CN104140129B - Rough nickel hydroxide process for separation and purification and the product obtaining - Google Patents
Rough nickel hydroxide process for separation and purification and the product obtaining Download PDFInfo
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- CN104140129B CN104140129B CN201410371129.3A CN201410371129A CN104140129B CN 104140129 B CN104140129 B CN 104140129B CN 201410371129 A CN201410371129 A CN 201410371129A CN 104140129 B CN104140129 B CN 104140129B
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Abstract
The present invention relates to a kind of process for separation and purification of rough nickel hydroxide, comprise alkali cleaning separation circuit, ammonia treatment operation, dissolve removal of impurities operation. Method process conditions gentleness of the present invention, by rough nickel hydroxide separating-purifying, has improved the organic efficiency of full nickel, and the nickelous sulfate product purity being obtained by the method is high, and impurity content is low.
Description
Technical field
The present invention relates to fine inorganic chemicals technical field, particularly relate to dividing of a kind of rough nickel hydroxideThe high-purity sulphuric acid nickel product obtaining from method of purification and by the method.
Background technology
Along with the development of lithium ion battery ternary material, the quality cost of nickel compound is proposed to new wantingAsk, part manufacture of materials producer adopts metallic nickel or tertiary cathode body reclaimed materials through relatively simply processing or carryingPure production nickelous sulfate or nickel chloride product. But, for the larger rough nickel hydroxide raw material of quantity, due toIts complicated components, thereby be not yet utilized effectively.
The main component of the rough nickel hydroxide of certain company of Canada is as follows:
| Ni | Co | S | Cr | Cu | Fe |
| 39.29％ | 2.83％ | 4.73％ | 0.014％ | 0.009％ | 0.164％ |
| Mg | Mn | Al | Ca | Si | Zn |
| 2.06％ | 5.32％ | 0.14％ | 0.19％ | 0.43％ | 0.80％ |
As can be seen from the above table, the composition complexity of rough nickel hydroxide raw material, only carries out simple process or purificationTo realize effective recovery to nickel.
Summary of the invention
Technical problem to be solved by this invention is: a kind of process for separation and purification of rough nickel hydroxide is provided,To improve the organic efficiency of full nickel.
The process for separation and purification that the invention provides a kind of rough nickel hydroxide, the method comprises the steps:
(1) alkali cleaning separation circuit
(1.1) according to the ratio of 200-250 gram of every liter of NaOH solution, rough nickel hydroxide is joinedIn 1.8-2.5mol/LNaOH solution, Separation of Solid and Liquid after sufficient reacting, filter cake enters next step;
(1.2) according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution, step (1.1) is obtainedFilter cake joins in the NaOH solution of 0.1-0.15mol/L, Separation of Solid and Liquid after sufficient reacting, and filter cake entersNext step;
(2) ammonia treatment operation
(2.1) filter cake according to the ratio of per kilogram filter cake 1.5-3.5L solution, step (1.2) being obtained addsEnter to 8-10.5mol/LNH4In OH solution, carry out Separation of Solid and Liquid after sufficient reacting, filtrate enters next stepSuddenly;
(2.2) content of magnesium in the filtrate that determination step (2.1) obtains, mole H such as adds2SiF6Be stirred toSufficient reacting, Separation of Solid and Liquid, filtrate enters next step;
(2.3) filtrate step (2.2) being obtained is heated, and is warming up to gradually 70-85 DEG C, and maintainsTo sufficient reacting, Separation of Solid and Liquid, filter cake enters next step;
(3) dissolve removal of impurities operation
(3.1) filter cake sulfuric acid dissolution step (2.3) being obtained, adjustment pH value of solution is 1.0-1.5,Measure cobalt content in solution, mole oxalic acid such as add, be stirred to sufficient reacting, Separation of Solid and Liquid, filtrate entersNext step;
(3.2) filtrate step (3.1) being obtained is carried out electrolysis, until copper content is less than 0.02ppm in filtrateTime stop electrolysis, in filtrate, add hydrogen peroxide, heating is boiled, with adding Ba (OH) in backward solution2Solution is neutralized to pH value for 6-6.5, Separation of Solid and Liquid, to filtrate evaporate, cooling, crystallization, fromAnd obtain nickelous sulfate product.
