CN112481501B - Method for preparing nickel powder by using decoppering final solution - Google Patents
Method for preparing nickel powder by using decoppering final solution Download PDFInfo
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- CN112481501B CN112481501B CN202011260590.3A CN202011260590A CN112481501B CN 112481501 B CN112481501 B CN 112481501B CN 202011260590 A CN202011260590 A CN 202011260590A CN 112481501 B CN112481501 B CN 112481501B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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- 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
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Abstract
The invention provides a method for preparing nickel powder by using decoppered final solution, which comprises the following steps: a) evaporating and concentrating the final copper-removing solution to obtain an evaporated solution; b) freezing and crystallizing the evaporated liquid to obtain a nickel sulfate crystal; c) deeply removing impurities from the nickel sulfate crystals to obtain impurity-removed liquid; the deep impurity removal comprises the following steps: removing copper, calcium and magnesium, cobalt and cadmium and zinc and iron; d) reacting the impurity-removed solution with sodium carbonate to form nickel carbonate; and (3) after the nickel carbonate is dissolved by using sulfuric acid solution, adding a reducing agent to carry out reduction reaction to form nickel powder. The method provided by the invention can be used for preparing the nickel powder from the final copper-removing solution, and the recovery rate and the purity of the obtained nickel powder are higher.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a method for preparing nickel powder by using decoppered final solution.
Background
In the copper electrolytic refining process, the impurity nickel content in the electrolyte can be continuously enriched, the impurity nickel content can influence the electrolytic process and the product quality when reaching a certain concentration, and the concentration of the impurity nickel in the electrolyte is balanced by a method of firstly removing copper and impurities from the electrolyte to obtain a final copper-removing solution, and then carrying out concentration crystallization on the final copper-removing solution to produce crude nickel sulfate in the current industry. The specific process is as follows: firstly, removing copper and impurities from the electrolyte, and converting the electrolyte into a final copper-removing solution, wherein the copper content is reduced to below 0.5 g/L; and then carrying out vacuum evaporation on the final copper removal solution, and obtaining a byproduct, namely crude nickel sulfate by adopting a water-cooling crystallization method.
The nickel crystallization rate in the treatment method is low, generally only about 50%, and the production efficiency is low. And the obtained crude nickel sulfate comprises the following components: 10 to 15% of Ni, 0.1 to 2% of Cu, 1 to 5% of Fe, 1 to 6% of Zn, 0.1 to 0.5% of Ca, 0.1 to 0.5% of Mg, 0.1 to 0.3% of Co, and 0.1 to 0.3% of Cd. Because the crude nickel sulfate has high content of impurities such as copper, iron, zinc and the like, can not be directly utilized, has low price, low additional value and large accumulated amount of stockpiling stock, causes the occupation of funds, and can bring certain economic loss to production enterprises.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing nickel powder by using a final copper removal solution. The method provided by the invention can prepare the nickel powder from the final copper removal solution, and the recovery rate and the purity of the obtained nickel powder are higher.
The invention provides a method for preparing nickel powder by using decoppered final solution, which comprises the following steps:
a) evaporating and concentrating the final copper-removing solution to obtain an evaporated solution;
b) freezing and crystallizing the evaporated liquid to obtain a nickel sulfate crystal;
c) deeply removing impurities from the nickel sulfate crystals to obtain impurity-removed liquid;
the deep impurity removal comprises the following steps: removing copper, calcium and magnesium, cobalt and cadmium and zinc and iron;
d) reacting the impurity-removed solution with sodium carbonate to form nickel carbonate; and (3) after the nickel carbonate is dissolved by using sulfuric acid solution, adding a reducing agent to carry out reduction reaction to form nickel powder.
Preferably, the step c) comprises:
c1) dissolving the nickel sulfate crystal, and introducing H 2 S, reacting the gas to form copper sulfide precipitate, and performing solid-liquid separation to obtain copper-removed liquid;
c2) mixing the copper-removed liquid with ammonium fluoride for reaction to form calcium fluoride and magnesium fluoride precipitates, and then carrying out solid-liquid separation to obtain a calcium-magnesium-removed liquid;
c3) mixing the calcium and magnesium removed solution with zinc powder for reaction to form cobalt precipitate and cadmium precipitate, and then carrying out solid-liquid separation to obtain a cobalt and cadmium removed solution;
c4) and removing zinc and iron impurities from the solution after removing the cobalt and the cadmium by an extraction method to obtain solution after removing impurities.
Preferably, in the step a), the end point of the evaporation concentration is controlled as follows: the content of sulfuric acid in the evaporated liquid is 800-1200 g/L, and the specific gravity of the evaporated liquid is 1.45-1.65.
Preferably, the evaporative concentration is vacuum evaporative concentration;
the vacuum evaporation and concentration conditions are as follows: the steam pressure is 0.3-0.4 MPa, and the vacuum degree is 0.65-0.86 KPa.
Preferably, in the step b), the temperature of the frozen crystallization is-15 to-25 ℃;
controlling the end point of the freezing crystallization as follows: until the nickel content in the crystallization mother liquor is less than or equal to 8 g/L.
Preferably, in the step c 1):
the dissolving is to add water to dissolve to form a nickel sulfate solution;
controlling the nickel content in the obtained nickel sulfate solution to be 60-80 g/L;
said H 2 The introduction amount of S gas and Cu in the nickel sulfate solution 2+ The molar ratio of (4-5) to 1;
the reaction temperature is 50-70 ℃, and the reaction time is 2-3 h.
Preferably, in the step c 2):
the molar ratio of the molar quantity of the ammonium fluoride to the total molar quantity of calcium and magnesium elements in the copper-removed liquid is (4-6) to 1;
the reaction temperature is 80-90 ℃, and the reaction time is 2-3 h.
Preferably, in the step c 3):
the molar ratio of the molar quantity of the zinc powder to the total molar quantity of the cobalt and cadmium elements in the calcium and magnesium removed solution is (4-5) to 1;
the reaction temperature is 45-55 ℃, and the reaction time is 40-60 min.
Preferably, the step c4) includes:
c4-1) diluting the solution after removing the cobalt and the cadmium by sulfonated kerosene, and then saponifying by using sodium hydroxide to obtain a saponified solution;
c4-2) extracting the saponified solution by using an extracting agent to obtain an organic phase and a solution after impurity removal;
the extractant is a P204 extractant;
the extraction conditions were controlled as follows: the volume fraction of the extracting agent is 20-40%, the saponification rate is 60-70%, the pH value is 1.5-2.5, and the extraction ratio of V (O) to V (A) is 1: 1.
