CN103114205A - Two-step method for extracting valuable metal nickel and copper from sodium jarosite slag - Google Patents
Two-step method for extracting valuable metal nickel and copper from sodium jarosite slag Download PDFInfo
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- CN103114205A CN103114205A CN2012105221919A CN201210522191A CN103114205A CN 103114205 A CN103114205 A CN 103114205A CN 2012105221919 A CN2012105221919 A CN 2012105221919A CN 201210522191 A CN201210522191 A CN 201210522191A CN 103114205 A CN103114205 A CN 103114205A
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Abstract
The invention provides a two-step method for extracting valuable metal nickel and copper from sodium jarosite slag. The method comprises the following steps of: crushing the sodium jarosite slag to obtain raw material slag; baking the raw material slag; leaching with water and vacuum-filtering to obtain primary leaching slag and primary leaching solution; regulating the pH value of the primary leaching solution by using concentrated sulfuric acid and adding an ammonium sulfide solution, stirring at a certain rotating speed and a certain temperature, and filtering to obtain a nickel sulfate solution and copper sulfide; leaching the primary leaching slag by using sulfuric acid, vacuum-filtering to obtain a secondary leaching solution; adding common iron powder into the secondary leaching solution, stirring and filtering, and washing the filter residues by using dilute sulfuric acid to obtain elementary copper; and cooling and crystallizing the filtrate in an ice-water bath, and filtering to obtain iron sulfate heptahydrate. The extraction method is finished by two steps, is simple and feasible in process and high in benefits; and the extraction rates of the valuable metal nickel and copper can be 90 percent and 85 percent respectively.
Description
Technical field
The invention belongs to and belong to technical field of wet metallurgy, relate to a kind of extract valuable metal waste residue produced from the wet method nickel metallurgy method, particularly a kind of two-step approach is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium.
Background technology
In hydrometallurgy and inorganic chemical industry production, when having relatively large iron to remove, extensively adopt and generate the ihleite deferrization process with good strainability at present.Jinchuan Non-ferrous Metals Company is in the wet method nickel metallurgy, and the separation of iron, nickel is exactly to adopt this technological process.
The ihleite method is first iron to be oxidized to the iron ion of trivalent, and ferric ion is containing Na
+, K
+, NH
4 +be easy to form faint yellow compd A in isoionic sulfate liquor
2fe
6(SO
4)
4(OH)
12and crystalline deposit out, A represents Na
+, K
+, NH
4 +plasma.Its reaction equation is as follows:
Fe
2(SO
4)
3+12H
2O+A
2SO
4?=?A
2Fe
6(SO
4)
4(OH)
12+6H
2SO
4
Wherein A is Na
+the time be called yellow modumite.This method is compared with traditional neutralizing hydrolysis method, and slag particle is thick, filterableness good, and slag metal-containing is less, is conducive to metal recovery.Yet can produce a large amount of waste residues in this way, the iron of often removing 1kg just has the ihleite waste residue of 2.5～3.0kg to generate.And contain the non-ferrous metals such as a certain amount of nickel, copper because following three reasons make in the ihleite waste residue, cause the loss of valuable metal: 1) the iron vitriol dreg of yellow sodium iron removal has 5%～8% Fe (OH)
3form, also contain SiO in slag
2deng amorphous sediment, this colloidal precipitation has stronger adsorptive power to nonferrous metal ion; 2) yellow modumite can be carried the wrapping portion non-ferrous metal secretly in filtration procedure; 3) yellow modumite produces a large amount of acid in forming process, and acidity increases precipitation capacity and the speed that can reduce iron, therefore need add a certain amount of neutralizing agent, is accompanied by adding of neutralizing agent, owing to may existing local overrich to cause having a small amount of nickel hydroxide precipitate to produce.
Iron vitriol dreg of yellow sodium is stable under certain acidic conditions, and the pH value raises or is heated and will be hydrolyzed or decompose the environmentally harmful material of generation.If a large amount of ihleite waste residues is in addition disposal and utilization and long-term the stacking not, not only land occupation waste resource but also contaminate environment.In addition, due to China's nickel resources scarcity, be again important strategic resource, nickel and copper have widespread use as a kind of functional materials.From iron vitriol slag compositional analysis result, the content of metallic nickel and copper reaches 3.57% and 1.88% respectively again.So, from economic benefit, resources circulation, carry out that the recycling research of valuable metal nickel and copper in nickeliferous copper junk iron vitriol dreg of yellow sodium is had to very important meaning.