The process for separation and purification of aforesaid rough nickel hydroxide, in step (1.1), by rough nickel hydroxideJoin in NaOH solution, stir 2.0-2.5 hour temperature 70-90 DEG C of making beating, then at temperature 20-25 DEG CContinue to stir 1.5-2.0 hour, to react fully.
The process for separation and purification of aforesaid rough nickel hydroxide, in step (1.2), joins NaOH by filter cakeIn solution, carry out agitator treating 2.0-2.5 hour at 25-30 DEG C.
The process for separation and purification of aforesaid rough nickel hydroxide, the filter cake that step (1.2) obtains is entering ammoniaBefore treatment process, first use deionized water to filter cake according to the ratio of every liter of deionized water 300-350 gram filter cakeCarry out heat and wash, preferably, wash 2 times each 2 hours 60-70 DEG C of heat.
The process for separation and purification of aforesaid rough nickel hydroxide, in step (2.1), carries out after sufficient reactingThe filter cake 1.2-2.0mol/LNH that Separation of Solid and Liquid obtains4OH solution washing, and then Separation of Solid and Liquid,After the filtrate obtaining and sufficient reacting, carry out the filtrate that Separation of Solid and Liquid obtains and together enter step (2.2).
The process for separation and purification of aforesaid rough nickel hydroxide, in step (2.2), adds H2SiF6After,Stirring at normal temperature processing, preferred process 1.5-2.0 hour.
The process for separation and purification of aforesaid rough nickel hydroxide, in step (3.1), adds after oxalic acid, controlTemperature 45-50 processed DEG C stir process, preferred process 1.5-2 hour.
The process for separation and purification of aforesaid rough nickel hydroxide, in step (3.2), two to adding in solutionOxygen water heating preferably maintain gentle boil 30 minutes after boiling; With Ba (OH)2Solution is neutralized toPH value is 6-6.5, and stir process, preferably stir process 30 minutes.
Method process conditions gentleness of the present invention, taking the rough nickel hydroxide of complicated components as raw material, by rightIts separating-purifying, has improved the organic efficiency of full nickel, has reduced production cost, nickel recovery >=96.32%(weight); By method of the present invention, rough nickel hydroxide raw material is carried out to the product obtaining after separating-purifying processingProduct, its nickel sulfate content >=99.90% (weight), and impurity content is low, particularly, by weight, KContent < 5ppm, Na content < 10ppm, Ca content≤2.4ppm, Mg content≤3.6ppm, Cu containsAmount < 0.5ppm, Cr content < 0.5ppm, Fe content < 2.0ppm, Al content < 0.5ppm, and notContaining Zn, Si, Mn.
Brief description of the drawings
Fig. 1 is the process chart of the rough nickel hydroxide process for separation and purification of the present invention.
Detailed description of the invention
In order fully to understand object of the present invention, feature and effect, by following detailed description of the invention, to thisInvention elaborates. Process of the present invention is except following content, and all the other all adopt the routine of this areaMethod or device.
The present invention separates by alkali treatment, ammonia and common-ion effect is purified to rough nickel hydroxide raw materialSeparate, improved raw materials recovery rate. Method of the present invention does not have special requirement to rough nickel hydroxide raw material,The rough nickel hydroxide that the conventional commercial run of every employing obtains, all can adopt method of the present invention to separatePurify, and can prepare the nickelous sulfate product that purity is high, impurity content is low.
As shown in Figure 1, the process for separation and purification of rough nickel hydroxide of the present invention comprises the steps:
(1) alkali cleaning separation circuit
(1.1) preparation 1.8-2.5mol/L (preferably 2mol/L) NaOH solution, according to every liter of NaOHThe ratio of solution 200-250 gram adds rough nickel hydroxide raw material, is stirred to sufficient reacting, and squeezing press filtration dividesFrom, the filtrate obtaining can be reclaimed the element such as Zn and Cr, and the filter cake obtaining enters next step operation.
Preferably, according to the ratio of 200-250 gram of every liter of NaOH solution, rough nickel hydroxide raw material is addedAfter arriving in 1.8-2.5mol/L (preferably 2mol/L) NaOH solution, first temperature is controlled to 70-90 DEG C,2.0-2.5 hour is stirred in making beating, processes and is conducive to improve the reaction speed such as Zn, Al, so under higher temperatureAfter, then temperature is controlled to 20-25 DEG C, and continue to stir 1.5-2.0 hour, reduce temperature and process mainlyIt is the hydrolysis in order to prevent Cr.