Preferably, in step d):
after the nickel carbonate is dissolved by using sulfuric acid and before the reducing agent is added, the method further comprises the following steps: adjusting the pH value to 10-12;
the reducing agent is hydrazine hydrate;
the temperature of the reduction reaction is 80-90 ℃, and the time is 1-2 h.
The invention provides a method for preparing nickel powder by using a copper-removing final solution, which comprises the following steps: a) evaporating and concentrating the final copper-removing solution to obtain an evaporated solution; b) freezing and crystallizing the evaporated liquid to obtain a nickel sulfate crystal; c) deeply removing impurities from the nickel sulfate crystals to obtain impurity-removed liquid; the deep impurity removal comprises the following steps: removing copper, calcium and magnesium, cobalt and cadmium and zinc and iron; d) reacting the impurity-removed solution with sodium carbonate to form nickel carbonate; and (3) after the nickel carbonate is dissolved by using sulfuric acid solution, adding a reducing agent to carry out reduction reaction to form nickel powder. Evaporating and concentrating the final copper-removed solution, then performing freeze crystallization to obtain nickel sulfate crystals, and then performing deep impurity removal on the nickel sulfate crystals, specifically, sequentially removing copper, calcium and magnesium, cobalt and cadmium, and zinc and iron to obtain an impurity-removed solution; and reacting the solution after impurity removal with sodium carbonate to form nickel carbonate, dissolving the nickel carbonate by using sulfuric acid solution, and adding a reducing agent to perform a reduction reaction to form nickel powder. The invention provides an invention idea for preparing nickel powder from the final copper-removing solution, and obtains a certain solution after impurity removal by a specific treatment mode of steps a) -c), so that the solution can be used for preparing the nickel powder, high-purity nickel powder can be obtained with high yield, and the added value of the final copper-removing solution is improved.
Experimental results show that the method enables the recovery rate of the nickel powder to reach more than 96%, and the nickel powder meets the high-purity nickel powder specified in the national standard YS/T925-2013.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of a process for preparing nickel powder by using a final copper removal solution according to an embodiment of the present invention.
Detailed Description
The invention provides a method for preparing nickel powder by using decoppered final solution, which comprises the following steps:
a) evaporating and concentrating the final copper-removing solution to obtain an evaporated solution;
b) freezing and crystallizing the evaporated liquid to obtain a nickel sulfate crystal;
c) deeply removing impurities from the nickel sulfate crystals to obtain impurity-removed liquid;
the deep impurity removal comprises the following steps: removing copper, calcium and magnesium, cobalt and cadmium and zinc and iron;
d) reacting the impurity-removed solution with sodium carbonate to form nickel carbonate; and (3) after the nickel carbonate is dissolved by using sulfuric acid solution, adding a reducing agent to carry out reduction reaction to form nickel powder.
Evaporating and concentrating the final copper-removed solution, then performing freeze crystallization to obtain nickel sulfate crystals, and then performing deep impurity removal on the nickel sulfate crystals, specifically, sequentially removing copper, calcium and magnesium, cobalt and cadmium, and zinc and iron to obtain an impurity-removed solution; and then reacting the solution after impurity removal with sodium carbonate to form nickel carbonate, dissolving the nickel carbonate by using sulfuric acid solution, and adding a reducing agent to perform reduction reaction to form nickel powder. The invention provides an invention idea for preparing nickel powder from the final copper-removing solution, and obtains a certain solution after impurity removal by a specific treatment mode of steps a) -c), so that the solution can be used for preparing the nickel powder, high-purity nickel powder can be obtained with high yield, and the added value of the final copper-removing solution is improved.
With respect to step a): and (4) evaporating and concentrating the final copper-removing solution to obtain an evaporated solution.
The final copper-removing solution is a solution obtained by electrodepositing, copper-removing, purifying, arsenic-removing, antimony-removing and bismuth-removing partial electrolytic stock solution which is divided during the process of producing cathode copper by copper electrolysis; specifically, in the copper electrolytic refining process, the content of impurity nickel in the electrolyte can be continuously enriched, the electrolytic process and the product quality can be influenced when the content of impurity nickel reaches a certain concentration, and the electrolyte is firstly subjected to decoppering and impurity removal to obtain a decoppering final solution in the current industry. The final copper-removing solution mainly contains Ni 5-20 g/L, Cu 0.01-0.6 g/L, and free acid 200-300 g/L. The final copper-removing solution is not particularly limited in the present invention, and is a conventional final copper-removing solution well known to those skilled in the art.
Firstly, evaporating and concentrating the final copper-removing solution; the end point of the evaporation concentration is preferably controlled as follows: the content of sulfuric acid in the evaporated liquid is 800-1200 g/L, and the specific gravity of the evaporated liquid is 1.45-1.65. In some embodiments of the invention, the sulfuric acid content of the post-evaporation liquor is controlled to be 800g/L, 900g/L, 1000g/L or 1200 g/L. In some embodiments of the invention, the specific gravity of the liquid after evaporation is controlled to be 1.45, 1.50, 1.55 or 1.65.
In the present invention, the evaporation concentration is preferably vacuum evaporation concentration. Specifically, the evaporative concentration may be carried out by: and pumping the final copper-removing solution to an evaporation head tank, continuously flowing to a plate type vacuum evaporator group, heating and evaporating by adopting steam, and continuously evaporating and concentrating. In the present invention, the conditions for vacuum evaporation concentration are preferably: the steam pressure is 0.3-0.4 MPa, and the vacuum degree (namely the vacuum degree of the head tank) is 0.65-0.86 KPa. And controlling the evaporation concentration to reach the end point under the conditions to obtain the evaporated liquid.
With respect to step b): and (4) performing freezing crystallization on the evaporated liquid to obtain a nickel sulfate crystal.
In the present invention, the freeze crystallization may be performed by: pumping the evaporated liquid obtained in the step a) to a freezing crystallization tank through a circulating pump, and continuously pumping to a brine freezing unit for freezing crystallization. In the present invention, the temperature of the frozen crystallization is preferably-15 to-25 ℃; in some embodiments of the invention, the temperature of the freeze crystallization is-15 ℃, -22 ℃, or-25 ℃. In the process of freezing crystallization, nickel sulfate crystals are continuously separated out to form a mixed system containing the nickel sulfate crystals and crystallization mother liquor. In the present invention, it is preferable to control the end point of the freeze crystallization to: until the nickel content in the crystallization mother liquor is less than or equal to 8g/L, and the nickel content is more preferably 4-8 g/L. After the crystallization end point is reached, preferably, solid-liquid separation is also carried out, so that crystals are separated from crystallization mother liquor; the solid-liquid separation mode is not particularly limited in the invention, and the solid-liquid separation mode can be a conventional separation mode well known to those skilled in the art, such as filtration and the like; and (4) carrying out solid-liquid separation to obtain nickel sulfate crystals and crystallization mother liquor.
