CN103370428A - 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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- CN103370428A CN103370428A CN2011800675656A CN201180067565A CN103370428A CN 103370428 A CN103370428 A CN 103370428A CN 2011800675656 A CN2011800675656 A CN 2011800675656A CN 201180067565 A CN201180067565 A CN 201180067565A CN 103370428 A CN103370428 A CN 103370428A
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- nickel
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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
The present invention relates to from the starting material of nickeliferous (Ni) and iron (Fe) method with high density enrichment ferronickel, more specifically, relate to the starting material of and iron nickeliferous with the acid dissolving, and received back and forth the method for nickel enriched material by its precipitation ferronickel.
In addition, the invention still further relates to the method that reclaims high-purity nickel from the nickel enriched material, and the method that Fe solution recycles that contains in nickel enriched material removal process, producing and wasting.
Background technology
Contain nickel minerals and comprise limonite and saprolite, because they have passive characteristic, so highly-acidproof causes acid dissolution reaction slow.Therefore, proposed to dissolve to reclaim by acid the whole bag of tricks of nickel in the autoclave of high temperature and high pressure, as the method for effective leaching nickel from ore, these methods all are called " (HPAL) carried in the high pressure acidleach ".
When at room temperature carrying out nickel lixiviate reaction, even carry out in several months or the situation more of a specified duration in lixiviate, nickel recovery also can't surpass about 85%.But when adopting the HPAL method, the nickel recovery of the nickel lixiviate in two hours is more than or equal to 90%, and therefore, the HPAL method can be considered to a kind of typical method of the hydrometallurgy of nickel oxide ore.
Korean patent application special permission disclose 2007-7020915 number and Japanese patent application discloses and discloses the example that relates to the technology that employing HPAL method reclaims nickel for 2010-031341 number.But the common 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 thereof are all very high.In addition, because the nickel enrichment must be adopted sodium hydroxide (a kind of precipitation agent of costliness) or the harmful precipitation agent (H of environment
2S), thus meeting so that process the equipment cost of these precipitation agents and increase.
Disclose in 2009-0031321 number in the korean patent application special permission, the present inventor has proposed a kind of method, and the method carries reclaiming nickel by acidleach after with the nickeliferous starting material of hydrogen reduction.The technology of aforementioned patent has disclosed a kind of residue of petrochemical industry desulfurization spent catalyst that reclaims for the preparation of iron content (Fe) and the raw-material method of nickel (Ni), the method comprises: reclaiming vanadium (V) and molybdenum (Mo) afterwards from petrochemical industry desulfurization spent catalyst with acid, residue is processed to remove alkaline element; The residue of having removed alkaline element is carried out drying and be heated to 600 ℃-1300 ℃ temperature range in reducing atmosphere, Ni and the Fe that exists with oxide form in the residue is reduced into metal; With acid the reduzate that obtains is carried out lixiviate, with selective dissolution iron and nickel; Filtering solution is to obtain containing the nickel ion of lixiviate and the solution of iron ion; Contain the solution of Ni ion and Fe ion with preparation ironic hydroxide and nickel hydroxide with the alkali neutralization; And the product that obtains filtered and dry, to obtain containing the starting material of Fe and Ni.
When aforementioned method is used for lixiviate limonite nickel ores, can carry out the high speed lixiviate.But limonite has high Fe content and low Ni content, therefore, when by acid dissolving during by its lixiviate Ni, lixiviate relatively large Fe and only lixiviate a small amount of Ni.Therefore may be difficult to separation of iron and nickel from leach liquor.
Summary of the invention
Technical problem
One aspect of the present invention provides a kind of method of the effectively concentrated nickel (Ni) of starting material (particularly inferior grade Ni ore deposit) from nickeliferous and iron, the method by separate and reclaim nickel and iron (Fe) and from enriched material recovery nickel carry out.
Another aspect of the present invention provides a kind of method that reduces innovatively the amount of the by product that produces in the nickel smelting process, and the method recycles the Fe solution that contains that is produced by the inventive method, to be provided for making the starting material of 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 reduce nickeliferous and iron starting material and add entry and prepare slurry; In described slurry, add hydrochloric acid or sulfuric acid, nickeliferous and starting material iron through reduction are carried out acid treatment, to prepare through acid-treated solution, wherein in the molar weight of (Fe+Ni) in the starting material of described nickeliferous and iron, the molar weight of the hydrochloric acid that adds is 0.5-1.5 times, and the molar weight of the sulfuric acid of adding is 0.25-0.75 times; Starting material at the nickeliferous and iron that in acid-treated solution, mixes reduction, wherein when the amount of the nickel that in acid-treated solution, dissolves during less than 5g/L, the molar weight of the iron that comprises in the starting material of described nickeliferous and iron through reduction can be greater than 5 times of the integral molar quantity of the nickel in the solution, 10 times of integral molar quantity that are less than or equal to the nickel in the solution, and, when the amount of the nickel that in acid-treated solution, dissolves during more than or equal to 5g/L, the molar weight of the iron that comprises in the starting material of described nickeliferous and iron through reduction can be greater than 2.5 times of the integral molar quantity of the nickel in the solution, are less than or equal to 5 times of integral molar quantity of the nickel in the solution.
The starting material that are blended in the nickeliferous and iron in the slurry can obtain from the limonite reduction.