(1.2) the NaOH solution of preparation 0.1-0.15mol/L, according to every liter of NaOH solution 400-450The filter cake that the ratio of gram filter cake adds above-mentioned steps (1.1) to obtain, agitator treating 2 times, press filtration separates,Filter cake enters next step.
Preferably, according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution, filter cake is joined to 0.1-0.15After in the NaOH solution of mol/L, at 25-30 DEG C, agitator treating 2.0-2.5 hour, press filtration separates,Filtrate is processed discharge, and filter cake uses the NaOH solution of 0.1-0.15mol/L at 25-30 DEG C of agitator treating again2.0-2.5 hour, press filtration subsequently separates, and filtrate is processed discharge, and filter cake enters next step.
Preferably, according to the ratio of every liter of deionized water 300-350 gram filter cake, at 60-70 DEG C, spend fromThe filter cake heat that sub-water obtains above-mentioned steps (1.2) is washed 2 times, and each 2 hours, then press filtration separated,Filtrate is processed discharge, and filter cake enters ammonia treatment operation.
Alkali cleaning separation circuit relates generally to following chemical reaction:
Cr(OH)3+NaOH＝NaCrO2+2H2O
Zn(OH)2+NaOH＝NaHZnO2+H2O
Al(OH)3+NaOH＝NaAlO2+2H2O
(2) ammonia treatment operation
(2.1) according to the ratio of per kilogram filter cake 1.5-3.5L (preferably 2.5L) solution by step (1.3)The filter cake obtaining joins 8-10.5mol/L (preferably 10mol/L) NH4In OH solution, pull an oar,NH4The amount of OH solution is controlled at the scope that can normally pull an oar, the airtight sufficient reacting that is stirred to of normal temperature,Press filtration separates, 1.2-2.0mol/L for filter cake (preferably 1.5mol/L) NH4OH solution washing 2 times, excellentBe selected under normal temperature condition agitator treating 2 times, each 1.0-1.5 hour. Then, press filtration separates, three filtersLiquid merges, and filter residue is used for reclaiming the valuable metals such as manganese, and filtrate enters next step.
Preferably, filter cake joins NH4After OH solution is pulled an oar, (slurry first crosses 100 mesh sieves150 tm screen), and then the airtight stirring of normal temperature 3-4 hour is to react fully.
(2.2) content of magnesium in the filtrate that determination step (2.1) obtains, mole H such as adds2SiF6Be stirred toSufficient reacting, preferably stir process 1.5-2.0 hour at normal temperatures. Then carry out secondary filter, preferably makeWith the filter membrane of 0.45 μ m. After secondary filter, separation after the washing of 1:4 deionized water for filter residue, merging filtrateEnter next step.
(2.3) filtrate above-mentioned steps (2.2) being obtained is placed in heating kettle (for example, coil pipe heating kettle)In, Steam Heating, uses deionized water absorbing ammonia, is warming up to gradually 70-85 DEG C (preferably 80-85 DEG C),And be maintained until sufficient reacting (preferably maintaining 30 minutes), and press filtration separates, and filtrate is processed discharge, and filter cake is usedDeionized water washing (preferably 1:460-70 DEG C of agitator treating 1.5-2 hour), press filtration separates again, obtainsFilter cake enter and dissolve removal of impurities operation.
Ammonia treatment operation relates generally to following chemical reaction:
Mg(OH)2+H2SiF6＝MgSiF6↓+2H2O
(3) dissolve removal of impurities operation
(3.1) sulfuric acid for filter cake (preferably 3.0-3.5mol/L sulfuric acid) above-mentioned steps (2.3) being obtainedDissolve, adjustments pH value of solution is 1.0-1.5, and cobalt content in mensuration solution, mole oxalic acid such as adds under stirring,Be stirred to sufficient reacting, press filtration separates, and filter cake is for the preparation of cobalt salt after washing, and a small amount of wash water is incorporated to solution,This solution enters next step.
Preferably, add etc. after mole oxalic acid, control temperature and stir 1.5-2.0 hour at 45-50 DEG C, so thatSufficient reacting.