At present, generally adopt that acid is molten, alkali is molten, thermolysis, cure and reclaim the methods such as valuable metal and added regent solidify and process iron vitriol slag.Molten the referring to strong acid sulfuric acid of acid dissolved former iron vitriol slag again at about 95 ℃, and sour molten technique is more numerous and diverse, complicated problem, and benefit neither be very remarkable.Baking process(of sulfonation) is that iron vitriol slag is baked at 95～100 ℃, destroys the colloidalmaterial of absorption nonferrous metal ion, then reclaims washing and dries the non-ferrous metal in thing.Obviously, baking process(of sulfonation) can not enter water to a small amount of nickel hydroxide existed in iron vitriol slag and the recovery of indissoluble Basic Chrome Sulphate, not high to the leaching yield of valuable metal.
Summary of the invention
The purpose of this invention is to provide a kind of two-step approach and extract the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, can make nickel and copper in iron vitriol dreg of yellow sodium enter water, reclaim respectively, have higher leaching yield, and technique is simple, effect is remarkable.
For achieving the above object, the technical solution adopted in the present invention is: a kind of two-step approach is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, technique is simple, the valuable metal leaching yield is higher, can fully reclaim nickel and copper in iron vitriol dreg of yellow sodium, it is characterized in that, this extracting method specifically carries out according to the following steps:
Step 1: pulverize iron vitriol dreg of yellow sodium, obtain the raw material slag;
Step 2: baking material slag;
Step 3: 1 ︰ 2.8～3.2 in mass ratio, get respectively raw material slag and the water of oven dry, the raw material slag of oven dry is added to the water, under the condition that is 80～90 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, after leaching 2～4 hours, suction filtration, the washing filter residue, obtain once soaking slag and a leaching liquid;
Step 4: with the content of nickel ion and cupric ion in leaching liquid of metric measurement; The pH value of regulating a leaching liquid with the vitriol oil is 0.9～1.1, then add ammonium sulfide solution in a leaching liquid of regulating after the pH value, under the condition that is 80～100 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, stir 30～40 minutes, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution;
1 ︰ 2.8～3.2 in mass ratio, get respectively and once soak the sulfuric acid that slag and concentration are 2mol/L, and under the condition that is 80～90 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, leaching is once soaked slag 2～4 hours, and suction filtration obtains the secondary leaching liquid; Content with cupric ion in metric measurement secondary leaching liquid, by 1.3～1.4 times of the required iron powder theoretical amount of cupric ion in reduction secondary leaching liquid, at room temperature commercially available common iron powder is added in the secondary leaching liquid, and stir 30～40 minutes with the speed of 150～200 rev/mins, filter, filter residue is the metallic copper that contains a small amount of iron, with after the dilute sulphuric acid washing, obtaining copper simple substance; Filtrate is for containing Fe
2+solution, through the ice-water bath crystallisation by cooling, obtain iron vitriol after filtration.
The inventive method completes in two steps, at first, cures slag with water extraction under certain condition, filter, and washing, obtaining rich nickel does not have the leaching liquid of iron ion containing a certain amount of copper, thus take ammonium sulfide solution separates out cupric sulfide as precipitation agent and reaches the purpose that copper nickel separates; Then, use rare H
2sO
4an above-mentioned filter residue is carried out to the secondary leaching, filter, washing, the secondary filter residue discards, secondary mother liquid contains a large amount of ferric ions and a certain amount of cupric ion, use iron powder for separating agent, copper to be separated out with the form reduction of simple substance, the ferric iron in solution is reduced into to divalence simultaneously, can obtain nearly chemical pure green vitriol FeSO after mother liquor crystallization
47H
2the O byproduct.The method is simple, and high efficiency can reach respectively 90% and 85% to the extraction yield of valuable metal nickel and copper.