According to another aspect of the present invention, provide a kind of starting material from nickeliferous (Ni) and iron (Fe) to reclaim the method for nickel enriched material, the method comprises: by reduce nickeliferous and iron starting material and add entry and prepare slurry; Slurry is carried out acid treatment, to produce simultaneously ferronickel throw out and iron lixiviate reaction, and add hydrochloric acid or sulfuric acid prepares solution by the raw-material slurry through the nickeliferous and iron of reduction that obtains during slurry to preparation, molar weight in (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, the molar weight of the hydrochloric acid that adds is 0.5-1.5 times, and the molar weight of the sulfuric acid of adding is 0.25-0.75 times; And the solution that the acid treatment slurry obtains filtered and separate the solid matter that contains ferronickel, to remove iron-containing liquor.
Described method also can comprise from filter and the separate solid material the solid matter that contains ferronickel that obtains prepare slurry, and this slurry is mixed to prepare slurry with nickeliferous and starting material iron through reduction; And slurry carried out acid treatment and solid matter is filtered and separates to come the enrichment ferronickel.
Can repeat the enrichment of ferronickel, until with the solid matter weighing scale of ferronickel enriched material, nickel concentration reaches the 5-20 % by weight, thereby can reclaim the nickel enriched material from the starting material of nickeliferous and iron.
After ferronickel precipitation and iron lixiviate reaction, acid can be added so that the final pH scope is 1-6.
Reclaim the method for nickel enriched material at the starting material from nickeliferous and iron, can be by at the lower dry nickel minerals of certain temperature (described temperature be fit to be removed the crystal water 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 250 ℃-850 ℃ temperature range calcining particle, obtain nickeliferous and starting material iron.
Can adopt hydrogen-containing gas as reducing gas, carry out nickeliferous in 550 ℃-950 ℃ temperature range and raw-material reduction iron, described hydrogen-containing gas can be the mixed gas of pure hydrogen or nitrogen and hydrogen.
Described method can also comprise, when the nickel content in the nickel enriched material accounts for the 5-20 % by weight of solid matter weight of ferronickel enriched material, in cleaning with after filtering the nickel enriched material carried out drying.
According to another aspect of the present invention, provide a kind of method from nickeliferous starting material recovery high-purity nickels (Ni), the method comprises: the nickel enriched material that the method by sour leaching nickel and filtration is reclaimed dissolves the nickel solution that obtains high density; And remove iron (Fe) from the nickel solution of described high density.
Described acid can be hydrochloric acid, the molar weight of the hydrochloric acid of adding can be the molar weight of (Fe+Ni) in the nickel enriched material 2-4 doubly, when acid was sulfuric acid, the molar weight of the sulfuric acid of adding can be more than or equal to 2 times of the molar weight of (Fe+Ni) in the nickel enriched material.
When the pH of high concentration of nickel solution is controlled in the scope of 2.5-5.5, can produces ironic hydroxide by injecting oxygen-containing gas, and filter the ironic hydroxide that produces or adopt the solvent extraction method deironing of making a return journey.
According to another aspect of the present invention, a kind of method that iron-containing liquor is recycled is provided, the method comprises: add basic component in filtration and separate solid material, be controlled at the pH with solution in the scope of 9.5-10.5 in the iron-containing liquor of removing; And inject oxygen-containing gas to produce magnetite by oxidation.
Beneficial effect
According to the present invention, can be from the starting material efficient recovery nickel (Ni) such as containing nickel minerals.Specifically, the present invention can be from the effectively enrichment and reclaim nickel of low-grade nickel minerals, thereby smelts applicable to nickel.
Particularly, owing to separating from limonite (nickel minerals with high ferro (Fe) content) and having reclaimed nickel and iron, the nickel enriched material can be used as stainless starting material, and the iron of separation and removal can be made into magnetite, is suitable as the agglomerate starting material of carbon steel.As a result of, can reduce innovatively the amount of the by product that produces in the nickel smelting.
Embodiment
The below will describe the present invention in detail.
The present invention relates to a kind of method that reclaims the nickel enriched material from the starting material of nickeliferous (Ni) and iron (Fe).Specifically, dissolving by acid in the situation of leaching nickel because starting material have the Ni of lower concentration and the Fe of high density, so lixiviate relatively large iron and only lixiviate a small amount of nickel.Therefore, the present invention's situation of being difficult to separate applicable to iron and nickel.
Can be used for nickeliferous and starting material iron of the present invention and have no particular limits, as long as these starting material contain nickel and iron, can comprise the nickel minerals such as limonite and saprolite.Nickel minerals comprises the Ni of 1-2.5% and the Fe of 15-55% usually, although can be different according to the difference of nickel minerals type, in nickel minerals, limonite has the lower concentration Ni of 1-1.8% and the high density Fe of 30-55%.The present invention can be used for reclaiming from the limonite with low Ni content the situation of nickel effectively.
When reclaiming nickel from nickel minerals, can carry out for example dry, grind and the pretreatment operation of calcining and so on, thereby effectively reduce hereinafter nickel minerals in the described reduction process.Hereinafter can describe pretreatment operation in detail, i.e. drying, grinding and calcination operation.
As a rule, when when containing nickel minerals and reclaim nickel, adopt the wet method lixiviate, for this reason, contain nickel minerals and usually be ground into the state with moisture.But, because the present invention comprises the subsequent heat treatment operation, so can remove in advance the drying operation of moisture.Than wet lapping technique, the drying and grinding after the drying operation can further increase mill efficiency.In addition, when need to evenly control the granularity that desired ore is reacted in reduction and lixiviate, can adopt the wind speed of fly-ash separator that varigrained particle is carried out the air classifying of particle, thereby can obtain to reduce and the desired powder with uniform particle size of lixiviate reaction.