(3.2) solution above-mentioned steps (3.1) being obtained carries out electrolysis, until copper content is less than in solutionWhen 0.02ppm, stop electrolysis, in a kind of detailed description of the invention, taking titanium plate as anode, copper coin is negative electrode,At 95 DEG C, 45A/m2Under electric current, carry out electrolysis.
Stop after electrolysis, in solution, add hydrogen peroxide, preferably, add 1.5mol according to every liter of solutionRatio add technical grade 27.5% (weight) hydrogen peroxide. Then, heating is boiled, with adding in backward solutionEnter Ba (OH)2Solution (the preferably Ba (OH) of 3mol/L2Solution) be neutralized to pH value for 6-6.5,Stir process 30 minutes, press filtration separates, and by a small amount of deionized water, filter residue is washed, and wash water is incorporated to moltenLiquid. By above-mentioned solution evaporation crystallisation by cooling, centrifugation, mother liquor is back to above-mentioned steps (3.1), knotBrilliant use hot-air flow (preferably 125 DEG C) is dried, and excessively after 100 mesh sieves, obtains product.
Embodiment
First determinator and mensuration side used during, to the raw material relating in embodiment below and product analysisMethod is described as follows:
The purity of rough nickel hydroxide raw material is: Ni (OH)2Mass content is more than 5%.
Constituent content analysis method: inductively coupled plasma (ICP) atomic emission spectrometry.
Constituent content analysis device: IRISIntrepidIIXSP type inductively coupled plasma atomic emissions lightSpectrometer, power & light company of the U.S. manufactures.
PH pH-value determination pH: acidometer, model is PHS-3C, purchased from Shanghai Precision Scientific Apparatus Co., Ltd.
Nickelous sulfate weight content assay method: adopt EDTA complexometry.
Nickel recovery assay method: adopt ICP method.
The various reagent that use in embodiment are conventional commercial obtaining.
Embodiment 1
(1) alkali cleaning separation circuit
Preparation 2mol/LNaOH solution, adds rough nickel hydroxide former in the ratio of 230 grams of every liter of solutionMaterial, controls 80 DEG C of temperature, and making beating is stirred 2.2 hours, then controls 23 DEG C and continue to stir 1.8 hours, filtrateCan reclaim the element such as Zn, Cr, filter cake enters next-step operation.
Preparation 0.13mol/LNaOH solution, adds the wet of upper step processing in the ratio of 430 grams of every liter of solutionFilter cake, agitator treating 2.3 hours at 28 DEG C, press filtration separates, and filtrate is processed discharge, and filter cake is used againAgitator treating 2.3 hours at 28 DEG C of 0.13mol/LNaOH solution, press filtration separates, and filtrate is processed discharge,Filter cake enters next-step operation.
Wash 2 times in 65 DEG C of heat of the ratio of every liter of deionized water 330g wet cake, each 2 hours, press filtration dividedFrom, filtrate is processed discharge, and filter cake enters ammonia treatment operation.
(2) ammonia treatment operation
According to per kilogram filter cake 2.5L10mol/LNH4The ratio of OH solution is pulled an oar, and slurry crosses 100Mesh sieve, the airtight stirring of normal temperature 4 hours, press filtration separates, filter cake 1.5mol/LNH4OH solution normal temperature stirsMix washing 2 times, each 1.3 hours, press filtration separated, and three times filtrate merges, and filter residue recovery manganese etc. has valency goldBelong to, filtrate enters next-step operation.
Measure the content of Mg in solution, mole H such as add2SiF6Stirring at normal temperature is processed 1.8 hours, with 0.45The secondary filter of μ m filter membrane, filter residue is with separating after the washing of 1:4 deionized water, and merging filtrate enters next-step operation.
Above-mentioned filtrate is placed in coil pipe heating kettle, and Steam Heating, uses deionized water absorbing ammonia, heats up graduallyTo 85 DEG C and maintain 30 minutes, press filtration separates, and filtrate is processed discharge, filter cake with deionized water 1:4 at 65 DEG CAgitator treating 1.8 hours, press filtration separates, and filter cake enters and dissolves removal of impurities operation.
