CN112553472A - Method for extracting nickel from smelting sulfide waste residue and application thereof - Google Patents
Method for extracting nickel from smelting sulfide waste residue and application thereof Download PDFInfo
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- CN112553472A CN112553472A CN202011317480.6A CN202011317480A CN112553472A CN 112553472 A CN112553472 A CN 112553472A CN 202011317480 A CN202011317480 A CN 202011317480A CN 112553472 A CN112553472 A CN 112553472A
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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
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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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
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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
- C22B7/007—Wet processes by acid leaching
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- 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
Abstract
The invention provides a method for extracting nickel from smelting sulfide waste residues and application thereof, and relates to the technical field of solid waste resource recycling. According to the method for extracting nickel from the smelting vulcanized waste residue, firstly, the smelting vulcanized waste residue is dried and then dissolved by dilute acid, and then the smelting vulcanized waste residue is filtered and dried to obtain the vulcanized residue A; then immersing the sulfide slag A into an acid solution for oxygen pressure extraction to obtain sulfate filtrate; and finally, removing impurities in the sulfate filtrate by using an acidic organic phosphorus extractant to obtain the nickel sulfate. The treatment method has the advantages of simple process flow, easy operation and no need of adding additional additives in the extraction process.
Description
Technical Field
The invention relates to the technical field of solid waste resource recycling, in particular to a method for extracting nickel from smelting vulcanization waste residue and application thereof.
Background
Nickel metal has excellent corrosion resistance, high temperature resistance, magnetism and high strength, and is widely applied to various fields. In recent years, along with economic development, the demand of nickel is continuously increased, and the resources of nickel sulfide ore in China are increasingly exhausted, so that the smelting of nickel sulfide waste slag becomes an important raw material for extracting nickel, and the treatment process is generally a fire method and a wet method. The pyrometallurgical treatment process is to smelt nickel in nickel sulfide ore into low-nickel matte, to blow the low-nickel matte into high-nickel matte in a converter, and to produce different nickel products by different refining methods, but the method produces a large amount of sulfur dioxide gas and pollutes the environment. The wet treatment process generally refers to a process of leaching nickel in nickel sulfide ore into a solution and then extracting the nickel, and the existing wet treatment generally adopts pressure leaching for treatment.
Pressure leaching is one of new hydrometallurgy processes for treating complex metal mineral resources, but the pressure leaching has the problems of difficult impurity removal, long leaching time and low leaching efficiency; although smelting is not needed, the process is more complex, the equipment investment is large, and the auxiliary material cost is high.
The method comprises the steps of firstly grinding nickel sulfide ores, adding dilute acid to remove impurities, then adding sulfuric acid, an oxidant, a sulfur binding agent, a calcium sulfate inhibitor and the like, uniformly mixing, then adding into an autoclave, introducing high-pressure air, reacting and filtering to obtain a nickel sulfate solution and leaching residues. The method has the advantages of large consumption of auxiliary materials, high reaction energy consumption, low safety, difficult treatment of leaching residues, and harm to the environment and human body.
Therefore, it is necessary and urgent to develop a method for extracting nickel from smelting sulfide slag, which has the advantages of high leaching rate, short process, low energy consumption and no need of additives.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for extracting nickel from smelting sulfide waste residues, which has the advantages of simple process flow, easy operation and no need of adding additional additives in the extraction process.
The second purpose of the invention is to provide the application of the method for extracting nickel from the smelting sulfuration waste slag in the recycling of the cobalt-nickel smelting waste slag.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for extracting nickel from smelting sulfide waste residues, which comprises the following steps:
(a) drying the smelting vulcanized waste residue, dissolving the dried smelting vulcanized waste residue by using dilute sulfuric acid, and then filtering and drying to obtain vulcanized residue A;
(b) immersing the sulfide slag A into an acid solution for oxygen pressure extraction, and filtering to obtain sulfate filtrate;
(c) and removing impurities in the sulfate filtrate by using an acidic organic phosphorus extractant to obtain nickel sulfate.
Further, the smelting sulfuration waste residue in the step (a) is acidic waste water sulfide precipitate after cobalt and nickel smelting;
preferably, the acidic wastewater sulfide precipitate contains the following components: 28-30% of Ni, 1.5-2.0% of Co, 0.04-0.08% of Fe, 4.3-5.0% of Mg and 30-33% of S.