In the present invention, can use particle diameter to be less than or equal to the mineral dust of 1mm.When the granularity of mineral dust during greater than 1mm, reduction and extraction rate are understood step-down, and especially, workability is variation also, because propose very likely generating pump and line clogging in the reaction process in acidleach.When powder size was less than or equal to 1mm, powder was applicable to the present invention, thereby its lower limit has no particular limits.But, process of lapping must carry out one section needn't be oversize time or carry out several, thereby obtain granularity less than the powder of 10 μ m.Therefore, can use granularity more than or equal to the powder of 10 μ m.
As a rule, nickel minerals contains crystal water, when not carrying out calcination process, can discharge the crystal water that is included in the ore in follow-up reduction process, hinders reduction reaction.Therefore, can be to calcining through the powder that grinds.In nickel minerals, limonite and saprolite have respectively in about 250 ℃-350 ℃ and 650 ℃-750 ℃ characteristics that discharge crystal water.Calcine in 250 ℃-850 ℃ temperature range by the mineral dust that process of lapping obtains, thereby can remove crystal water contained in the nickel minerals.
Simultaneously, have the saprolite of high nickel content mainly as the starting material of Nickel pyrometallurgy, reclaim nickel in the rotary kiln dust that can also adopt the present invention from pyrometallurgical processes, to produce.But because the granularity of dust is included in and is applicable in the OK range of the present invention, and dust has been exposed to the condition of high temperature in pyrometallurgical processes, therefore need not grinding and calcination process in the nickel-containing ore situation.But, owing to the factor the moisture on dust and contact with air band causes granularity to depart from the situation of scope of the presently claimed invention, can grind as required or calcination process.
In addition, when oil refinery company adopts nickel-containing catalyst, may produce the spent catalyst residue, can adopt nickeliferous desulfurization spent catalyst residue method of the present invention to come enrichment and recovery nickel.Because the granularity of spent catalyst residue is usually included in and is applicable in the proper range of the present invention, so need not process of lapping.But, when the spent catalyst residue is reunited, can adopt appropriate means to grind the spent catalyst residue.In addition, can carry out as required aforesaid calcination process.
Following table 1 has shown nickeliferous and raw-material main ingredient iron.The unit of each component concentration is % by weight in the table 1, 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 |
| The spent catalyst residue | 4.8 | 3.5 | 0.1 | 35.5 |
Present invention resides in nickeliferous and starting material iron are carried out after the pre-treatment restoring operation that nickel and iron are reduced.Can adopt the reducing gas that comprises hydrogen to carry out described restoring operation, temperature range can be 550 ℃-950 ℃.When reduction temperature is less than or equal to 550 ℃, nickel recovery in follow-up leaching process can descend, because reduction may be insufficient, and when reduction temperature during more than or equal to 950 ℃, reduction ratio can further not increase, only sintering can occur, thereby workability is caused negative impact between particle.
Hydrogen can be used as reducing gas individually, can use with rare gas element, thereby remove the oxygen except hydrogen that exists in the reduction furnace in the reduction reaction process.The example of rare gas element can be nitrogen.
When adopting hydrogen to reduce the starting material (for example, limonite Ni:Fe=1:30) of nickeliferous and iron as reducing gas, the theory reaction of following reaction formula (1) expression occurs.
(Ni
0.1Fe
0.9)OFe
2O
3+4H
2=(Ni
0.1Fe
0.9)+2Fe+4H
2O (1)
From separating from waste gas with the starting material of iron through the nickeliferous of reduction that reduction process obtains, then described nickeliferous and starting material iron through reduction are discharged in the moisture oxygen obstruct tank, make slurry.Because the content of iron component may be very high, when reducing nickel minerals, after reduction, extract in the airborne process and may reoxidize, and may accelerated oxidation react owing to producing heat, thereby increased the risk of lighting.Therefore, prepare slurry from nickeliferous and starting material iron through reduction, thereby can prevent the oxidation of iron component and light.
The present invention includes the acid treatment operation, in this operation, in the slurry that obtains, add acid, with precipitation ferronickel and iron.In the acid treatment operation, the starting material of nickeliferous and iron are introduced in the anoxic reactor, and dissolved nickel minerals to wherein adding acid.Hydrochloric acid and sulfuric acid can be used as the acid in the acid treatment operation, but described acid is not limited to this.
Usually, when with acid nickeliferous and starting material iron according to reaction formula (1) reduction being carried out lixiviate, carry out metal acid according to following reaction formula (2) and process, thereby ferronickel is dissolved into ion.
(Ni
0.1Fe
0.9)+2Fe+6HCl=(Ni
0.1Fe
0.9)Cl
2+2FeCl
2+3H
2 (2)
Simultaneously, when the ore that adds the separative limonite of tool that will reduce according to the reaction of reaction formula (1), thereby when making the ferronickel ion precipitation of dissolving in the reaction formula (2), the reaction of following reaction formula (3) occurs.
(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 to say, by the metal Fe of reduction, so that the ferronickel ion of dissolving is substituted and precipitates into metal.The principle of reaction is based on the natural potential difference of iron and nickel, and for example cell reaction of described reaction of following reaction formula and so on may occur.That is to say, owing in the aqueous solution, formed battery according to the natural potential difference between the metallic iron of nickel ion and reduction, oxidation by Fe is carried out solubilizing reaction in the positive column of the ore of reduction, by the reduction of the nickel ion in the aqueous solution, carry out precipitin reaction in the cathodic area of the ore that reduces.
