CN103370428B - Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same - Google Patents
Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same Download PDFInfo
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- CN103370428B CN103370428B CN201180067565.6A CN201180067565A CN103370428B CN 103370428 B CN103370428 B CN 103370428B CN 201180067565 A CN201180067565 A CN 201180067565A CN 103370428 B CN103370428 B CN 103370428B
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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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by 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
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Abstract
The present invention relates to a method for enriching ferronickel to a high density from a raw material containing nickel and iron, and more particularly comprising: a step of slurrifying for reducing the raw material containing nickel-iron and then slurrifying same by adding water; a step of acid treating for simultaneously inducing ferronickel separation and iron leaching reactions by injecting into the slurry of the reduced raw material containing nickel-iron, which is obtained from the step of slurrifying, hydrochloric acid having 0.5-1.5 times more moles or sulfuric acid having 0.25-0.75 times more moles than the moles in the reduced raw material containing nickel-iron; a step of filter-separating for eliminating a solution containing iron from the solution which is obtained from the step of acid treating by separating solids containing ferronickel by means of a filter; and a step of enriching for slurrifying the solids containing ferronickel from the step of filter-separating and mixing same with the raw material containing nickel-iron that is reduced, and enriching ferronickel by performing the step of acid treating and the step of filter-separating. Furthermore, the present invention provides a method for recycling a solution containing iron, which is produced and wasted in a method for recovering highly pure nickel from the nickel enriched product and in a method for recovering the nickel enriched product.
Description
Technical field
To the present invention relates to from the starting material of nickeliferous (Ni) and iron (Fe) with the method for high density enrichment ferronickel, more specifically, relate to starting material that are nickeliferous with acid dissolve and iron, and receive the method for nickel enriched material back and forth by its precipitation ferronickel.
In addition, the invention still further relates to the method reclaiming high-purity nickel from nickel enriched material, and to producing in nickel enriched material removal process and the method recycled containing Fe solution of wasting.
Background technology
Limonite and saprolite is comprised, because they have negative traits, so highly-acidproof causes acid dissolution reaction slow containing nickel minerals.Therefore, proposed the various methods being reclaimed nickel in the autoclave of high temperature and high pressure by acid dissolve, as the method for leaching nickel effective from ore, these methods are all called " high pressure acidleach is carried (HPAL) ".
When at room temperature carrying out nickel lixiviate reaction, even when lixiviate is carried out the several months or be more of a specified duration, nickel recovery also cannot exceed about 85%.But when adopting HPAL method, the nickel recovery of the nickel lixiviate in two hours is more than or equal to 90%, and therefore, HPAL method can be considered to a kind of typical method of the hydrometallurgy of nickel oxide ore.
Korean patent application special permission disclose No. 2007-7020915 and No. 2010-031341st, Japanese Patent Application Laid-Open and discloses and relate to employing HPAL method to the example of the technology that nickel reclaims.But the usual known HPAL method of the technical field of the invention must be carried out in the autoclave of high temperature and high pressure, and can only use titanium, because it has strong acid resistance.Therefore, the equipment cost of HPAL and maintenance cost all very high.In addition, because nickel enrichment must adopt the precipitation agent (H of sodium hydroxide (a kind of precipitation agent of costliness) or bad environmental
2s), so the equipment cost processing these precipitation agents can be made to increase.
Disclose in No. 2009-0031321 in korean patent application special permission, the present inventor proposes a kind of method, and the method after with the nickeliferous starting material of hydrogen reduction, is carried by acidleach and reclaimed nickel.The technology of aforementioned patent discloses a kind of residue reclaiming petrochemical industry desulfurization spent catalyst for the preparation of iron content (Fe) and nickel (Ni) raw-material method, the method comprises: after reclaiming vanadium (V) and molybdenum (Mo) with acid from petrochemical industry desulfurization spent catalyst, process to remove alkaline element to residue; Drying is carried out to the residue eliminating alkaline element and in reducing atmosphere, is heated to the temperature range of 600 DEG C-1300 DEG C, Ni and Fe existed in the form of an oxide in residue is reduced into metal; With acid, lixiviate is carried out, with selective dissolution iron and nickel to the reduzate obtained; Filtering solution is to obtain containing the nickel ion of lixiviate and the solution of iron ion; The solution of Ni ion and Fe ion is contained to prepare ironic hydroxide and nickel hydroxide with alkali neutralization; And the product obtained is filtered and drying, to obtain the starting material containing Fe and Ni.
When preceding method is used for lixiviate limonite nickel ores, high speed lixiviate can be carried out.But limonite has high Fe content and low Ni content, therefore, when by acid dissolve by its lixiviate Ni time, lixiviate relatively large Fe and the only a small amount of Ni of lixiviate.Therefore separation of iron and nickel from leach liquor may be difficult to.
Summary of the invention
Technical problem
One aspect of the present invention provides the method for the effectively concentrated nickel (Ni) of a kind of starting material (particularly inferior grade Ni ore deposit) from nickeliferous and iron, and the method is by being separated and reclaiming nickel and iron (Fe) and reclaiming nickel to carry out from enriched material.
Another aspect of the present invention provides a kind of method reducing the amount of the by product produced in nickel fibers process innovatively, and the method recycles the Fe solution that contains produced by the inventive method, to be provided for the starting material manufacturing magnetic iron ore.
Technical scheme
According to an aspect of the present invention, provide a kind of method of the starting material enriching nickel from nickeliferous (Ni) and iron (Fe), the method comprises: by reducing nickeliferous starting material with iron add water and prepare slurry, hydrochloric acid or sulfuric acid is added in described slurry, acid treatment is carried out to the starting material that are nickeliferous and iron through reduction, with preparation through acid-treated solution, wherein with the molar amount of (Fe+Ni) in the starting material of described nickeliferous and iron, the molar weight of the hydrochloric acid added is 0.5-1.5 times, and the molar weight of the sulfuric acid added is 0.25-0.75 times, the starting material of the nickeliferous of reduction and iron are being mixed in acid-treated solution, wherein when the amount of the nickel dissolved in acid-treated solution is less than 5g/L, the molar weight of the described iron comprised in the nickeliferous of reduction with the starting material of iron can be greater than 5 times of the integral molar quantity of the nickel in solution, be less than or equal to 10 times of the integral molar quantity of the nickel in solution, and, when the amount of the nickel dissolved in acid-treated solution is more than or equal to 5g/L, the molar weight of the described iron comprised in the nickeliferous of reduction with the starting material of iron can be greater than 2.5 times of the integral molar quantity of the nickel in solution, be less than or equal to 5 times of the integral molar quantity of the nickel in solution.