Further, the diluted acid in the step (a) comprises at least one of hydrochloric acid, nitric acid and sulfuric acid, and the hydrogen ion concentration is 0.5 mol/L;
preferably, the concentration of the sulfuric acid is 0.25 mol/L.
Further, the acidic solution in the step (b) is an acidic solution with a hydrogen ion concentration of 0.25-0.6 mol/L, and preferably a hydrogen ion concentration of 0.5 mol/L.
Preferably, the solid-to-liquid ratio of the sulfide slag to the acidic solution in the step (b) is 1g: 30-40 ml, preferably 1g:40 ml.
Further, the reaction conditions of the oxygen pressure extraction in the step (b) at least satisfy at least one of the following conditions:
the temperature of the oxygen pressure extraction is 100-150 ℃, the pressure of the oxygen pressure extraction is 0.3-0.5 MPa, and the time of the oxygen pressure extraction is 6-8 h;
preferably, the reaction conditions of the oxygen pressure extraction in the step (b) at least satisfy at least one of the following conditions:
the temperature of oxygen pressure extraction is 100 ℃, the pressure of oxygen pressure extraction is 0.3MPa, and the time of oxygen pressure extraction is 6 h.
Further, the acidic organic phosphorus extractant in step (c) comprises one or a combination of at least two of P507, P204 and Cyanex 272.
Further, the step (c) of removing impurities in the sulfate filtrate by using the acidic organophosphorus extractant comprises the following steps:
the method is characterized in that a Cyanex272 extracting agent is adopted, the concentration is 10% -15%, a diluent is sulfonated kerosene, the saponification rate is 25% -30%, and the volume ratio of an organic phase to a water phase is 0.5-3: 1, extracting the sulfate filtrate obtained in the step (b) by using nickel soap to remove most of cobalt and magnesium, thereby obtaining nickel sulfate.
Further, the method also comprises the step of neutralizing the residual acid in the sulfate filtrate by using an acid-base regulator before the step (c) of extracting the sulfate filtrate by using the acidic organophosphorus extractant.
Further, the pH regulator includes at least one of ammonium bicarbonate, ammonia water and nickel hydroxide, preferably nickel hydroxide.
The invention provides an application of the method for extracting nickel from smelting sulfuration waste residues in cobalt-nickel smelting waste residue recycling.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for extracting nickel from smelting vulcanized waste residues, which comprises the steps of drying the smelting vulcanized waste residues, dissolving the dried smelting vulcanized waste residues by using dilute acid, and then filtering and drying the obtained product to obtain vulcanized residue A; then immersing the sulfide slag A into an acid solution for oxygen pressure extraction to obtain sulfate filtrate; and finally, removing impurities in the sulfate filtrate by using an acidic organic phosphorus extractant to obtain the nickel sulfate. The treatment method has the advantages of simple process flow, easy operation and no need of adding additional additives in the extraction process.
The method for extracting nickel from smelting and vulcanizing waste residues provided by the invention can be widely applied to recycling of cobalt-nickel smelting waste residues.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic process flow diagram of a method for extracting nickel from smelting sulfidic slag provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the invention, a method for extracting nickel from smelting sulfidic slag comprises the following steps:
(a) drying the smelting vulcanized waste residue, dissolving the smelted vulcanized waste residue by using dilute acid, and then filtering and drying to obtain vulcanized residue A;
(b) immersing the sulfide slag A into an acid solution for oxygen pressure extraction to obtain sulfate filtrate;
(c) and removing impurities in the sulfate filtrate by using an acidic organic phosphorus extractant to obtain nickel sulfate.
The invention provides a method for extracting nickel from smelting vulcanized waste residues, which comprises the steps of drying the smelting vulcanized waste residues, dissolving the dried smelting vulcanized waste residues by using dilute acid, and then filtering and drying the obtained product to obtain vulcanized residue A; then immersing the sulfide slag A into an acid solution for oxygen pressure extraction to obtain sulfate filtrate; and finally, removing impurities in the sulfate filtrate by using an acidic organic phosphorus extractant to obtain the nickel sulfate. The treatment method has the advantages of simple process flow, easy operation and no need of adding additional additives in the extraction process.