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
Simultaneously, because the reaction of reaction formula (2) is very fast, and the sluggish of reaction formula (3), the reaction of reaction formula (3) becomes the rate-controlling reaction of the precipitation after the ferronickel lixiviate.Specifically, because the solubleness of iron in the aqueous solution is about 150g/L, carry in the process in acidleach, the concentration of ferronickel is limited to and is less than or equal to 5g/L.Therefore, when the concentration of ferronickel was hanged down, meeting was restricted equally according to the concentration of the ferronickel of the reaction enrichment of reaction formula (3).
That is to say, when nickeliferous and starting material iron through reduction that will hang down Fe content join Ni concentration less than 5g/L in acid-treated solution the time, may be difficult to the nickel ion with high recovery rate resolution of precipitate.Reason be the to react reaction of formula (3), thereby so that nickel be substituted and precipitate, but when nickel concentration was low, the rate of diffusion of the reaction in the reaction formula (3) was understood fast-descending.
Therefore, in the nickel precipitin reaction, in the situation of Ni concentration less than 5g/L in acid-treated solution, when nickeliferous and starting material iron reduce with certain ratio of mixture (hereinafter being called " ratio of mixture of Fe/Ni "), the nickel recovery rate can significantly increase, wherein, in the molar weight of Ni in acid-treated solution, in the starting material of the nickeliferous and iron through reducing, comprise the iron more than or equal to 5 times of molar weights.But ratio of mixture can not be greater than 10.When ratio of mixture greater than 10 the time, the increase of nickel recovery rate may and not obvious, and high Fe content may cause the Ni density loss in the Ni enriched material.
Simultaneously, in the Ni concentration in acid-treated solution during more than or equal to 5g/L, even be less than or equal in the ratio of mixture of Fe/Ni in 5 the situation, when the concentration through the ore slurry of reduction increases, also can obtain excellent nickel recovery rate.Its reason is to increase along with the concentration of the ore slurry through reducing, and may introduce a large amount of iron in the solution.
Limonite with high Fe content as shown in table 1 can be used as the starting material of the nickeliferous and iron that is applicable to obtain aforementioned result.But, even adopting in the situation of limonite, when the Ni concentration in acid-treated solution during more than or equal to 5g/L, when the Fe/Ni ratio of mixture less than 3 the time, even in solution in the situation of high nickel concentration, the nickel recovery rate also may not can increase.
Simultaneously, described when carrying the starting material (for example limonite) with low nickel content with acidleach, because the low nickel concentration in the solution may cause nickel to be difficult to replace and precipitation, but when the metal Fe content in the solution increases, can be with recovered in high yields nickel.Carry out in the acid-treated situation at the starting material that adopt aforementioned principles to nickeliferous and iron with low nickel content, when iron when fully dissolving and permission do not remain as metal, can obtain as above identical result.
Therefore, when the ratio of the molar weight of acid and (Fe+Ni) molar weight during less than the equivalence ratio of acid dissolving, after the acid dissolving, can stay iron, and iron can replace nickel ion and make its precipitation.
In the present invention, hydrochloric acid and sulfuric acid can be used as the acid of nickel lixiviate reaction.Since between hydrochloric acid and sulfuric acid chemical equivalent poor, sulfuric acid and hydrochloric acid have identical principle provides identical effect, so followingly mainly be described as an example with hydrochloric acid.
Shown in reaction formula (2), during the nickel lixiviate, the theoretical equivalence ratio of the molar weight of (Fe+Ni) in the molar weight of the hydrochloric acid of adding and the ore is 1:2.But in the present invention, the add-on of hydrochloric acid is less than theoretical equivalence ratio, thereby can promote the enrichment of nickel.Therefore, in the present invention, in the molar weight of (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, the scope of the molar weight of the hydrochloric acid of adding is 0.5-1.5 times.
In the molar weight 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 that adds is limited in 0.5-1.5 times, the lixiviate of Fe and the precipitation of ferronickel optionally and simultaneously occurs, thereby can make the ferronickel enrichment.For example, when the ratio of the molar weight of hydrochloric acid and molar weight (Fe+Ni) is 1.0, the reaction of following reaction formula (4) occurs.
(Ni
0.1Fe
0.9)+2Fe+3HCl=(Ni
0.1Fe
0.9)+0.5Fe+1.5FeCl
2+1.5H
2 (4)
That is to say, ferronickel and iron dissolve according to the reaction of reaction formula (2), because the equivalence ratio of hydrochloric acid is not enough, cause the react reaction of formula (3) of undissolved metallic iron, the ferronickel ion is substituted and precipitates into the ferronickel metal, and the reaction of the formula that finally reacts (4) is in this reaction, ferronickel is not dissolving fully, and the Fe dissolving is only arranged.
Simultaneously, molar weight in (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, when the scope of the molar weight of the hydrochloric acid that adds during greater than 1.5 times, nickel dissolves to reduce nickel precipitation recovery rate, when the scope of the molar weight of the hydrochloric acid that adds during less than 0.5 times, the concentration ratio of nickel is low, thereby may increase the multiplicity of the reaction of reaction formula (4).
Adopting in the situation of sulfuric acid as aforementioned acid, utilize same principle can obtain the result identical with hydrochloric acid.But, shown in following reaction formula (5), than the situation of using hydrochloric acid, owing to use the chemical equivalent of sulfuric acid poor, in the molar weight of (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, the scope of the molar weight of the sulfuric acid of adding 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 separate the nickel enriched material of the ferronickel form that the reaction according to reaction formula (4) or (5) obtains and as FeCl by solid-liquid separator
2Or FeSO
4The Fe ion of dissolving is so can come only enriching nickel by selective removal Fe ion.