In the invention, the nickel sulfate crystal obtained by the treatment comprises the following components in percentage by mass: 16 to 20 percent of Ni, 0.01 to 0.2 percent of Cu, 0.1 to 0.5 percent of Fe, 0.1 to 0.5 percent of Zn, 0.01 to 0.05 percent of Ca, 0.01 to 0.05 percent of Mg, 0.01 to 0.03 percent of Co and 0.01 to 0.03 percent of Cd. In the invention, the separated crystallization mother liquor can be heated to 50-60 ℃ by steam and then returned to the electrolysis system for recycling.
With respect to step c): and deeply removing impurities from the nickel sulfate crystals to obtain impurity-removed liquid.
In the invention, the deep impurity removal comprises the following steps of: copper removal, calcium and magnesium removal, cobalt and cadmium removal and zinc and iron removal. Preferably, the method specifically comprises the following steps:
c1) dissolving the nickel sulfate crystal, and introducing H 2 S, reacting the gas to form copper sulfide precipitate, and performing solid-liquid separation to obtain copper-removed liquid;
c2) mixing the copper-removed liquid with ammonium fluoride for reaction to form calcium fluoride and magnesium fluoride precipitates, and then carrying out solid-liquid separation to obtain a calcium-magnesium-removed liquid;
c3) mixing the calcium and magnesium removed solution with zinc powder for reaction to form cobalt precipitate and cadmium precipitate, and then carrying out solid-liquid separation to obtain a cobalt and cadmium removed solution;
c4) removing zinc and iron impurities from the solution after cobalt and cadmium removal by an extraction method to obtain solution after impurity removal.
With respect to step c 1):
in the invention, the dissolving is to mix and dissolve nickel sulfate crystals with water to form a nickel sulfate solution. In the invention, the nickel content in the nickel sulfate solution is preferably controlled to be 60-80 g/L; if the nickel content is too low, the nickel sulfate is not easy to crystallize, and if the nickel content is too high, the nickel is easy to enter slag along with impurities in the impurity removal process, so that the loss amount of the nickel is increased, and the recovery rate of the nickel is reduced. In some embodiments of the invention, the nickel content of the nickel sulfate solution is controlled to be 60g/L, 65g/L, 75g/L, or 80 g/L.
In the invention, after the nickel sulfate solution is obtained by the dissolution, H is introduced 2 S gas reacts, in the process, H 2 S reacts with copper impurities in the solution to generate copper sulfide precipitate. In the present invention, it is preferable to control H 2 The introduction amount of S gas is 4-5 times of the theoretical amount; the theoretical quantity is H 2 The theoretical molar ratio of S to Cu reaction, namely 1: 1; 4-5 times of theoretical amount is H 2 The introduction amount of S gas and Cu in the nickel sulfate solution 2+ The molar ratio of (4-5) to 1.
In the invention, the reaction temperature is preferably 50-70 ℃; in some embodiments of the invention, the temperature is 50 ℃, 60 ℃ or 70 ℃. In the invention, the reaction time is 2-3 h; in some embodiments of the invention, the time is 2h, 2.5h, or 3 h. After the reaction, copper sulfide precipitate is generated in the system.
In the present invention, it is preferable to further perform solid-liquid separation after the above-mentioned reaction; the solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation method known to those skilled in the art, such as filtration. And removing the copper sulfide through the solid-liquid separation to obtain a copper-removed liquid. According to the invention, the Cu content in the nickel sulfate solution can be reduced to below 0.5mg/L through the copper sulfide deposition treatment.
With respect to step c 2):
in the invention, after the copper-removing solution is obtained, calcium and magnesium are removed by fluorination; specifically, the solution after copper removal is mixed with ammonium fluoride for reaction to form calcium fluoride and magnesium fluoride precipitates. In the invention, the adding amount of the ammonium fluoride is preferably 2-3 times of the theoretical amount, the theoretical amount is that the molar ratio of the ammonium fluoride to M (namely Ca and Mg) is 2: 1, and 2-3 times of the theoretical amount is that the molar ratio of the molar amount of the ammonium fluoride to the total molar amount of calcium and magnesium elements in the copper-removed liquid is controlled to be (4-6): 1.
In the present invention, the pH of the solution after copper removal is preferably adjusted before adding ammonium fluoride. In the present invention, the pH is preferably adjusted to 4.5 to 5.5. After the pH was adjusted to the above value, ammonium fluoride was added to the reaction mixture to carry out a reaction.
In the invention, the reaction temperature is preferably 80-90 ℃; in some embodiments of the invention, the temperature of the reaction is 80 ℃, 83 ℃, 85 ℃ or 90 ℃. In the invention, the reaction time is preferably 2-3 h; in some embodiments of the invention, the reaction time is 2h, 2.5h, or 3 h. After the reaction, calcium fluoride and magnesium fluoride are formed and precipitated from the solution system.
In the present invention, it is preferable to further perform solid-liquid separation after the above-mentioned reaction; the solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation method known to those skilled in the art, such as filtration. And removing calcium fluoride and magnesium fluoride through the solid-liquid separation to obtain the calcium and magnesium removed liquid. According to the invention, the calcium and magnesium contents in the nickel sulfate solution can be reduced to below 1mg/L through the fluorination calcium and magnesium removal treatment.
With respect to step c 3):
in the invention, after the calcium and magnesium removal solution is obtained, the calcium and magnesium removal solution and zinc powder are subjected to a displacement reaction to remove cobalt and cadmium. In the invention, the adding amount of the zinc powder is preferably 4-5 times of the theoretical amount, and specifically, the molar ratio of the molar amount of the zinc powder to the total molar amount of the cobalt and cadmium elements in the calcium and magnesium removed solution is controlled to be (4-5): 1. After zinc powder is added, the zinc powder and cobalt ions and cadmium ions in the system are subjected to a displacement reaction to form cobalt simple substance precipitate and cadmium simple substance precipitate.
In the invention, the reaction temperature is preferably 45-55 ℃; in some embodiments of the invention, the temperature is 45 ℃, 48 ℃, 50 ℃ or 55 ℃. In the invention, the reaction time is preferably 40-60 min; in some embodiments of the invention, the time of the reaction is 40min, 45min, 50min or 60 min.