Preferably, the dilute acid in the present application comprises at least one of hydrochloric acid, nitric acid and sulfuric acid, and the hydrogen ion concentration is 0.5 mol/L.
In a preferred embodiment of the invention, the smelting sulfuration waste residue in the step (a) is sulfide precipitate obtained by adding sodium sulfide into P507 raffinate obtained after cobalt and nickel smelting;
as a preferred embodiment, the acidic wastewater sulfide precipitate contains the following components: 28-30% of Ni, 1.5-2.0% of Co, 0.04-0.08% of Fe, 4.3-5.0% of Mg and 30-33% of S.
In a preferred embodiment of the present invention, the diluted acid in the step (a) comprises at least one of hydrochloric acid, nitric acid and sulfuric acid, and the hydrogen ion concentration is 0.5 mol/L;
preferably, the concentration of the sulfuric acid is 0.25 mol/L.
As a preferred embodiment, the dilute acid can effectively leach soluble substances (NaS and trace NiSO) in the smelting sulfide slag4And CoSO4And the like), and then the sulfur content of the smelting vulcanized waste residue can be reduced by 30-40% through filtering and drying.
In a preferred embodiment of the present invention, the particle size of the smelted and vulcanized waste residue in the step (a) after drying is 200-mesh sieve particles.
Preferably, the step (a) includes the steps of: putting the smelting vulcanized waste residues into a drying oven at 100 ℃ for drying for 12 hours, putting the dried smelting vulcanized waste residues into a ball mill for grinding, and sieving the ground smelting vulcanized waste residues with a 200-mesh sieve; dissolving the sulfide precipitate with dilute acid, and leaching soluble substances (NaS and trace NiSO)4And CoSO4And the like) and then drying the soluble substances during filtering to obtain the sulfide slag, wherein the sulfur content of the smelting sulfide slag can be reduced by 30-40 percent through the steps.
In a preferred embodiment of the present invention, the acidic solution in step (b) is an acidic solution with a hydrogen ion concentration of 0.25 to 0.6mol/L, preferably 0.5 mol/L.
In a preferred embodiment, the hydrogen ion concentration of the acidic solution is 0.5 mol/L.
In a preferred embodiment of the present invention, the solid-to-liquid ratio of the sulfide slag a to the acidic solution in the step (b) is 1g: 30-40 ml, preferably 1g:40 ml.
In a preferred embodiment, the solid-to-liquid ratio of the sulfide slag a to the acidic solution is 1g: 30-40 ml, in the range of the high solid-to-liquid ratio, the sulfide slag can be fully dispersed in the solution, the acid in the acid solution is fully contacted with the oxygen, so that the additive is not required to be added in the reaction, and the auxiliary material cost is saved. The leaching rate of the sulfide slag A can reach more than 95 percent in the range of the solid-to-liquid ratio through detection.
In a preferred embodiment of the present invention, the reaction conditions of the oxygen pressure extraction in the step (b) at least satisfy at least one of the following conditions:
the temperature of the oxygen pressure extraction is 100-150 ℃, the pressure of the oxygen pressure extraction is 0.3-0.5 MPa, and the time of the oxygen pressure extraction is 6-8 h;
as a preferable embodiment, the temperature of the oxygen pressure extraction is only 100-150 ℃, the energy consumption in the extraction process can be effectively reduced, the pressure of the oxygen pressure extraction is only 0.3-0.5 MPa, and the reaction has higher safety.
In the above preferred embodiment, the reaction conditions of the oxygen pressure extraction of the step (b) at least satisfy at least one of the following conditions:
the temperature of oxygen pressure extraction is 100 ℃, the pressure of oxygen pressure extraction is 0.3MPa, and the time of oxygen pressure extraction is 6 h.