The starting material of mixing nickeliferous and iron in the slurry can obtain from limonite reduction.
According to another aspect of the present invention, provide a kind of method that starting material from nickeliferous (Ni) and iron (Fe) reclaim nickel enriched material, the method comprises: by reducing nickeliferous starting material with iron add water and prepare slurry; Acid treatment is carried out to slurry, to produce ferronickel throw out and iron lixiviate reaction simultaneously, and by adding hydrochloric acid to the nickeliferous and raw-material slurry that is iron through reduction obtained when preparing slurry or sulfuric acid prepares solution, with the molar amount of (Fe+Ni) in the starting material of the nickeliferous of reduction and iron, the molar weight of the hydrochloric acid added is 0.5-1.5 times, and the molar weight of the sulfuric acid added is 0.25-0.75 times; And the solution that acid treatment slurry obtains filtered and is separated the solid matter containing ferronickel, to remove iron-containing liquor.
Described method also can comprise from filtration and the solid matter containing ferronickel obtained separate solid material prepares slurry, and is mixed to prepare slurry by the starting material of this slurry with the nickeliferous and iron through reducing; And acid treatment is carried out to slurry and solid matter is filtered and is separated enrichment ferronickel.
The enrichment of ferronickel can be repeated, until with the solid matter weighing scale of ferronickel enriched material, nickel concentration reaches 5-20 % by weight, thus nickel enriched material can be reclaimed from starting material that are nickeliferous and iron.
After ferronickel precipitation and iron lixiviate reaction, acid can be added and make final pH scope be 1-6.
Reclaiming in the method for nickel enriched material from the starting material of nickeliferous and iron, can by dry nickel minerals under certain temperature (described temperature is applicable to the crystal water removed in the starting material of nickeliferous and iron), nickel minerals is ground to form the particle that diameter is less than or equal to 1mm, and in the temperature range of 250 DEG C-850 DEG C calcining particle, obtain nickeliferous and starting material that are iron.
Hydrogen-containing gas can be adopted as reducing gas, and in the temperature range of 550 DEG C-950 DEG C, carry out nickeliferous and raw-material reduction that is iron, described hydrogen-containing gas can be the mixed gas of pure hydrogen or nitrogen and hydrogen.
Described method can also comprise, and when the nickel content in nickel enriched material accounts for the 5-20 % by weight of solid matter weight of ferronickel enriched material, after cleaning and filtering, carries out drying to nickel enriched material.
According to another aspect of the present invention, provide a kind of method reclaiming high-purity nickel (Ni) from nickeliferous starting material, the method comprises: dissolve to the nickel enriched material that the method for also being filtered by sour leaching nickel is reclaimed the nickel solution obtaining high density; And remove iron (Fe) from the nickel solution of described high density.
Described acid can be hydrochloric acid, and the molar weight of the hydrochloric acid added can be 2-4 times of the molar weight of (Fe+Ni) in nickel enriched material, and when acid is sulfuric acid, the molar weight of the sulfuric acid added can be more than or equal to 2 times of the molar weight of (Fe+Ni) in nickel enriched material.
When the pH of high concentration of nickel solution controls in the scope of 2.5-5.5, ironic hydroxide can be produced by injecting oxygen-containing gas, the deironing and the ironic hydroxide of filtration generation or employing solvent extraction method are made a return journey.
According to another aspect of the present invention, provide a kind of method that iron-containing liquor is recycled, the method comprises: to filtering and adding basic component, to control in the scope of 9.5-10.5 by the pH of solution in the iron-containing liquor removed in separate solid material; And inject oxygen-containing gas to produce magnetite by oxidation.
Beneficial effect
According to the present invention, can from the starting material efficient recovery nickel (Ni) such as containing nickel minerals and so on.Specifically, the present invention from the enrichment reclaim nickel effectively of low-grade nickel minerals, thus can be applicable to nickel fibers.
Particularly, owing to being separated from limonite (having the nickel minerals of high ferro (Fe) content) and having reclaimed nickel and iron, nickel enriched material can be used as stainless starting material, and is separated and the iron removed can be made into magnetite, is suitable as the agglomerate starting material of carbon steel.As a result, the amount of the by product produced in nickel fibers can be reduced innovatively.
Embodiment
The present invention will be described in detail below.
The present invention relates to a kind of method of the starting material recovery nickel enriched material from nickeliferous (Ni) and iron (Fe).Specifically, when carrying out leaching nickel by acid dissolve, because starting material have the Ni of lower concentration and the Fe of high density, so lixiviate relatively large iron and the only a small amount of nickel of lixiviate.Therefore, the present invention is applicable to the situation that iron and nickel are difficult to be separated.
Nickeliferous and starting material that are iron used in the present invention have no particular limits, as long as these starting material contain nickel and iron, can comprise the nickel minerals of such as limonite and saprolite and so on.Nickel minerals comprises the Fe of Ni and 15-55% of 1-2.5% usually, although can be different according to the difference of nickel minerals type, in nickel minerals, limonite has the high density Fe of lower concentration Ni and 30-55% of 1-1.8%.The present invention can effectively for reclaiming the situation of nickel from the limonite with lower Ni content.
When reclaiming nickel from nickel minerals, the pretreatment operation of such as dry, grinding and calcining and so on can be carried out, thus in reduction process hereinafter described, effectively reduce nickel minerals.Hereafter in detail pretreatment operation can be described, i.e. drying, grinding and calcination operation.
As a rule, when from when reclaiming nickel containing nickel minerals, adopt wet method lixiviate, for this reason, be usually ground into the state with moisture containing nickel minerals.But, because the present invention comprises subsequent heat treatment operation, so the drying operation of removing moisture can be carried out in advance.Compared to wet lapping technique, the drying and grinding after drying operation can increase mill efficiency further.In addition, in time needing to carry out equal control to the granularity of the ore required by reduction and lixiviate reaction, the wind speed of fly-ash separator can be adopted to carry out the air classifying of particle to varigrained particle, thus can obtain reduction and the powder with uniform particle size required by lixiviate reaction.
In the present invention, particle diameter can be used to be less than or equal to the mineral dust of 1mm.When the granularity of mineral dust is greater than 1mm, reduction and extraction rate meeting step-down, especially, workability is also deteriorated, because propose very likely generating pump and line clogging in reaction process in acidleach.When powder size is less than or equal to 1mm, powder is applicable to the present invention, and thus its lower limit has no particular limits.But, process of lapping must carry out one section need not be oversize time or carry out several, thus obtain the granularity powder that is less than 10 μm.Therefore, granularity can be used to be more than or equal to the powder of 10 μm.