In the present invention, it is preferable to further perform solid-liquid separation after the above-mentioned reaction; the solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation method known to those skilled in the art, such as filtration. And removing cobalt and cadmium through the solid-liquid separation to obtain the liquid after removing cobalt and cadmium. The invention can reduce the cobalt-cadmium content in the nickel sulfate solution to below 5mg/L through the replacement cobalt-cadmium removal treatment.
With respect to step c 4):
in the present invention, the extraction process preferably comprises:
c4-1) diluting the solution after removing the cobalt and the cadmium by sulfonated kerosene, and then saponifying by using sodium hydroxide to obtain a saponified solution;
c4-2) extracting the saponified solution by using an extracting agent to obtain an organic phase and a solution after impurity removal.
In the invention, sulfonated kerosene is used for dilution to reduce the viscosity of extracted organic matters so as to facilitate separation; the extractant and the sulfonated kerosene diluent are organic matters, have low solubility in water, can be converted into an ionic state after being saponified by adding sodium hydroxide, have increased solubility in water and are convenient for the reaction of the extractant and impurities. In addition, once extraction reaction occurs, the acidity of the system is increased, and once washing and back extraction occur, the acidity of the system is reduced, so that the initial acidity can not be maintained, the initial pH of the system can be maintained through saponification, and the extraction capacity of the extractant is enhanced.
In the present invention, in the above extraction system containing the sulfonated kerosene diluent, the sodium hydroxide saponifier and the extractant, it is preferable to mix the materials in the system by stirring. And then carrying out extraction reaction, wherein the temperature of the extraction reaction is not particularly limited, and the extraction reaction can be carried out at room temperature, specifically 15-35 ℃.
In the present invention, the extractant is preferably a P204 extractant. In the present invention, the extraction conditions are preferably controlled to be: the volume fraction of the extracting agent is 20-40%, the saponification rate is 60-70%, the pH value is 1.5-2.5, and the extraction ratio of V (O) to V (A) is 1: 1. By selecting the types of the extracting agent and the saponifying agent and controlling the volume fraction and the saponification rate of the extracting agent, the extraction effect can be effectively improved.
In the invention, the organic phase and the raffinate are quickly layered after extraction, the phase boundary is clear, and then the organic phase and the raffinate are separated. Wherein the raffinate is the impurity-removed liquid for removing iron and zinc, and is used for preparing the nickel powder subsequently. The organic phase can be back extracted by sulfuric acid solution and then continuously recycled. In the stripping, the mass concentration of the sulfuric acid solution used is preferably 20%, and v (o) to v (a) is preferably 1: 1.
According to the invention, through the extraction treatment, the iron and zinc content in the liquid (namely the raffinate) after impurity removal can be controlled below 1 mg/L.
Through the research of the applicant, the best impurity removal effect can be achieved only by carrying out the steps of copper sulfide precipitation, calcium magnesium fluoride removal, zinc powder replacement cobalt cadmium removal, iron and zinc extraction removal and impurity removal according to the specific treatment sequence and treatment means, and the impurity removal solution which is suitable for preparing the nickel powder and can improve the yield and the purity of the nickel powder is obtained, so that the impurity removal step sequence cannot be disturbed; specifically, the obtained nickel sulfate solution contains a certain amount of sulfuric acid, copper deposition by sulfuration is suitable for being carried out under the condition, and compared with other impurities, the impurity copper preferentially reacts with hydrogen sulfide; the fluorination for removing calcium and magnesium needs to adjust the pH value of the solution and is carried out after copper sulfide deposition. When the cobalt and the cadmium are removed by replacement, a small amount of zinc can be brought in by replacement of zinc powder, and the zinc brought in by replacement of the zinc powder can be removed simultaneously in the last step of the extraction and placing. According to the invention, through the sequential matching of the specific treatment sequence and the specific impurity removal means, the optimal impurity removal effect can be achieved, the impurity removal solution which is suitable for preparing the nickel powder and can improve the yield and the purity of the nickel powder is obtained, and if the impurity removal sequence is disturbed, the effect is difficult to achieve.
With respect to step d): reacting the impurity-removed solution with sodium carbonate to form nickel carbonate; and (3) after the nickel carbonate is dissolved by using sulfuric acid solution, adding a reducing agent to carry out reduction reaction to form nickel powder.
In the invention, sodium carbonate is adopted to react with the impurity-removed liquid, and nickel in the impurity-removed liquid is converted into nickel carbonate. Wherein the amount of the sodium carbonate is controlled to be proper excess, and the molar ratio of the sodium carbonate to the nickel in the impurity-removed liquid is preferably controlled to be (1.1-1.2) to 1. In the invention, the reaction temperature is preferably 50-80 ℃; in some embodiments of the invention, the temperature is 50 ℃, 60 ℃, 70 ℃ or 80 ℃. In the invention, the reaction time is preferably 30-50 min; in some embodiments of the invention, the time of the reaction is 30min, 40min or 50 min. After the reaction, nickel carbonate precipitate is generated.
In the present invention, it is preferable to further perform solid-liquid separation after the above-mentioned reaction; the solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation method known to those skilled in the art, such as filtration. And separating out the precipitate through the solid-liquid separation to obtain the nickel carbonate. In the present invention, it is preferable to further perform washing with water after obtaining nickel carbonate. The soluble sodium salt, potassium salt and the like can be removed by washing with water.
In the present invention, after nickel carbonate is obtained, it is dissolved in sulfuric acid solution to form a nickel sulfate solution. The dosage of the sulfuric acid solution is preferably that the nickel carbonate is just completely converted into nickel sulfate; specifically, H in the sulfuric acid solution is controlled 2 SO 4 The molar ratio of the nickel carbonate to the nickel carbonate is (1.05-1.1) to 1. The concentration of the sulfuric acid solution is not particularly limited, and the concentration and the dosage of the sulfuric acid solution are matched, so that the concentration of nickel ions in the nickel sulfate solution is preferably controlled to be 30-60 g/L.
In the present invention, after obtaining the nickel sulfate solution by the above dissolution, it is preferable to further perform: the pH is adjusted. In the invention, the pH value of the nickel sulfate solution is preferably adjusted to 10-12, if the pH value is too low, the subsequent reduction reaction is difficult to perform, and if the pH value exceeds 12, the reduction rate is obviously reduced. In some embodiments of the invention, the pH is 10, 11 or 12. The pH regulator is not particularly limited in kind, and is a conventional alkaline regulator in the field, preferably no other metal ions are introduced, and specifically one or more of ammonia water and nickel hydroxide can be selected.
