Method for extracting nickel from high nickel matte leaching residue
阅读说明：本技术 从高冰镍浸出渣中提取镍的方法 (Method for extracting nickel from high nickel matte leaching residue ) 是由 余海军 谢英豪 李爱霞 张学梅 李长东 于 2021-07-29 设计创作，主要内容包括：本发明公开了一种从高冰镍浸出渣中提取镍的方法,先将高冰镍浸出渣的粉碎料加入溶解有硫磺的有机溶剂中,加热进行反应,固液分离得到第一滤液和第一滤渣,第一滤渣加入到硫酸铜溶液中,加热进行反应,固液分离得到第二滤液和第二滤渣,将第二滤液进行蒸发冷凝浓缩,过滤得到硫酸铜晶体和含镍滤液。本发明利用硫单质在有机溶剂中的氧化性,将高冰镍浸出渣中的Cu-(2)S、Ni-(3)S-(2)、CuFeS-(2)、镍铁铜合金等氧化为CuS、NiS、FeS,且在有机溶剂的存在下,高冰镍浸出渣中的单质硫则溶解于溶剂中,再采用硫酸铜溶液将NiS、FeS置换为更难溶的CuS,镍离子与亚铁离子则进入溶液中,进一步提高了浸出渣中铜含量。整个反应中仅有少量硫磺和硫酸铜的消耗,有机溶剂可循环再用。(The invention discloses a method for extracting nickel from high nickel matte leaching residue, which comprises the steps of adding a crushed material of the high nickel matte leaching residue into an organic solvent in which sulfur is dissolved, heating for reaction, carrying out solid-liquid separation to obtain a first filtrate and a first filter residue, adding the first filter residue into a copper sulfate solution, heating for reaction, carrying out solid-liquid separation to obtain a second filtrate and a second filter residue, carrying out evaporation condensation concentration on the second filtrate, and filtering to obtain a copper sulfate crystal and a nickel-containing filtrate. The invention utilizes the oxidability of sulfur in an organic solvent to leach Cu in the high nickel matte leaching residue 2 S、Ni 3 S 2 、CuFeS 2 The nickel-iron-copper alloy and the like are oxidized into CuS, NiS and FeS, and the leaching residue of the high nickel matte is obtained in the presence of an organic solventThe elemental sulfur in the leaching residue is dissolved in the solvent, the NiS and the FeS are replaced by the more insoluble CuS by adopting a copper sulfate solution, and the nickel ions and the ferrous ions enter the solution, so that the copper content in the leaching residue is further improved. Only a small amount of sulfur and copper sulfate are consumed in the whole reaction, and the organic solvent can be recycled.)
1. A method for extracting nickel from high nickel matte leaching residues is characterized by comprising the following steps:
s1: adding the crushed material of the high nickel matte leaching residue into an organic solvent in which sulfur is dissolved, heating for reaction, and carrying out solid-liquid separation to obtain a first filtrate and a first filter residue;
s2: adding the first filter residue into a copper sulfate solution, heating for reaction, and performing solid-liquid separation to obtain a second filtrate and a second filter residue;
s3: and evaporating, condensing and concentrating the second filtrate, and filtering to obtain copper sulfate crystals and nickel-containing filtrate.
2. The method according to claim 1, wherein in step S1, the organic solvent is one or more of carbon disulfide, carbon tetrachloride, methylcyclohexane, trichloroethane, trichloroethylene, tetrachloroethane, diglyme, tetralin, or decahydronaphthalene.
3. The method of claim 1, wherein in step S1, the concentration of the sulfur in the organic solvent is 10-700 g/L.
4. The method as claimed in claim 1, wherein in step S1, the solid-to-liquid ratio of the crushed material to the organic solvent is 1 g: (0.5-5) mL.
5. The method of claim 1, wherein the heating temperature in step S1 is 80-120 ℃, and the reaction time is preferably 1-5 h.
6. The method as claimed in claim 1, wherein the concentration of the copper sulfate solution is 0.1-4.0mol/L in step S2.
7. The method as claimed in claim 1, wherein in step S2, the solid-to-liquid ratio of the first filter residue to the copper sulfate solution is 1 g: (0.5-5) mL.
8. The method of claim 1, wherein the heating temperature in step S2 is 80-180 ℃, and the reaction time is preferably 2-8 h.
9. The method of claim 1, wherein in step S2, the second filter residue is used for copper production.
10. The method according to claim 1, wherein in step S3, the nickel-containing filtrate is extracted by adding an extractant, left standing, separated to obtain a nickel-containing organic extract phase and a raffinate, and then the nickel is back-extracted from the nickel-containing organic extract phase by using a sulfuric acid solution to obtain a nickel sulfate solution.