As a rule, nickel minerals contains crystal water, when not carrying out calcination process, can discharge the crystal water be included in ore, hinder reduction reaction in sequential reduction process.Therefore, can the powder through grinding be calcined.In nickel minerals, limonite and saprolite have the characteristic at about 250 DEG C-350 DEG C and 650 DEG C-750 DEG C release crystal water respectively.The mineral dust obtained by process of lapping is calcined in the temperature range of 250 DEG C-850 DEG C, thus can remove crystal water contained in nickel minerals.
Meanwhile, the saprolite with high nickel content is mainly used as the starting material of Nickel pyrometallurgy, reclaims nickel in the rotary kiln dust that the present invention can also be adopted to produce from pyrometallurgical processes.But the granularity due to dust is included in and is applicable in OK range of the present invention, and dust is exposed to the condition of high temperature in pyrometallurgical processes, therefore without the need to the grinding in nickel-containing ore situation and calcination process.But, when due on such as dust and air contact zones, the factor of moisture and so on causes granularity to depart from scope of the presently claimed invention, can carry out as required grinding or calcination process.
In addition, when oil refinery company adopts nickel-containing catalyst, spent catalyst residue may be produced, method of the present invention can be adopted nickeliferous desulfurization spent catalyst residue to carry out enrichment and reclaim nickel.Granularity due to spent catalyst residue is usually included in and is applicable in proper range of the present invention, so without the need to process of lapping.But, when spent catalyst residue is reunited, appropriate means can be adopted to grind spent catalyst residue.In addition, aforesaid calcination process can be carried out as required.
Following table 1 shows nickeliferous and raw-material main ingredient that is iron.In table 1, the unit of each component concentration is % by weight, and remainder is magnesium (Mg) and the manganese (Mn) of oxygen and trace.
[table 1]
| Ni | Fe | Mg | Al | |
| Limonite | 1.76 | 61.9 | 1.4 | 2.5 |
| Saprolite | 2.57 | 18.7 | 13.5 | 0.7 |
| Spent catalyst residue | 4.8 | 3.5 | 0.1 | 35.5 |
Present invention resides in the restoring operation of after pre-treatment is carried out to starting material that are nickeliferous and iron, nickel and iron being reduced.The reducing gas comprising hydrogen can be adopted to carry out described restoring operation, and temperature range can be 550 DEG C-950 DEG C.When reduction temperature is less than or equal to 550 DEG C, nickel recovery in follow-up leaching process can decline, because reduction may be insufficient, and when reduction temperature is more than or equal to 950 DEG C, reduction ratio can not increase further, only can sinter between particle, thus negative impact is caused to workability.
Hydrogen can be used as reducing gas individually, can use together with rare gas element, thus removes the oxygen in addition to hydrogen existed in reduction furnace in reduction reaction process.The example of rare gas element can be nitrogen.
When employing hydrogen reduces nickeliferous starting material (such as, limonite Ni:Fe=1:30) with iron as reducing gas, there is the theory reaction that following reaction formula (1) represents.
(Ni
0.1Fe
0.9)OFe
2O
3+4H
2=(Ni
0.1Fe
0.9)+2Fe+4H
2O (1)
What obtain from reduction process is separated from waste gas with the starting material of iron through the nickeliferous of reduction, and then described nickeliferous the and starting material that are iron through reducing are discharged in moisture oxygen obstruct tank, make slurry.Because the content of iron component may be very high, when reduction nickel minerals, extract after the reduction in the process in air and may reoxidize, and may accelerated oxidation react owing to producing heat, thus add the risk of lighting.Therefore, prepare slurry from through the nickeliferous of reduction and starting material that are iron, thus the oxidation of iron component can be prevented and light.
The present invention includes acid treatment operation, in this operation, in the slurry obtained, add acid, to precipitate ferronickel and iron.In acid treatment operation, starting material that are nickeliferous and iron are introduced in anoxic reactor, and adds acid wherein to dissolve nickel minerals.Hydrochloric acid and sulfuric acid can be used as the acid in acid treatment operation, but described acid is not limited to this.
Usually, when carrying out lixiviate with the starting material of acid to the nickeliferous and iron reduced according to reaction formula (1), carry out metal acid process according to following reaction formula (2), thus ferronickel is dissolved into ion.
(Ni
0.1Fe
0.9)+2Fe+6HCl=(Ni
0.1Fe
0.9)Cl
2+2FeCl
2+3H
2(2)
Meanwhile, when adding the ore that will carry out the separative limonite of tool reduced according to the reaction of reaction formula (1), thus during the ferronickel ion precipitation dissolved in making reaction formula (2), there is the reaction of following reaction formula (3).
(Ni
0.1Fe
0.9)Cl
2+{(Ni
0.1Fe
0.9)+2Fe}=Ni
0.2Fe
0.8+2Fe+0.1FeCl
2(3)
That is, by the metal Fe of reduction, make the ferronickel ion dissolved be substituted and precipitate into metal.The principle of reaction is natural potential difference based on iron and nickel, the cell reaction that may occur such as to react described in following reaction formula and so on.That is, owing to defining battery according to the natural potential difference between nickel ion and the metallic iron of reduction in aqueous, solubilizing reaction is carried out in the positive column of the ore of reduction by the oxidation of Fe, by the reduction of the nickel ion in the aqueous solution, carry out precipitin reaction in the cathodic area of the ore of reduction.
Anodic reaction: Fe=Fe
+ 2+ 2e E °=0.44
Cathodic reaction: Ni
+ 2+ 2e=Ni E °=-0.25
Total reaction: Fe+Ni
+ 2=Fe
+ 2+ Ni E °=0.19
Meanwhile, due to reaction formula (2) reaction quickly, and the sluggish of reaction formula (3), the reaction of reaction formula (3) becomes the rate-controlling reaction of the precipitation after ferronickel lixiviate.Specifically, because iron solubleness is in aqueous about 150g/L, in sour leaching process, the concentration of ferronickel is limited to and is less than or equal to 5g/L.Therefore, when the concentration of ferronickel is low, can be restricted equally according to the concentration of the ferronickel of the reaction enrichment of reaction formula (3).
That is, when the nickeliferous and starting material that are iron through reduction of low Fe content are joined Ni concentration be less than 5g/L in acid-treated solution time, may be difficult to the nickel ion of high recovery rate resolution of precipitate.Reason is to react the reaction of formula (3), thus nickel is substituted and precipitates, but when nickel concentration is low, the rate of diffusion of the reaction in reaction formula (3) can decline fast.