In a preferred embodiment of the present invention, SO released after the oxygen pressure extraction in the step (b) is2Tail gas can be used for absorbing SO by liquid caustic soda2To obtain CaSO3Oxidized to CaSO in air4。
Preferably, the step (b) includes the steps of:
adding the sulfide slag A obtained in the step (a) into an autoclave, adding sulfuric acid and pure water, keeping the hydrogen ion concentration at 0.5mol/L, and adjusting the solid-to-liquid ratio to be 1g:30 ml-1 g:40 ml. Checking gas tightness, introducing oxygen to remove the gas, heating to 100-150 deg.C, and coolingIntroducing oxygen to keep the pressure in the kettle at 0.3-0.5 MPa, and reacting for 6-8 h. After the reaction is finished, cooling is started until the temperature in the kettle is reduced to normal temperature, and the gas valve is opened to release SO2Tail gas, absorbing SO with liquid alkali2To obtain CaSO3Oxidized to CaSO in air4. And (4) releasing the pressure in the kettle until the number is zero, and filtering the leaching solution to obtain sulfate filtrate.
In a preferred embodiment of the present invention, the acidic organophosphorus extractant of step (c) comprises one or a combination of at least two of P507, P204 and Cyanex 272.
In the above preferred embodiment, the step (c) of removing impurities in the sulfate filtrate using the acidic organophosphorus extractant includes the following steps:
the method is characterized in that a Cyanex272 extracting agent is adopted, the concentration is 10% -15%, a diluent is sulfonated kerosene, the saponification rate is 25% -30%, and the volume ratio of an organic phase to a water phase is 0.5-3: 1, extracting the sulfate filtrate obtained in the step (b) by using nickel soap to remove all cobalt and magnesium to obtain nickel sulfate.
In a preferred embodiment of the present invention, the method further comprises the step of neutralizing the residual acid in the sulfate filtrate with an acid-base modifier before extracting the sulfate filtrate with the acidic organophosphorus extractant in step (c).
In the above preferred embodiment, the acid-base modifier includes at least one of ammonium bicarbonate, ammonia water, and nickel hydroxide, preferably nickel hydroxide.
Preferably, the step (c) includes the steps of:
neutralizing the residual acid of the sulfate filtrate obtained in the step (b) by using nickel hydroxide, and adjusting the pH value to 3-3.5; the method is characterized in that a Cyanex272 extracting agent is adopted, the concentration is 10% -15%, a diluent is sulfonated kerosene, the saponification rate is 25% -30%, and the volume ratio of an organic phase to a water phase is 0.5-3: 1, extracting the sulfate filtrate obtained in the step (b) by using nickel soap to remove all cobalt and magnesium to obtain nickel sulfate.
According to one aspect of the invention, the method for extracting nickel from smelting sulfuration waste residues is applied to recycling of cobalt-nickel smelting waste residues.
The method for extracting nickel from smelting and vulcanizing waste residues provided by the invention can be widely applied to recycling of cobalt-nickel smelting waste residues.
The technical solution of the present invention will be further described with reference to examples and comparative examples.
Example 1
As shown in fig. 1, a method for extracting nickel from smelting sulfidation slag comprises the following steps:
(1) and putting the smelting vulcanized waste residues into a drying oven at 100 ℃ for drying for 12 hours, then grinding, and then sieving by a 200-mesh sieve. Dissolving the undersize product with dilute sulphuric acid, filtering, washing off the soluble substances, and drying to obtain the sulfide residue A.
The smelting sulfuration waste residue is acidic waste water sulfide precipitate after cobalt and nickel smelting; the detection proves that the sulfide precipitate of the acidic wastewater contains the following components: 29.12 wt% of Ni, 1.78 wt% of Co, 0.06 wt% of Fe, 4.66 wt% of Mg and 32.7 wt% of S.
(2) Adding 100g of the sulfide slag A into a reaction kettle, adding 3L of sulfuric acid solution with the concentration of 0.25mol/L, wherein the solid-to-liquid ratio is 1g:30ml, heating to 150 ℃, introducing oxygen to keep the pressure in the kettle at 0.3MPa, reacting for 6 hours, cooling to room temperature, opening an exhaust valve, and absorbing sulfur dioxide tail gas by using liquid caustic soda to finally obtain calcium sulfate.
And filtering the leaching solution to obtain sulfate filtrate when the indication of the pressure gauge is zero.