The accompanying drawing explanation
Fig. 1 is the process flow sheet of extracting method of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The waste residue of deironing in wet method nickel metallurgy process-iron vitriol dreg of yellow sodium is dried the XRF compositional analysis result of sample, as shown in table 1.And carried out material phase analysis by the X-ray powder diffraction to drying the iron vitriol dreg of yellow sodium sample, through database retrieval, shown that copper in the iron vitriol dreg of yellow sodium sample is mainly with the Cu of indissoluble
4(SO
4) (OH)
6 .2H
2the O form exists, and nickel is mainly with solubility NiSO
4form exists, and also contains multiple amorphous substance simultaneously.
Table 1 iron vitriol dreg of yellow sodium XRF compositional analysis result
Table 1 demonstration, in iron vitriol dreg of yellow sodium, the content of nickel and copper reaches 3.57% and 1.88% respectively.And nickel is the important relatively deficient strategic resource of China, simultaneously, nickel and copper have widespread use as a kind of functional materials.If iron vitriol dreg of yellow sodium is banked up as melting waste slag, not only waste resource, and the land occupation contaminate environment.Therefore, adopt diverse ways to process iron vitriol dreg of yellow sodium, reclaim nickel and copper wherein, but traditional method exists the problems such as complex process, valuable metal leaching yield are lower, can not fully reclaim nickel and copper in iron vitriol dreg of yellow sodium, can not accomplish the end in view.The problem existed in order to solve traditional method, the invention provides a kind of two-step approach of extracting nickel and copper from iron vitriol dreg of yellow sodium, improves the leaching yield of nickel and copper, makes the extraction yield of nickel and copper reach respectively 90% and 85%, and resource is fully used.Extracting method of the present invention specifically carries out according to the following steps:
Step 1: pulverize iron vitriol dreg of yellow sodium, agglomerate body is become to grain of rice size, obtain thinner raw material slag;
Step 2: the raw material slag is placed in to dry 6～8 hours of the environment of 90 ℃～100 ℃;
Step 3: 1 ︰ 2.8～3.2 in mass ratio, get respectively raw material slag and the water of oven dry, the raw material slag of oven dry is added to the water, under the condition that is 80～90 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, after leaching 2～4 hours, suction filtration, the washing filter residue, obtain once soaking slag and a leaching liquid;
Step 4: with the content of nickel ion and cupric ion in leaching liquid of metric measurement; The pH that regulates a leaching liquid with the commercially available vitriol oil (concentration is 18.4 mol/L) is 0.9～1.1, then to commercially available 8% the ammonium sulfide solution that adds certain volume in a leaching liquid of regulating after the pH value, the concrete calculating of ammonium sulfide solution volume used: due to about sulfur-bearing 0.0025mol in 1mL 8% ammonium sulfide, therefore be multiplied by 1.6～1.8 again divided by 0.0025 with cupric ion mole number in leaching liquid, the numerical value calculated is the volume of ammonium sulfide used; Under the condition that is 80～100 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, stir 30～40 minutes, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution;
1 ︰ 2.8～3.2 in mass ratio, get respectively and once soak the sulfuric acid that slag and concentration are 2mol/L, and under the condition that is 80～90 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, leaching is once soaked slag 2～4 hours, and suction filtration obtains the secondary leaching liquid; Content with cupric ion and iron ion in metric measurement secondary leaching liquid, by 1.3～1.4 times of the required iron powder theoretical amount of cupric ion in reduction secondary leaching liquid, at room temperature commercially available common iron powder is added in the secondary leaching liquid, and stir 30～40 minutes with the speed of 150～200 rev/mins, filter, filter residue is the metallic copper that contains a small amount of iron, with after the dilute sulphuric acid washing, obtaining copper simple substance; Filtrate is for containing Fe
2+solution, through the ice-water bath crystallisation by cooling, obtain green vitriol (FeSO after filtration
47H
2o) byproduct.
