CN112645907B - Preparation method and use method of additive - Google Patents
Preparation method and use method of additive Download PDFInfo
- Publication number
- CN112645907B CN112645907B CN202010911666.8A CN202010911666A CN112645907B CN 112645907 B CN112645907 B CN 112645907B CN 202010911666 A CN202010911666 A CN 202010911666A CN 112645907 B CN112645907 B CN 112645907B
- Authority
- CN
- China
- Prior art keywords
- additive
- cobalt
- ethanol
- beta
- naphthol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation method and a use method of an additive, and relates to the technical field of wet metallurgy. The additive is added into the purified slag leaching solution containing cobalt, and after the additive is uniformly mixed, a beta-naphthol cobalt precipitation process is used, the additive forms an effective protective layer on the surface of the generated alpha-nitroso-beta-naphthol cobalt slag, so that the capability of the additive for absorbing impurity ions such as Zn, fe, mn, cu, cd and the like in the leaching solution in a wrapping and clamping manner is effectively weakened, the grade of the alpha-nitroso-beta-naphthol cobalt slag is improved, and the quality of the subsequently prepared cobalt concentrate is improved. Solves the technical problems of serious environmental pollution and more impurities in the cobalt concentrate product in the traditional method. The preparation method is simple to operate, low in cost, convenient for large-scale production and beneficial to production and market putting.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a preparation method and a use method of an additive.
Background
Cobalt has good high temperature resistance, corrosion resistance and magnetic properties, is widely used in the industrial fields of aerospace, mechanical manufacturing, electrical and electronic, chemistry, ceramics and the like, and is one of important raw materials for manufacturing high-temperature alloys, hard alloys, ceramic pigments, catalysts and batteries. Cobalt is called as "industrial monosodium glutamate" and "industrial teeth", and is one of important strategic resources.
The cobalt resource is mostly associated with copper-cobalt ore, nickel-cobalt ore, arsenic-cobalt ore and pyrite deposit, the independent cobalt mineral is few, the content is less, the extraction is relatively difficult, and the cobalt smelting characteristics are represented by low raw material grade, long extraction process and many extraction methods. In zinc smelting, some high-iron sphalerite and some zinc oxide ores contain small amounts of cobalt. When these zinc ores containing a small amount of cobalt are subjected to zinc hydrometallurgy, the cobalt associated therewith is leached into solution by sulfuric acid, which is eventually subjected to purification without substantial loss in subsequent neutralization iron removal and the like. Zinc powder is used for displacement and copper, cadmium and cobalt removal in the purification section, and enters the purification slag to become an important cobalt resource. The purified slag is leached by sulfuric acid to obtain a solution containing cobalt, and the cobalt can be recovered through the solution.
According to different cobalt recovery methods, two common treatment methods are provided at present, namely a xanthate cobalt precipitation process and a beta-naphthol cobalt precipitation process. The yellow drug is far lower than beta-naphthol in price, but the yellow drug has serious environmental pollution in cobalt removal, and belongs to the obsolete laggard process. The beta-naphthol cobalt precipitation process has high cobalt precipitation selectivity, and the generated alpha-nitroso-beta-naphthol cobalt slag has high cobalt content and fine cobalt slag granularity, and after calcination, the cobalt content in the cobalt slag is high and can reach over 50 percent, thereby being beneficial to further recovery of the cobalt. Because impurity elements such as zinc, iron, cadmium and the like in the cobalt-containing purification slag are high, the impurity content such as zinc, iron, copper, cadmium and the like in a cobalt-containing leachate obtained when the purification slag is leached by sulfuric acid is high, and because alpha-nitroso-beta-naphthol cobalt slag generated in the cobalt production process by adopting beta-naphthol is fluffy reddish brown inner complex salt precipitate, a large amount of impurity ions such as Zn, fe, cd and the like in the leachate are easily mixed, the impurity content in the obtained cobalt slag is high, the grade of cobalt is reduced, the quality of cobalt concentrate obtained by subsequent treatment is reduced, and the quality of the cobalt concentrate directly influences the quality and the yield of a cobalt product. Therefore, in order to produce a cobalt concentrate product with high quality and meet the requirement of cobalt smelting, technological measures should be taken to reduce the content of impurities in the cobalt concentrate.
Disclosure of Invention
The invention aims to provide a preparation method of an additive, which aims to solve the technical problems of serious environmental pollution and more impurities in a cobalt concentrate product of the traditional product.
The preparation method of the additive provided by the invention comprises the following steps:
(1) Adding isomeric dodecyl alcohol polyoxyethylene ether, sorbitan trioleate and triethylamine into ethanol, reacting under the protection of inert gas, and removing ethanol to obtain solid particles a;
(2) Adding the solid particles a, tartaric acid and hexadecyl trimethyl quaternary ammonium bromide into ethanol, heating for reaction, cooling to room temperature, and removing ethanol to obtain a residue;
(3) Adding a certain amount of water into the residue, heating and stirring, filtering while the mixture is hot, cooling the filtrate to room temperature, then dropwise adding an NaOH aqueous solution to adjust the pH value, and then filtering, washing and drying to obtain the additive.