(3) And (3) adding nickel hydroxide to the sulfate filtrate (pH 1.6) obtained in the step (2), adjusting the pH to 3.0, then extracting with a Cyanex272 extracting agent at a concentration of 10%, using sulfonated kerosene as a diluent, having a saponification rate of 25%, comparing the volume ratio of an organic phase to an aqueous phase to 1: 1, extracting the sulfate filtrate by using nickel soap to remove all cobalt and magnesium to obtain nickel sulfate.
The content of the nickel sulfate prepared in the embodiment is detected, the detection results are 28.3g/L of Ni, 0.003g/L of Co0.003g/L of Fe and 0.002g/L of Mg, and the leaching rate of nickel is 95%.
Example 2
A method for extracting nickel from smelting sulfide slag, which comprises the following steps:
(1) and putting the smelting vulcanized waste residues into a drying oven at 100 ℃ for drying for 12 hours, then grinding, and then sieving by a 200-mesh sieve. Dissolving the undersize product with dilute sulphuric acid, filtering, washing off the soluble substances, and drying to obtain the sulfide residue A.
The smelting sulfuration waste residue is acidic waste water sulfide precipitate after cobalt and nickel smelting; the detection proves that the sulfide precipitate of the acidic wastewater contains the following components: 29.73 wt% of Ni, 1.63 wt% of Co, 0.05 wt% of Fe, 4.88 wt% of Mg and 31.4 wt% of S.
(2) Adding 75g of the sulfide slag A into a reaction kettle, adding 3L of sulfuric acid solution with the concentration of 0.4mol/L, wherein the solid-liquid ratio is 1g:40ml, heating to 120 ℃, introducing oxygen to keep the pressure in the kettle at 0.3MPa, reacting for 6 hours, cooling to room temperature, opening an exhaust valve, and absorbing sulfur dioxide tail gas by using liquid caustic soda to finally obtain calcium sulfate.
And filtering the leaching solution to obtain sulfate filtrate when the indication of the pressure gauge is zero.
(3) And (3) adding nickel hydroxide to the sulfate filtrate (pH is 1.7) obtained in the step (2), adjusting the pH to 3.5, then extracting with a Cyanex272 extracting agent at a concentration of 15%, using sulfonated kerosene as a diluent, having a saponification rate of 25%, comparing the volume ratio of an organic phase to an aqueous phase to 2: 1, extracting the sulfate filtrate by using nickel soap to remove all cobalt and magnesium to obtain nickel sulfate.
The content of the nickel sulfate prepared in the embodiment is detected, the detection results are 28.9g/L of Ni, 0.003g/L of Co0.003g/L of Fe and 0.003g/L of Mg, and the leaching rate of nickel is 97%.
Example 3
A method for extracting nickel from smelting sulfide slag, which comprises the following steps:
(1) and putting the smelting vulcanized waste residues into a drying oven at 100 ℃ for drying for 12 hours, then grinding, and then sieving by a 200-mesh sieve. Dissolving the undersize product with dilute sulphuric acid, filtering, washing off the soluble substances, and drying to obtain the sulfide residue A.
The smelting sulfuration waste residue is acidic waste water sulfide precipitate after cobalt and nickel smelting; the detection proves that the sulfide precipitate of the acidic wastewater contains the following components: ni 28.98 wt%, Co 1.88 wt%, Fe 0.08 wt%, Mg 4.53 wt% and S32.4 wt%.
(2) Adding 75g of the sulfide slag A into a reaction kettle, adding 3L of sulfuric acid solution with the concentration of 0.25mol/L, wherein the solid-to-liquid ratio is 1g:40ml, heating to 100 ℃, introducing oxygen to keep the pressure in the kettle at 0.5MPa, reacting for 8 hours, cooling to room temperature, opening an exhaust valve, and absorbing sulfur dioxide tail gas by using liquid caustic soda to finally obtain calcium sulfate.
And filtering the leaching solution to obtain sulfate filtrate when the indication of the pressure gauge is zero.
(3) And (3) adding nickel hydroxide into the sulfate filtrate (pH is 1.76) obtained in the step (2), adjusting the pH to 3.5, then extracting with a Cyanex272 extracting agent at a concentration of 15%, using sulfonated kerosene as a diluent, having a saponification rate of 30%, comparing the volume ratio of an organic phase to an aqueous phase to be 3: 1, extracting the sulfate filtrate obtained in the step (b) by using nickel soap to remove all cobalt and magnesium to obtain nickel sulfate.