Extract the method for valuable metal nickel and copper the waste residue that the present invention produces from yellow modumite deferrization process, complete in two steps, at first, cure slag with water extraction under certain condition, filter, washing, obtaining rich nickel does not have the leaching liquid of iron ion containing a certain amount of copper, thus take ammonium sulfide solution separates out cupric sulfide as precipitation agent and reaches the purpose that copper nickel separates; Then, use rare H
2sO
4an above-mentioned filter residue is carried out to the secondary leaching, filter, washing, the secondary filter residue discards, secondary mother liquid contains a large amount of ferric ions and a certain amount of cupric ion, use iron powder for separating agent, copper to be separated out with the form reduction of simple substance, the ferric iron in solution is reduced into to divalence simultaneously, can obtain nearly chemical pure green vitriol byproduct after mother liquor crystallization.The method is simple, and high efficiency can reach respectively 90% and 85% to the extraction yield of valuable metal nickel and copper.
The reason that the rationale of the inventive method and some important parameters are chosen:
1) aboutthe leaching valuable metal
Consider that the gelatinous precipitate formed in the iron vitriol dreg of yellow sodium iron removal has stronger adsorptive power to nonferrous metal ion and yellow modumite can be carried the wrapping portion non-ferrous metal secretly in filtration procedure, so, iron vitriol dreg of yellow sodium is pulverized, and cure and dry be necessary to destroy colloidalmaterial at 90～100 ℃, if the too high meeting of stoving temperature causes iron vitriol dreg of yellow sodium, decompose, stoving temperature can not effectively destroy colloidalmaterial lower than 90 ℃.
The application's applicant is leaching agent by the dilute sulphuric acid that makes water, different concns, a series of condition experiments have been carried out, investigated the impact of iron vitriol dreg of yellow sodium bake out temperature on leaching rate, the impact of the factors such as leaching agent concentration, solid-to-liquid ratio, leaching temperature and leaching time on leaching rate.Experimental result shows: the slag leaching rate that the slag ratio that (1) use was cured was not cured is high; (2) leaching time is longer, and nickel, copper leaching rate are higher, selects leaching time 2～4 h to be advisable; (3) leaching rate of ambrose alloy increases along with the rising of temperature, and selecting leaching temperature is 80～90 ℃, and this also approaches with stoving temperature, with conserve energy; (4) solution acidity is little on the leaching of nickel impact, but the high leaching rate to copper and iron of solution acidity is all high, but and the low leaching rate to nickel of solution acidity also the high leaching rate to iron is low.Consider that yellow modumite forms under acidic conditions, therefore, the selection water is leaching agent.And find that when solid-to-liquid ratio the pH value of solution is in 3 left and right during at 1 ︰ 2.8～3.2, this is just Fe
3+precipitation needs the pH value of controlling fully, and under this experiment condition, yellow modumite is difficult to decompose, even be partly dissolved, iron ion also can be separated out Fe (OH)
3precipitation, therefore not having obvious amount iron ion enters liquid phase, this loaded down with trivial details operation of deironing while having avoided ambrose alloy to separate, this is a remarkable advantage of present method.In addition, under this pH value condition, a small amount of nickel hydroxide precipitate existed in iron vitriol dreg of yellow sodium also can be dissolved, and meanwhile, the Basic Chrome Sulphate precipitation existed in iron vitriol dreg of yellow sodium also has and is partly dissolved.When solid-to-liquid ratio is less than 1 ︰ 2.8, pH increases, and is unfavorable for nickel hydroxide and Basic Chrome Sulphate resolution of precipitate, also can make leaching liquid excessively rare simultaneously; When solid-to-liquid ratio is greater than 1 ︰ 3.2, pH reduces, and iron vitriol dreg of yellow sodium has and is partly dissolved, and just has a large amount of iron ions in leaching liquid, causes the difficulty on later separation.(5) stir speed (S.S.) is little on the leaching rate impact, is chosen in 100～150 rev/mins and is advisable.
Because copper in iron vitriol dreg of yellow sodium mainly exists with the Basic Chrome Sulphate form of indissoluble, water or diluted acid are limited to the leaching of copper, must be with denseer acid that sulfuric acid secondary that concentration is 2mol/L soaks molten, and such two steps operations just can realize the high extraction of copper.Use the sulfuric acid to leach of 2mol/L once to soak slag, can make most of dissolving of Basic Chrome Sulphate precipitation existed in iron vitriol dreg of yellow sodium, reached the index request of cupric ion extraction yield more than 80%; If sulfuric acid concentration lower than 2mol/L, dissolves Basic Chrome Sulphate, precipitation is limited, and the leaching rate of cupric ion is not high; If sulfuric acid concentration is greater than 2mol/L, iron vitriol dreg of yellow sodium dissolves too much, separates to follow-up copper iron and brings difficulty.Therefore, select the sulfuric acid to leach of 2mol/L once to soak slag.Other processing parameter is with once leaching experiment.