In the present invention, after the above-mentioned pH adjustment, a reducing agent is added to carry out a reduction reaction. In the invention, the reducing agent is preferably hydrazine hydrate, and compared with other reducing agents, in the system disclosed by the invention, the nickel powder prepared by using hydrazine hydrate for reduction reaction has high purity and good dispersity. In the invention, the usage amount of the hydrazine hydrate is preferably 2 times of the theoretical amount, namely, the molar ratio of the hydrazine hydrate to the nickel in the nickel sulfate solution is controlled to be 4: 1.
In the invention, the temperature of the reduction reaction is preferably 80-90 ℃; in some embodiments of the invention, the temperature is 80 ℃, 85 ℃ or 90 ℃. In the invention, the time of the reduction reaction is preferably 1-2 h; in some embodiments of the invention, the time is 1h, 1.5h, or 2 h. After the reduction reaction, nickel powder precipitate is generated in the system.
In the present invention, it is preferable to further perform solid-liquid separation after the above-mentioned reaction; the solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation method known to those skilled in the art, such as filtration. And separating out the precipitate through the solid-liquid separation to obtain the nickel powder. In the present invention, after obtaining the nickel powder, it is preferable to further perform washing with water, and after washing with water, high purity nickel powder meeting the national standard is obtained.
The invention creatively provides an invention idea for preparing nickel powder by using the final decoppering solution, and provides a feasible and effective preparation scheme, wherein the final decoppering solution is evaporated and concentrated, and then is subjected to freeze crystallization to obtain nickel sulfate crystals, and then the nickel sulfate crystals are subjected to deep impurity removal, specifically, copper removal, calcium and magnesium removal, cobalt and cadmium removal and zinc and iron removal are sequentially performed to obtain an impurity-removed solution; and then reacting the solution after impurity removal with sodium carbonate to form nickel carbonate, dissolving the nickel carbonate by using sulfuric acid solution, and adding a reducing agent to perform reduction reaction to form nickel powder. The method can obtain high-purity nickel powder with high yield, and improves the added value of the final copper removal solution.
Compared with the prior art, the method provided by the invention has the following beneficial effects:
1. the final copper-removing solution is evaporated and concentrated, and then is frozen and crystallized to obtain nickel sulfate crystals, the obtained crystals have low impurity content and high nickel sulfate crystallization rate, and the nickel recovery rate and the production efficiency can be improved.
2. According to the specific sequence and means of copper sulfide precipitation, calcium and magnesium fluoride removal, cobalt and cadmium replacement removal, iron and zinc extraction removal, impurities are removed in sequence, copper, calcium, magnesium, cobalt, cadmium, iron and zinc impurities can be removed deeply, new metal impurities are not introduced, and the loss rate of nickel is very low by combining the means, so that the recovery rate of nickel and the purity of nickel powder are improved; the invention provides a new means for preparing nickel powder, and the nickel powder is prepared by taking the copper-removing final solution with low added value as a raw material, so that low-value resources are recycled to obtain high-value resources, and the added value of the product is increased.
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
Example 1
1.1 preparation
Referring to fig. 1, fig. 1 is a schematic process flow diagram of nickel powder preparation by using final copper removal solution in the embodiment of the present invention.
S1, vacuum evaporation: pumping the final copper-removing solution containing 0.2g/L of copper to an evaporation head tank, and continuously flowing to a plate type vacuum evaporator group for continuous evaporation and concentration. The control conditions are as follows: steam pressure is 0.3MPa, and the vacuum degree of the head tank is 0.65 KPa; controlling the evaporation concentration end point as follows: the content of sulfuric acid in the evaporated liquid is 900g/L, and the specific gravity of the evaporated liquid is 1.50.
S2, freezing and crystallizing: and pumping the evaporated liquid to a freezing crystallization tank through a circulating pump, and continuously pumping the liquid to a brine freezing unit for freezing crystallization. Controlling the freezing crystallization temperature to be-22 ℃, controlling the freezing crystallization end point to ensure that the nickel content in the crystallization mother liquor reaches 5g/L, and filtering after the crystallization end point is reached to obtain nickel sulfate crystals.
The nickel sulfate crystal obtained comprises the following components: 17.6 percent of Ni, 0.05 percent of Cu, 0.3 percent of Fe, 0.36 percent of Zn, 0.025 percent of Ca, 0.03 percent of Mg, 0.015 percent of Co and 0.021 percent of Cd.
S3, deeply removing impurities:
sulfurizing and depositing copper: and dissolving the nickel sulfate crystal in water to obtain a nickel sulfate solution containing 65g/L of nickel. H is added into the solution in an amount which is 4 times of the theoretical amount 2 S gas is vulcanized to deposit copper, the reaction temperature is controlled at 60 ℃, and the reaction time is controlled at 2 h. Reaction(s) ofAfter the completion of the reaction, the precipitate (copper sulfide) was filtered off to obtain a copper-removed solution in which the Cu content was reduced to 0.3 mg/L.
② fluorination calcium and magnesium removal: after the pH value of the copper-removed solution is adjusted to 4.8, ammonium fluoride with 2 times of the theoretical amount is added into the copper-removed solution, the temperature of the copper-removed solution is controlled to be 83 ℃, and the reaction time is 2 hours. After the reaction is finished, the precipitate (calcium fluoride and magnesium fluoride) is filtered to obtain the calcium and magnesium removed liquid, and the calcium and magnesium contents are both reduced to 1 mg/L.
And (3) replacing and removing cobalt and cadmium: adding zinc powder 4 times of the theoretical amount into the solution after calcium and magnesium removal, and controlling the reaction temperature at 48 ℃ and the reaction time at 45 min. After the reaction is finished, filtering out precipitates (cobalt and cadmium) to obtain a solution after cobalt and cadmium are removed, wherein the calcium content is reduced to 3mg/L, and the cadmium content is reduced to 4 mg/L.
Extracting to remove iron and zinc: diluting the solution after removing cobalt and cadmium by adopting sulfonated kerosene, saponifying by using sodium hydroxide, taking P204 as an extracting agent, and controlling the conditions as follows: p204 volume fraction of 20%, saponification rate of 60%, mixed liquor pH of 1.7, V (O) and V (A) of 1: 1; the mixed system was stirred for 3min and the extraction reaction was carried out at 30 ℃. The organic phase and the raffinate are quickly layered after extraction, the phase boundary is clear, and then the organic phase and the raffinate are separated to obtain the raffinate (namely the solution after impurity removal), wherein the iron content of the raffinate is reduced to 0.5mg/L, and the zinc content of the raffinate is 0.4 mg/L.