Further, the additive is prepared from the following substances: isomeric dodecyl alcohol polyoxyethylene ether, ethanol, sorbitan trioleate, triethylamine, tartaric acid, hexadecyl trimethyl quaternary ammonium bromide, water and NaOH aqueous solution.
Further, in the step (1), the mass of the isomeric decyl alcohol polyoxyethylene ether is 10.0-30.0 g;
and/or the mass of the sorbitan trioleate is 30.0-50.0 g;
and/or the triethylamine accounts for 5.0-15.0 g in mass;
and/or the volume of the ethanol is 30.0-80.0 ml.
Further, in the step (1), the reaction temperature is 90.0-150.0 ℃;
and/or the reaction time is 2.0-8.0 h.
Further, in the step (2), the mass of the solid particles a is 20.0-40.0 g;
and/or the tartaric acid has the mass of 30.0-80.0 g;
and/or the mass of the hexadecyl trimethyl quaternary ammonium bromide is 70.0 to 120.0g;
and/or the volume of the ethanol is 100.0-200.0 ml.
Further, in the step (2), the temperature of the reaction is 100.0-150.0 ℃;
and/or the reaction time is 0.5-3.5 h.
Further, in the step (3), the temperature of the reaction is 50.0-100.0 ℃;
and/or the concentration of the NaOH aqueous solution is 0.50-1.00 mol/L;
and/or the pH value is 2.0-4.0.
The invention also aims to provide a using method of the additive, which comprises the following steps: and adding the additive into the purification slag leachate containing cobalt, uniformly mixing, and then precipitating the cobalt by using a beta-naphthol method, wherein the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted to obtain the cobalt concentrate with higher grade.
Furthermore, the addition amount of the additive is 10.0-20.0 g/m 3 。
The preparation method of the additive provided by the invention is simple to operate, low in cost, convenient for large-scale production and beneficial to production and market putting.
The additive provided by the invention has the advantages of simple use method, less consumption and high efficiency, can obtain a cobalt concentrate product with high quality, and has a good application prospect.
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 conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The additive has the action principle that the additive can slow down the formation speed of cobalt slag in the beta-naphthol cobalt precipitation process after being added, and form an effective protective layer on the surface of the generated alpha-nitroso-beta-naphthol cobalt slag, so that impurity ions adsorbed on the surface of the cobalt slag can leave the surface of the precipitate in time, the occlusion phenomenon is reduced, and meanwhile, the additive can enlarge cobalt slag particles, reduce the contact area of the cobalt slag and a solution, and further reduce the adsorption of the impurity ions. The additive can also change the characteristics of a liquid layer on an interface between the cobalt slag and the solution, so that the adsorption performance of an adsorption layer on the surface of the cobalt slag precipitate is reduced, and the adsorption of the cobalt slag on impurity ions is reduced due to the weakened adsorption force. Meanwhile, the defect of the internal structure of the cobalt slag precipitate is filled, and inclusion and mixed crystal of impurity ions are reduced. Through the interaction, the grade of the alpha-nitroso-beta-naphthol cobalt slag is effectively improved, and the grade of the cobalt concentrate obtained by oxidizing roasting treatment is greatly improved. The preparation method disclosed by the invention is simple to operate, low in cost, convenient for large-scale production and beneficial to production and market putting. Meanwhile, the additive is less in dosage and high in efficiency, and the excessive additive which cannot participate in the reaction is stable in property, has no influence on the subsequent process, and has great economic value.
According to one aspect of the present invention, there is provided a method of preparing an additive, comprising the steps of:
(1) Adding isomeric dodecyl alcohol polyoxyethylene ether, sorbitan trioleate and triethylamine into ethanol, reacting under the protection of inert gas, and removing ethanol to obtain solid particles a;
(2) Adding the solid particles a, tartaric acid and hexadecyl trimethyl quaternary ammonium bromide into ethanol, heating for reaction, cooling to room temperature, and removing ethanol to obtain a residue;
(3) Adding a certain amount of water into the residue, heating and stirring, filtering while the mixture is hot, cooling the filtrate to room temperature, then dropwise adding an NaOH aqueous solution to adjust the pH value, and then filtering, washing and drying to obtain the additive.
The preparation method of the additive provided by the invention is simple to operate, low in cost, convenient for large-scale production and beneficial to production and market putting.
In a preferred embodiment of the invention, the additive is prepared from: isomeric dodecyl alcohol polyoxyethylene ether, ethanol, sorbitan trioleate, triethylamine, tartaric acid, hexadecyl trimethyl quaternary ammonium bromide, water and NaOH aqueous solution.