In addition, because according to the concentration of slurry and the concentration of hydrochloric acid, can change the molar weight of the hydrochloric acid of the molar weight that joins (Fe+Ni), so the final pH of carrying out Fe lixiviate and Ni precipitin reaction solution afterwards can be controlled in the scope of 1.0-6.0.When pH less than 1.0 the time, the precipitation of ferronickel be than descending because ferronickel lixiviate reaction is principal reaction, and when pH greater than 6.0 the time, may produce the hydroxide ferronickel to cause the precipitation of Ni.Therefore, the pH in the time of reaction can being finished is controlled in the scope of 1.0-6.0 for example.
The present invention includes and filter and lock out operation, the solution that wherein the acid treatment operation is obtained filters and separates the solid matter that comprises ferronickel, removes iron-containing liquor.By to filtering through acid-treated solution and separating the solid matter that comprises nickel, can obtain the nickel enriched material that nickel concentration increases.
Simultaneously, when owing to filter and lock out operation when obtaining comprising the ferronickel enriched material of abundant nickel concentration, can dissolve the ferronickel enriched material that obtains thus with acid and obtain high-purity nickel.Nickel content can be more than or equal to 5 % by weight in the ferronickel enriched material, thereby from ferronickel enriched material separating nickel.When the nickel content in the ferronickel enriched material during less than 5 % by weight, because high Fe content still, may be difficult to separate and reclaim nickel from the ferronickel enriched material.
When owing to filter and lock out operation, when causing comprising nickel content in the ferronickel enriched material of capacity nickel content less than 5 % by weight, can in the ferronickel enriched material that obtains, add entry, be made into slurry, reduce new nickeliferous starting material and mix with described slurry, then can carry out acid treatment operation and filtration and lock out operation to it.Meanwhile, the acid content in the acid treatment operation be wherein add the integral molar quantity that (Fe+Ni) in the nickeliferous raw-material slurry of reduction arranged 0.25-1.5 doubly.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)
Shown in reaction formula (1), (4) and (5), can reduce constantly Fe content and enriching nickel constantly in the enriched material.Therefore, along with Fe content continuous decrease (for example the ratio of Fe and Ni can drop to 30:1,14:1 and 10:1 successively in the ore of reduction), can be so that the nickel enrichment.
In the iron-containing liquor of removing according to the present invention, the impurity that exists in the ore for example magnesium (Mg) and manganese (Mn) comes along with iron and removes, and wherein said impurity can promote the acid dissolving still the electrochemistry substitution reaction can not occur.Simultaneously, the SiO that is not dissolved by acid in fact
2, Al
2O
3And Cr
2O
3With the enrichment of ferronickel enriched material.
When the concentration range of the ferronickel enriched material that obtains according to the present invention reaches 5-20%, can obtain the starting material of ferronickel form.That is to say that add inorganic and organic binder bond in enriched material, for example then cement and molasses add entry and come the mold enriched material, thereby can make for the granular Ni of containing of stainless steel dissolving and the starting material of Fe.
In addition, owing to spherolite mixes with reductive agent (for example carbon and aluminium), and melting and reduction, with SiO
2, Al
2O
3And Cr
2O
3Make slag, can make the iron of so-called " ferronickel " and the metal alloy of nickel.
When the concentration range of the ferronickel enriched material that obtains according to the present invention reaches 5-20%, reclaim the ferronickel enriched material carrying with acidleach, by filtering and remove not by sour dissolved impurity (SiO for example
2, Al
2O
3And Cr
2O
3) reclaim nickel.
Removing impurity (SiO for example
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 the lixiviate operation, but used acid is not limited to this in the lixiviate operation.But, for wastewater treatment and cost consideration, can adopt hydrochloric acid and sulfuric acid.Adopting in the situation of hydrochloric acid, the molar weight of the hydrochloric acid of adding can be nickeliferous raw-material (Fe+Ni) molar weight 2-4 doubly, in the situation that adopts sulfuric acid, the molar weight of the sulfuric acid of adding can equal 2 times of molar weight of (Fe+Ni).
When adopting acid to come lixiviate through the nickeliferous starting material of reduction, carry out the metal-acid-respons 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 optionally are dissolved into ion, contained Al in the nickeliferous starting material
2O
3, SiO
2Or Cr
2O
3Do not dissolved by acid in fact, thereby obtain solids phase residue.Therefore, utilize to filter and can easily the solution containing nickel that obtains in the lixiviate operation be separated with solids phase residue, and can by solid-liquid separator for example pressure filter and decanting vessel separate, to obtain solution containing nickel.
Obtain nickeliferous and solution iron, thereby can obtain highly purified nickel by from solution, removing the Fe component.When the pH of solution is controlled in the scope of 2.5-5.5, thereby when injecting air and remove the Fe component, along with Fe is varied to ironic hydroxide, producing color is orange ironic hydroxide, can come separating nickel and iron by filtering solution.Equally, in addition, can also utilize solvent extration to come separation of iron ion and nickel ion.