) about copper nickel in leaching liquid, separate
Utilize the difference of CuS and NiS solubleness, control the pH value of a leaching liquid, take ammonium sulfide as precipitation agent, make the Cu in leaching liquid one time
2+fully Precipitation and Ni
2+substantially do not separate out.
Selecting ammonium sulfide in the inventive method is precipitation agent and without sodium sulphite, be because the alkalescence of ammonium sulfide than sodium sulphite a little less than, on itself being that the pH value impact of acid leaching solution is little, the loss of minimizing nickel; And sodium sulphite alkalescence is strong, may be because local overrich can make a part of nickel ion precipitation.Testing 8% ammonium sulfide solution used (its concentration 8% is calculated according to sulphur content) is commercial reagent, directly uses, if the dilution ammonium sulfide solution can be unfavorable for the cupric ion precipitation fully because two hydrolytic action runs off the part sulfonium ion, also can cause waste.Regulating the pH value of a leaching liquid with the vitriol oil, is because the vitriol oil is commercially available ready-made reagent on the one hand, if the dilution use can make the volume of solution increase obviously on the other hand, copper ion concentration is reduced and is unfavorable for that its precipitation is complete.
By exploring condition experiment, find, the factor that affects the ambrose alloy separation has temperature, acidity, churning time, sulphur copper mol ratio etc.Experimental result shows:, along with acidity reduces, the eduction rate of nickel increases gradually (1), and the eduction rate of copper changes not quite.Because the pH value of a leaching liquid increases, the NiS precipitation forms and heats not soluble gradually, and CuS just can form when acidity is larger.Select the pH value of a leaching liquid to be advisable with 1 left and right.(2) along with the prolongation of churning time, the eduction rate of nickel is reducing gradually, and the eduction rate of copper changes not quite.The CuS that may just start to form is gelatinous precipitate, can the absorbed Ni ion, and have the NiS Precipitation because of local overrich while just having started, when heated and stirred, destroyed the CuS colloid, and also be conducive to NiS and be deposited in acidic solution and dissolve.Churning time is advisable with 30～40min.(3) along with the rising of temperature, the nickel eduction rate reduces gradually, and the eduction rate of copper changes not quite, because temperature raises, is conducive to destroy the CuS colloid and is conducive to the dissolving of NiS in acidic solution.Select temperature to be advisable with 80～100 ℃.(4) along with the increase of sulphur copper mol ratio, the eduction rate of nickel increases gradually, and the rate of removing of copper also increases rear constant.Because the sulfonium ion increased content, can form the NiS precipitation and the nickel eduction rate is increased, therefore selecting the S/Cu mol ratio is 1.6～1.8 to be advisable.
) about copper iron in the secondary leaching liquid, separate
Utilize the principle of iron powder reducing copper that copper is separated out with the form of simple substance, the ferric ion in solution can be reduced into to divalence simultaneously, can obtain nearly chemical pure green vitriol FeSO after mother liquor crystallization
47H
2the O byproduct.
By exploring condition experiment, find: (1) temperature does not have great impact to iron powder reducing, is because this redox processes itself is exactly the process of a heat release, therefore needn't heat, and under normal temperature, carries out; (2) add-on of iron powder should very little, can not by the displacement of the cupric ion in solution fully, can not cause because the ferrous ion concentration in solution is too high remaining iron powder to be difficult to mix with acid-respons and copper very little too much.Determine and take 1.3～1.4 times be advisable (theoretical molar numbers that theoretical amount follows ferric ion and cupric ion all to react completely as iron powder) of theoretical amount; (3) in order to increase the liquid-solid reaction contact surface, need comparatively strong stirring that iron powder is suspended as far as possible in solution, 150～200 rev/mins of stir speed (S.S.)s are advisable; (4) the too short iron powder reaction of churning time is not thorough, with 30～40 minutes, is advisable.
