CN103114205B - 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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- CN103114205B CN103114205B CN201210522191.9A CN201210522191A CN103114205B CN 103114205 B CN103114205 B CN 103114205B CN 201210522191 A CN201210522191 A CN 201210522191A CN 103114205 B CN103114205 B CN 103114205B
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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 producing from 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, in the time 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 wet method nickel metallurgy, and the separation of iron, nickel is exactly to adopt this technological process.
Ihleite method is the iron ion that first iron is oxidized to trivalent, and ferric ion is containing Na
+, K
+, NH
4 +in isoionic sulfate liquor, be easy to form faint yellow compd A
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
+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.But can produce in this way a large amount of waste residues, the iron of often removing 1kg just has the ihleite waste residue of 2.5～3.0kg to generate.And because following three reasons make to contain the non-ferrous metals such as a certain amount of nickel, copper in ihleite waste residue, cause the loss of valuable metal: 1) iron vitriol dreg of yellow sodium iron removal has 5%～8% Fe (OH)
3form, in slag, also contain SiO
2deng amorphous sediment, this colloidal precipitation has stronger adsorptive power to nonferrous metal ion; 2) yellow modumite can be carried 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 needs to 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 pH value raises or is heated and will be hydrolyzed or decompose the environmentally harmful material of generation.If not disposal and utilization and stacking for a long time in addition of a large amount of ihleite waste residues, 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 acid-soluble, alkali is molten, thermolysis, cure and reclaim the methods such as valuable metal and added regent solidify and process iron vitriol slag.Acid-soluble referring to dissolved former iron vitriol slag at about 95 DEG C again with strong acid sulfuric acid, and acid-soluble technique is more numerous and diverse, and problem is complicated, and benefit neither be very remarkable.Baking process(of sulfonation) is that iron vitriol slag is baked at 95～100 DEG C, 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 a small amount of nickel hydroxide existing 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 object of this invention is to provide a kind of two-step approach and from iron vitriol dreg of yellow sodium, extract the method for valuable metal nickel and copper, 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, 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 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, be, under the condition of 80～90 DEG C, to leach after 2～4 hours suction filtration in 100～150 revs/min of stir speed (S.S.)s, temperature, washing filter residue, is once soaked slag and a leaching liquid;
Step 4: with the content of nickel ion and cupric ion in leaching liquid of metric measurement; Regulating the pH value of a leaching liquid with the vitriol oil is 0.9～1.1, then in the leaching liquid regulating after pH value, add ammonium sulfide solution, be under the condition of 80～100 DEG C in 100～150 revs/min of stir speed (S.S.)s, temperature, stir 30～40 minutes, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution;
1 ︰ 2.8～3.2 in mass ratio, gets respectively and once soaks the sulfuric acid that slag and concentration are 2mol/L, is that under the condition of 80～90 DEG C, leaching is once soaked slag 2～4 hours in 100～150 revs/min of stir speed (S.S.)s, temperature, and suction filtration obtains secondary leaching liquid; With the content of 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 secondary leaching liquid, and stir 30～40 minutes with the speed of 150～200 revs/min, filter, filter residue is the metallic copper that contains a small amount of iron, with obtaining copper simple substance after dilute sulphuric acid washing; Filtrate is for containing Fe
2+solution, through ice-water bath crystallisation by cooling, after filtration, obtain iron vitriol.
The inventive method completes in two steps, first, cures slag under certain condition with water extraction, filter, and washing, obtaining rich nickel does not have the leaching liquid of iron ion containing a certain amount of copper, reach thereby separate out cupric sulfide taking ammonium sulfide solution as precipitation agent the object that copper nickel separates; Then, use rare H
2sO
4an above-mentioned filter residue is carried out to secondary leaching, filter, washing, 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 divalence simultaneously, after mother liquor crystallization, can obtain nearly chemical pure green vitriol FeSO
47H
2o byproduct.The method is simple, and high efficiency can reach respectively 90% and 85% to the extraction yield of valuable metal nickel and copper.