Simultaneously, in filtration and lock out operation, remove the iron component of lixiviate in the acid treatment operation, and can process the iron-containing liquor of removing, to regenerate as magnetite and to recycle.In with basic component (for example Wingdale or calcium hydroxide) and iron-containing liquor when being controlled in the scope of 9.5-10.5 with the pH with solution, to wherein injecting oxygen-containing gas such as air, can the 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, shown in reaction formula (9) and (10), when adopting hydrochloric acid, can obtain soluble calcium chloride, and in the situation that adopts hydrochloric acid, recycling by product, because can separate magnetite and calcium chloride, thereby so that the waste that produces is as much as possible little.On the contrary, when using sulfuric acid, can produce gypsum, because magnetite and insoluble gypsum precipitate simultaneously, can't recycle precipitated product as the starting material of steel, but the starting material that can be used as cement recycle.
The invention embodiment
Hereinafter will describe the present invention in detail according to embodiment.But following independent embodiment only provides the present invention is carried out clearer understanding, and unrestricted the present invention.
Embodiment
Embodiment 1
The spent catalyst residue of limonite, saprolite ore deposit and nickeliferous and iron is carried out drying and is ground to mean particle size is 0.8mm, and particle prepares sample 600 ℃ of calcinings.
725 ℃ with hydrogen reduce each sample prepare through the reduction sample, the mol ratio of the molar weight of (Ni+Fe) in described hydrogen and each sample is 1:1.It is the composition through each sample of reduction shown in the table 1.The unit of each component concentration is % by weight in the table 1, and remainder is magnesium (Mg) and the manganese (Mn) of oxygen and trace.
The described water that adds 200mL through each sample of reduction to 200g, to make slurry through the sample of reduction, and add hydrochloric acid of 20% to each sample slurry through reduction and dissolve each through the sample of reduction, the add-on of described hydrochloric acid is 3.75 times of (hydrochloric acid add-ons: 750g), thereby obtain through acid-treated solution of each weight through going back raw sample.
(ICP) studies nickel concentration contained in acid-treated solution by inductively coupled plasma.The nickel concentration in acid-treated solution (through acid-treated solution 1) of the limonite sample through reducing is 4.3g/L, the nickel concentration in acid-treated solution (through acid-treated solution 2) of the saprolite sample through reducing is 6.4g/L, and the nickel concentration in acid-treated solution (through acid-treated solution 3) of the spent catalyst residue sample through reducing is 11.5g/L.
Each sample through reduction that preparation has a same composition shown in the table 1, and the identical Fe/Ni ratio of mixture shown in the following table 2 mixes through acid-treated solution with resulting, has the described same slurry concentration of table 2 (unit: slurry g/L) with preparation.
Utilize the nickel concentration of ICP research, calculate the nickel recovery that causes according to through acid-treated solution and ferronickel precipitation through the ratio of mixture of the sample of reduction.Adopt following equation to calculate through acid-treated solution and ratio of mixture and nickel recovery through going back raw sample, the results are shown in table 2.
The molar weight of the Ni of the molar weight/in acid-treated solution of the Fe in the sample of reduction of the ratio of mixture of Fe/Ni=adding
The Ni rate of recovery=(1-Ni rate of loss)
Ni concentration in the solution before Ni rate of loss=(the Ni concentration in the Ni concentration in the solution before reaction-reacted solution)/reaction
[table 2]
As shown in table 2, for the Ni concentration in acid-treated solution less than 5g/L through acid-treated solution 1, when the sample that adds with the ratio of mixture that is less than or equal to 5 Fe/Ni through reduction, can't obtain enough Ni rate of recovery (comparative example 1).But, be understandable that, when the sample that adds with the ratio of mixture more than or equal to 5 Fe/Ni through reduction, the Ni rate of recovery be significantly improved (embodiments of the invention 1 and 3).
That is to say, for the Ni concentration in acid-treated solution less than 5g/L through acid-treated solution, when employing have low Fe content through the sample of reduction the time, may be difficult to obtain the precipitation of the dissolving nickel ion of high-recovery.Reason be the to react reaction of formula (3), thereby so that nickel be substituted and precipitate, but when nickel concentration was low, the rate of diffusion of the reaction in the reaction formula (3) was understood fast-descending.
Simultaneously, for the Ni concentration in acid-treated solution more than or equal to 5g/L through acid-treated solution 2 and 3, be understandable that, slurry concentration increase when the ore through reducing, even adding with the ratio of mixture that is less than or equal to 5 Fe/Ni in the situation of the sample of reduction, still obtain the excellent Ni rate of recovery (embodiments of the invention 2 and 4).Reason is to occur energetically so that the reaction of the reaction formula (3) of Ni precipitation, because because the concentration increase in the ore slurry of reduction causes a large amount of metal Fe to introduce in the solution.On the contrary, when the ratio of mixture of Fe/Ni less than 3 the time (comparative example 1 and 2), even in solution, in the situation of high Ni concentration, also can't increase the Ni rate of recovery.
Therefore, control adds the Fe/Ni of the ore through reducing that is used for enriching nickel than more than or equal to 3, specifically, is understandable that, can adopt the limonite with high Fe content.
Embodiment 2
According to the comparative example 1 of embodiment 1, for the limonite sample through reduction with low nickel content, may be difficult to carry out replacement and the precipitation of nickel, because the nickel concentration in leaching process is low, less than 5g/L.On the contrary, according to embodiments of the invention 4, confirm when the concentration of the metal Fe in the solution increases, can obtain high-recovery.Therefore, the purpose of present embodiment is to have disclosed to increase nickel content and reclaim nickel by carrying out a kind of like this reaction, in the described reaction from the sample of nickeliferous and iron through acid-treated solution, Fe is only arranged by lixiviate, Ni precipitates.