embodiment 1
Iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size, takes 40g this raw material slag 95 ℃ of oven dry, with 120 mL water, under 85 ℃, with 100 rev/mins of stir speed (S.S.)s, leach 2 hours, suction filtration also washs filter residue, obtains once soaking slag and a leaching liquid.Leach 2 hour with 100 rev/mins of stir speed (S.S.)s with the sulfuric acid of 120 mL 2 mol/L under 85 ℃ again once soaking slag, suction filtration obtains the secondary leaching liquid, and the secondary filter residue discards.Get leaching liquid of 100mL, with the vitriol oil, adjust a leaching liquid pH to 1, add 8% ammonium sulfide solution precipitation agent 2.3 mL, stir 30 minutes under 80 ℃ with 150 rev/mins, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution.Get 100mL secondary leaching liquid at room temperature, the 4.1g iron powder is joined in the secondary leaching liquid and reduces, with 150 rev/mins of stirrings 30 minutes, filter, filter residue is metallic copper, and filtrate can obtain green vitriol FeSO through the frozen water crystallisation by cooling
47H
2the O byproduct, its purity is in 97% left and right.Extraction yield 91%, two step of valuable metal nickel adds up to valuable metal copper extraction yield 85%.
embodiment 2
Iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size, takes 400g this raw material slag 95 ℃ of oven dry, with 1200 mL water, under 85 ℃, with 100 rev/mins of stir speed (S.S.)s, leach 2 hours, suction filtration washing, obtain once soaking slag and a leaching liquid.Leach 2 hour with 100 rev/mins of stir speed (S.S.)s with the sulfuric acid of 1200 mL 2 mol/L under 85 ℃ again once soaking slag, suction filtration obtains the secondary leaching liquid, and the secondary filter residue discards.Get leaching liquid of 100mL, with the vitriol oil, adjust a leaching liquid pH to 1, add 8% ammonium sulfide solution precipitation agent 2.2 mL, stir 30 minutes under 80 ℃ with 150 rev/mins, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution.Get 100mL secondary leaching liquid at room temperature, the 3.9g iron powder is joined in the secondary leaching liquid and reduces, with 150 rev/mins of stirrings 30 minutes, filter, filter residue is metallic copper, and filtrate can obtain green vitriol FeSO through the frozen water crystallisation by cooling
47H
2the O byproduct, its purity is in 97% left and right.Extraction yield 91%, two step of valuable metal nickel adds up to valuable metal copper extraction yield 83%.
embodiment 3
Iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size, takes 800 g this raw material slag 95 ℃ of oven dry, with 2400 mL water, under 85 ℃, with 100 rev/mins of stir speed (S.S.)s, leach 2 hours, suction filtration washing, obtain once soaking slag and a leaching liquid.Leach 2 hour with 100 rev/mins of stir speed (S.S.)s with the sulfuric acid of 2400 mL 2 mol/L under 85 ℃ again once soaking slag, suction filtration obtains the secondary leaching liquid, and the secondary filter residue discards.Get leaching liquid of 100mL, with the vitriol oil, adjust a leaching liquid pH to 1, add 8% ammonium sulfide solution precipitation agent 2.4mL, stir 30 minutes under 80 ℃ with 150 rev/mins, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution.Get 100mL secondary leaching liquid at room temperature, the 3.7g iron powder is joined in the secondary leaching liquid and reduces, with 150 rev/mins of stirrings 30 minutes, filter, filter residue is metallic copper, and filtrate can obtain green vitriol FeSO through the frozen water crystallisation by cooling
47H
2the O byproduct, its purity is in 97% left and right.Extraction yield 89 % of valuable metal nickel, two steps add up to valuable metal copper extraction yield 81%.