Brief description of the drawings
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 carry out material phase analysis by X-ray powder diffraction to drying iron vitriol dreg of yellow sodium sample, through database retrieval, shown that copper in iron vitriol dreg of yellow sodium sample is mainly with the Cu of indissoluble
4(SO
4) (OH)
6 .2H
2o 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 shows, the content of nickel and copper respectively nearly 3.57% and 1.88% in iron vitriol dreg of yellow sodium.And nickel is the important relatively deficient strategic resource of China, meanwhile, 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 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 existing 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 environment that raw material slag is placed in to 90 DEG C～100 DEG C is dried 6～8 hours;
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, be, under the condition of 80～90 DEG C, to leach after 2～4 hours suction filtration in 100～150 revs/min of stir speed (S.S.)s, temperature, washing filter residue, is once soaked slag and a leaching liquid;
Step 4: with the content of nickel ion and cupric ion in leaching liquid of metric measurement; Regulating the pH of 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 the leaching liquid regulating after 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 a leaching liquid, the numerical value calculating is the volume of ammonium sulfide used; Be, under the condition of 80～100 DEG C, to stir 30～40 minutes in 100～150 revs/min of stir speed (S.S.)s, temperature, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution;
1 ︰ 2.8～3.2 in mass ratio, gets respectively and once soaks the sulfuric acid that slag and concentration are 2mol/L, is that under the condition of 80～90 DEG C, leaching is once soaked slag 2～4 hours in 100～150 revs/min of stir speed (S.S.)s, temperature, and suction filtration obtains secondary leaching liquid; With the content of 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 secondary leaching liquid, and stir 30～40 minutes with the speed of 150～200 revs/min, filter, filter residue is the metallic copper that contains a small amount of iron, with obtaining copper simple substance after dilute sulphuric acid washing; Filtrate is for containing Fe
2+solution, through ice-water bath crystallisation by cooling, after filtration, obtain green vitriol (FeSO
47H
2o) byproduct.
The waste residue that the present invention produces from yellow modumite deferrization process, extract the method for valuable metal nickel and copper, complete in two steps, 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, reach thereby separate out cupric sulfide taking ammonium sulfide solution as precipitation agent the object that copper nickel separates; Then, use rare H
2sO
4an above-mentioned filter residue is carried out to secondary leaching, filter, washing, 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 divalence simultaneously, after mother liquor crystallization, can obtain nearly chemical pure green vitriol 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 reason that the rationale of the inventive method and some important parameters are chosen:
1) aboutleaching valuable metal
Consider that the gelatinous precipitate forming in iron vitriol dreg of yellow sodium iron removal has stronger adsorptive power to nonferrous metal ion and yellow modumite can be carried 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 DEG C, decompose if the too high meeting of stoving temperature causes iron vitriol dreg of yellow sodium, stoving temperature can not effectively destroy colloidalmaterial lower than 90 DEG C.
The application's applicant is leaching agent by making the dilute sulphuric acid of water, different concns, a series of condition experiments are carried out, investigate the impact of iron vitriol dreg of yellow sodium bake out temperature on leaching rate, the impacts of factor on leaching rate such as leaching agent concentration, solid-to-liquid ratio, leaching temperature and leaching time.Experimental result shows: the slag leaching rate that (1) is used the slag ratio of curing not cure 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 DEG C, and this also approaches with stoving temperature, with conserve energy; (4) solution acidity is little on the leaching impact of nickel, but solution acidity is high all high to the leaching rate of copper and iron, but and solution acidity is low low to the leaching rate of the nickel also high leaching rate to iron.Consider that yellow modumite forms under acidic conditions, therefore, selection water is leaching agent.And find that the pH value of solution is in 3 left and right when solid-to-liquid ratio is during at 1 ︰ 2.8～3.2, this is just Fe
3+precipitation needs the pH value of controlling completely, and under this experiment condition, yellow modumite is difficult to decompose, even if be partly dissolved, iron ion also can be separated out Fe (OH)
3precipitation, does not therefore have obvious amount iron ion and enters liquid phase, this loaded down with trivial details operation of deironing while having avoided ambrose alloy to separate, and this is a remarkable advantage of present method.In addition, under this pH value condition, a small amount of nickel hydroxide precipitate existing in iron vitriol dreg of yellow sodium also can be dissolved, and meanwhile, the Basic Chrome Sulphate precipitation existing in iron vitriol dreg of yellow sodium also has and is partly dissolved.In the time that 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; In the time that 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 in later separation.(5) stir speed (S.S.) is little on leaching rate impact, is chosen in 100～150 revs/min 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 that concentration is that the sulfuric acid secondary of 2mol/L soaks with denseer acid 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 the Basic Chrome Sulphate precipitation major part existing in iron vitriol dreg of yellow sodium dissolve, reached more than 80% index request of cupric ion extraction yield; 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.
) separate about copper nickel in a leaching liquid
Utilize the difference of CuS and NiS solubleness, control the pH value of a leaching liquid, taking ammonium sulfide as precipitation agent, make the Cu in leaching liquid one time
2+completely Precipitation and Ni
2+substantially do not separate out.