S4, preparing nickel powder:
adding sodium carbonate with the theoretical amount of 1.1 times into the obtained impurity-removed solution, controlling the reaction temperature at 50 ℃ and the reaction time at 50min to generate nickel carbonate precipitate; filtering to obtain the nickel carbonate.
Dissolving nickel carbonate in sulfuric acid solution to obtain a nickel sulfate solution; controlling H in sulfuric acid solution 2 SO 4 The molar ratio of the nickel sulfate to the nickel carbonate is 1.05: 1, and the concentration of nickel ions in the nickel sulfate solution is 30 g/L.
Adjusting the pH value of the nickel sulfate solution to 11, adding hydrazine hydrate with 2 times of the theoretical amount into the solution, and controlling the reaction temperature to be 80 ℃ and the reaction time to be 1 h; and after the reaction is finished, filtering to obtain nickel powder, and washing with hot water twice to obtain a nickel powder product.
1.2 testing
(1) According to the nickel content in the original feeding and the nickel powder product amount, the nickel recovery rate is calculated, and the result shows that the nickel yield is 96.3%.
(2) And detecting the components of the obtained nickel powder, wherein the result shows that the nickel powder meets the high-purity nickel powder specified by the national standard YS/T925-2013. See table 1 for ingredient composition:
TABLE 1 composition of Nickel powder obtained in example 1
Example 2
1.1 preparation
S1, vacuum evaporation: pumping the final copper-removing solution containing 0.3g/L of copper to an evaporation head tank, and continuously flowing to a plate type vacuum evaporator group for continuous evaporation and concentration. The control conditions are as follows: steam pressure is 0.4MPa, and the vacuum degree of the head tank is 0.86 KPa; controlling the evaporation concentration end point as follows: the content of sulfuric acid in the evaporated liquid is 1000g/L, and the specific gravity of the evaporated liquid is 1.55.
S2, freezing and crystallizing: and pumping the evaporated liquid to a freezing crystallization tank through a circulating pump, and continuously pumping the liquid to a brine freezing unit for freezing crystallization. Controlling the freezing crystallization temperature to be-25 ℃, controlling the freezing crystallization end point to ensure that the nickel content in the crystallization mother liquor reaches 4g/L, and filtering after the crystallization end point is reached to obtain nickel sulfate crystals.
The nickel sulfate crystal obtained comprises the following components: 18.3 percent of Ni, 0.04 percent of Cu, 0.32 percent of Fe, 0.39 percent of Zn, 0.021 percent of Ca, 0.029 percent of Mg, 0.012 percent of Co and 0.022 percent of Cd.
S3, deeply removing impurities:
sulfurizing and depositing copper: and dissolving the nickel sulfate crystal in water to obtain nickel sulfate solution containing 75g/L of nickel. H is added to the solution in an amount 4.5 times the theoretical amount 2 S gas is vulcanized to deposit copper, the reaction temperature is controlled at 60 ℃, and the reaction time is controlled at 2.5 h. After the reaction, the precipitate (copper sulfide) was filtered off to obtain a copper-removed solution, and the Cu content was reduced to 0.4 mg/L.
② fluorination and calcium and magnesium removal: after the pH value of the copper-removed solution is adjusted to 5.0, ammonium fluoride with the theoretical amount of 2.5 times is added into the copper-removed solution, the temperature of the copper-removed solution is controlled to be 85 ℃, and the reaction time is 2.5 hours. After the reaction is finished, the precipitate (calcium fluoride and magnesium fluoride) is filtered to obtain the calcium and magnesium removed liquid, and the calcium and magnesium contents are both reduced to 0.5 mg/L.
And thirdly, removing cobalt and cadmium by replacement: adding zinc powder 4.5 times of the theoretical amount into the solution after calcium and magnesium removal, and controlling the reaction temperature at 50 ℃ and the reaction time at 50 min. After the reaction is finished, filtering out precipitates (cobalt and cadmium) to obtain a solution after cobalt and cadmium removal, wherein the calcium content is reduced to 2mg/L, and the cadmium content is reduced to 3 mg/L.
Extracting and removing iron and zinc: diluting the solution after removing cobalt and cadmium by adopting sulfonated kerosene, saponifying by using sodium hydroxide, taking P204 as an extracting agent, and controlling the conditions as follows: p204 volume fraction of 30%, saponification rate of 70%, mixed liquor pH of 2.0, V (O) and V (A) of 1: 1; the mixed system was stirred for 5min and the extraction reaction was carried out at 25 ℃. The organic phase and the raffinate are quickly layered after extraction, the phase boundary is clear, and then the organic phase and the raffinate are separated to obtain the raffinate (namely the liquid after impurity removal), wherein the iron content is reduced to 0.4mg/L, and the zinc content is 0.4 mg/L.
S4, preparing nickel powder:
adding sodium carbonate with the theoretical amount of 1.2 times into the obtained impurity-removed solution, controlling the reaction temperature at 80 ℃ and the reaction time at 30min to generate nickel carbonate precipitate; filtering to obtain the nickel carbonate.
Dissolving nickel carbonate in sulfuric acid solution to obtain a nickel sulfate solution; control of H in sulfuric acid solution 2 SO 4 The molar ratio of the nickel sulfate to the nickel carbonate is 1.10: 1, and the concentration of nickel ions in the nickel sulfate solution is 60 g/L.
Adjusting the pH value of the nickel sulfate solution to 11, adding hydrazine hydrate with 2.5 times of the theoretical amount into the solution, and controlling the reaction temperature to be 85 ℃ and the reaction time to be 1.5 h; and after the reaction is finished, filtering to obtain nickel powder, and washing with hot water twice to obtain a nickel powder product.
1.2 testing
(1) According to the nickel content in the original feeding and the nickel powder product amount, the nickel recovery rate is calculated, and the result shows that the nickel yield is 96.2%.
(2) And detecting the components of the obtained nickel powder, wherein the result shows that the nickel powder meets the high-purity nickel powder specified by the national standard YS/T925-2013. See table 2 for ingredient composition:
TABLE 2 composition of Nickel powder obtained in example 2
Example 3
1.1 preparation
S1, vacuum evaporation: pumping the final copper-removing solution containing 0.3g/L of copper to an evaporation head tank, and continuously flowing to a plate type vacuum evaporator group for continuous evaporation and concentration. The control conditions are as follows: steam pressure is 0.35MPa, and vacuum degree of the head tank is 0.75 KPa; controlling the evaporation concentration end point as follows: the content of sulfuric acid in the evaporated liquid is 800g/L, and the specific gravity of the evaporated liquid is 1.45.