The isomeric decyl alcohol polyoxyethylene ether is a dispersing agent, can disperse products of sorbitan trioleate and triethylamine which react in an ethanol solution to promote the reaction, and can react with the sorbitan trioleate and the triethylamine in a system. After the reaction, ethanol was recovered under reduced pressure and filtered to obtain solid particles a. The solid particles a can be reacted with a mixture of tartaric acid and cetyltrimethylammonium bromide in an ethanol solvent, after cooling to room temperature, the ethanol is distilled off under reduced pressure to give a residue present as a mixture. Because side reaction occurs in the reaction, a small amount of impurities are mixed in a target product, purification treatment is needed, the characteristic that the target product can be dissolved in water is utilized, the residue is added into the water, the mixture is heated and dissolved, filtration is carried out, insoluble impurities are contained in filter residues, the target product exists in filtrate, the filtrate needs to be cooled to room temperature, and the purification is carried out by utilizing the characteristic that the target product has low solubility in a solution with a specific pH value. And filtering to obtain a filter cake containing a target product with high purity, washing the filter cake with a small amount of water, and drying to obtain the additive.
In a preferred embodiment of the present invention, in step (1), the mass of the isomeric decahydric polyoxyethylene ether is 10.0 to 30.0g.
In a typical, but non-limiting embodiment of the invention, the mass of isomeric tridecanol polyoxyethylene ethers is, for example, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5 or 30.0g.
The quality of the isomeric dodecyl alcohol polyoxyethylene ether is adjusted, so that the action effect of the additive can be improved, and the quality of the cobalt concentrate is improved. The heterogeneous dodecanol polyoxyethylene ether provided by the invention has a mass of 10.0-30.0 g, and the additive has a good effect.
In a preferred embodiment of the present invention, in the step (1), the sorbitan trioleate has a mass of 30.0 to 50.0g.
In a typical, but non-limiting embodiment of the invention, the sorbitan trioleate has a mass, for example, of 30.0, 30.5, 31.0, 31.5, 32.0, 32.5, 33.0, 33.5, 34.0, 34.5, 35.0, 35.5, 36.0, 36.5, 37.0, 37.5, 38.0, 38.5, 39.0, 39.5, 40.0, 40.5, 41.0, 41.5, 42.0, 42.5, 43.0, 43.5, 44.0, 44.5, 45.0, 45.5, 46.0, 46.5, 47.0, 47.5, 48.0, 48.5, 49.0, 49.5 or 50.0g.
The effect of the additive can be improved by adjusting the quality of the sorbitan trioleate, so that the quality of the cobalt concentrate is improved. Within the mass range of 30.0-50.0 g of the sorbitan trioleate provided by the invention, the additive has a good effect.
In a preferred embodiment of the present invention, in step (1), the triethylamine has a mass of 5.0 to 15.0g.
In a typical but non-limiting embodiment of the invention, the triethylamine is, for example, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5 or 15.0g by mass.
The effect of the additive can be improved by adjusting the quality of triethylamine, so that the quality of the cobalt concentrate is improved. The additive has good effect within the range that the weight of the triethylamine provided by the invention is 5.0-15.0 g.
In a preferred embodiment of the present invention, in step (1), the volume of ethanol is 30.0 to 80.0ml.
In typical but non-limiting embodiments of the invention, the volume of ethanol in step (1) is, for example, 30.0, 35.0, 40.0, 45.0, 50.0, 55.0, 60.0, 65.0, 70.0, 75.0 or 80.0ml.
The effect of the additive can be improved by adjusting the volume of the ethanol in the step (1), so that the quality of the cobalt concentrate is improved. In the step (1), the volume of the ethanol is 30.0-80.0 ml, and the additive has good effect.
In a preferred embodiment of the present invention, in step (1), the temperature of the reaction is 90.0 to 150.0 ℃.
In typical but non-limiting embodiments of the invention, the temperature of the reaction in step (1) is, for example, 90.0, 95.0, 100.0, 105.0, 110.0, 115.0, 120.0, 125.0, 130.0, 135.0, 140.0, 145.0 or 150.0 ℃.
The effect of the additive can be improved by adjusting the reaction temperature in the step (1), so that the quality of the cobalt concentrate is improved. The reaction temperature in the step (1) provided by the invention is in the range of 90.0-150.0 ℃, and the additive has good effect.
In a preferred embodiment of the present invention, in step (1), the reaction time is 2.0 to 8.0 hours.
In a typical but non-limiting embodiment of the invention, the time of the reaction in step (1) is for example 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5 or 8.0h.
By adjusting the reaction time in the step (1), the action effect of the additive can be improved, and the quality of the cobalt concentrate is further improved. The reaction time in the step (1) provided by the invention is within the range of 2.0-8.0 h, and the additive has a good effect.
In a preferred embodiment of the present invention, in the step (2), the mass of the solid particles a is 20.0 to 40.0g.