Therefore, in nickel precipitin reaction, when the Ni concentration in acid-treated solution is less than 5g/L, when nickeliferous and starting material that are iron reduce with certain ratio of mixture (being hereafter called " ratio of mixture of Fe/Ni "), nickel recovery rate can significantly increase, wherein, with the molar amount of Ni in acid-treated solution, in the starting material through the nickeliferous of reduction and iron, comprise the iron being more than or equal to 5 times of molar weights.But ratio of mixture can not be greater than 10.When ratio of mixture is greater than 10, the increase of nickel recovery rate is possible and not obvious, and in Ni enriched material, high Fe content may cause Ni density loss.
Meanwhile, when the Ni concentration in acid-treated solution is more than or equal to 5g/L, even when the ratio of mixture of Fe/Ni is less than or equal to 5, when the concentration of the ore slurry through reduction increases, excellent nickel recovery rate also can be obtained.Its reason is, along with the concentration of the ore slurry through reduction increases, may introduce a large amount of iron in solution.
The limonite with high Fe content as shown in table 1 can be used as the starting material being applicable to the nickeliferous and iron obtaining aforementioned result.But, even when adopting limonite, when the Ni concentration in acid-treated solution is more than or equal to 5g/L, when Fe/Ni ratio of mixture is less than 3, even in the solution high nickel concentration when, nickel recovery rate also may can not increase.
Meanwhile, describe when carrying starting material (such as the limonite) with low nickel content with acidleach, because the low nickel concentration in solution may cause nickel to be difficult to replace and precipitation, but when the metal Fe content in solution increases, can with recovered in high yields nickel.Under employing aforementioned principles carries out acid-treated situation to the starting material with the nickeliferous of low nickel content and iron, when iron does not fully dissolve and allows to remain as metal, as above identical result can be obtained.
Therefore, when the molar weight of acid is less than the equivalence ratio of acid dissolve with the ratio of the molar weight of (Fe+Ni), iron can be left after acid dissolve, and iron can replace nickel ion and make it precipitate.
In the present invention, hydrochloric acid and sulfuric acid can be used as the acid of nickel lixiviate reaction.Due to except chemical equivalent difference between hydrochloric acid and sulfuric acid, sulfuric acid and hydrochloric acid have the effect that identical principle provides identical, are described as an example so main below with hydrochloric acid.
As shown in reaction formula (2), during nickel lixiviate, the theoretical equivalence of the molar weight of (Fe+Ni) in the molar weight of the hydrochloric acid added and ore is than being 1:2.But in the present invention, the add-on of hydrochloric acid is less than theoretical equivalence ratio, thus can promote the enrichment of nickel.Therefore, in the present invention, with the molar amount of (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, the scope of the molar weight of the hydrochloric acid added is 0.5-1.5 times.
With the molar amount of (Fe+Ni) in the starting material of the nickeliferous and iron of reduction, when the scope of the molar weight of the hydrochloric acid added is limited in 0.5-1.5 times, optionally and the lixiviate of Fe and the precipitation of ferronickel occur simultaneously, thus ferronickel enrichment can be made.Such as, when the molar weight of hydrochloric acid is 1.0 with the ratio of the molar weight of (Fe+Ni), there is the reaction of following reaction formula (4).
(Ni
0.1Fe
0.9)+2Fe+3HCl=(Ni
0.1Fe
0.9)+0.5Fe+1.5FeCl
2+1.5H
2(4)
That is, ferronickel and iron dissolve according to the reaction of reaction formula (2), because the equivalence ratio of hydrochloric acid is not enough, undissolved metallic iron is caused to react the reaction of formula (3), ferronickel ion is substituted and precipitates into ferronickel metal, the reaction of the formula that finally reacts (4), in the reaction, ferronickel does not dissolve completely, only has Fe to dissolve.
Simultaneously, with the molar amount of (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, when the scope of the molar weight of the hydrochloric acid added is greater than 1.5 times, nickel dissolves to reduce nickel precipitation recovery rate, when the scope of the molar weight of the hydrochloric acid added is less than 0.5 times, the concentration ratio of nickel is low, thus may increase the multiplicity of the reaction of reaction formula (4).
When adopting sulfuric acid as aforementioned acid, utilize same principle can obtain the result identical with hydrochloric acid.But, as shown in following reaction formula (5), compared to the situation using hydrochloric acid, owing to using the chemical equivalent of sulfuric acid poor, with the molar amount of (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, the scope of the molar weight of the sulfuric acid added can be 0.25-0.75 times.
(Ni
0.1Fe
0.9)+2Fe+1.5H
2SO
4=(Ni
0.1Fe
0.9)+0.5Fe+1.5FeSO
4+1.5H
2(5)
Therefore, owing to can be separated according to the nickel enriched material of the ferronickel form be obtained by reacting of reaction formula (4) or (5) and as FeCl by solid-liquid separator
2or FeSO
4the Fe ion dissolved, so can carry out only enriching nickel by selective removal Fe ion.
In addition, due to according to the concentration of slurry and the concentration of hydrochloric acid, the molar weight of the hydrochloric acid of the molar weight joining (Fe+Ni) can be changed, so the final pH of the solution carried out after Fe lixiviate and Ni precipitin reaction can be controlled in the scope of 1.0-6.0.When pH is less than 1.0, the precipitation ratio of ferronickel can decline, because ferronickel lixiviate reaction is principal reaction, and when pH is greater than 6.0, may produce hydroxide ferronickel to cause the precipitation of Ni.Therefore, can the pH at the end of reaction be controlled in the scope of such as 1.0-6.0.
The present invention includes filtration and lock out operation, wherein the solution obtained is operated to acid treatment and filter and be separated the solid matter comprising ferronickel, remove iron-containing liquor.By to filtering through acid-treated solution and being separated the solid matter comprising nickel, the nickel enriched material that nickel concentration increases can be obtained.
Meanwhile, when obtaining due to filtration and lock out operation the ferronickel enriched material comprising abundant nickel concentration, the ferronickel enriched material that can obtain thus with acid dissolve obtains high-purity nickel.In ferronickel enriched material, nickel content can be more than or equal to 5 % by weight, thus from ferronickel enriched material separating nickel.When the nickel content in ferronickel enriched material is less than 5 % by weight, due to still high Fe content, may be difficult to be separated from ferronickel enriched material and reclaim nickel.