In the inventive method, selecting ammonium sulfide 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 dilution ammonium sulfide solution can, because two hydrolytic action runs off part sulfonium ion, be unfavorable for cupric ion precipitation completely, 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 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.
Find by exploring condition experiment, affect ambrose alloy separation because have temperature, acidity, churning time, sulphur copper mol ratio etc.Experimental result shows: (1), along with acidity reduces, the eduction rate of nickel increases gradually, and the eduction rate of copper changes not quite.Because the pH value of a leaching liquid increases, NiS precipitation forms and heats not soluble gradually, and CuS just can form in the time that 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 absorbed Ni ion, and while just having started because local overrich has NiS Precipitation, in the time of heated and stirred, destroyed CuS colloid, be also 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, nickel eduction rate reduces gradually, and the eduction rate of copper changes not quite, is conducive to destroy CuS colloid and is conducive to the dissolving of NiS in acidic solution because temperature raises.Select temperature to be advisable with 80～100 DEG C.(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 sulfonium ion increased content, can form NiS precipitation and nickel eduction rate is increased, therefore selecting S/Cu mol ratio is 1.6～1.8 to be advisable.
) separate about copper iron in secondary leaching liquid
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 divalence simultaneously, after mother liquor crystallization, can obtain nearly chemical pure green vitriol FeSO
47H
2o byproduct.
Finding by exploring condition experiment: (1) temperature does not have great impact to iron powder reducing, is because redox processes itself is for this reason 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 cupric ion displacement in solution completely, 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 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) taking theoretical amount; (3) in order to increase liquid-solid reaction contact surface, need comparatively strong stirring that iron powder is suspended as far as possible in solution, 150～200 revs/min of stir speed (S.S.)s are advisable; (4) the too short iron powder reaction of churning time is not thorough, is advisable with 30～40 minutes.
embodiment 1
Iron vitriol dreg of yellow sodium is ground into the raw material slag of grain of rice size, takes 40g this raw material slag 95 DEG C of oven dry, with 120 mL water at 85 DEG C with 100 revs/min of stir speed (S.S.)s leaching 2 hours, suction filtration also washs filter residue, is once soaked slag and a leaching liquid.At 85 DEG C, leach 2 hour with 100 revs/min of stir speed (S.S.)s with the sulfuric acid of 120 mL 2 mol/L again once soaking slag, suction filtration obtains secondary leaching liquid, and secondary filter residue discards.Get leaching liquid of 100mL, adjust a leaching liquid pH to 1 with the vitriol oil, add 8% ammonium sulfide solution precipitation agent 2.3 mL, stir 30 minutes with 150 revs/min at 80 DEG C, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution.Get bis-leaching liquids of 100mL at room temperature, 4.1g iron powder is joined in secondary leaching liquid and reduced, with 150 revs/min of stirrings 30 minutes, filter, filter residue is metallic copper, and filtrate can obtain green vitriol FeSO through frozen water crystallisation by cooling
47H
2o 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 the raw material slag of grain of rice size, takes 400g this raw material slag 95 DEG C of oven dry, with 1200 mL water at 85 DEG C with 100 revs/min of stir speed (S.S.)s leaching 2 hours, suction filtration washing, once soaked slag and a leaching liquid.At 85 DEG C, leach 2 hour with 100 revs/min of stir speed (S.S.)s with the sulfuric acid of 1200 mL 2 mol/L again once soaking slag, suction filtration obtains secondary leaching liquid, and secondary filter residue discards.Get leaching liquid of 100mL, adjust a leaching liquid pH to 1 with the vitriol oil, add 8% ammonium sulfide solution precipitation agent 2.2 mL, stir 30 minutes with 150 revs/min at 80 DEG C, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution.Get bis-leaching liquids of 100mL at room temperature, 3.9g iron powder is joined in secondary leaching liquid and reduced, with 150 revs/min of stirrings 30 minutes, filter, filter residue is metallic copper, and filtrate can obtain green vitriol FeSO through frozen water crystallisation by cooling
47H
2o 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 the raw material slag of grain of rice size, takes 800 g this raw material slag 95 DEG C of oven dry, with 2400 mL water at 85 DEG C with 100 revs/min of stir speed (S.S.)s leaching 2 hours, suction filtration washing, once soaked slag and a leaching liquid.At 85 DEG C, leach 2 hour with 100 revs/min of stir speed (S.S.)s with the sulfuric acid of 2400 mL 2 mol/L again once soaking slag, suction filtration obtains secondary leaching liquid, and secondary filter residue discards.Get leaching liquid of 100mL, adjust a leaching liquid pH to 1 with the vitriol oil, add 8% ammonium sulfide solution precipitation agent 2.4mL, stir 30 minutes with 150 revs/min at 80 DEG C, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution.Get bis-leaching liquids of 100mL at room temperature, 3.7g iron powder is joined in secondary leaching liquid and reduced, with 150 revs/min of stirrings 30 minutes, filter, filter residue is metallic copper, and filtrate can obtain green vitriol FeSO through frozen water crystallisation by cooling