In a typical, but non-limiting embodiment of the invention, the mass of the solid particles is, for example, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0g, 30.0, 30.5, 31.0, 31.5, 32.0, 32.5, 33.0, 33.5, 34.0, 34.5, 35.0, 35.5, 36.0, 36.5, 37.0, 37.5, 38.0, 38.5, 39.0, 39.5 or 40.0g.
The effect of the additive can be improved by adjusting the quality of the solid particles a, so that the quality of the cobalt concentrate is improved. The additive has good effect within the range that the mass of the solid particles a is 20.0-40.0 g.
In a preferred embodiment of the present invention, in the step (2), the tartaric acid has a mass of 30.0 to 80.0g.
In typical but non-limiting embodiments of the invention, the tartaric acid has a mass of, for example, 30.0, 35.0, 40.0, 45.0, 50.0, 55.0, 60.0, 65.0, 70.0, 75.0, or 80.0g.
By adjusting the quality of the tartaric acid, the action effect of the additive can be improved, and the quality of the cobalt concentrate is further improved. The additive has good effect within the range of 30.0-80.0 g of tartaric acid.
In a preferred embodiment of the present invention, in step (2), the mass of the cetyltrimethyl quaternary ammonium bromide is 70.0 to 120.0g.
In a typical, but non-limiting embodiment of the invention, the mass of the cetyltrimethyl quaternary ammonium bromide is, for example, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0, 100.0, 105.0, 110.0, 115.0 or 120.0g.
By adjusting the quality of the hexadecyl trimethyl quaternary ammonium bromide, the action effect of the additive can be improved, and the quality of the cobalt concentrate is further improved. The quality of the hexadecyl trimethyl quaternary ammonium bromide provided by the invention is in the range of 70-120 g, and the additive has good effect.
In a preferred embodiment of the present invention, in the step (2), the volume of ethanol is 100.0 to 200.0ml.
In typical but non-limiting embodiments of the invention, the volume of ethanol in step (2) is, for example, 100.0, 105.0, 110.0, 115.0, 120.0, 125.0, 130.0, 135.0, 140.0, 145.0, 150.0, 155.0, 160.0, 165.0, 170.0, 175.0, 180.0, 185.0, 190.0, 195.0 or 200.0ml.
The effect of the additive can be improved by adjusting the volume of the ethanol in the step (2), so that the quality of the cobalt concentrate is improved. In the step (2), the volume of the ethanol is 100.0-200.0 ml, and the additive has good effect.
In a preferred embodiment of the present invention, in the step (2), the temperature of the reaction is 100.0 to 150.0 ℃.
In typical but non-limiting embodiments of the invention, the temperature of the reaction in step (2) is, for example, 100.0, 105.0, 110.0, 115.0, 120.0, 125.0, 130.0, 135.0, 140.0, 145.0 or 150.0 ℃.
The effect of the additive can be improved by adjusting the reaction temperature in the step (2), so that the quality of the cobalt concentrate is improved. The reaction temperature in the step (2) provided by the invention is in the range of 100.0-150.0 ℃, and the additive has good effect.
In a preferred embodiment of the present invention, in step (2), the reaction time is 0.5 to 3.5 hours.
In typical but non-limiting embodiments of the invention, the time of the reaction in step (2) is for example 0.5, 1.0, 1.5, 2.0, 2.5 or 3.0h.
By adjusting the reaction time in the step (2), the action effect of the additive can be improved, and the quality of the cobalt concentrate is further improved. The reaction time in the step (2) provided by the invention is within the range of 0.5-3.5 h, and the additive has a good effect.
In a preferred embodiment of the present invention, in step (3), the temperature of the reaction is 50.0 to 100.0 ℃.
In typical, but non-limiting embodiments of the present invention, the temperature of the reaction in step (3) is, for example, 50.0, 55.0, 60.0, 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0 or 100.0 ℃.
The effect of the additive can be improved by adjusting the reaction temperature in the step (3), so that the quality of the cobalt concentrate is improved. The reaction temperature in the step (3) provided by the invention is 50.0-100.0 ℃, and the additive has good effect.
In a preferred embodiment of the present invention, in the step (3), the concentration of the aqueous NaOH solution is 0.50 to 1.00mol/L.
In typical, but non-limiting embodiments of the invention, the concentration of the aqueous NaOH solution is, for example, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90 or 1.00mol/L.
The effect of the additive can be improved by adjusting the concentration of the NaOH aqueous solution, so that the quality of the cobalt concentrate is improved. The concentration of the NaOH aqueous solution provided by the invention is within the range of 0.50-1.00 mol/L, and the additive has good effect.
In a preferred embodiment of the present invention, in step (3), the pH is 2.0 to 4.0.
In typical but non-limiting embodiments of the invention, the pH is, for example, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8 or 4.