When due to filter and lock out operation, when causing the nickel content comprised in the ferronickel enriched material of enough nickel content to be less than 5 % by weight, water can be added in the ferronickel enriched material obtained, be made into slurry, reduce new nickeliferous starting material mixing with described slurry, then can carry out acid treatment operation and filtration & separation operation to it.Meanwhile, the acid content in acid treatment operation is 0.25-1.5 times of the integral molar quantity wherein adding (Fe+Ni) that have in the nickeliferous raw-material slurry of reduction.This can represent with following reaction formula (6).
(Ni
0.1Fe
0.9)+0.5Fe+{1/2(Ni
0.1Fe
0.9)+2Fe}+3HCl=1.5(Ni
0.1Fe
0.9)+1.5FeCl
2+1.5H
2(6)
As shown in reaction formula (1), (4) and (5), Fe content in enriched material can be reduced constantly and enriching nickel constantly.Therefore, along with Fe content continuous decrease (ratio of Fe and Ni can drop to 30:1,14:1 and 10:1 successively in the ore such as reduced), nickel enrichment can be made.
In the iron-containing liquor removed according to the present invention, the impurity existed in ore such as magnesium (Mg) and manganese (Mn) are removed together with iron, and wherein said impurity can promote acid dissolve but electrochemistry substitution reaction can not occur.Meanwhile, in fact not by the SiO of acid dissolve
2, Al
2o
3and Cr
2o
3with the enrichment of ferronickel enriched material.
When the concentration range of the ferronickel enriched material obtained according to the present invention reaches 5-20%, the starting material of ferronickel form can be obtained.That is, in enriched material, add inorganic and organic binder bond, such as cement and molasses, then add water and carry out mold enriched material, thus the granular starting material containing Ni and Fe dissolved for stainless steel can be manufactured.
In addition, because spherolite mixes with reductive agent (such as carbon and aluminium), and melting and reduction, by SiO
2, Al
2o
3and Cr
2o
3make slag, the so-called iron of " ferronickel " and the metal alloy of nickel can be manufactured.
When the concentration range of the ferronickel enriched material obtained according to the present invention reaches 5-20%, reclaim ferronickel enriched material to carry with acidleach, by filtering and remove not by the impurity of acid dissolve (such as SiO
2, Al
2o
3and Cr
2o
3) reclaim nickel.
At removal impurity (such as SiO
2, Al
2o
3and Cr
2o
3) time, hydrochloric acid, sulfuric acid, nitric acid and other various acid can be used as the acid in leaching step, but acid used in leaching step is not limited thereto.But, for wastewater treatment and cost consideration, hydrochloric acid and sulfuric acid can be adopted.When adopting hydrochloric acid, the molar weight of the hydrochloric acid added can be 2-4 times of the molar weight of nickeliferous raw-material (Fe+Ni), and when adopting sulfuric acid, the molar weight of the sulfuric acid added can equal 2 times of the molar weight of (Fe+Ni).
When adopting acid to carry out lixiviate when the nickeliferous starting material of reduction, carry out the metal-acid-respons of such as following reaction formula (7) and (8).
(NiFe)+2Fe+6HCl→(NiFe)Cl
2+2FeCl
2+3H
2(7)
(NiFe)+2Fe+3H
2SO
4→(NiFe)SO
4+2FeSO
4+3H
2(8)
Therefore, nickel and iron are optionally dissolved into ion, Al contained in nickeliferous starting material
2o
3, SiO
2or Cr
2o
3in fact not by acid dissolve, thus obtain solids phase residue.Therefore, utilize and filter and can easily the solution containing nickel obtained in leaching step be separated with solids phase residue, and by solid-liquid separator such as pressure filter and decanting vessel separately, to obtain solution containing nickel.
Obtain nickeliferous and solution that is iron, thus highly purified nickel can be obtained by removing Fe component from solution.When the pH of solution controls in the scope of 2.5-5.5, when injecting air thus remove Fe component, along with Fe is changing into ironic hydroxide, producing color is orange ironic hydroxide, can come separating nickel and iron by filtering solution.Equally, in addition, solvent extration can also be utilized to come separation of iron ion and nickel ion.
Meanwhile, filtering and removing in lock out operation the iron component of lixiviate in acid treatment operation, and can the iron-containing liquor removed processed, to regenerate as magnetite and to recycle.When with in basic component (such as Wingdale or calcium hydroxide) and iron-containing liquor so that the pH of solution is controlled in the scope of 9.5-10.5 time, wherein inject oxygen-containing gas as air, can ferric oxide ion to produce magnet.This can represent with following reaction formula (9) and (10).
3FeCl
2+6Ca(OH)
2+3O
2=Fe
3O
4+3CaCl
2+6H
2O (9)
3FeSO
4+6Ca(OH)
2+3O
2=Fe
3O
4+3CaSO
4+6H
2O (10)
Thus obtained magnetite can be used as the starting material of carbon steel.But, as shown in reaction formula (9) and (10), solvable calcium chloride can be obtained when adopting hydrochloric acid, and when adopting hydrochloric acid, recycling by product, because can be separated magnetite and calcium chloride, thus makes the waste of generation little as much as possible.On the contrary, can gypsum be produced when using sulfuric acid, because magnetite and insoluble gypsum precipitate simultaneously, the starting material of precipitated product as steel cannot be recycled, but can recycle as the starting material of cement.
Invention embodiment
Hereafter will describe the present invention in detail according to embodiment.But embodiment independent as follows only provides carries out clearer understanding to the present invention, and unrestricted the present invention.
Embodiment
Embodiment 1
Carry out drying and be ground to mean particle size being 0.8mm to limonite, saprolite ore deposit and spent catalyst residue that is nickeliferous and iron, particle prepares sample 600 DEG C of calcinings.
Reduce each sample at 725 DEG C with hydrogen and prepare sample through reduction, the mol ratio of the molar weight of (Ni+Fe) in described hydrogen and each sample is 1:1.It is the composition of each sample through reduction shown in table 1.In table 1, the unit of each component concentration is % by weight, and remainder is magnesium (Mg) and the manganese (Mn) of oxygen and trace.
Described each sample through reduction to 200g adds the water of 200mL, sample through reduction is made slurry, and the hydrochloric acid adding 20% through sample slurry of reduction to each is to dissolve each sample through reduction, the add-on of described hydrochloric acid be each through going back 3.75 times (hydrochloric acid add-ons: 750g) of the weight of raw sample, thus to obtain through acid-treated solution.