(3) dissolve removal of impurities operation
By above-mentioned filter cake 3.3mol/L sulfuric acid dissolution, adjusting pH is 1.3, measures Co in solutionContent, under stirring, add equimolar oxalic acid, control 49 DEG C of temperature and stir 1.8 hours, press filtration separates,After solids wash, prepare cobalt salt, a small amount of wash water is incorporated to solution.
Use titanium plate as anode above-mentioned solution, copper coin is negative electrode, under 95 DEG C of 45A/ ㎡ electric currents, carries out electrolysisProcess, until copper content is less than 0.02ppm in solution, stop electrolysis, solution is in the ratio of every liter of 1.5molAdd technical grade 27.5% hydrogen peroxide, heating is boiled, and maintains gentle boil and uses 3mol/L after 30 minutesBa(OH)2It is 6.3 that solution is neutralized to pH value, and stir process is press filtration separation after 30 minutes, and filter residue goes on a small quantityAfter ion-cleaning, wash water is incorporated to solution.
(4) finished product operation
By above-mentioned solution evaporation crystallisation by cooling, centrifugation, mother liquor is back to dissolution process, and crystallization is with 125 DEG CHot-air flow is dried, and excessively after 100 mesh sieves, obtains product 1#.
Embodiment 2
(1) alkali cleaning separation circuit
Preparation 2.5mol/LNaOH solution, adds rough nickel hydroxide former in the ratio of 200 grams of every liter of solutionMaterial, controls temperature 70 C, and making beating is stirred 2.0 hours, then controls 20 DEG C and continue to stir 1.5 hours, filtrateCan reclaim the element such as Zn, Cr, filter cake enters next-step operation.
Preparation 0.10mol/LNaOH solution, adds the wet of upper step processing in the ratio of 400 grams of every liter of solutionFilter cake, agitator treating 2.0 hours at 25 DEG C, press filtration separates, and filtrate is processed discharge, and filter cake is used againAgitator treating 2.0 hours at 25 DEG C of 0.10mol/LNaOH solution, press filtration separates, and filtrate is processed discharge,Filter cake enters next-step operation.
Wash 2 times in 60 DEG C of heat of the ratio of every liter of deionized water 300g wet cake, each 2 hours, press filtration dividedFrom, filtrate is processed discharge, and filter cake enters ammonia treatment operation.
(2) ammonia treatment operation
According to per kilogram filter cake 1.5L8mol/LNH4The ratio of OH solution is pulled an oar, and slurry crosses 100Mesh sieve, the airtight stirring of normal temperature 3 hours, press filtration separates, filter cake 1.2mol/LNH4OH solution normal temperature stirsMix washing 2 times, each 1.0 hours, press filtration separated, and three times filtrate merges, and filter residue recovery manganese etc. has valency goldBelong to, filtrate enters next-step operation.
Measure the content of Mg in solution, mole H such as add2SiF6Stirring at normal temperature is processed 1.5 hours, with 0.45The secondary filter of μ m filter membrane, filter residue is with separating after the washing of 1:4 deionized water, and merging filtrate enters next-step operation.
Above-mentioned filtrate is placed in coil pipe heating kettle, and Steam Heating, uses deionized water absorbing ammonia, heats up graduallyTo 80 DEG C and maintain 30 minutes, press filtration separates, and filtrate is processed discharge, filter cake with deionized water 1:4 at 60 DEG CAgitator treating 1.5 hours, press filtration separates, and filter cake enters and dissolves removal of impurities operation.
(3) dissolve removal of impurities operation
By above-mentioned filter cake 3.0mol/L sulfuric acid dissolution, adjusting pH is 1.0, measures Co in solutionContent, under stirring, add equimolar oxalic acid, control temperature 45 C stir 1.5 hours, press filtration separate,After solids wash, prepare cobalt salt, a small amount of wash water is incorporated to solution.
Use titanium plate as anode above-mentioned solution, copper coin is negative electrode, under 95 DEG C of 45A/ ㎡ electric currents, carries out electrolysisProcess, until copper content is less than 0.02ppm in solution, stop electrolysis, solution is in the ratio of every liter of 1.5molAdd technical grade 27.5% hydrogen peroxide, heating is boiled, and maintains gentle boil and uses 3mol/L after 30 minutesBa(OH)2It is 6.0 that solution is neutralized to pH value, and stir process is press filtration separation after 30 minutes, and filter residue goes on a small quantityAfter ion-cleaning, wash water is incorporated to solution.