The content of the nickel sulfate prepared in the embodiment is detected, the detection results are 29.5g/L of Ni, 0.002g/L of Co0.002g/L, 0.0028g/L of Fe and 0.0028g/L of Mg, and the leaching rate of nickel is 99%.
Example 4
In this embodiment, except that the solid-to-liquid ratio in step (2) is 1: the same as example 3 except for 10.
The content of the nickel sulfate prepared in the embodiment is detected, the detection result is that Ni is 25.4g/L, Co0.002g/L, Fe is 0.003g/L, Mg is 0.002g/L, and the leaching rate of nickel is 85.6%.
Example 5
In this embodiment, except for the step (2):
adding 75g of the sulfide slag A into a reaction kettle, adding 3L of sulfuric acid solution with the concentration of 0.7mol/L, wherein the solid-to-liquid ratio is 1g:40ml, the solid-liquid ratio is 1:40g/ml, the temperature is raised to 150 ℃, then oxygen is introduced, the pressure in the kettle is kept at 0.5MPa, the reaction is carried out for 8 hours, the temperature is cooled to room temperature, an exhaust valve is opened, liquid caustic soda is used for absorbing sulfur dioxide tail gas, and finally calcium sulfate is obtained. The same procedure as in example 3 was repeated except that the leachate was filtered to obtain a sulfate filtrate when the pressure gauge indicated zero.
The content of the nickel sulfate prepared in the embodiment is detected, and the detection results are 28.0g/L of Ni, 0.002g/L of Co0.002g/L, 0.0027g/L of Fe and 0.002g/L of Mg, and the leaching rate of nickel is 94.3%.
Example 6
This example is the same as example 3 except that the temperature in step (2) was 200 ℃.
The content of the nickel sulfate prepared in the embodiment is detected, and the detection results are that the Ni is 28.8g/L, the Co0.0015g/L, the Fe is 0.0026g/L, the Mg is 0.0021g/L, and the leaching rate of the nickel is 97%.
Example 7
This example was conducted in the same manner as example 3 except that the pressure in step (2) was 0.1 MPa.
The content of the nickel sulfate prepared in the embodiment is detected, and the detection result is that the nickel sulfate is 25.8g/L, Co0.0019g/L, Fe 0.0029g/L and Mg 0.003g/L, and the leaching rate of nickel is 86.7%.
Comparative example 1
A method for preparing nickel sulfate from nickel sulfide ores, which comprises the following steps:
(1) pretreatment: grinding nickel sulfide ore, adding 100g of dilute acid (sulfuric acid, sulfuric acid and nitric acid) into 100g of the ground nickel sulfide ore, stirring for 1 hour, performing pressure filtration to obtain pretreated nickel sulfide ore and an aqueous solution, and concentrating and crystallizing the aqueous solution to recover magnesium salt. Wherein the fineness of the nickel sulfide ore after grinding is 80 mu m.
The same procedure of example 3 was used to smelt the sulfidation slag.
(2) Oxygen pressure leaching: adding 100g of sulfuric acid (the concentration of sulfuric acid is 20 percent), 10g of oxidant, 1g of sulfur binder, 1g of calcium sulfate inhibitor and 1g of iron oxide seed crystal into the pretreated nickel sulfide ore, uniformly mixing, adding into an autoclave, introducing high-pressure air, reacting at 140 ℃, and carrying out solid-liquid separation to obtain a nickel sulfate solution and leaching residues. Wherein the adding amount of the ferric oxide crystal seeds is 5 percent of the mass of the pretreated nickel sulfide ore, the pressure of high-pressure air is 2MPa, and the reaction time is 6 hours.