Nickel concentration contained in acid-treated solution is studied by inductively coupled plasma (ICP).The nickel concentration in acid-treated solution (through acid-treated solution 1) through the limonite sample of reduction is 4.3g/L, the nickel concentration in acid-treated solution (through acid-treated solution 2) through the saprolite sample of reduction is 6.4g/L, and the nickel concentration in acid-treated solution (through acid-treated solution 3) through the spent catalyst residue samples of reduction is 11.5g/L.
Preparation has each sample through reduction of same composition shown in table 1, and mixes through acid-treated solution with obtained with the identical Fe/Ni ratio of mixture shown in following table 2, to prepare the slurry with same slurry concentration described in table 2 (unit: g/L).
Utilize the nickel concentration that ICP studies, calculate and precipitate according to through acid-treated solution and the ferronickel of the ratio of mixture of the sample through reducing the nickel recovery caused.Adopting following equation to calculate through acid-treated solution and through going back ratio of mixture and the nickel recovery of raw sample, the results are shown in table 2.
The molar weight of the Ni of the molar weight of the Fe in the sample of reduction of the ratio of mixture of Fe/Ni=add/in acid-treated solution
The Ni rate of recovery=(1-Ni rate of loss)
Ni concentration in solution before Ni rate of loss=(the Ni concentration in the Ni concentration in solution before the reaction-reacted solution)/reaction
[table 2]
As shown in table 2, for the Ni concentration in acid-treated solution be less than 5g/L through acid-treated solution 1, when add with the ratio of mixture of the Fe/Ni being less than or equal to 5 through reduction sample time, enough Ni rate of recovery (comparative example 1) cannot be obtained.But be understandable that, when adding the sample through reduction with the ratio of mixture of the Fe/Ni being more than or equal to 5, the Ni rate of recovery is significantly improved (embodiments of the invention 1 and 3).
That is, for the Ni concentration in acid-treated solution be less than 5g/L through acid-treated solution, when adopting the sample through reduction with low Fe content, the precipitation of dissolving nickel ion obtaining high-recovery may be difficult to.Reason is to react the reaction of formula (3), thus nickel is substituted and precipitates, but when nickel concentration is low, the rate of diffusion of the reaction in reaction formula (3) can decline fast.
Simultaneously, for the Ni concentration in acid-treated solution be more than or equal to 5g/L through acid-treated solution 2 and 3, be understandable that, when the slurry concentration of the ore through reduction increases, even when adding the sample through reduction with the ratio of mixture of the Fe/Ni being less than or equal to 5, still obtain the excellent Ni rate of recovery (embodiments of the invention 2 and 4).Reason is the reaction of the reaction formula (3) that can Ni be made energetically to precipitate, because cause a large amount of metal Fe to introduce in solution due to the concentration increase in the ore slurry of reduction.On the contrary, when the ratio of mixture of Fe/Ni is less than 3 (comparative example 1 and 2), even in the solution high Ni concentration when, also cannot increase the Ni rate of recovery.
Therefore, control the Fe/Ni ratio added for the ore through reduction of enriching nickel and be more than or equal to 3, specifically, be understandable that, the limonite with high Fe content can be adopted.
Embodiment 2
According to the comparative example 1 of embodiment 1, for the limonite sample through reduction with low nickel content, replacement and the precipitation of carrying out nickel may be difficult to, because the nickel concentration in leaching process is low, be less than 5g/L.On the contrary, according to embodiments of the invention 4, confirm, when the concentration of the metal Fe in solution increases, can high-recovery be obtained.Therefore, the object of present embodiment discloses to increase nickel content and reclaim nickel by carrying out so a kind of reaction, from the sample of nickeliferous and iron in described reaction through acid-treated solution, only have Fe to be leached, Ni precipitates.
Limonite carries out the dry granularity then grinding to form 0.8mm.Particle, 600 DEG C of calcinings, then uses hydrogen 725 DEG C of reduction, to prepare the sample through reduction.In the sample of reduction, adding water to described with the weight ratio of 1:2, thus the described sample through reduction is not oxidized, is then that the acid of 12% adds wherein by concentration.By changing the molar weight of the acid in table 3 and the ratio ([H+]/[Ni+Fe]) of the molar weight of (Fe+Ni) in the sample through reducing, carry out acid treatment.
Being separated to from through the acid-treated solution iron ion that lixiviate and precipitation obtain respectively with ferronickel metal and filtering, then obtaining ferronickel enriched material (enrichment order: first) by therefrom removing iron-containing liquor.
Adopt the equation described in embodiment 1, calculate nickel rate of loss, then by its calculating nickel recovery by the nickel total content in the sample of reduction and by the relation between the nickel loss amount that obtains nickel concentration research contained in the iron-containing liquor removed.The results are shown in Table 3.
[table 3]
According to the input of acid than the comparative example 4 and the embodiment of the present invention 5 that are less than or equal to 0.5, owing to nickel ion not detected, so the nickel recovery of gained is 100% in the iron-containing liquor be separated and remove.But for the comparative example 4 with low acid input ratio, because the meltage of the iron removed from the ore added is reduced to 10.9g, so relative to the concentration of the Fe in ferronickel enriched material, actual nickel enriching quantity is little.On the contrary, for embodiments of the invention 5, be understandable that, the meltage due to iron is 27g, apparently higher than the meltage of comparative example 4, so nickel recovery is also high.Therefore, more may wish that there is high acid input ratio in the scope guaranteeing nickel recovery.
On the contrary, as shown in comparative example 5, be understandable that, when the input ratio of acid is greater than 1.5(such as 1.8) time, nickel recovery declines.According to analytical results, the total amount of remaining Fe be 27g(comprise about 15g stay Fe in the solution as metal), as a result, be understandable that, the meltage of Fe is about 84g or higher.Thus, enough metal Fe of precipitating nickel ions can not leave solution, because iron excessive dissolution.That is, reason is that the precipitation of nickel is not enough, and its reason is the result of the decline of the Fe/Ni ratio that there occurs in embodiment 1, has dissolved a part of Ni.Meanwhile, the Fe in sample is not all that the reason of metal Fe is that Fe reduction ratio is not 100%, in lixiviate reaction, due to the oxygen in solution and acid dissolve, causes Fe generating portion oxidizing reaction.
, as shown in the embodiment of the present invention 7, be understandable that, even under employing sulfuric acid carries out acid-treated situation, still obtain the nickel recovery with the situation same excellent adopting hydrochloric acid meanwhile.The reason that can obtain identical result is, only except sulfuric acid is different from the stoichiometric ratio of hydrochloric acid, the effect identical with when employing hydrochloric acid can occur when adopting sulfuric acid.