Limonite carries out the dry granularity that then grinds to form 0.8mm.Then particle uses hydrogen 725 ℃ of reduction 600 ℃ of calcinings, with the sample of preparation through reduction.In the sample of reduction, add entry to described with the weight ratio of 1:2, thereby so that oxidation does not occur described sample through reduction, then be that 12% acid adds wherein with concentration.The ratio ([H+]/[Ni+Fe]) of the molar weight by changing the acid in the table 3 and the molar weight of (Fe+Ni) in the sample of reduction carries out acid treatment.
To from through acid-treated solution respectively the iron ion that obtains of lixiviate and precipitation separate with the ferronickel metal and filter, then obtain ferronickel enriched material (enrichment order: first) by therefrom removing iron-containing liquor.
Adopt the equation described in the embodiment 1, calculate the nickel rate of loss by the nickel total content in the sample of reduction and by the relation between the nickel loss amount that nickel concentration research contained in the iron-containing liquor of removing is obtained, then calculate nickel recovery by it.The results are shown in Table 3.
[table 3]
Input ratio according to acid is less than or equal to 0.5 comparative example 4 and the embodiment of the invention 5, owing in the iron-containing liquor that separates and remove, do not detect nickel ion, so the nickel recovery of gained is 100%.But, for the comparative example 4 with low sour input ratio, because the meltage of the iron of removing from the ore that adds is reduced to 10.9g, so with respect to the concentration of the Fe in the ferronickel enriched material, actual nickel enriching quantity is little.On the contrary, for embodiments of the invention 5, be understandable that, because the meltage of iron is 27g, apparently higher than the meltage of comparative example 4, so nickel recovery also is high.Therefore, may more wish in guaranteeing the scope of nickel recovery, to have high sour input ratio.
On the contrary, shown in comparative example 5, be understandable that, when the input ratio of acid greater than 1.5(for example 1.8) time, nickel recovery descends.According to analytical results, the total amount of remaining Fe is that 27g(comprises that about 15g's stays Fe in the solution as metal), as a result of, be understandable that the meltage of Fe is about 84g or higher.Thereby capacity metal Fe that can the coprecipitated nickel hydroxide ion does not leave solution, because iron excessive dissolution.That is to say that reason is that the precipitation of nickel is not enough, its reason is the result that the decline of the Fe/Ni ratio in the embodiment 1 has occured, and has dissolved a part of Ni.Simultaneously, the Fe in the sample all is not that the reason of metal Fe is that the Fe reduction ratio is not 100%, in the lixiviate reaction, because the oxygen in the solution and acid dissolving cause Fe that partial oxidation reaction occurs.
Simultaneously, shown in the embodiment of the invention 7, be understandable that, even adopting sulfuric acid to carry out in the acid-treated situation, still obtained the nickel recovery with the situation same excellent that adopts hydrochloric acid.The reason that can obtain identical result is, only except the stoichiometric ratio of sulfuric acid and hydrochloric acid is different, and can be in situation about occuring in the situation that adopts sulfuric acid with employing hydrochloric acid identical effect.
According to aforementioned result, when the ratio of the molar weight of control acid and the molar weight of (Fe+Ni) in the acid-treated solution equivalence ratio less than the acid dissolving, thereby so that when the sample of the nickeliferous and iron with low nickel content through reduction being carried out Fe does not have excessive dissolution in the acid-treated process, when the scope of the hydrochloric acid that namely adds and the mol ratio of sulfuric acid is respectively 0.5-1.5 and 0.25-0.75, the Fe lixiviate is only arranged after acid dissolution reaction, and remaining Fe so that the Ni ion occurs to replace and precipitin reaction precipitating Ni, thereby can enriching nickel.
Embodiment 3
From embodiments of the invention 6 through acid-treated solution removal iron-containing liquor, then the weight ratio with 1:2 adds entry to remaining ferronickel enriched material, and described remaining ferronickel enriched material is made slurry.
Adopt the method identical with embodiment 2 to prepare limonite sample through reduction, in the sample of reduction, add entry to 180g with the weight ratio of 1:2, thereby prevent described sample generation oxidation through reducing.
Ferronickel enriched material slurry and mix through the sample slurry of reduction adds concentration and is 12% hydrochloric acid and carries out acid treatment, and the molar weight of the hydrochloric acid of adding equals the molar weight of (Fe+Ni) in the mixed slurry.
To from gained through acid-treated solution respectively the iron ion that obtains of lixiviate and precipitation separate with the ferronickel metal and filter, then obtain the ferronickel enriched material (embodiment of the invention 8) of the second enrichment by therefrom removing iron-containing liquor.
The mode identical with the embodiment of the invention 8 carried out enrichment to the ferronickel enriched material of the second enrichment of obtaining in the embodiment of the invention 8, to obtain the third and fourth ferronickel enriched material (embodiment of the invention 9 and 10).
[table 4]
Employing inductively coupled plasma (ICP) is studied according to contained nickel concentration in the ferronickel enriched material of the 4th enrichment of the embodiment of the invention 10, and nickel content is 6.5 % by weight.Be understandable that the ratio of the nickel of enrichment is through 3 times of the limonite sample of reduction or higher.The theoretical amount of nickel enrichment is inevitable more than or equal to 12%, but the amount of nickel enrichment is less than 12%.Reason is, except nickel, the nickel enriched material also enrichment be insoluble to the material of acid, for example SiO
2, Al
2O
3And Cr
2O
3
Embodiment 4
Add calcium hydroxide to the iron-containing liquor of through acid-treated solution, removing from embodiment 2, with the pH regulator to 10 of solution, and inject air and come oxidizing solution, as a result of, obtain iron containing compounds.