S2, freezing and crystallizing: and pumping the evaporated liquid to a freezing crystallization tank through a circulating pump, and continuously pumping the liquid to a brine freezing unit for freezing crystallization. Controlling the freezing crystallization temperature to be-15 ℃, and the freezing crystallization end point is that the nickel content in the crystallization mother liquor reaches 4g/L, and filtering after the crystallization end point is reached to obtain nickel sulfate crystals.
The nickel sulfate crystal obtained comprises the following components: 17.2 percent of Ni, 0.04 percent of Cu0.04 percent of Fe, 0.28 percent of Zn, 0.35 percent of Ca, 0.043 percent of Mg, 0.031 percent of Co, 0.013 percent of Cd, 0.02 percent of Cd.
S3, deeply removing impurities:
sulfurizing and depositing copper: and dissolving the nickel sulfate crystal in water to obtain a nickel sulfate solution containing 60g/L of nickel. H is added into the solution in an amount which is 4.5 times of the theoretical amount 2 And S gas is vulcanized to precipitate copper, and the reaction temperature is controlled at 50 ℃ for 3 hours. After the reaction, the precipitate (copper sulfide) was filtered off to obtain a copper-removed solution.
② fluorination and calcium and magnesium removal: after the pH value of the copper-removed solution is adjusted to 4.5, ammonium fluoride with the theoretical amount being 3 times that of the copper-removed solution is added into the copper-removed solution, the temperature of the copper-removed solution is controlled to be 80 ℃, and the reaction time is 3 hours. After the reaction is finished, the precipitate (calcium fluoride and magnesium fluoride) is filtered out to obtain the calcium and magnesium removed liquid.
And thirdly, removing cobalt and cadmium by replacement: adding zinc powder with the theoretical amount of 4.5 times of that of the solution after calcium and magnesium removal, controlling the reaction temperature at 45 ℃ and the reaction time at 60 min. After the reaction is finished, filtering out precipitates (cobalt and cadmium) to obtain a solution after cobalt and cadmium are removed.
Extracting to remove iron and zinc: diluting the solution after removing cobalt and cadmium by adopting sulfonated kerosene, saponifying by using sodium hydroxide, taking P204 as an extracting agent, and controlling the conditions as follows: p204 volume fraction of 40%, saponification rate of 70%, mixed liquor pH of 2.5, V (O) and V (A) of 1: 1; the mixed system was stirred for 5min and the extraction reaction was carried out at 25 ℃. The organic phase and the raffinate are quickly layered after extraction, the phase boundary is clear, and then the organic phase and the raffinate are separated to obtain the raffinate (namely the liquid after impurity removal).
S4, preparing nickel powder:
adding sodium carbonate with the theoretical amount of 1.2 times into the obtained impurity-removed solution, controlling the reaction temperature at 60 ℃ and the reaction time at 40min to generate nickel carbonate precipitate; filtering to obtain the nickel carbonate.
Dissolving nickel carbonate in sulfuric acid solution to obtain a nickel sulfate solution; control of H in sulfuric acid solution 2 SO 4 The molar ratio of the nickel sulfate solution to the nickel carbonate is 1.10: 1, and the concentration of nickel ions in the nickel sulfate solution is 40 g/L.
Adjusting the pH value of the nickel sulfate solution to 10, adding hydrazine hydrate with 2.5 times of the theoretical amount into the solution, and controlling the reaction temperature to be 90 ℃ and the reaction time to be 1 h; and after the reaction is finished, filtering to obtain nickel powder, and washing with hot water twice to obtain a nickel powder product.
1.2 testing
(1) According to the nickel content in the original feeding and the nickel powder product amount, the nickel recovery rate is calculated, and the result shows that the nickel yield is 96.4%.
(2) And detecting the components of the obtained nickel powder, wherein the result shows that the nickel powder meets the high-purity nickel powder specified by the national standard YS/T925-2013. See table 3 for ingredient composition details:
TABLE 3 composition of Nickel powder obtained in example 3
Example 4
1.1 preparation
S1, vacuum evaporation: pumping the final copper-removing solution containing 0.3g/L of copper to an evaporation head tank, and continuously flowing to a plate type vacuum evaporator group for continuous evaporation and concentration. The control conditions are as follows: steam pressure is 0.35MPa, and the vacuum degree of the head tank is 0.75 KPa; controlling the evaporation concentration end point as follows: the sulfuric acid content of the evaporated liquid is 1200g/L, and the specific gravity of the evaporated liquid is 1.65.
S2, freezing and crystallizing: and pumping the evaporated liquid to a freezing crystallization tank through a circulating pump, and continuously pumping the liquid to a brine freezing unit for freezing crystallization. Controlling the freezing crystallization temperature to be-22 ℃, and the freezing crystallization end point is that the nickel content in the crystallization mother liquor reaches 4g/L, and filtering after the crystallization end point is reached to obtain nickel sulfate crystals.
The nickel sulfate crystal obtained comprises the following components: 18.6 percent of Ni, 0.041 percent of Cu, 0.34 percent of Fe, 0.36 percent of Zn, 0.023 percent of Ca, 0.026 percent of Mg, 0.015 percent of Co and 0.024 percent of Cd.
S3, deeply removing impurities:
sulfurizing and depositing copper: and dissolving the nickel sulfate crystal in water to obtain a nickel sulfate solution containing 80g/L of nickel. H is added to the solution in an amount 4.5 times the theoretical amount 2 S gas is vulcanized to deposit copper, the reaction temperature is controlled to be 70 ℃, and the reaction time is controlled to be 2 hours. After the reaction, the precipitate (copper sulfide) was filtered off to obtain a copper-removed solution.
② fluorination and calcium and magnesium removal: after the pH value of the copper-removed solution is adjusted to 5.5, ammonium fluoride with the theoretical amount being 3 times of that of the copper-removed solution is added into the copper-removed solution, the temperature of the copper-removed solution is controlled to be 90 ℃, and the reaction time is 2 hours. After the reaction, the precipitate (calcium fluoride and magnesium fluoride) is filtered to obtain the calcium and magnesium removed solution.
And thirdly, removing cobalt and cadmium by replacement: adding zinc powder 4.5 times of the theoretical amount into the solution after calcium and magnesium removal, and controlling the reaction temperature at 55 ℃ and the reaction time at 40 min. After the reaction is finished, filtering out precipitates (cobalt and cadmium) to obtain a solution after cobalt and cadmium are removed.