According to aforementioned result, when the ratio of the molar weight of the molar weight with (Fe+Ni) in acid-treated solution that control acid is less than the equivalence ratio of acid dissolve, thus make to carry out through the sample with the nickeliferous of low nickel content and iron of reduction Fe in acid-treated process there is no an excessive dissolution time, when the scope of the hydrochloric acid namely added and the mol ratio of sulfuric acid is respectively 0.5-1.5 and 0.25-0.75, Fe lixiviate is only had after acid dissolution reaction, and the Fe of remainder makes Ni ion generation replacement and precipitin reaction to precipitate Ni, thus can enriching nickel.
Embodiment 3
From embodiments of the invention 6 through acid-treated solution removal iron-containing liquor, then add water with the weight ratio of 1:2 to remaining ferronickel enriched material, described remaining ferronickel enriched material made slurry.
Adopting the method identical with embodiment 2 to prepare limonite sample through reducing, in the sample of reduction, adding water to 180g with the weight ratio of 1:2, thus prevent the described sample through reduction to be oxidized.
Ferronickel enriched material slurry and through reduction sample slurry mix, add concentration be 12% hydrochloric acid carry out acid treatment, the molar weight of the hydrochloric acid added equals the molar weight of (Fe+Ni) in mixed slurry.
To being separated with ferronickel metal and filtering through the acid-treated solution iron ion that lixiviate and precipitation obtain respectively, then by therefrom removing iron-containing liquor to obtain the ferronickel enriched material (embodiment of the present invention 8) of the second enrichment from gained.
The ferronickel enriched material of the mode identical with the embodiment of the present invention 8 to the second enrichment obtained in the embodiment of the present invention 8 carries out enrichment, to obtain the third and fourth ferronickel enriched material (embodiment of the present invention 9 and 10).
[table 4]
Nickel concentration contained in the ferronickel enriched material according to the 4th enrichment of the embodiment of the present invention 10 is studied in employing inductively coupled plasma (ICP), and nickel content is 6.5 % by weight.Be understandable that, the ratio of the nickel of enrichment is 3 times or higher of the limonite sample through reduction.The theoretical amount of nickel enrichment must be more than or equal to 12%, but the amount of nickel enrichment is less than 12%.Reason is, in addition to nickel, nickel enriched material is also enriched the material being insoluble to acid, such as SiO
2, Al
2o
3and Cr
2o
3.
Embodiment 4
Add calcium hydroxide to the iron-containing liquor removed in acid-treated solution from embodiment 2, by the pH regulator to 10 of solution, and inject air and carry out oxidizing solution, as a result, obtain iron containing compounds.
XRD analysis is carried out to the iron containing compounds of gained, confirms that this iron containing compounds is magnetite.The Fe concentration of magnetite is more than or equal to 65%, thus is suitable as the starting material of carbon steel.
Although show in conjunction with illustrative embodiments and describe the present invention, it will be apparent for a person skilled in the art that when do not deviate from claims limit the spirit and scope of the present invention can carry out various modifications and variations.
Claims (15)
1., from a nickeliferous method with the starting material enriching nickel of iron, the method comprises:
Nickeliferous and starting material that are iron are made to reduce and add water to prepare slurry;
By adding hydrochloric acid or sulfuric acid in slurry, acid treatment is carried out with preparation through acid-treated solution to the starting material that are nickeliferous and iron through reduction, wherein, with the nickeliferous molar amount with the iron+nickel in the starting material of iron, the scope of the molar weight that described hydrochloric acid adds is 0.5-1.5 times, and the scope of the molar weight that described sulfuric acid adds is 0.25-0.75 times; And
The starting material through the nickeliferous of reduction and iron are being mixed in acid-treated solution,
Wherein, when the amount of the nickel dissolved in acid-treated solution is less than 5g/L, the molar weight of the described iron comprised in the nickeliferous of reduction with the starting material of iron is greater than 5 times of the integral molar quantity of the nickel in solution, be less than or equal to 10 times of the integral molar quantity of the nickel in solution, and, when the amount of the nickel dissolved in acid-treated solution is more than or equal to 5g/L, the molar weight of the described iron comprised in the nickeliferous of reduction with the starting material of iron is greater than 2.5 times of the integral molar quantity of the nickel in solution, is less than or equal to 5 times of the integral molar quantity of the nickel in solution.
2. the method for claim 1, is characterized in that, the starting material of the nickeliferous and iron mixed in the slurry are reduced by limonite and obtain.
3. reclaim a method for nickel from starting material that are nickeliferous and iron, the method comprises:
Nickeliferous and starting material that are iron are made to reduce and add water to prepare slurry;
By adding hydrochloric acid or sulfuric acid to what obtain in slurry preparation in the nickeliferous of reduction with the raw-material slurry of iron, to slurry carry out acid treatment with produce simultaneously ferronickel precipitation and iron lixiviate react and prepare solution, wherein, with the molar amount of the iron+nickel in the starting material of the nickeliferous of reduction and iron, the scope of the molar weight that described hydrochloric acid adds is 0.5-1.5 times, and the scope of the molar weight that described sulfuric acid adds is 0.25-0.75 times; And
The solution obtained in the acid treatment of slurry filtered and is separated the solid matter comprising ferronickel, removing iron-containing liquor.
4. method as claimed in claim 3, the method also comprises from filtration and the solid matter containing ferronickel obtained separate solid material prepares slurry, and is mixed to prepare slurry by the starting material of this slurry with the nickeliferous and iron through reducing; And acid treatment is carried out to slurry and solid matter is filtered and is separated enrichment ferronickel.
5. method as claimed in claim 4, is characterized in that, repeat the enrichment of ferronickel, until with the solids content weighing scale of ferronickel enriched material, nickel concentration reaches the scope of 5-20 % by weight.
6. method as claimed in claim 3, is characterized in that, after ferronickel precipitation and iron lixiviate reaction, adds acid and makes final pH scope be 1-6.
7. the method according to any one of claim 1-6, is characterized in that, by dry nickel minerals, nickel minerals is ground to form the particle that diameter is less than or equal to 1mm, and calcining particle obtains the starting material of described nickeliferous and iron in the temperature range of 250 DEG C-850 DEG C.
8. the method according to any one of claim 1-6, is characterized in that, adopts hydrogen-containing gas as reducing gas, carries out the raw-material reduction of described nickeliferous and iron in the temperature range of 550 DEG C-950 DEG C.