47H
2o 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 the raw material slag of grain of rice size; The environment that raw material slag is placed in to 90 DEG C is dried 8 hours; 1 ︰ 2.8 in mass ratio, gets respectively raw material slag and the water of oven dry, and the raw material slag of oven dry is added to the water, in 150 revs/min of stir speed (S.S.)s, temperature be, under the condition of 80 DEG C, to leach after 4 hours, and suction filtration, washing filter residue, is once soaked slag and a leaching liquid; With the content of nickel ion and cupric ion in leaching liquid of metric measurement; Regulating the pH of a leaching liquid with the vitriol oil that commercially available concentration is 18.4 mol/L is 0.9, then to commercially available 8% the ammonium sulfide solution that adds certain volume in the leaching liquid regulating after 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 a leaching liquid, the numerical value calculating is the volume of ammonium sulfide used; Be, under the condition of 100 DEG C, to stir 30 minutes in 125 revs/min of stir speed (S.S.)s, temperature, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution; 1 ︰ 3.2 in mass ratio, gets respectively and once soaks the sulfuric acid that slag and concentration are 2mol/L, is that under the condition of 80 DEG C, leaching is once soaked slag 4 hours in 100 revs/min of stir speed (S.S.)s, temperature, and suction filtration obtains secondary leaching liquid; With the content of 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 secondary leaching liquid, and stir 30 minutes with the speed of 200 revs/min, filter, filter residue is metallic copper, and filtrate obtains green vitriol (FeSO through ice-water bath crystallisation by cooling
47H
2o) byproduct.
embodiment 5
Iron vitriol dreg of yellow sodium is ground into the raw material slag of grain of rice size; The environment that raw material slag is placed in to 100 DEG C is dried 6 hours; 1 ︰ 3.2 in mass ratio, gets respectively raw material slag and the water of oven dry, and the raw material slag of oven dry is added to the water, in 125 revs/min of stir speed (S.S.)s, temperature be, under the condition of 85 DEG C, to leach after 3 hours, and suction filtration, washing filter residue, is once soaked slag and a leaching liquid; With the content of nickel ion and cupric ion in leaching liquid of metric measurement; Regulating the pH of a leaching liquid with the vitriol oil that commercially available concentration is 18.4 mol/L is 1.1, then to commercially available 8% the ammonium sulfide solution that adds certain volume in the leaching liquid regulating after 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 a leaching liquid, and the numerical value calculating is the volume of ammonium sulfide used; Be, under the condition of 80 DEG C, to stir 40 minutes in 150 revs/min of stir speed (S.S.)s, temperature, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution; 1 ︰ 2.8 in mass ratio, gets respectively and once soaks the sulfuric acid that slag and concentration are 2mol/L, is that under the condition of 90 DEG C, leaching is once soaked slag 2 hours in 150 revs/min of stir speed (S.S.)s, temperature, and suction filtration obtains secondary leaching liquid; With the content of 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 secondary leaching liquid, and stir 40 minutes with the speed of 150 revs/min, filter, filter residue is metallic copper, and filtrate obtains green vitriol (FeSO through ice-water bath crystallisation by cooling
47H
2o) byproduct.
embodiment 6
Iron vitriol dreg of yellow sodium is ground into the raw material slag of grain of rice size; The environment that raw material slag is placed in to 95 DEG C is dried 7 hours; 1 ︰ 2.9 in mass ratio, gets respectively raw material slag and the water of oven dry, and the raw material slag of oven dry is added to the water, in 100 revs/min of stir speed (S.S.)s, temperature be, under the condition of 90 DEG C, to leach after 2 hours, and suction filtration, washing filter residue, is once soaked slag and a leaching liquid; With the content of nickel ion and cupric ion in leaching liquid of metric measurement; Regulating the pH of a leaching liquid with the vitriol oil that commercially available concentration is 18.4 mol/L is 1, then to commercially available 8% the ammonium sulfide solution that adds certain volume in the leaching liquid regulating after 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 a leaching liquid, the numerical value calculating is the volume of ammonium sulfide used; Be, under the condition of 90 DEG C, to stir 35 minutes in 100 revs/min of stir speed (S.S.)s, temperature, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution; 1 ︰ 3.1 in mass ratio, gets respectively and once soaks the sulfuric acid that slag and concentration are 2mol/L, is that under the condition of 85 DEG C, leaching is once soaked slag 3 hours in 125 revs/min of stir speed (S.S.)s, temperature, and suction filtration obtains secondary leaching liquid; With the content of 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 revs/min, filter, filter residue is metallic copper, and filtrate obtains green vitriol (FeSO through ice-water bath crystallisation by cooling
47H
2o) byproduct.