By adjusting the pH value, the action effect of the additive can be improved, and the quality of the cobalt concentrate is further improved. The additive has better action effect within the pH value range of 2.0-4.0.
In a preferred embodiment of the present invention, in step (1), the inert gas is at least one selected from nitrogen, argon, carbon dioxide or helium.
According to a second aspect of the present invention, there is provided a method of using an additive comprising the steps of: adding the additive into the purifying slag leachate containing cobalt, uniformly mixing, then precipitating cobalt by using a beta-naphthol method, and oxidizing and roasting the obtained alpha-nitroso-beta-naphthol cobalt slag to obtain the cobalt concentrate with higher grade.
The additive provided by the invention is simple in use method, low in consumption and high in efficiency, can obtain a cobalt concentrate product with high quality, and has a good application prospect.
In the invention, when the beta-naphthol method is used for cobalt precipitation, the cobalt content in the purification slag leachate is 100-1500 mg/L, the zinc content is 10-250 g/L, the cadmium content is 0.1-100 g/L, the iron content is 0.1-10 g/L, the manganese content is 1.0-90 g/L, and the copper content is 0.1-10 g/L.
In a preferred embodiment of the invention, the additive is added in an amount of 10.0 to 20.0g/m 3 。
In typical, but non-limiting embodiments of the invention, the additive is added in an amount of, for example, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, or 20.0g/m 3 。
By adjusting the addition amount of the additive, the action effect of the additive can be improved, and the quality of the cobalt concentrate is further improved. The addition amount of the additive provided by the invention is 10.0-20.0 g/m 3 Within the range of (1), the additive has a good effect.
The technical solution provided by the present invention is further described below with reference to examples and comparative examples.
Example 1:
the embodiment provides a preparation method of an additive, which comprises the following steps:
1. weighing 10.0g of isomeric dodecyl alcohol polyoxyethylene ether, dissolving the isomeric dodecyl alcohol polyoxyethylene ether in 45.0ml of ethanol, adding 10.0g of sorbitan trioleate and 7.50g of triethylamine, reacting for 4.50h at the reaction temperature of 100.0 ℃ under the protection of helium, and then decompressing and recovering ethanol to obtain solid particles a.
2. 10.0g of the solid particles a, 45.0g of tartaric acid and 80.0g of cetyltrimethyl quaternary ammonium bromide were weighed into 125.0ml of an ethanol solvent, reacted at a reaction temperature of 100.0 ℃ for 1.5 hours, cooled to room temperature, and then the solvent was distilled off under reduced pressure to obtain a residue.
3. And adding 75.0ml of water into the residue, heating to 70.0 ℃, stirring for 30.0min at the reaction temperature, filtering while the mixture is hot, cooling the filtrate to room temperature, dropwise adding 0.60mol/L NaOH aqueous solution until the pH is =2.5, filtering, washing the filter cake with a small amount of water, and drying to obtain the additive.
4. In the purified slag leachate with the cobalt content of 460.2mg/L, the zinc content of 125.0g/L, the iron content of 0.5g/L, the manganese content of 20.0g/L, the cadmium content of 92.3g/L and the copper content of 2.4g/L, the concentration is 10.0g/m 3 The additive is added in the amount, after being mixed evenly, cobalt precipitation is carried out by using a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted to obtain cobalt concentrate with the cobalt content of 45.47%, the zinc content of 4.29%, the cadmium content of 0.83%, the iron content of 0.16%, the manganese content of 0.31% and the copper content of 0.24%. Under the same condition, the additive is not added before the cobalt precipitation is carried out by adopting a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted to obtain cobalt concentrate with 25.74 percent of cobalt, 26.49 percent of zinc, 25.97 percent of cadmium, 0.96 percent of iron, 4.79 percent of manganese and 0.51 percent of copper. The comparison of the test results shows that the additive is helpful for improving the grade of the cobalt concentrate.
Example 2:
this example provides a method for preparing an additive, comprising the steps of:
1. weighing 15.0g of isomeric dodecyl polyoxyethylene ether, dissolving the isomeric dodecyl polyoxyethylene ether in 35.0ml of ethanol, adding 15.0g of sorbitan trioleate and 5.0g of triethylamine, reacting for 3.0h at the reaction temperature of 110.0 ℃ under the protection of nitrogen, and then decompressing and recovering ethanol to obtain solid particles a.
2. 15.0g of the solid particles a, 35.0g of tartaric acid and 90.0g of cetyltrimethyl quaternary ammonium bromide were weighed into 100.0ml of an ethanol solvent, reacted at a reaction temperature of 115.0 ℃ for 1.0 hour, cooled to room temperature, and then the solvent was distilled off under reduced pressure to obtain a residue.