9. method as claimed in claim 8, it is characterized in that, described hydrogen-containing gas is the mixture of pure hydrogen or nitrogen and hydrogen.
10. the method according to any one of claim 1-6, described method also comprises, and when the nickel content in nickel enriched material accounts for the 5-20 % by weight of solid matter weight of ferronickel enriched material, after cleaning and filtering, carries out drying to nickel enriched material.
11. 1 kinds are reclaimed the method for high-purity nickel from nickeliferous starting material, and the method comprises:
Nickel enriched material is obtained by method according to claim 10;
Carry out leaching nickel with the nickel enriched material that acid dissolve method according to claim 10 reclaims and filter, obtaining the nickel solution of high density; And
Iron is removed from the nickel solution of described high density.
12. methods as claimed in claim 11, it is characterized in that, described acid is hydrochloric acid, and the molar weight of the hydrochloric acid added is 2-4 times of the molar weight of the iron+nickel in nickel enriched material.
13. methods as claimed in claim 11, it is characterized in that, described acid is sulfuric acid, and the molar weight of the sulfuric acid added equals 2 times of the molar weight of the iron+nickel in nickel enriched material.
14. methods as claimed in claim 11, it is characterized in that, when the pH of high concentration of nickel solution controls in the scope of 2.5-5.5, produce ironic hydroxide by injecting oxygen-containing gas, the deironing and the ironic hydroxide of filtration generation or employing solvent extraction method are made a return journey.
15. 1 kinds of methods that iron-containing liquor is recycled, the method comprises:
Iron-containing liquor is obtained by filtering the solid matter of method according to claim 3 and be separated;
To claim 3 filtration and add basic component, to control in the scope of 9.5-10.5 by the pH of solution in the iron-containing liquor removed in the solid matter be separated; And
Inject oxygen-containing gas, produce magnet by oxidation.
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| KR20100128249A KR101203731B1 (en) | 2010-12-15 | 2010-12-15 | METHODS FOR CONCENTRATING AND RECOVERING FERRO NICKEL FROM NICKEL CONTAINING RAW MATERIAL, METHODS FOR RECOVERING NICKEL CONCENTRATE FROM THE CONCENTRATED FERRO NICKEL AND REUSING METHOD OF Fe CONTAINING SOLUTION WASTED FROM THE METHODS |
| KR10-2010-0128249 | 2010-12-15 | ||
| PCT/KR2011/009602 WO2012081897A2 (en) | 2010-12-15 | 2011-12-13 | Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same |
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| KR101439626B1 (en) * | 2012-09-28 | 2014-09-15 | 주식회사 포스코 | Ferro-Nickel recovery method by recycling the leached and washed solution |
| KR101403185B1 (en) * | 2012-12-21 | 2014-06-11 | 재단법인 포항산업과학연구원 | Recycling Method of byproduct from nickel extraction |
| KR101403209B1 (en) * | 2012-12-21 | 2014-06-03 | 재단법인 포항산업과학연구원 | Method for recovering nickel from ni ore |
| KR101372622B1 (en) * | 2012-12-21 | 2014-03-26 | 재단법인 포항산업과학연구원 | Method for preparing nmc(ni-co-mn) hydroxide from ni ore |
| KR101537068B1 (en) * | 2013-12-24 | 2015-07-15 | 주식회사 포스코 | Method for collection of valid metal |
| KR102287827B1 (en) * | 2014-06-26 | 2021-08-10 | 에스케이이노베이션 주식회사 | Catalysts Based on Natural Minerals and Process for Gasification Using the Same |
| KR101630947B1 (en) * | 2014-10-17 | 2016-06-16 | 주식회사 포스코 | PROCESS FOR ENHANCED ACID LEACHING OF Ni BY CONTROLING ACID INPUT AND METHOD FOR RECOVERING FERRONICKEL USING THE SAME |
| KR101654198B1 (en) | 2014-12-30 | 2016-09-05 | 엘에스니꼬동제련 주식회사 | Method for recovering cobalt and nickel from a waste liquor upon smelting low-grade nickel ore |
| CN113802001B (en) * | 2021-08-13 | 2022-11-22 | 广东邦普循环科技有限公司 | Method for recovering and purifying nickel from nickel iron |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001253719A (en) * | 2000-03-08 | 2001-09-18 | Sumitomo Metal Mining Co Ltd | Method for recovering nickel sulfate from nickel- containing sludge |
| KR100406367B1 (en) * | 1998-12-21 | 2003-12-18 | 주식회사 포스코 | RECYCLING METHOD OF SLUDGE INCLUDING FeNi GENERATED FROM RECYCLING PROCESS OF Ni CONTAINED SPENT ETCHING SOLUTION |
| JP2004284848A (en) * | 2003-03-20 | 2004-10-14 | Nippon Steel Corp | Method of recovering nickel sulfate from nickel-containing waste water sludge |
| CN101255494A (en) * | 2008-04-11 | 2008-09-03 | 中南大学 | Method for leaching nickel-cobalt from low-grade laterite nickel ore |
| CN101801853A (en) * | 2007-09-21 | 2010-08-11 | 浦项产业科学研究院 | Method of manufacturing Fe and Ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the Fe and Ni containing material and method of manufacturing Fe-Ni alloy |
Family Cites Families (2)
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| CN101104885A (en) * | 2006-06-02 | 2008-01-16 | 李智才 | Normal pressure leaching method for treating low-iron nickel oxide ore |
| CN101559986A (en) * | 2009-05-14 | 2009-10-21 | 上海一品颜料有限公司 | Method for producing iron oxide black |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100406367B1 (en) * | 1998-12-21 | 2003-12-18 | 주식회사 포스코 | RECYCLING METHOD OF SLUDGE INCLUDING FeNi GENERATED FROM RECYCLING PROCESS OF Ni CONTAINED SPENT ETCHING SOLUTION |
| JP2001253719A (en) * | 2000-03-08 | 2001-09-18 | Sumitomo Metal Mining Co Ltd | Method for recovering nickel sulfate from nickel- containing sludge |
| JP2004284848A (en) * | 2003-03-20 | 2004-10-14 | Nippon Steel Corp | Method of recovering nickel sulfate from nickel-containing waste water sludge |
| CN101801853A (en) * | 2007-09-21 | 2010-08-11 | 浦项产业科学研究院 | Method of manufacturing Fe and Ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the Fe and Ni containing material and method of manufacturing Fe-Ni alloy |
| CN101255494A (en) * | 2008-04-11 | 2008-09-03 | 中南大学 | Method for leaching nickel-cobalt from low-grade laterite nickel ore |
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