Iron containing compounds to gained carries out XRD analysis, confirms that this iron containing compounds is magnetite.The Fe concentration of magnetite is more than or equal to 65%, thereby is suitable as the starting material of carbon steel.
Although show in conjunction with illustrative embodiments and described the present invention, it will be apparent for a person skilled in the art that in the situation of the spirit and scope of the present invention that do not deviate from the claims restriction and can carry out various modifications and variations.
Claims (15)
1. method from the starting material enriching nickel of nickeliferous (Ni) and iron (Fe), the method comprises:
Make the starting material reduction of nickeliferous and iron and add entry and prepare slurry;
By in slurry, adding hydrochloric acid or sulfuric acid, nickeliferous and starting material iron through reduction are carried out acid treatment to prepare through acid-treated solution, wherein, molar weight in (Fe+Ni) in the starting material of nickeliferous 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
At the starting material that in acid-treated solution, mix through the nickeliferous and iron of reduction,
Wherein, when the amount of the nickel that in acid-treated solution, dissolves during less than 5g/L, the molar weight of the iron that comprises in the starting material of described nickeliferous and iron through reduction is greater than 5 times of the integral molar quantity of the nickel in the solution, 10 times of integral molar quantity that are less than or equal to the nickel in the solution, and, when the amount of the nickel that in acid-treated solution, dissolves during more than or equal to 5g/L, the molar weight of the iron that comprises in the starting material of described nickeliferous and iron through reduction is greater than 2.5 times of the integral molar quantity of the nickel in the solution, is less than or equal to 5 times of integral molar quantity of the nickel in the solution.
2. the method for claim 1 is characterized in that, the starting material of the described nickeliferous and iron that mixes in slurry are obtained by the limonite reduction.
3. one kind is reclaimed the method for nickel from the starting material of nickeliferous (Ni) and iron (Fe), and the method comprises:
Make the starting material reduction of nickeliferous and iron and add entry and prepare slurry;
By in the raw-material slurry of the nickeliferous and iron through reducing that in the slurry preparation, obtains, adding hydrochloric acid or sulfuric acid, slurry is carried out acid treatment to produce simultaneously ferronickel precipitation and iron lixiviate reaction and preparation solution, wherein, molar weight in (Fe+Ni) in the starting material of the nickeliferous and iron through reducing, 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 that obtains in the acid treatment to slurry filters and separates the solid matter that comprises ferronickel, removes iron-containing liquor.
4. method as claimed in claim 3, the method also comprise from filter and the separate solid material the solid matter that contains ferronickel that obtains prepare slurry, and this slurry is mixed to prepare slurry with nickeliferous and starting material iron through reduction; And slurry carried out acid treatment and solid matter is filtered and separates to come the enrichment ferronickel.
5. method as claimed in claim 4 is characterized in that, repeats 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 so that the final pH scope is 1-6.
7. such as each described method among the claim 1-6, it 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 250 ℃-850 ℃ temperature range.
8. such as each described method among the claim 1-6, it is characterized in that, adopt hydrogen-containing gas as reducing gas, in 550 ℃-950 ℃ temperature range, carry out the raw-material reduction of described nickeliferous and iron.
9. method as claimed in claim 8 is characterized in that, described hydrogen-containing gas is the mixture of pure hydrogen or nitrogen and hydrogen.
10. such as each described method among the claim 1-6, described method also comprises, when the nickel content in the nickel enriched material accounts for the 5-20 % by weight of solid matter weight of ferronickel enriched material, in cleaning with after filtering the nickel enriched material carried out drying.
11. the method from nickeliferous starting material recovery high-purity nickels (Ni), the method comprises:
The nickel enriched material that reclaims with the described method of acid dissolving claim 10 comes leaching nickel and filters, and obtains the nickel solution of high density; And
Remove iron (Fe) from the nickel solution of described high density.
12. method as claimed in claim 11 is characterized in that, described acid is hydrochloric acid, and the molar weight of the hydrochloric acid of adding is 2-4 times of the molar weight of (Fe+Ni) in the nickel enriched material.
13. method as claimed in claim 11 is characterized in that, described acid is sulfuric acid, and the molar weight of the sulfuric acid of adding equals 2 times of molar weight of (Fe+Ni) in the nickel enriched material.
14. method as claimed in claim 11, it is characterized in that, when the pH of high concentration of nickel solution is controlled in the scope of 2.5-5.5, produces ironic hydroxide by injecting oxygen-containing gas, and filter the ironic hydroxide that produces or adopt the solvent extraction method deironing of making a return journey.
15. the method that iron-containing liquor is recycled, the method comprises:
In the iron-containing liquor of in filtration claimed in claim 3 and separate solid material, removing, add basic component, be controlled at the pH with solution in the scope of 9.5-10.5; And
Inject oxygen-containing gas, produce magnet by oxidation.
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| KR10-2010-0128249 | 2010-12-15 | ||
| 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 |
| 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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| WO2023016055A1 (en) * | 2021-08-13 | 2023-02-16 | 广东邦普循环科技有限公司 | Method for recovering and purifying nickel from ferronickel |
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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 |
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| KR20120066902A (en) | 2012-06-25 |
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| CN103370428B (en) | 2015-06-17 |
| WO2012081897A2 (en) | 2012-06-21 |
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