3. And adding 100.0ml of water into the residue, heating to 60.0 ℃, stirring for 60.0min at the reaction temperature, filtering while the mixture is hot, cooling the filtrate to room temperature, dropwise adding 0.70mol/L NaOH aqueous solution until the pH is =2.0, filtering, washing a filter cake with a small amount of water, and drying to obtain the additive.
4. In the purified slag leachate with the cobalt content of 573.4mg/L, the zinc content of 175.0g/L, the iron content of 1.5g/L, the manganese content of 30.0g/L, the cadmium content of 72.3g/L and the copper content of 5.4g/L, the concentration is 12.5g/m 3 The additive is added in the amount, after being mixed evenly, cobalt precipitation is carried out by using a beta-naphthol method, and cobalt concentrate with the cobalt content of 48.14%, the zinc content of 3.79%, the iron content of 0.21%, the manganese content of 0.38%, the cadmium content of 0.54% and the copper content of 0.34% is obtained after the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted. Under the same condition, the additive is not added before the cobalt precipitation is carried out by adopting a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag is subjected to oxidizing roasting to obtain cobalt concentrate with 20.44% of cobalt, 29.48% of zinc, 0.81% of iron, 5.38% of manganese, 28.54% of cadmium and 0.76% of copper. The comparison of the test results shows that the additive is beneficial to improving the grade of the cobalt concentrate.
Example 3:
the embodiment provides a preparation method of an additive, which comprises the following steps:
1. weighing 20.0g of isomeric dodecyl polyoxyethylene ether, dissolving the isomeric dodecyl polyoxyethylene ether in 55.0ml of ethanol, adding 20.0g of sorbitan trioleate and 10.0g of triethylamine, reacting for 5.0h at the reaction temperature of 120.0 ℃ under the protection of nitrogen, and then decompressing and recovering ethanol to obtain solid particles a.
2. 20.0g of the solid particles a, 55.0g of tartaric acid and 100.0g of cetyltrimethyl quaternary ammonium bromide were weighed into 150.0ml of an ethanol solvent, reacted at a reaction temperature of 125.0 ℃ for 2.0 hours, cooled to room temperature, and then the solvent was distilled off under reduced pressure to obtain a residue.
3. And adding 125.0ml of water into the residue, heating to 80.0 ℃, stirring for 90.0min at the reaction temperature, filtering while the mixture is hot, cooling the filtrate to room temperature, dropwise adding 0.80mol/L NaOH aqueous solution until the pH is =3.0, filtering, washing the filter cake with a small amount of water, and drying to obtain the additive.
4. In the purified slag leachate with the cobalt content of 678.9mg/L, the zinc content of 145.0g/L, the iron content of 3.5g/L, the manganese content of 45.0g/L, the cadmium content of 42.8g/L and the copper content of 4.5g/L, the weight ratio of 15.0g/m 3 The additive is added in the amount, after being mixed evenly, cobalt precipitation is carried out by using a beta-naphthol method, and cobalt concentrate with the cobalt content of 40.77 percent, the zinc content of 4.21 percent, the iron content of 0.34 percent, the manganese content of 0.48 percent, the cadmium content of 0.41 percent and the copper content of 0.12 percent is obtained after the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted. Under the same condition, the additive is not added before the cobalt precipitation is carried out by adopting a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted to obtain cobalt concentrate with 19.88 percent of cobalt, 24.51 percent of zinc, 2.21 percent of iron, 7.43 percent of manganese, 30.45 percent of cadmium and 0.26 percent of copper. The comparison of the test results shows that the additive is helpful for improving the grade of the cobalt concentrate.
Example 4:
this example provides a method for preparing an additive, comprising the steps of:
1. weighing 25.0g of isomeric dodecyl polyoxyethylene ether, dissolving the isomeric dodecyl polyoxyethylene ether in 75.0ml of ethanol, adding 25.0g of sorbitan trioleate and 15.0g of triethylamine, reacting for 6.5 hours at the reaction temperature of 130.0 ℃ under the protection of carbon dioxide, and recovering ethanol under reduced pressure to obtain solid particles a.
2. 30.0g of the solid particles a, 65.0g of tartaric acid and 120.0g of cetyltrimethyl quaternary ammonium bromide were weighed into 175.0ml of an ethanol solvent, reacted at a reaction temperature of 150.0 ℃ for 2.5 hours, cooled to room temperature, and then the solvent was distilled off under reduced pressure to obtain a residue.
3. And adding 175.0ml of water into the residue, heating to 90.0 ℃, stirring for 150.0min at the reaction temperature, filtering while hot, cooling the filtrate to room temperature, dropwise adding 0.90mol/L NaOH aqueous solution until the pH is =3.5, filtering, washing the filter cake with a small amount of water, and drying to obtain the additive.