Claims (4)
1. two-step approach is extracted a method for valuable metal nickel and copper from iron vitriol dreg of yellow sodium, and technique is simple, and 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 raw material slag;
Step 2: baking material slag, the environment that raw material slag is placed in to 90 DEG C～100 DEG C is dried 6～8 hours;
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, be, under the condition of 80～90 DEG C, to leach after 2～4 hours suction filtration in 100～150 revs/min of stir speed (S.S.)s, temperature, washing filter residue, is once soaked slag and a leaching liquid;
Step 4: with the content of nickel ion and cupric ion in leaching liquid of metric measurement; Regulating the pH value of a leaching liquid with the vitriol oil is 0.9～1.1, then in the leaching liquid regulating after pH value, add ammonium sulfide solution, be under the condition of 80～100 DEG C in 100～150 revs/min of stir speed (S.S.)s, temperature, stir 30～40 minutes, filter, solid phase is the cupric sulfide precipitating completely, and mother liquor is nickel sulfate solution;
1 ︰ 2.8～3.2 in mass ratio, gets respectively and once soaks the sulfuric acid that slag and concentration are 2mol/L, is that under the condition of 80～90 DEG C, leaching is once soaked slag 2～4 hours in 100～150 revs/min of stir speed (S.S.)s, temperature, and suction filtration obtains secondary leaching liquid; With the content of 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 secondary leaching liquid, and stir 30～40 minutes with the speed of 150～200 revs/min, filter, filter residue is the metallic copper that contains a small amount of iron, with obtaining copper simple substance after dilute sulphuric acid washing; Filtrate is for containing Fe
2+solution, through ice-water bath crystallisation by cooling, after filtration, obtain iron vitriol.
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 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, it is that to regulate the pH value of a leaching liquid be 0.9～1.1 for the vitriol oil of 18.4 mol/L that described step 4 adopts commercially available concentration.
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, 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 a leaching liquid, the numerical value calculating is the volume of ammonium sulfide used, and this volume unit is mL.
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| CN103831442B (en) * | 2014-03-11 | 2015-11-25 | 斯莱登（北京）化工科技有限公司 | A kind of method being prepared Iron concentrate by copper nickel slag |
| CN103789554B (en) * | 2014-03-11 | 2015-09-30 | 中南大学 | A kind of substep concentration difference leaching method of copper nickel slag |
| CN114045397A (en) * | 2021-10-26 | 2022-02-15 | 广东佳纳能源科技有限公司 | Method for recovering wet smelting iron slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101407355A (en) * | 2008-10-31 | 2009-04-15 | 东北大学 | Method for comprehensively utilizing iron vitriol dreg of yellow sodium |
| CN102443701A (en) * | 2010-10-12 | 2012-05-09 | 中国科学院过程工程研究所 | Clean metallurgic comprehensive utilization method of iron vitriol slags |
| CN102718267A (en) * | 2012-07-18 | 2012-10-10 | 广西大学 | Method for preparing black iron oxide by utilizing yellow ammonium iron alum slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101407355A (en) * | 2008-10-31 | 2009-04-15 | 东北大学 | Method for comprehensively utilizing iron vitriol dreg of yellow sodium |
| CN102443701A (en) * | 2010-10-12 | 2012-05-09 | 中国科学院过程工程研究所 | Clean metallurgic comprehensive utilization method of iron vitriol slags |
| CN102718267A (en) * | 2012-07-18 | 2012-10-10 | 广西大学 | Method for preparing black iron oxide by utilizing yellow ammonium iron alum slag |
Non-Patent Citations (2)
| Title |
|---|
| 热酸浸出黄钠铁矾渣工艺;王玉棉等;《兰州理工大学学报》;20091231;第35卷(第6期);17-21 * |
| 王玉棉等.热酸浸出黄钠铁矾渣工艺.《兰州理工大学学报》.2009,第35卷(第6期),17-21. |
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