embodiment 4
Iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size; The raw material slag is placed in to dry 8 hours of the environment of 90 ℃; 1 ︰ 2.8, get respectively raw material slag and the water of oven dry in mass ratio, the raw material slag of oven dry is added to the water, and under the condition that is 80 ℃ in 150 rev/mins of stir speed (S.S.)s, temperature, after leaching 4 hours, suction filtration, the washing filter residue, obtain once soaking slag and a leaching liquid; Content with nickel ion and cupric ion in leaching liquid of metric measurement; The pH that the vitriol oil that is 18.4 mol/L by commercially available concentration is regulated a leaching liquid is 0.9, then to commercially available 8% the ammonium sulfide solution that adds certain volume in a leaching liquid of regulating after the pH value, the concrete calculating of ammonium sulfide solution volume used: be multiplied by 1.6 again divided by 0.0025 with cupric ion mole number in leaching liquid, the numerical value calculated is the volume of ammonium sulfide used; Under the condition that is 100 ℃ in 125 rev/mins of stir speed (S.S.)s, temperature, stir 30 minutes, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution; 1 ︰ 3.2 in mass ratio, get respectively and once soak the sulfuric acid that slag and concentration are 2mol/L, and under the condition that is 80 ℃ in 100 rev/mins of stir speed (S.S.)s, temperature, leaching is once soaked slag 4 hours, and suction filtration obtains the secondary leaching liquid; Content with cupric ion in metric measurement secondary leaching liquid, by 1.3 times of the required iron powder theoretical amount of cupric ion in reduction secondary leaching liquid, at room temperature commercially available common iron powder is added in the secondary leaching liquid, and stir 30 minutes with the speed of 200 rev/mins, filter, filter residue is metallic copper, and filtrate obtains green vitriol (FeSO through the ice-water bath crystallisation by cooling
47H
2o) byproduct.
embodiment 5
Iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size; The raw material slag is placed in to dry 6 hours of the environment of 100 ℃; 1 ︰ 3.2, get respectively raw material slag and the water of oven dry in mass ratio, the raw material slag of oven dry is added to the water, and under the condition that is 85 ℃ in 125 rev/mins of stir speed (S.S.)s, temperature, after leaching 3 hours, suction filtration, the washing filter residue, obtain once soaking slag and a leaching liquid; Content with nickel ion and cupric ion in leaching liquid of metric measurement; The pH that the vitriol oil that is 18.4 mol/L by commercially available concentration is regulated a leaching liquid is 1.1, then to commercially available 8% the ammonium sulfide solution that adds certain volume in a leaching liquid of regulating after the pH value, the concrete calculating of ammonium sulfide solution volume used: this is multiplied by 1.8 again divided by 0.0025 with cupric ion mole number in leaching liquid, and the numerical value calculated is the volume of ammonium sulfide used; Under the condition that is 80 ℃ in 150 rev/mins of stir speed (S.S.)s, temperature, stir 40 minutes, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution; 1 ︰ 2.8 in mass ratio, get respectively and once soak the sulfuric acid that slag and concentration are 2mol/L, and under the condition that is 90 ℃ in 150 rev/mins of stir speed (S.S.)s, temperature, leaching is once soaked slag 2 hours, and suction filtration obtains the secondary leaching liquid; Content with cupric ion in metric measurement secondary leaching liquid, by 1.4 times of the required iron powder theoretical amount of cupric ion in reduction secondary leaching liquid, at room temperature commercially available common iron powder is added in the secondary leaching liquid, and stir 40 minutes with the speed of 150 rev/mins, filter, filter residue is metallic copper, and filtrate obtains green vitriol (FeSO through the ice-water bath crystallisation by cooling
47H
2o) byproduct.