4. In the purified slag leachate with the cobalt content of 789.9mg/L, the zinc content of 95.0g/L, the iron content of 5.5g/L, the manganese content of 60.0g/L, the cadmium content of 32.8g/L and the copper content of 3.5g/L, the concentration of the copper is 20.0g/m 3 The additive is added in the amount, after being mixed evenly, cobalt precipitation is carried out by using a beta-naphthol method, and cobalt concentrate with 50.12 percent of cobalt, 3.56 percent of zinc, 0.53 percent of iron, 0.68 percent of manganese, 0.21 percent of cadmium and 0.10 percent of copper is obtained after the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted. Under the same condition, the additive is not added before the cobalt precipitation is carried out by adopting a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted to obtain cobalt concentrate with 21.06% of cobalt, 32.19% of zinc, 3.11% of iron, 8.34% of manganese, 27.58% of cadmium and 0.36% of copper. The comparison of the test results shows that the additive is helpful for improving the grade of the cobalt concentrate.
Example 5:
the embodiment provides a preparation method of an additive, which comprises the following steps:
1. weighing 30.0g of isomeric dodecyl polyoxyethylene ether, dissolving the isomeric dodecyl polyoxyethylene ether in 65.0ml of ethanol, adding 30.0g of sorbitan trioleate and 12.5g of triethylamine, reacting for 7.5h at the reaction temperature of 140.0 ℃ under the protection of argon, and then decompressing and recovering ethanol to obtain solid particles a.
2. 25.0g of the solid particles a, 75.0g of tartaric acid and 110.0g of cetyltrimethyl quaternary ammonium bromide were weighed into 200.0ml of an ethanol solvent, reacted at 135.0 ℃ for 3.0 hours, cooled to room temperature, and then the solvent was distilled off under reduced pressure to obtain a residue.
3. And adding 150.0ml of water into the residue, heating to the reaction temperature of 100.0 ℃, stirring for 120.0min, filtering while the mixture is hot, cooling the filtrate to room temperature, dropwise adding 1.00mol/L NaOH aqueous solution until the pH is =4.0, filtering, washing the filter cake with a small amount of water, and drying to obtain the additive.
4. In the purified slag leachate with the cobalt content of 800.2mg/L, the zinc content of 45.0g/L, the iron content of 7.5g/L, the manganese content of 80.0g/L, the cadmium content of 12.8g/L and the copper content of 1.5g/L, 17.5g/m 3 The additive is added in the amount, after being mixed evenly, cobalt precipitation is carried out by using a beta-naphthol method, and cobalt concentrate with 54.42 percent of cobalt, 2.66 percent of zinc, 0.71 percent of iron, 0.98 percent of manganese, 0.11 percent of cadmium and 0.07 percent of copper is obtained after the obtained alpha-nitroso-beta-naphthol cobalt slag is oxidized and roasted. Under the same condition, the additive is not added before the cobalt precipitation is carried out by adopting a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag is subjected to oxidizing roasting to obtain cobalt concentrate with the cobalt content of 24.53%, the zinc content of 24.15%, the iron content of 8.21%, the manganese content of 11.38%, the cadmium content of 23.54% and the copper content of 0.27%. The comparison of the test results shows that the additive is helpful for improving the grade of the cobalt concentrate.
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 these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. The preparation method of the additive is characterized in that the additive is prepared from the following substances: isomeric dodecyl alcohol polyoxyethylene ether, ethanol, sorbitan trioleate, triethylamine, tartaric acid, hexadecyl trimethyl quaternary ammonium bromide, water and NaOH aqueous solution; the preparation method of the additive comprises the following steps:
(1) Adding 10.0-30.0 g of isomeric dodecyl alcohol polyoxyethylene ether, 30.0-50.0 g of sorbitan trioleate and 5.0-15.0 g of triethylamine into 30.0-80.0 ml of ethanol, heating under the protection of inert gas for reaction, wherein the reaction temperature is 90.0-150.0 ℃, the reaction time is 2.0-8.0 h, and then removing the ethanol to obtain solid particles a;
(2) Adding 20.0-40.0 g of solid particles a, 30.0-80.0 g of tartaric acid and 70.0-120.0 g of hexadecyl trimethyl quaternary ammonium bromide into 100.0-200.0 ml of ethanol for heating reaction, wherein the reaction temperature is 100.0-150.0 ℃, the reaction time is 0.5-3.5 h, then cooling to room temperature, and removing ethanol to obtain a residue;
(3) Adding quantitative water into the remainder, heating and stirring, filtering while the mixture is hot, wherein the reaction temperature is 50.0-100.0 ℃, cooling the filtrate to room temperature, then dropwise adding 0.50-1.00 mol/L NaOH aqueous solution to adjust the pH value to 2.0-4.0, and filtering, washing and drying to obtain the additive.
2. The method for preparing an additive according to claim 1, wherein in the step (1), the inert gas is at least one selected from nitrogen, argon, carbon dioxide or helium.
