency is influenced, and the cost of casting the anode plate is increased; too low a duty ratio may affect current efficiency and increase power consumption cost.
In one embodiment, the electrolyte comprises a sulfuric acid solution; the sulfuric acid solution has an equivalent concentration of 0.1 to 2N, for example, 0.2N, 0.5N, 0.6N, 0.8N, 1N, 1.2N, 1.5N, 1.7N, 2N, etc.
In one embodiment, the voltage during the electrolysis is 4 to 10V, such as 5V, 6V, 7V, 8V, 9V, etc.; in one embodiment, the current density is from 100 to 300A/m 2 E.g. 120A/m 2 、150A/m 2 、170A/m 2 、200A/m 2 、250A/m 2 、270A/m 2 、290A/m 2 And the like. Further preferably, the cell voltage is 5 to 8V, and too low and too high affect the current efficiency and increase the power consumption cost. More preferably, the current density is 120 to 200A/m 2 Too low and too high may affect the physical properties and quality of the electrolytic copper product.
In one embodiment, the fluorine-containing acid solution has equivalent concentrations of hydrogen ions and fluorine ions of 0.1 to 1N, for example, 0.2N, 0.5N, 0.6N, 0.8N, 0.9N, 1N, and the like. The anode surface is treated with a fluorine-containing acid solution of appropriate concentration to better remove silicon and silicon oxides.
In one embodiment, the fluorine-containing acid solution comprises a hydrofluoric acid solution.
In one embodiment, the soaking treatment is performed for 0.5 to 1.5 hours, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.2 hour, 1.4 hour, 1.5 hour, and the like.
In one embodiment, the anodes are washed after each soaking treatment during electrolysis.
In one embodiment, the method further comprises: and washing the n-th defective anode.
In one embodiment, the copper ions in the solution gradually rise as the white alloy dissolves, and when the concentration of the copper ions in the electrolyte is above 20g/L, the copper is precipitated at the cathode.
In one embodiment, the shape of the anode comprises a sheet.
In one embodiment, the white alloy is melted in an electric furnace, and cast plate equipment for electrolytic refining of blister copper is adopted.
In one embodiment, the material of the cathode comprises stainless steel.
In a preferred embodiment, the method for processing the white alloy comprises the following steps:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; preparing a first anode from a first part of white alloy;
(b) The first anode is placed in an electrolytic tank filled with electrolyte for electrolysis, the electrolyte adopts sulfuric acid solution with equivalent concentration of 0.1-2N, the tank pressure of the electrolytic tank is 4-10V, and the current density is 100-300A/m 2 (ii) a When a large amount of bubbles appear in the first anode region, taking out the first anode, soaking the first anode for 0.5 to 1.5 hours by adopting a hydrofluoric acid solution with the equivalent concentration of 0.1 to 1N, and then putting the first anode into the electrolyte to repeatedly carry out the electrolysis operation until the anode dissolves defects (the dissolving defects refer to that the white alloy anode plate can have perforations or defects in the process of electrodissolutionCorner phenomenon), namely obtaining a first defect anode, wherein the area of the first defect anode accounts for 80-90% of the original area of the first anode;
(c) Taking out the first defective anode, washing the first defective anode to be clean, returning the first defective anode to the electric furnace again, mixing the first defective anode with the second part of white alloy, preparing a second anode, repeating the operation in the step (b) to obtain a second defective anode, and repeating the operation in the same way until the nth part of white alloy is prepared into the nth anode and the electrolysis is completed; during the electrolysis, when the concentration of copper ions in the electrolyte is above 20g/L, copper is precipitated at the cathode.
The following is further illustrated with reference to specific examples.
The white alloy in each embodiment of the invention comprises the following components in percentage by mass: 25% of Co, 30% of Cu, 15% of Fe and 30% of Si.
Example 1
The white alloy treatment method comprises the following steps:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; melting a first part of white alloy by adopting an electric furnace, and then casting to prepare a first anode;
(b) The first anode is placed in an electrolytic bath filled with electrolyte for electrolysis, the electrolyte adopts sulfuric acid solution with equivalent concentration of 1.6N, the bath pressure of the electrolytic bath is 5-8V, and the current density is 120-200A/m 2 The cathode is made of stainless steel; when a large amount of bubbles are generated near the anode plate, taking out the first anode, soaking for 1h by adopting a hydrofluoric acid solution with the equivalent concentration of 0.6N, then washing, and then putting into the electrolyte to repeat the electrolysis operation to obtain a first defect anode, wherein the area of the first defect anode accounts for 80% of the original area of the first anode;
(c) Taking out the first defective anode, washing the first defective anode clean, returning the first defective anode to the electric furnace again, mixing the first defective anode with the second part of white alloy, preparing a second anode, repeating the operation of the step (b) to obtain a second defective anode, repeating the steps in this way until the batch of white alloy is completely processed; during the electrolysis, when the concentration of copper ions in the electrolyte is above 20g/L, copper is precipitated at the cathode.