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for extracting nickel from high nickel matte leaching residues.
Background
The high nickel matte is a sulfide eutectic of metals such as nickel, copper, cobalt, iron and the like which are primarily smelted from nickel concentrate by an electric converter. Can be used for producing electrolytic nickel, nickel oxide, nickel-iron, nickel-containing alloy and various nickel salts, and can also be directly used for steel making after special treatment.
After the high nickel matte is finely ground and crushed, the high nickel matte is separated by flotation and magnetic separation to obtain nickel concentrate containing 67 to 68 percent of nickel, and simultaneously, copper concentrate and copper-nickel alloy are selected to respectively recover copper and platinum group gold. The nickel concentrate is melted by a reverberatory furnace to obtain nickel sulfide, and then is sent to electrolytic refining or is reduced and melted by an electric furnace (or reverberatory furnace) to obtain crude nickel, and then the crude nickel is subjected to electrolytic refining.
The high nickel matte can be used for producing electrolytic nickel by adopting a conventional electrolytic process and can also be used for producing nickel sulfate by adopting a high-pressure leaching process, so that several nickel products such as electrolytic nickel, nickel iron and nickel sulfate can be mutually converted and balanced in the market through the intermediate product of the high nickel matte, and the healthy and robust development of the market is facilitated generally.
Meanwhile, with the rapid development of the electric automobile market, the demand of the power battery for cobalt and nickel sulfate rises. The main raw materials of the nickel sulfate comprise high nickel matte, nickel wet-process intermediate products, nickel bean/nickel powder, waste nickel and the like. The process has the characteristics of short flow, strong raw material adaptability, high recovery rate of valuable metals and low solution slag quality, and is widely applied.
However, after the nickel matte is selectively leached by three stages of sulfuric acid, the nickel content in the leaching residue is still high, which causes waste of nickel resources. The form of each element in the high nickel matte leaching residue is complex and mainly comprises CuS and Cu2S、NiS、Ni3S2、FeS、CuFeS2And sulfur simple substance, nickel-iron-copper alloy and the like in the simple substance form. At present, no effective method is available for the recovery treatment of nickel in the leaching residue of high grade nickel matte.
Therefore, a method for treating the leaching residue of high grade nickel matte is needed to extract the nickel element in the leaching residue and improve the utilization rate of nickel resources.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for extracting nickel from high nickel matte leaching residue.
According to one aspect of the invention, the method for extracting nickel from high nickel matte leaching residue comprises the following steps:
s1: adding the crushed material of the high nickel matte leaching residue into an organic solvent in which sulfur is dissolved, heating for reaction, and carrying out solid-liquid separation to obtain a first filtrate and a first filter residue;
s2: adding the first filter residue into a copper sulfate solution, heating for reaction, and performing solid-liquid separation to obtain a second filtrate and a second filter residue;
s3: and evaporating, condensing and concentrating the second filtrate, and filtering to obtain copper sulfate crystals and nickel-containing filtrate.
In some embodiments of the present invention, in step S1, the organic solvent is one or more of carbon disulfide, carbon tetrachloride, methylcyclohexane, trichloroethane, trichloroethylene, tetrachloroethane, diglyme, tetralin, or decahydronaphthalene.
In some embodiments of the invention, in step S1, the concentration of sulfur in the organic solvent is 10 to 700 g/L.
In some embodiments of the invention, in step S1, the solid-to-liquid ratio of the crushed material to the organic solvent is 1 g: (0.5-5) mL.
In some embodiments of the present invention, in step S1, the heating temperature is 80-120 ℃, and preferably, the reaction time is 1-5 h. Elemental sulfur can only oxidize metals to sub-ions, such as Cu, under ordinary heating conditions2S, and elemental sulfur in the CS2 solution, at 100 ℃, can oxidize the metal into ions, such as CuS. Thus, the oxidation performance of sulfur can be improved under the aforementioned reaction conditions.
In some embodiments of the present invention, in step S1, the first filtrate is an organic solvent, and can be recycled after sulfur is supplemented.
In some embodiments of the present invention, in step S2, the copper sulfate solution has a concentration of 0.1 to 4.0 mol/L. Further preferably 2.0 to 4.0 mol/L. The higher the concentration of the copper sulfate solution is, the faster the reaction speed is, and the nickel ions and the ferrous ions are replaced more completely.
In some embodiments of the invention, in step S2, the solid-to-liquid ratio of the first filter residue to the copper sulfate solution is 1 g: (0.5-5) mL.
In some embodiments of the present invention, in step S2, the heating temperature is 80-180 ℃, and preferably, the reaction time is 2-8 h.
In some embodiments of the present invention, in step S2, the second filter residue is used for copper production, and the second filter residue is CuS.