The content of the nickel sulfate prepared in the embodiment is detected, and the detected result is that the leaching rate of Ni is more than 95%, but in comparative example 1, a plurality of additives are required to be added, the reaction temperature is 140 ℃, and the reaction pressure is 2 MPa. In the embodiment 3, the reaction temperature is 100 ℃, the reaction pressure is 0.5MPa, and the auxiliary material is sulfuric acid, so that the energy consumption and the auxiliary material consumption are reduced, and the safety is improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for extracting nickel from smelting sulfide waste residues is characterized by comprising the following steps:
(a) drying the smelting vulcanized waste residue, dissolving the smelted vulcanized waste residue by using dilute acid, and then filtering and drying to obtain vulcanized residue A;
(b) immersing the sulfide slag A into an acid solution for oxygen pressure extraction to obtain sulfate filtrate;
(c) and removing impurities in the sulfate filtrate by using an acidic organic phosphorus extractant to obtain nickel sulfate.
2. The method for extracting nickel from smelting sulfidation slag according to claim 1, wherein the smelting sulfidation slag in the step (a) is acidic waste water sulfide precipitation after cobalt nickel smelting;
preferably, the acidic wastewater sulfide precipitate contains the following components: 28-30 wt% of Ni, 1.5-2.0 wt% of Co1.04-0.08 wt% of Fe, 0.43-0.50 wt% of Mg and 30-33 wt% of S.
3. The method for extracting nickel from smelting sulfidic slag according to claim 1, wherein the dilute acid in step (a) comprises at least one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of hydrogen ion is 0.5 mol/L;
preferably, the concentration of the sulfuric acid is 0.25 mol/L.
4. The method for extracting nickel from smelting sulfide waste residues according to claim 1, wherein the acidic solution in the step (b) is an acidic solution with a hydrogen ion concentration of 0.25-0.6 mol/L, preferably 0.5 mol/L;
preferably, the solid-to-liquid ratio of the sulfide slag to the acidic solution in the step (b) is 1g: 30-40 ml, preferably 1g:40 ml.
5. The method for extracting nickel from smelting sulfidic slag as claimed in claim 1, wherein the reaction condition of the oxygen pressure extraction in the step (b) at least satisfies at least one of the following conditions:
the temperature of the oxygen pressure extraction is 100-150 ℃, the pressure of the oxygen pressure extraction is 0.3-0.5 MPa, and the time of the oxygen pressure extraction is 6-8 h;
preferably, the reaction conditions of the oxygen pressure extraction in the step (b) at least satisfy at least one of the following conditions:
the temperature of oxygen pressure extraction is 100 ℃, the pressure of oxygen pressure extraction is 0.3MPa, and the time of oxygen pressure extraction is 6 h.
6. The method for extracting nickel from smelting sulfidic slag as claimed in claim 1, wherein the acidic organophosphorus extractant in step (c) comprises one or a combination of at least two of P507, P204 and Cyanex 272.
7. The method for extracting nickel from smelting sulfidic slag according to claim 6, wherein the step (c) of removing impurities in the sulfate filtrate by using acidic organophosphorus extractant comprises the following steps:
the method is characterized in that a Cyanex272 extracting agent is adopted, the concentration is 10% -15%, a diluent is sulfonated kerosene, the saponification rate is 25% -30%, and the volume ratio of an organic phase to a water phase is 0.5-3: 1, extracting the sulfate filtrate obtained in the step (b) by using nickel soap to remove all cobalt and magnesium to obtain nickel sulfate.
8. The method for extracting nickel from smelting sulfidic slag according to claim 1, further comprising the step of neutralizing the residual acid in the sulfate filtrate with an acid-base modifier before extracting the sulfate filtrate with an acidic organophosphorus extractant in step (c).
9. The method for extracting nickel from smelting sulfidation slag according to claim 8, wherein the acid-base modifier comprises at least one of ammonium bicarbonate, ammonia water and nickel hydroxide, preferably nickel hydroxide.
10. The application of the method for extracting nickel from smelting sulfuration waste residues according to any one of claims 1 to 9 in recycling of cobalt-nickel smelting waste residues.
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| CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352308A (en) * | 2001-11-09 | 2002-06-05 | 北京矿冶研究总院 | Method for extracting nickel from nickel sulfide material with low copper content |
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| CN1352308A (en) * | 2001-11-09 | 2002-06-05 | 北京矿冶研究总院 | Method for extracting nickel from nickel sulfide material with low copper content |
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| CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
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