(4) finished product operation
By above-mentioned solution evaporation crystallisation by cooling, centrifugation, mother liquor is back to dissolution process, and crystallization is with 125 DEG CHot-air flow is dried, and excessively after 100 mesh sieves, obtains product 2#.
Embodiment 3
(1) alkali cleaning separation circuit
Preparation 1.8mol/LNaOH solution, adds rough nickel hydroxide former in the ratio of 250 grams of every liter of solutionMaterial, controls 90 DEG C of temperature, and making beating is stirred 2.5 hours, then controls 25 DEG C and continue to stir 2.0 hours, filtrateCan reclaim the element such as Zn, Cr, filter cake enters next-step operation.
Preparation 0.15mol/LNaOH solution, adds the wet of upper step processing in the ratio of 450 grams of every liter of solutionFilter cake, agitator treating 2.5 hours at 30 DEG C, press filtration separates, and filtrate is processed discharge, and filter cake is used againAgitator treating 2.5 hours at 30 DEG C of 0.15mol/LNaOH solution, press filtration separates, and filtrate is processed discharge,Filter cake enters next-step operation.
Wash 2 times in 70 DEG C of heat of the ratio of every liter of deionized water 350g wet cake, each 2 hours, press filtration dividedFrom, filtrate is processed discharge, and filter cake enters ammonia treatment operation.
(2) ammonia treatment operation
According to per kilogram filter cake 2.5L10.5mol/LNH4The ratio of OH solution is pulled an oar, and slurry crosses 100Mesh sieve, the airtight stirring of normal temperature 4 hours, press filtration separates, filter cake 2mol/LNH4OH solution stirring at normal temperatureWash 2 times, each 1.5 hours, press filtration separated, and three times filtrate merges, and filter residue reclaims the valuable metals such as manganese,Filtrate enters next-step operation.
Measure the content of Mg in solution, mole H such as add2SiF6Stirring at normal temperature is processed 2.0 hours, with 0.45The secondary filter of μ m filter membrane, filter residue is with separating after the washing of 1:4 deionized water, and merging filtrate enters next-step operation.
Above-mentioned filtrate is placed in coil pipe heating kettle, and Steam Heating, uses deionized water absorbing ammonia, heats up graduallyTo 70 DEG C and maintain 30 minutes, press filtration separates, and filtrate is processed discharge, filter cake with deionized water 1:4 at 70 DEG CAgitator treating 2.0 hours, press filtration separates, and filter cake enters and dissolves removal of impurities operation.
(3) dissolve removal of impurities operation
By above-mentioned filter cake 3.5mol/L sulfuric acid dissolution, adjusting pH is 1.5, measures Co in solutionContent, under stirring, add equimolar oxalic acid, control temperature 50 C stir 2 hours, press filtration separate,After solids wash, prepare cobalt salt, a small amount of wash water is incorporated to solution.
Use titanium plate as anode above-mentioned solution, copper coin is negative electrode, under 95 DEG C of 45A/ ㎡ electric currents, carries out electrolysisProcess, until copper content is less than 0.02ppm in solution, stop electrolysis, solution is in the ratio of every liter of 1.5molAdd technical grade 27.5% hydrogen peroxide, heating is boiled, and maintains gentle boil and uses 3mol/L after 30 minutesBa(OH)2It is 6.5 that solution is neutralized to pH value, and stir process is press filtration separation after 30 minutes, and filter residue goes on a small quantityAfter ion-cleaning, wash water is incorporated to solution.
(4) finished product operation
By above-mentioned solution evaporation crystallisation by cooling, centrifugation, mother liquor is back to dissolution process, and crystallization is with 125 DEG CHot-air flow is dried, and excessively after 100 mesh sieves, obtains product 3#.
Nickelous sulfate weight content to product 1#-3#, each impurity weight content and nickel recovery are measured,The results are shown in following table
| 1# | 2# | 3# | |
| Nickel sulfate content % | 99.94 | 99.90 | 99.92 |
| K ppm | <5 | <5 | <5 |
| Na ppm | <10 | <10 | <10 |
| Ca ppm | 1.7 | 2.4 | 2.0 |
| Mg ppm | 3.2 | 3.6 | 3.2 |
| Cu ppm | <0.5 | <0.5 | <0.5 |
| Cr ppm | <0.5 | <0.5 | <0.5 |
| Fe ppm | <2.0 | <2.0 | <2.0 |
| Al ppm | <0.5 | <0.5 | <0.5 |
| Zn ppm | ND | ND | ND |
| Si ppm | ND | ND | ND |
| Mn ppm | ND | ND | ND |
| Nickel recovery % | 96.47 | 96.32 | 96.40 |
As seen from the above table, by method of the present invention, rough nickel hydroxide raw material is carried out obtaining after separating-purifying processingThe product arriving, nickel recovery >=96.32% (weight), nickel sulfate content >=99.90% (weight), andImpurity content is low, particularly, by weight, K content < 5ppm, Na content < 10ppm, Ca content≤ 2.4ppm, Mg content≤3.6ppm, Cu content < 0.5ppm, Cr content < 0.5ppm, Fe content< 2.0ppm, Al content < 0.5ppm, and not containing Zn, Si, Mn. As can be seen here, by of the present inventionMethod is carried out separating-purifying processing to rough nickel hydroxide raw material, has improved full nickel recovery, the sulfuric acid obtainingNickel product purity is high, can meet the requirement of downstream industry completely.
Claims (15)
1. a process for separation and purification for rough nickel hydroxide, is characterized in that, the method comprises following stepRapid:
(1) alkali cleaning separation circuit
(1.1) according to the ratio of 200-250 gram of every liter of NaOH solution, rough nickel hydroxide is joinedIn 1.8-2.5mol/LNaOH solution, Separation of Solid and Liquid after sufficient reacting, filter cake enters next step;
(1.2) according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution, step (1.1) is obtainedFilter cake joins in the NaOH solution of 0.1-0.15mol/L, Separation of Solid and Liquid after sufficient reacting, and filter cake entersNext step;
(2) ammonia treatment operation
(2.1) filter cake according to the ratio of per kilogram filter cake 1.5-3.5L solution, step (1.2) being obtained addsEnter to 8-10.5mol/LNH4In OH solution, carry out Separation of Solid and Liquid after sufficient reacting, filtrate enters next stepSuddenly;
(2.2) content of magnesium in the filtrate that determination step (2.1) obtains, mole H such as adds2SiF6Be stirred toSufficient reacting, Separation of Solid and Liquid, filtrate enters next step;
(2.3) filtrate step (2.2) being obtained is heated, and is warming up to gradually 70-85 DEG C, and maintainsTo sufficient reacting, Separation of Solid and Liquid, filter cake enters next step;
(3) dissolve removal of impurities operation
(3.1) filter cake sulfuric acid dissolution step (2.3) being obtained, adjustment pH value of solution is 1.0-1.5,Measure cobalt content in solution, mole oxalic acid such as add, be stirred to sufficient reacting, Separation of Solid and Liquid, filtrate entersNext step;
(3.2) filtrate step (3.1) being obtained is carried out electrolysis, until copper content is less than 0.02ppm in filtrateTime stop electrolysis, in filtrate, add hydrogen peroxide, heating is boiled, with adding Ba (OH) in backward solution2Solution is neutralized to pH value for 6-6.5, Separation of Solid and Liquid, to filtrate evaporate, cooling, crystallization, fromAnd obtain nickelous sulfate product.
2. the process for separation and purification of rough nickel hydroxide according to claim 1, is characterized in that,In step (1.1), rough nickel hydroxide is joined in NaOH solution, stir in a temperature 70-90 DEG C making beatingMix 2.0-2.5 hour, then continue to stir 1.5-2.0 hour at temperature 20-25 DEG C, to react fully.
3. the process for separation and purification of rough nickel hydroxide according to claim 1 and 2, its feature existsIn, in step (1.2), filter cake is joined in NaOH solution, carry out agitator treating at 25-30 DEG C2.0-2.5 hour.
4. the process for separation and purification of rough nickel hydroxide according to claim 1, is characterized in that,The filter cake that step (1.2) obtains is entering before ammonia treatment operation, first according to every liter of deionized water 300-350The ratio of gram filter cake is used deionized water to carry out heat to filter cake and washes.
5. the process for separation and purification of rough nickel hydroxide according to claim 4, is characterized in that,The filter cake that step (1.2) obtains is entering before ammonia treatment operation, first according to every liter of deionized water 300-350The ratio of gram filter cake is used deionized water, at 60-70 DEG C, filter cake is carried out to heat and washes 2 times, each 2 hours.
6. the process for separation and purification of rough nickel hydroxide according to claim 1, is characterized in that,In step (2.1), after sufficient reacting, carry out the filter cake 1.2-2.0mol/LNH that Separation of Solid and Liquid obtains4OHSolution washing, and then Separation of Solid and Liquid, carry out after the filtrate obtaining and sufficient reacting that Separation of Solid and Liquid obtainsFiltrate together enters step (2.2).
7. the process for separation and purification of rough nickel hydroxide according to claim 1, is characterized in that,In step (2.2), add H2SiF6After, stirring at normal temperature processing.
8. the process for separation and purification of rough nickel hydroxide according to claim 6, is characterized in that,In step (2.2), add H2SiF6After, stirring at normal temperature is processed 1.5-2.0 hour.
9. the process for separation and purification of rough nickel hydroxide according to claim 1, is characterized in that,In step (3.1), add after oxalic acid, control 45-50 DEG C of stir process of temperature.
10. the process for separation and purification of rough nickel hydroxide according to claim 9, is characterized in that,In step (3.1), add after oxalic acid, control 45-50 DEG C of stir process 1.5-2 hour of temperature.
The process for separation and purification of 11. rough nickel hydroxides according to claim 1, is characterized in that,In step (3.2), in solution, add hydrogen peroxide heating to boil; With Ba (OH)2Solution neutralizesTo pH value be 6-6.5, and stir process.
The process for separation and purification of 12. rough nickel hydroxides according to claim 11, is characterized in that,In step (3.2), after adding in solution hydrogen peroxide heating to boil, maintain gentle boil 30 minutes;With Ba (OH)2Solution is neutralized to pH value for 6-6.5, and stir process 30 minutes.
The process for separation and purification of 13. rough nickel hydroxides according to claim 1, is characterized in that,Nickel recovery >=96.32% (weight).
Prepared by the process for separation and purification of the rough nickel hydroxide described in 14. employing claim 1-9 any oneProduct, is characterized in that, nickel sulfate content >=99.90% (weight).
15. products according to claim 14, is characterized in that, by weight, and K content < 5ppm,Na content < 10ppm, Ca content≤2.4ppm, Mg content≤3.6ppm, Cu content < 0.5ppm,Cr content < 0.5ppm, Fe content < 2.0ppm, Al content < 0.5ppm.
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| CN87103814A (en) * | 1987-05-23 | 1988-12-14 | 张铨 | Electrolytic process is POV nickel from the nickel plating waste residue |
| CN101054685A (en) * | 2007-01-28 | 2007-10-17 | 罗爱平 | Method of supplying nickel to electrolyte for preparing cathode nickel by infusible anode electrodeposition method |
| CN101168453A (en) * | 2006-10-27 | 2008-04-30 | 北京有色金属研究总院 | Method for treating (SO4)2- impurity of spherical nickel hydroxide |
| CN103320811A (en) * | 2013-06-05 | 2013-09-25 | 中南大学 | Method for removing impurities from nickel electrolysis anolyte |
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| JP4746853B2 (en) * | 2004-07-12 | 2011-08-10 | 和光 加藤 | High purity metal hydroxide, purification method and production method thereof, hydroxide and oxide obtained by these methods, and synthetic resin composition and synthetic resin molded article |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103814A (en) * | 1987-05-23 | 1988-12-14 | 张铨 | Electrolytic process is POV nickel from the nickel plating waste residue |
| CN101168453A (en) * | 2006-10-27 | 2008-04-30 | 北京有色金属研究总院 | Method for treating (SO4)2- impurity of spherical nickel hydroxide |
| CN101054685A (en) * | 2007-01-28 | 2007-10-17 | 罗爱平 | Method of supplying nickel to electrolyte for preparing cathode nickel by infusible anode electrodeposition method |
| CN103320811A (en) * | 2013-06-05 | 2013-09-25 | 中南大学 | Method for removing impurities from nickel electrolysis anolyte |
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