embodiment 6
Iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size; The raw material slag is placed in to dry 7 hours of the environment of 95 ℃; 1 ︰ 2.9, get respectively raw material slag and the water of oven dry in mass ratio, the raw material slag of oven dry is added to the water, and under the condition that is 90 ℃ in 100 rev/mins of stir speed (S.S.)s, temperature, after leaching 2 hours, suction filtration, the washing filter residue, obtain once soaking slag and a leaching liquid; Content with nickel ion and cupric ion in leaching liquid of metric measurement; The pH that the vitriol oil that is 18.4 mol/L by commercially available concentration is regulated a leaching liquid is 1, then to commercially available 8% the ammonium sulfide solution that adds certain volume in a leaching liquid of regulating after the pH value, the concrete calculating of ammonium sulfide solution volume used: be multiplied by 1.7 again divided by 0.0025 with cupric ion mole number in leaching liquid, the numerical value calculated is the volume of ammonium sulfide used; Under the condition that is 90 ℃ in 100 rev/mins of stir speed (S.S.)s, temperature, stir 35 minutes, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution; 1 ︰ 3.1 in mass ratio, get respectively and once soak the sulfuric acid that slag and concentration are 2mol/L, and under the condition that is 85 ℃ in 125 rev/mins of stir speed (S.S.)s, temperature, leaching is once soaked slag 3 hours, and suction filtration obtains the secondary leaching liquid; Content with cupric ion in metric measurement secondary leaching liquid, by 1.35 times of the required iron powder theoretical amount of cupric ion in reduction secondary leaching liquid, at room temperature commercially available common iron powder is added in time leaching liquid, and stir 35 minutes with the speed of 175 rev/mins, filter, filter residue is metallic copper, and filtrate obtains green vitriol (FeSO through the ice-water bath crystallisation by cooling
47H
2o) byproduct.
Claims (5)
1. a two-step approach is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, and technique is simple, and the valuable metal leaching yield is higher, can fully reclaim nickel and copper in iron vitriol dreg of yellow sodium, it is characterized in that, this extracting method specifically carries out according to the following steps:
Step 1: pulverize iron vitriol dreg of yellow sodium, obtain the raw material slag;
Step 2: baking material slag;
Step 3: 1 ︰ 2.8～3.2 in mass ratio, get respectively raw material slag and the water of oven dry, the raw material slag of oven dry is added to the water, under the condition that is 80～90 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, after leaching 2～4 hours, suction filtration, the washing filter residue, obtain once soaking slag and a leaching liquid;
Step 4: with the content of nickel ion and cupric ion in leaching liquid of metric measurement; The pH value of regulating a leaching liquid with the vitriol oil is 0.9～1.1, then add ammonium sulfide solution in a leaching liquid of regulating after the pH value, under the condition that is 80～100 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, stir 30～40 minutes, filter, solid phase is the cupric sulfide precipitated fully, and mother liquor is nickel sulfate solution;
1 ︰ 2.8～3.2 in mass ratio, get respectively and once soak the sulfuric acid that slag and concentration are 2mol/L, and under the condition that is 80～90 ℃ in 100～150 rev/mins of stir speed (S.S.)s, temperature, leaching is once soaked slag 2～4 hours, and suction filtration obtains the secondary leaching liquid; Content with cupric ion in metric measurement secondary leaching liquid, by 1.3～1.4 times of the required iron powder theoretical amount of cupric ion in reduction secondary leaching liquid, at room temperature commercially available common iron powder is added in the secondary leaching liquid, and stir 30～40 minutes with the speed of 150～200 rev/mins, filter, filter residue is the metallic copper that contains a small amount of iron, with after the dilute sulphuric acid washing, obtaining copper simple substance; Filtrate is for containing Fe
2+solution, through the ice-water bath crystallisation by cooling, obtain iron vitriol after filtration.
2. two-step approach as claimed in claim 1 is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, it is characterized in that, in described step 1, iron vitriol dreg of yellow sodium is ground into to the raw material slag of grain of rice size.
3. two-step approach as claimed in claim 1 is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, it is characterized in that, in described step 2, the raw material slag is placed in to dry 6～8 hours of the environment of 90 ℃～100 ℃.
4. two-step approach as claimed in claim 1 is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, it is characterized in that, it is 0.9～1.1 that described step 4 adopts the pH value of the leaching liquid of vitriol oil adjusting that commercially available concentration is 18.4 mol/L.
5. two-step approach as claimed in claim 1 is extracted the method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, it is characterized in that, the ammonium sulfide solution of using in described step 4 is the ammonium sulfide solution that commercially available concentration is 8%, the volume of ammonium sulfide solution used is: be multiplied by 1.6～1.8 again divided by 0.0025 with cupric ion mole number in leaching liquid, the numerical value calculated is the volume of ammonium sulfide used.
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| Publication number | Priority date | Publication date | Assignee | Title |
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