Example 2
The white alloy treatment method comprises the following steps:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; melting a first part of white alloy by adopting an electric furnace, and then casting to prepare a first anode;
(b) The first anode is arranged in an electrolytic tank filled with electrolyte for electrolysis, the electrolyte adopts sulfuric acid solution with equivalent concentration of 0.2N, the tank pressure of the electrolytic tank is 5-8V, and the current density is 120-200A/m 2 The cathode is made of stainless steel; when a large amount of bubbles are generated near the anode plate, taking out the first anode, soaking for 0.5h by adopting a hydrofluoric acid solution with the equivalent concentration of 1N, then washing, and then putting into the electrolyte to repeat the electrolysis operation to obtain a first defect anode, wherein the area of the first defect anode accounts for 90% of the original area of the first anode;
(c) Taking out the first defective anode, washing the first defective anode clean, returning the first defective anode to the electric furnace again, mixing the first defective anode with the second part of white alloy, preparing a second anode, repeating the operation in the step (b) to obtain a second defective anode, repeating the steps in the same way until the batch of white alloy is completely processed; during the electrolysis, when the concentration of copper ions in the electrolyte is above 20g/L, copper is precipitated at the cathode.
Example 3
The white alloy treatment method comprises the following steps:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; melting a first part of white alloy by adopting an electric furnace, and then casting to prepare a first anode;
(b) The first anode is arranged in an electrolytic tank filled with electrolyte for electrolysis, the electrolyte adopts sulfuric acid solution with equivalent concentration of 2N, the tank pressure of the electrolytic tank is 5-8V, and the current density is 120-200A/m 2 The cathode is made of stainless steel; when a large amount of bubbles are generated near the anode plate, taking out the first anode, soaking for 1.5h by adopting a hydrofluoric acid solution with the equivalent concentration of 0.1N, then washing, putting into the electrolyte, and repeating the electrolysis operation to obtain a first defect anode, wherein the area of the first defect anode accounts for 8 of the original area of the first anode5％；
(c) Taking out the first defective anode, washing the first defective anode clean, returning the first defective anode to the electric furnace again, mixing the first defective anode with the second part of white alloy, preparing a second anode, repeating the operation in the step (b) to obtain a second defective anode, repeating the steps in the same way until the batch of white alloy is completely processed; during the electrolysis, when the concentration of copper ions in the electrolyte is above 20g/L, copper is precipitated at the cathode.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for processing a white alloy, comprising the steps of:
(a) Dividing the white alloy to be treated into n parts, wherein n is more than or equal to 3; preparing a first anode from a first part of white alloy;
(b) Placing the first anode in an electrolyte for electrolysis; when a large amount of bubbles appear in a first anode region, taking out the first anode, soaking the first anode by adopting a fluorine-containing acid solution, and then placing the first anode in the electrolyte to repeatedly carry out the electrolysis operation to obtain a first defect anode, wherein the area of the first defect anode accounts for 80-90% of the original area of the first anode;
(c) Mixing the first defective anode with a second part of white alloy and preparing a second anode, repeating the operation of the step (b) to obtain a second defective anode, and so on until the nth part of white alloy is prepared into the nth anode and the electrolysis is completed;
during electrolysis, copper is precipitated at the cathode.
2. The method for processing the white alloy according to claim 1, wherein the white alloy comprises the following components in percentage by mass:
10% -45% of Co, 5% -30% of Cu, 15% -35% of Fe and 5% -30% of Si.
3. The method of treating a white alloy as claimed in claim 1, wherein the electrolyte comprises a sulfuric acid solution; the equivalent concentration of the sulfuric acid solution is 0.1-2N.
4. The method for treating white alloy according to claim 1, wherein the voltage is 4-10V and the current density is 100-300A/m during the electrolysis 2 。
5. The method according to claim 1, wherein the fluorine-containing acid solution has equivalent concentrations of hydrogen ions and fluorine ions of 0.1 to 1N, respectively.
6. The method of treating a white alloy as claimed in claim 1, wherein the fluorine-containing acid solution comprises a hydrofluoric acid solution.
7. The method for treating a white alloy according to claim 1, wherein the soaking treatment is carried out for 0.5 to 1.5 hours.
8. The method of treating a white alloy according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) In the process of electrolysis, the anode is washed after being soaked every time;
(2) Further comprising: and washing the n-th defective anode.
9. The method according to claim 1, wherein the copper is precipitated at a cathode when the concentration of copper ions in the electrolyte is 20g/L or more.
10. The method of claim 1, wherein the cathode comprises stainless steel.
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| CN202211502971.7A CN115679379A (en) | 2022-11-28 | 2022-11-28 | White alloy treatment method |
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| CN202211502971.7A CN115679379A (en) | 2022-11-28 | 2022-11-28 | White alloy treatment method |
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