Extracting to remove iron and zinc: diluting the solution after removing the cobalt and the cadmium by adopting sulfonated kerosene, saponifying by using sodium hydroxide, taking P204 as an extracting agent, and controlling the conditions as follows: p204 volume fraction of 40%, saponification rate of 70%, mixed liquor pH of 2.5, V (O) and V (A) of 1: 1; the mixed system was stirred for 5min and the extraction reaction was carried out at 25 ℃. The organic phase and the raffinate are quickly layered after extraction, the phase boundary is clear, and then the organic phase and the raffinate are separated to obtain the raffinate (namely the liquid after impurity removal).
S4, preparing nickel powder:
adding sodium carbonate with the theoretical amount of 1.2 times into the obtained impurity-removed solution, controlling the reaction temperature at 70 ℃ and the reaction time at 40min to generate nickel carbonate precipitate; filtering to obtain the nickel carbonate.
Dissolving nickel carbonate in sulfuric acid solution to obtain a nickel sulfate solution; controlling H in sulfuric acid solution 2 SO 4 The molar ratio of the nickel sulfate to the nickel carbonate is 1.10: 1, and the concentration of nickel ions in the nickel sulfate solution is 50 g/L.
Adjusting the pH value of the nickel sulfate solution to 12, adding hydrazine hydrate into the solution in an amount which is 2.5 times of the theoretical amount, and controlling the reaction temperature to be 85 ℃ and the reaction time to be 2 hours; and after the reaction is finished, filtering to obtain nickel powder, and washing with hot water twice to obtain a nickel powder product.
1.2 testing
(1) According to the nickel content in the original feeding and the nickel powder product amount, the nickel recovery rate is calculated, and the result shows that the nickel yield is 96.3%.
(2) And detecting the components of the obtained nickel powder, wherein the result shows that the nickel powder meets the high-purity nickel powder specified by the national standard YS/T925-2013. See table 4 for ingredient composition:
TABLE 4 composition of nickel powder obtained in example 4
According to the embodiment, the method provided by the invention can be used for efficiently recovering the nickel powder, and the obtained nickel powder is high-purity nickel powder, so that the additional value of the crude nickel sulfate product is greatly improved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A method for preparing nickel powder by using decoppering final solution is characterized by comprising the following steps:
a) evaporating and concentrating the final copper-removing solution to obtain an evaporated solution;
b) freezing and crystallizing the evaporated liquid to obtain a nickel sulfate crystal;
c) deeply removing impurities from the nickel sulfate crystals to obtain impurity-removed liquid;
the deep impurity removal comprises the following steps: removing copper, calcium and magnesium, cobalt and cadmium and zinc and iron; the method specifically comprises the following steps:
c1) dissolving the nickel sulfate crystal, and introducing H 2 S, reacting the gas to form copper sulfide precipitate, and performing solid-liquid separation to obtain copper-removed liquid;
c2) mixing the copper-removed liquid with ammonium fluoride for reaction to form calcium fluoride and magnesium fluoride precipitates, and then carrying out solid-liquid separation to obtain a calcium-magnesium-removed liquid;
c3) mixing the calcium and magnesium removed solution with zinc powder for reaction to form cobalt precipitate and cadmium precipitate, and then carrying out solid-liquid separation to obtain a cobalt and cadmium removed solution;
c4) removing zinc and iron impurities from the cobalt and cadmium removed liquid by an extraction method to obtain impurity removed liquid;
d) reacting the impurity-removed solution with sodium carbonate to form nickel carbonate; and (3) after the nickel carbonate is dissolved by using sulfuric acid solution, adding a reducing agent to carry out reduction reaction to form nickel powder.
2. The method according to claim 1, wherein in the step a), the end point of the evaporation concentration is controlled as follows: the content of sulfuric acid in the evaporated liquid is 800-1200 g/L, and the specific gravity of the evaporated liquid is 1.45-1.65.
3. The method of claim 1, wherein the evaporative concentration is vacuum evaporative concentration;
the vacuum evaporation and concentration conditions are as follows: the steam pressure is 0.3-0.4 MPa, and the vacuum degree is 0.65-0.86 KPa.
4. The method according to claim 1, wherein in the step b), the temperature of the frozen crystallization is-15 to-25 ℃;
controlling the end point of the freezing crystallization as follows: until the nickel content in the crystallization mother liquor is less than or equal to 8 g/L.
5. The method according to claim 1, wherein in step c 1):
the dissolving is to add water to dissolve to form a nickel sulfate solution;
controlling the nickel content in the obtained nickel sulfate solution to be 60-80 g/L;
said H 2 The introduction amount of S gas and Cu in the nickel sulfate solution 2+ The molar ratio of (4-5) to 1;
the reaction temperature is 50-70 ℃, and the reaction time is 2-3 h.
6. The method according to claim 1, wherein in step c 2):
the molar ratio of the molar quantity of the ammonium fluoride to the total molar quantity of calcium and magnesium elements in the copper-removed liquid is (4-6) to 1;
the reaction temperature is 80-90 ℃, and the reaction time is 2-3 h.
7. The method according to claim 1, wherein in step c 3):
the molar ratio of the molar quantity of the zinc powder to the total molar quantity of the cobalt and cadmium elements in the calcium and magnesium removed solution is (4-5) to 1;
the reaction temperature is 45-55 ℃, and the reaction time is 40-60 min.
8. The method according to claim 1, wherein the step c4) comprises:
c4-1) diluting the solution after removing the cobalt and the cadmium by sulfonated kerosene, and then saponifying by using sodium hydroxide to obtain a saponified solution;
c4-2) extracting the saponified solution by using an extracting agent to obtain an organic phase and a solution after impurity removal;
the extractant is a P204 extractant;
the extraction conditions were controlled as follows: the volume fraction of the extracting agent is 20-40%, the saponification rate is 60-70%, the pH value is 1.5-2.5, and the extraction ratio of V (O) to V (A) is 1: 1.
9. The method according to claim 1, wherein in step d):
after the nickel carbonate is dissolved by using sulfuric acid and before the reducing agent is added, the method further comprises the following steps: adjusting the pH value to 10-12;
the reducing agent is hydrazine hydrate;
the temperature of the reduction reaction is 80-90 ℃, and the time is 1-2 h.
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| CN110129585A (en) * | 2019-06-06 | 2019-08-16 | 何耀 | A kind of method of Purification of zinc sulfate solution removing heavy metals |
| CN110669932A (en) * | 2019-09-25 | 2020-01-10 | 中南大学 | Method for comprehensively utilizing copper electrolyte purification resources |
| CN110983070A (en) * | 2019-11-29 | 2020-04-10 | 长沙华时捷环保科技发展股份有限公司 | Method for preparing refined nickel sulfate from copper electrolyte decoppered liquid |
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