In some embodiments of the present invention, in step S3, the condensate generated by evaporation and condensation and the copper sulfate crystals may be configured to be recycled as the copper sulfate solution.
In some embodiments of the present invention, in step S3, an extractant is added to the nickel-containing filtrate for extraction, the mixture is left standing and separated to obtain a nickel-containing organic extract phase and a raffinate, and then a sulfuric acid solution is used to strip nickel from the nickel-containing organic extract phase to obtain a nickel sulfate solution.
In some preferred embodiments of the invention, the extractant is selected from one or more of P204, P507, DEHPA or Cyanex 272; preferably, the extracted organic phase obtained after the back extraction can be saponified and recycled.
In some preferred embodiments of the present invention, the raffinate, after iron removal, may be recycled as a copper sulfate solution.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the method firstly converts complex components of the high nickel matte leaching residue into simple components, and then replaces and extracts nickel elements in the high nickel matte leaching residue. The oxidation of the sulfur in the organic solvent is utilized to leach Cu in the high nickel matte leaching residue2S、Ni3S2、CuFeS2The nickel-iron-copper alloy and the like are oxidized into CuS, NiS and FeS, and in the presence of an organic solvent, elemental sulfur in the leaching residue of the high nickel matte is dissolved in the solvent; for nickel and iron in the high nickel matte leaching residue, conventional acid leaching cannot be carried out, compared with hydrogen ions, copper ions are more easily separated out, the solubility product constant of CuS is smaller and more insoluble, so that NiS and FeS are replaced by more insoluble CuS by adopting a copper sulfate solution, and nickel ions and ferrous ions enter the solution, so that the copper content in the leaching residue is further improved, and the subsequent copper smelting is facilitated.
2. In the whole reaction flow, only a small amount of sulfur and copper sulfate are consumed, the organic solvent can be recycled, and the condensate in the evaporation and condensation process and the precipitated copper sulfate crystals can be recycled; the invention has short process flow, makes the best use of things, has low auxiliary material consumption, low cost and quick response, and is suitable for industrial popularization.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic process flow diagram of example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
In the embodiment, nickel is extracted from the high nickel matte leaching residue and nickel sulfate is prepared, and the components of the high nickel matte leaching residue are as follows: 7.38% of nickel, 42.3% of copper, 10.9% of iron and 23.35% of sulfur, and referring to fig. 1, the method comprises the following steps:
(1) pretreatment of raw materials: ball-milling the high nickel matte leaching residue into powder;
(2) sulfur oxidation: adding carbon disulfide dissolved with sulfur into the powder material obtained in the step (1), wherein the concentration of the sulfur is 700g/L, and the solid-to-liquid ratio is controlled to be 1 g: 0.5mL, the reaction temperature is 120 ℃, and the reaction time is 1 h;
(3) and (3) filtering treatment: after the reaction in the step (2) is finished, obtaining filtrate and filter residue through solid-liquid separation, wherein the filtrate is an organic solvent and can be recycled after sulfur is supplemented;
(4) copper replacement: adding a copper sulfate solution with the concentration of 4.0mol/L into the filter residue obtained in the step (3), and controlling the solid-liquid ratio of the filter residue to the copper sulfate solution to be 1 g: 0.5mL, the reaction temperature is 180 ℃, and the reaction time is 2 h.
(5) And (3) filtering: after the reaction in the step (4) is finished, obtaining filtrate and CuS filter residue through solid-liquid separation, and conveying the CuS filter residue to a copper factory for copper production;
(6) evaporation and condensation: evaporating, condensing and concentrating the filtrate obtained in the step (5), and filtering to obtain copper sulfate crystals and nickel-containing filtrate, wherein the condensate generated by evaporation and condensation and the copper sulfate crystals obtained by filtering can be configured into a copper sulfate solution for recycling;
(7) and (3) extraction treatment: and (3) extracting the nickel-containing filtrate obtained in the step (6) by using an extracting agent P204, standing, separating to obtain a nickel-containing extraction organic phase and a raffinate, back-extracting nickel from the nickel-containing extraction organic phase by using a 5mol/L sulfuric acid solution to obtain a nickel sulfate solution, wherein the obtained extraction organic phase can be saponified and recycled, and the raffinate is subjected to iron removal and then is recycled as a copper sulfate solution.
The CuS filter residue is detected to have the components of 0.36 percent of nickel, 59.86 percent of copper, 0.93 percent of iron and 28.22 percent of sulfur. Indicating substantial leaching of nickel and iron after the copper displacement reaction.
Example 2
In the embodiment, nickel is extracted from the high nickel matte leaching residue and nickel sulfate is prepared, and the components of the high nickel matte leaching residue are as follows: 5.58% of nickel, 55.7% of copper, 8.66% of iron and 20.37% of sulfur by the following steps:
(1) pretreatment of raw materials: ball-milling the high nickel matte leaching residue into powder;
(2) sulfur oxidation: adding carbon tetrachloride dissolved with sulfur into the powder material obtained in the step (1), wherein the concentration of the sulfur is 10g/L, and the solid-liquid ratio is controlled to be 1 g: 5mL, the reaction temperature is 80 ℃, and the reaction time is 5 h.
(3) And (3) filtering treatment: after the reaction in the step (2) is finished, obtaining filtrate and filter residue through solid-liquid separation, wherein the filtrate is an organic solvent and can be recycled after sulfur is supplemented;
(4) copper replacement: adding a copper sulfate solution with the concentration of 0.1mol/L into the filter residue obtained in the step (3), and controlling the solid-liquid ratio of the filter residue to the copper sulfate solution to be 1 g: 5mL, the reaction temperature is 80 ℃, and the reaction time is 8 h.
(5) And (3) filtering: after the reaction in the step (4) is finished, obtaining filtrate and CuS filter residue through solid-liquid separation, and conveying the CuS filter residue to a copper factory for copper production;
(6) evaporation and condensation: evaporating, condensing and concentrating the filtrate obtained in the step (5), and filtering to obtain copper sulfate crystals and nickel-containing filtrate, wherein the condensate generated by evaporation and condensation and the copper sulfate crystals obtained by filtering can be configured into a copper sulfate solution for recycling;
(7) and (3) extraction treatment: and (3) extracting the nickel-containing filtrate obtained in the step (6) by using an extracting agent P507, standing, separating to obtain a nickel-containing extraction organic phase and a raffinate, back-extracting nickel from the nickel-containing extraction organic phase by using a 3mol/L sulfuric acid solution to obtain a nickel sulfate solution, wherein the obtained extraction organic phase can be saponified and recycled, and the raffinate is subjected to iron removal and then is recycled as a copper sulfate solution.
The CuS filter residue is detected to have the components of 0.47% of nickel, 65.52% of copper, 0.75% of iron and 25.22% of sulfur. Indicating substantial leaching of nickel and iron after the copper displacement reaction.
Example 3
In the embodiment, nickel is extracted from the high nickel matte leaching residue and nickel sulfate is prepared, wherein the high nickel matte leaching residue comprises the following components: 6.28% of nickel, 58.73% of copper, 9.32% of iron and 17.23% of sulfur, and the method comprises the following steps:
(1) pretreatment of raw materials: ball-milling the high nickel matte leaching residue into powder;
(2) sulfur oxidation: adding decahydronaphthalene dissolved with sulfur into the powder material obtained in the step (1), wherein the concentration of the sulfur is 350g/L, and the solid-to-liquid ratio is controlled to be 1 g: 2.5mL, the reaction temperature is 100 ℃, and the reaction time is 3 h.
(3) And (3) filtering treatment: after the reaction in the step (2) is finished, obtaining filtrate and filter residue through solid-liquid separation, wherein the filtrate is an organic solvent and can be recycled after sulfur is supplemented;
(4) copper replacement: adding a copper sulfate solution with the concentration of 2.0mol/L into the filter residue obtained in the step (3), and controlling the solid-liquid ratio of the filter residue to the copper sulfate solution to be 1 g: 2.5mL, the reaction temperature is 130 ℃, and the reaction time is 5 h.
(5) And (3) filtering: after the reaction in the step (4) is finished, obtaining filtrate and CuS filter residue through solid-liquid separation, and conveying the CuS filter residue to a copper factory for copper production;
(6) evaporation and condensation: evaporating, condensing and concentrating the filtrate obtained in the step (5), and filtering to obtain copper sulfate crystals and nickel-containing filtrate, wherein the condensate generated by evaporation and condensation and the copper sulfate crystals obtained by filtering can be configured into a copper sulfate solution for recycling;
(7) and (3) extraction treatment: and (3) extracting the nickel-containing filtrate obtained in the step (6) by using an extracting agent Cyanex272, standing, separating to obtain a nickel-containing extraction organic phase and a raffinate, back-extracting nickel from the nickel-containing extraction organic phase by using a 4mol/L sulfuric acid solution to obtain a nickel sulfate solution, wherein the obtained extraction organic phase can be saponified and recycled, and the raffinate is used as a copper sulfate solution for recycling after iron is removed.
The CuS filter residue is detected to have the components of 0.51 percent of nickel, 64.53 percent of copper, 0.82 percent of iron and 24.29 percent of sulfur. Indicating substantial leaching of nickel and iron after the copper displacement reaction.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.