3. The use method of the additive is characterized by comprising the following steps: the additive prepared in the claim 1 is added into the purified slag leaching solution containing cobalt, after being uniformly mixed, the cobalt is precipitated by using a beta-naphthol method, and the obtained alpha-nitroso-beta-naphthol cobalt slag can be oxidized and roasted to obtain cobalt concentrate with higher grade.
4. The method for using additive according to claim 3, wherein the additive is added in an amount of 10.0 to 20.0g/m 3 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010911666.8A CN112645907B (en) | 2020-09-02 | 2020-09-02 | Preparation method and use method of additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010911666.8A CN112645907B (en) | 2020-09-02 | 2020-09-02 | Preparation method and use method of additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112645907A CN112645907A (en) | 2021-04-13 |
| CN112645907B true CN112645907B (en) | 2023-04-18 |
Family
ID=75346106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010911666.8A Active CN112645907B (en) | 2020-09-02 | 2020-09-02 | Preparation method and use method of additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112645907B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2831146A1 (en) * | 1978-07-15 | 1980-01-24 | Guenter Dipl Chem Barthel | Hydrometallurgical winning of cobalt from ores etc. - where cobalt is extracted from filtered leaching soln. by nitro-naphthol in organic solvent |
| CN101457301A (en) * | 2007-12-10 | 2009-06-17 | 巴彦淖尔紫金有色金属有限公司 | Technique for extracting cobalt from alpha-nitroso beta-naphthyl hydroxide cobalt slag |
| AU2008255245A1 (en) * | 2007-12-17 | 2009-07-09 | Bhp Billiton Ssm Development Pty Ltd | Selective recovery of cobalt |
| CN105950875A (en) * | 2016-05-09 | 2016-09-21 | 钟庆文 | Processing method for purified cobalt residues of zinc and manganese hydrometallurgy |
| CN112481504A (en) * | 2020-11-09 | 2021-03-12 | 昆明理工大学 | Preparation method of additive |
-
2020
- 2020-09-02 CN CN202010911666.8A patent/CN112645907B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2831146A1 (en) * | 1978-07-15 | 1980-01-24 | Guenter Dipl Chem Barthel | Hydrometallurgical winning of cobalt from ores etc. - where cobalt is extracted from filtered leaching soln. by nitro-naphthol in organic solvent |
| CN101457301A (en) * | 2007-12-10 | 2009-06-17 | 巴彦淖尔紫金有色金属有限公司 | Technique for extracting cobalt from alpha-nitroso beta-naphthyl hydroxide cobalt slag |
| AU2008255245A1 (en) * | 2007-12-17 | 2009-07-09 | Bhp Billiton Ssm Development Pty Ltd | Selective recovery of cobalt |
| CN105950875A (en) * | 2016-05-09 | 2016-09-21 | 钟庆文 | Processing method for purified cobalt residues of zinc and manganese hydrometallurgy |
| CN112481504A (en) * | 2020-11-09 | 2021-03-12 | 昆明理工大学 | Preparation method of additive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112645907A (en) | 2021-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10118224B2 (en) | Method for producing nickel powder | |
| CA2996277C (en) | Method for producing nickel powder | |
| WO2012014685A1 (en) | Process for production of ferronickel smelting raw material from low grade lateritic nickel ore | |
| AU2019310942B2 (en) | Method for homogeneous precipitation separation of iron and aluminum from laterite nickel ore acid leaching solution | |
| JP2017150063A5 (en) | ||
| JP6020971B2 (en) | Method for producing cobalt powder | |
| CN113265532A (en) | Method for leaching nickel-ammonia solution from nickel-iron alloy by wet method and application | |
| CN112645907B (en) | Preparation method and use method of additive | |
| CN107790740A (en) | A kind of application method of nickel slag | |
| AU2017223933A1 (en) | Method for producing nickel powder | |
| CN115491518A (en) | Method for producing nickel sulfate and cobalt sulfate by chlorination process | |
| CN115709979A (en) | Method for preparing battery-grade manganese iron phosphate by taking high-iron manganese ore as raw material | |
| CN109970105B (en) | Method for cleanly recovering iron in zinc hydrometallurgy process | |
| CN1021579C (en) | Process for separating cerium dioxicde from mixed rare earth | |
| CN115305355B (en) | Method for extracting zinc and precipitating iron from steel-making furnace dust | |
| WO2017038589A1 (en) | Process for producing nickel powder | |
| CN111057856B (en) | Method for leaching and recovering cobalt, nickel and molybdenum in catalyst | |
| CN110451554B (en) | Method for recovering feed-grade zinc oxide from zinc-containing sludge and recovered feed-grade zinc oxide | |
| AU2018392525B2 (en) | Method for producing nickel powder | |
| CN113846216A (en) | Method for preparing high-quality cobalt oxide from copper extraction raffinate of copper oxide cobalt ore | |
| KR20210002924A (en) | Method for recovering valuable metals from process sludge containing valuable metal | |
| JPH0455133B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |