CN104140129A - Separation and purification method of rough nickel hydroxide and obtained product thereof - Google Patents
Separation and purification method of rough nickel hydroxide and obtained product thereof Download PDFInfo
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- CN104140129A CN104140129A CN201410371129.3A CN201410371129A CN104140129A CN 104140129 A CN104140129 A CN 104140129A CN 201410371129 A CN201410371129 A CN 201410371129A CN 104140129 A CN104140129 A CN 104140129A
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Abstract
The invention relates to a separation and purification method of rough nickel hydroxide. The method comprises the alkali wash separation process, the ammonia treatment process and the dissolution and impurity removal process. According to the method, the technological condition is moderate, separation and purification are conducted on the rough nickel hydroxide, the recovery efficiency of all nickel is improved, a nickel sulfate product obtained through the method is high in purity, and the impurity content is low.
Description
Technical field
The present invention relates to fine inorganic chemicals technical field, the high-purity sulphuric acid nickel product that particularly relates to a kind of separating and purifying method of rough nickel hydroxide and obtained by the method.
Background technology
Along with the development of lithium ion battery ternary material, the quality cost of nickel compound has been proposed to new requirement, part material produce producer adopts metallic nickel or tertiary cathode body reclaimed materials process or purify and produce single nickel salt or nickelous chloride product through relatively simple.But, for the larger rough nickel hydroxide raw material of quantity, due to its 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 purification and is realizing efficient recovery to nickel.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of separating and purifying method of rough nickel hydroxide, to improve the organic efficiency of full nickel.
The separating and purifying method 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 joined in 1.8-2.5mol/L NaOH solution, solid-liquid separation after sufficient reacting, filter cake enters next step;
(1.2) filter cake according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution, step (1.1) being obtained joins in the NaOH solution of 0.1-0.15mol/L, solid-liquid separation after sufficient reacting, and filter cake enters next 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 joins 8-10.5mol/L NH
4in OH solution, carry out solid-liquid separation after sufficient reacting, filtrate enters next step;
(2.2) Mg content in the filtrate that determination step (2.1) obtains, mole H such as adds
2siF
6be stirred to sufficient reacting, solid-liquid separation, 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 is maintained until sufficient reacting, solid-liquid separation, and 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, measures cobalt contents in solution, mole oxalic acid such as adds, and is stirred to sufficient reacting, solid-liquid separation, filtrate enters next step;
(3.2) filtrate step (3.1) being obtained is carried out electrolysis, until stop electrolysis when copper content is less than 0.02ppm in filtrate, in filtrate, adds hydrogen peroxide, and heated and boiled, with adding Ba (OH) in backward solution
2solution is neutralized to pH value for 6-6.5, solid-liquid separation, to filtrate evaporate, cooling, crystallization, thereby obtain single nickel salt product.
The separating and purifying method of aforesaid rough nickel hydroxide, in step (1.1), rough nickel hydroxide is joined in NaOH solution, stir 2.0-2.5 hour temperature 70-90 DEG C of making beating, continue to stir 1.5-2.0 hour at temperature 20-25 DEG C again, to react fully.
The separating and purifying method of aforesaid rough nickel hydroxide, in step (1.2), joins filter cake in NaOH solution, carries out agitator treating 2.0-2.5 hour at 25-30 DEG C.
The separating and purifying method of aforesaid rough nickel hydroxide, the filter cake that step (1.2) obtains, entering before ammonia treatment operation, first uses deionized water to carry out heat to filter cake according to the ratio of every liter of deionized water 300-350 gram filter cake and washes, preferably, wash 2 times each 2 hours 60-70 DEG C of heat.
The separating and purifying method of aforesaid rough nickel hydroxide, in step (2.1), carries out the filter cake 1.2-2.0mol/L NH that solid-liquid separation obtains after sufficient reacting
4oH solution washing, and then solid-liquid separation, carry out the filtrate that solid-liquid separation obtains and together enter step (2.2) after the filtrate obtaining and sufficient reacting.
The separating and purifying method of aforesaid rough nickel hydroxide, in step (2.2), adds H
2siF
6after, stirring at normal temperature processing, preferably treatment 1.5-2.0 hour.
The separating and purifying method of aforesaid rough nickel hydroxide, in step (3.1), adds after oxalic acid, controls 45-50 DEG C of stir process of temperature, preferably treatment 1.5-2 hour.
The separating and purifying method of aforesaid rough nickel hydroxide in step (3.2), adds after hydrogen peroxide heated and boiled in solution, preferably maintains gentle boil 30 minutes; With Ba (OH)
2solution is neutralized to pH value for 6-6.5, and stir process, preferably stir process 30 minutes.
Method processing condition gentleness of the present invention, taking the rough nickel hydroxide of complicated components as raw material, by its 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 processing, its nickel sulfate content >=99.90% (weight), and foreign matter 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.
Brief description of the drawings
Fig. 1 is the process flow sheet of the rough nickel hydroxide separating and purifying method of the present invention.
Embodiment
In order fully to understand object of the present invention, feature and effect, by following embodiment, the present invention is elaborated.Processing method of the present invention is except following content, and all the other all adopt ordinary method or the device of this area.
The present invention separate by alkaline purification, ammonia and common-ion effcet to the separation of purifying of rough nickel hydroxide raw material, improved raw materials recovery rate.Method of the present invention does not have special requirement to rough nickel hydroxide raw material, and the rough nickel hydroxide that the conventional commercial run of every employing obtains, all can adopt method of the present invention to carry out separating-purifying, and can prepare the single nickel salt product that purity is high, foreign matter content is low.
As shown in Figure 1, the separating and purifying method 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, add rough nickel hydroxide raw material according to the ratio of 200-250 gram of every liter of NaOH solution, be stirred to sufficient reacting, squeezing press filtration separates, the filtrate obtaining can be reclaimed the element such as Zn and Cr, and the filter cake obtaining enters next step operation.
Preferably, after rough nickel hydroxide raw material being joined in 1.8-2.5mol/L (preferably 2mol/L) NaOH solution according to the ratio of 200-250 gram of every liter of NaOH solution, first temperature is controlled to 70-90 DEG C, 2.0-2.5 hour is stirred in making beating, under comparatively high temps, process and be conducive to improve the speed of response such as Zn, Al, then, then temperature is controlled to 20-25 DEG C, continue to stir 1.5-2.0 hour, it is mainly the hydrolysis in order to prevent Cr that reduction temperature is processed.
(1.2) the NaOH solution of preparation 0.1-0.15mol/L, the filter cake that adds above-mentioned steps (1.1) to obtain according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution, agitator treating 2 times, press filtration separates, and filter cake enters next step.
Preferably, after filter cake being joined according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution in the NaOH solution of 0.1-0.15mol/L, at 25-30 DEG C, agitator treating 2.0-2.5 hour, press filtration separates, and filtrate is processed discharge, filter cake uses the NaOH solution of 0.1-0.15mol/L at 25-30 DEG C of agitator treating 2.0-2.5 hour again, 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, wash 2 times by the filter cake heat that deionized water obtains above-mentioned steps (1.2), 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＝NaCrO
2+2H
2O
Zn(OH)
2+NaOH＝NaHZnO
2+H
2O
Al(OH)
3+NaOH＝NaAlO
2+2H
2O
(2) ammonia treatment operation
(2.1) filter cake according to the ratio of per kilogram filter cake 1.5-3.5L (preferably 2.5L) solution, step (1.3) being obtained joins 8-10.5mol/L (preferably 10mol/L) NH
4in OH solution, pull an oar, NH
4the 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, and press filtration separates, 1.2-2.0mol/L for filter cake (preferably 1.5mol/L) NH
4oH solution washing 2 times, preferably agitator treating 2 times under normal temperature condition, each 1.0-1.5 hour.Then, press filtration separates, and three times filtrate merges, and filter residue is used for reclaiming the valuable metals such as manganese, and filtrate enters next step.
Preferably, filter cake joins NH
4after OH solution is pulled an oar, slurry is first crossed 100 mesh sieves (i.e. 150 tm screen), and then the airtight stirring of normal temperature 3-4 hour is to react fully.
(2.2) Mg content in the filtrate that determination step (2.1) obtains, mole H such as adds
2siF
6be stirred to sufficient reacting, preferably stir process 1.5-2.0 hour at normal temperatures.Then carry out secondary filter, preferably use the filter membrane of 0.45 μ m.After secondary filter, filter residue is with separating after 1:4 deionized water wash, and merging filtrate enters next step.
(2.3) filtrate above-mentioned steps (2.2) being obtained (is for example placed in heating kettle, coil pipe heating kettle) in, steam heating, use deionized water absorbing ammonia, be warming up to gradually 70-85 DEG C (preferably 80-85 DEG C), and be maintained until sufficient reacting (preferably maintaining 30 minutes), press filtration separates, filtrate is processed discharge, deionized water wash for filter cake (preferably 1:460-70 DEG C of agitator treating 1.5-2 hour), press filtration separates again, and the filter cake obtaining enters and dissolves removal of impurities operation.
Ammonia treatment operation relates generally to following chemical reaction:
Mg(OH)
2+H
2SiF
6＝MgSiF
6↓+2H
2O
(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 obtained dissolves, adjustment pH value of solution is 1.0-1.5, measure cobalt contents in solution, mole oxalic acid such as under stirring, add, be stirred to sufficient reacting, press filtration separate, filter cake through washing after for the preparation of cobalt salt, a small amount of wash water is incorporated to solution, and 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, to react fully.
(3.2) solution above-mentioned steps (3.1) being obtained carries out electrolysis, until stop electrolysis when copper content is less than 0.02ppm in solution, in a kind of embodiment, taking titanium plate as anode, copper coin is negative electrode, at 95 DEG C, and 45A/m
2under electric current, carry out electrolysis.
Stop after electrolysis, in solution, add hydrogen peroxide, preferably, add the ratio of 1.5mol to add technical grade 27.5% (weight) hydrogen peroxide according to every liter of solution.Then, heated and boiled, with adding Ba (OH) in backward solution
2solution (the preferably Ba (OH) of 3mol/L
2solution) be neutralized to pH value for 6-6.5, stir process 30 minutes, press filtration separates, and with a small amount of deionized water, filter residue is washed, and wash water is incorporated to solution.By above-mentioned solution evaporation crystallisation by cooling, centrifugation, mother liquor is back to above-mentioned steps (3.1), and hot-air flow for crystallization (preferably 125 DEG C) is dried, and excessively after 100 mesh sieves, obtains product.
Embodiment
First during, to the raw material relating in embodiment below and product analysis, determinator and measuring method used 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: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, 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.
Single nickel salt weight content measuring method: adopt EDTA complexometry.
Nickel recovery measuring method: adopt ICP method.
The all ingredients using in embodiment is conventional commercial obtaining.
Embodiment 1
(1) alkali cleaning separation circuit
Preparation 2mol/L NaOH solution, adds rough nickel hydroxide raw material in the ratio of 230 grams of every liter of solution, controls 80 DEG C of temperature, making beating is stirred 2.2 hours, control 23 DEG C again and continue to stir 1.8 hours, filtrate can be reclaimed the element such as Zn, Cr, and filter cake enters next-step operation.
Preparation 0.13mol/L NaOH solution, add the wet cake of upper step processing in the ratio of 430 grams of every liter of solution, agitator treating 2.3 hours at 28 DEG C, press filtration separates, filtrate is processed discharge, and filter cake is used at 28 DEG C of 0.13mol/L NaOH solution agitator treating 2.3 hours again, and press filtration separates, filtrate is processed discharge, and 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 separated, and filtrate is processed discharge, and filter cake enters ammonia treatment operation.
(2) ammonia treatment operation
According to per kilogram filter cake 2.5L 10mol/L NH
4the ratio of OH solution is pulled an oar, and slurry is crossed 100 mesh sieves, the airtight stirring of normal temperature 4 hours, and press filtration separates, filter cake 1.5mol/L NH
4oH solution stirring at normal temperature washing 2 times, each 1.3 hours, press filtration separated, and three times filtrate merges, and filter residue reclaims the valuable metals such as manganese, and filtrate enters next-step operation.
Measure the content of Mg in solution, mole H such as add
2siF
6stirring at normal temperature is processed 1.8 hours, and with 0.45 μ m filter membrane secondary filter, filter residue is with separating after 1:4 deionized water wash, 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, be warming up to gradually 85 DEG C and maintain 30 minutes, press filtration separates, and filtrate is processed discharge, filter cake is with deionized water 1:4 65 DEG C of agitator treatings 1.8 hours, and 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 the content of Co in solution, adds equimolar oxalic acid under stirring, controls 49 DEG C of temperature and stirs 1.8 hours, and press filtration separates, and prepares cobalt salt after solids wash, and a small amount of wash water is incorporated to solution.
Use titanium plate as anode above-mentioned solution, copper coin is negative electrode, 95 DEG C of 45A/m
2under electric current, carry out electrolysis treatment, until copper content is less than 0.02ppm in solution, stop electrolysis, solution adds technical grade 27.5% hydrogen peroxide in the ratio of every liter of 1.5mol, and heated and boiled maintains gentle boil and after 30 minutes, uses 3mol/LBa (OH)
2it is 6.3 that solution is neutralized to pH value, and stir process is press filtration separation after 30 minutes, and after a small amount of deionization washing of filter residue, 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 dried with 125 DEG C of hot-air flows, excessively after 100 mesh sieves, obtains product 1#.
Embodiment 2
(1) alkali cleaning separation circuit
Preparation 2.5mol/L NaOH solution, adds rough nickel hydroxide raw material in the ratio of 200 grams of every liter of solution, controls temperature 70 C, making beating is stirred 2.0 hours, control 20 DEG C again and continue to stir 1.5 hours, filtrate can be reclaimed the element such as Zn, Cr, and filter cake enters next-step operation.
Preparation 0.10mol/L NaOH solution, add the wet cake of upper step processing in the ratio of 400 grams of every liter of solution, agitator treating 2.0 hours at 25 DEG C, press filtration separates, filtrate is processed discharge, and filter cake is used at 25 DEG C of 0.10mol/L NaOH solution agitator treating 2.0 hours again, and press filtration separates, filtrate is processed discharge, and 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 separated, and filtrate is processed discharge, and filter cake enters ammonia treatment operation.
(2) ammonia treatment operation
According to per kilogram filter cake 1.5L 8mol/L NH
4the ratio of OH solution is pulled an oar, and slurry is crossed 100 mesh sieves, the airtight stirring of normal temperature 3 hours, and press filtration separates, filter cake 1.2mol/L NH
4oH solution stirring at normal temperature washing 2 times, each 1.0 hours, press filtration separated, and three times filtrate merges, and filter residue reclaims the valuable metals such as manganese, and filtrate enters next-step operation.
Measure the content of Mg in solution, mole H such as add
2siF
6stirring at normal temperature is processed 1.5 hours, and with 0.45 μ m filter membrane secondary filter, filter residue is with separating after 1:4 deionized water wash, 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, be warming up to gradually 80 DEG C and maintain 30 minutes, press filtration separates, and filtrate is processed discharge, filter cake is with deionized water 1:4 60 DEG C of agitator treatings 1.5 hours, and press filtration separates, and filter cake enters and dissolves removal of impurities operation.
(3) dissolve removal of impurities operation
By 3.0 mol/L sulfuric acid dissolutions for above-mentioned filter cake, adjusting pH is 1.0, measures the content of Co in solution, under stirring, add equimolar oxalic acid, control temperature 45 C and stir 1.5 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, carry out electrolysis treatment, until copper content is less than 0.02ppm in solution, stop electrolysis, solution adds technical grade 27.5% hydrogen peroxide in the ratio of every liter of 1.5mol, and heated and boiled maintains gentle boil and after 30 minutes, uses 3mol/LBa (OH)
2it is 6.0 that solution is neutralized to pH value, and stir process is press filtration separation after 30 minutes, and after a small amount of deionization washing of filter residue, 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 dried with 125 DEG C of hot-air flows, excessively after 100 mesh sieves, obtains product 2#.
Embodiment 3
(1) alkali cleaning separation circuit
Preparation 1.8mol/L NaOH solution, adds rough nickel hydroxide raw material in the ratio of 250 grams of every liter of solution, controls 90 DEG C of temperature, making beating is stirred 2.5 hours, control 25 DEG C again and continue to stir 2.0 hours, filtrate can be reclaimed the element such as Zn, Cr, and filter cake enters next-step operation.
Preparation 0.15mol/L NaOH solution, add the wet cake of upper step processing in the ratio of 450 grams of every liter of solution, agitator treating 2.5 hours at 30 DEG C, press filtration separates, filtrate is processed discharge, and filter cake is used at 30 DEG C of 0.15mol/L NaOH solution agitator treating 2.5 hours again, and press filtration separates, filtrate is processed discharge, and 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 separated, and filtrate is processed discharge, and filter cake enters ammonia treatment operation.
(2) ammonia treatment operation
According to per kilogram filter cake 2.5L 10.5mol/L NH
4the ratio of OH solution is pulled an oar, and slurry is crossed 100 mesh sieves, the airtight stirring of normal temperature 4 hours, and press filtration separates, filter cake 2mol/L NH
4oH solution stirring at normal temperature washing 2 times, each 1.5 hours, press filtration separated, and three times filtrate merges, and filter residue reclaims the valuable metals such as manganese, and filtrate enters next-step operation.
Measure the content of Mg in solution, mole H such as add
2siF
6stirring at normal temperature is processed 2.0 hours, and with 0.45 μ m filter membrane secondary filter, filter residue is with separating after 1:4 deionized water wash, 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, be warming up to gradually 70 DEG C and maintain 30 minutes, press filtration separates, and filtrate is processed discharge, filter cake is with deionized water 1:4 70 DEG C of agitator treatings 2.0 hours, and 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 the content of Co in solution, adds equimolar oxalic acid under stirring, controls temperature 50 C and stirs 2 hours, and press filtration separates, and prepares cobalt salt after solids wash, and a small amount of wash water is incorporated to solution.
Use titanium plate as anode above-mentioned solution, copper coin is negative electrode, 95 DEG C of 45A/m
2under electric current, carry out electrolysis treatment, until copper content is less than 0.02ppm in solution, stop electrolysis, solution adds technical grade 27.5% hydrogen peroxide in the ratio of every liter of 1.5mol, and heated and boiled maintains gentle boil and after 30 minutes, uses 3mol/LBa (OH)
2it is 6.5 that solution is neutralized to pH value, and stir process is press filtration separation after 30 minutes, and after a small amount of deionization washing of filter residue, 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 dried with 125 DEG C of hot-air flows, excessively after 100 mesh sieves, obtains product 3#.
Single nickel salt weight content to product 1#-3#, each impurity weight content and nickel recovery are measured, and 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 to the product obtaining after separating-purifying processing, nickel recovery >=96.32% (weight), nickel sulfate content >=99.90% (weight), and foreign matter 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 method of the present invention, rough nickel hydroxide raw material is carried out to separating-purifying processing, improved full nickel recovery, the single nickel salt product purity obtaining is high, can meet the requirement of downstream industry completely.
Claims (11)
1. a separating and purifying method for rough nickel hydroxide, is characterized in that, 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 joined in 1.8-2.5mol/L NaOH solution, solid-liquid separation after sufficient reacting, filter cake enters next step;
(1.2) filter cake according to the ratio of 400-450 gram of filter cake of every liter of NaOH solution, step (1.1) being obtained joins in the NaOH solution of 0.1-0.15mol/L, solid-liquid separation after sufficient reacting, and filter cake enters next 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 joins 8-10.5mol/L NH
4in OH solution, carry out solid-liquid separation after sufficient reacting, filtrate enters next step;
(2.2) Mg content in the filtrate that determination step (2.1) obtains, mole H such as adds
2siF
6be stirred to sufficient reacting, solid-liquid separation, 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 is maintained until sufficient reacting, solid-liquid separation, and 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, measures cobalt contents in solution, mole oxalic acid such as adds, and is stirred to sufficient reacting, solid-liquid separation, filtrate enters next step;
(3.2) filtrate step (3.1) being obtained is carried out electrolysis, until stop electrolysis when copper content is less than 0.02ppm in filtrate, in filtrate, adds hydrogen peroxide, and heated and boiled, with adding Ba (OH) in backward solution
2solution is neutralized to pH value for 6-6.5, solid-liquid separation, to filtrate evaporate, cooling, crystallization, thereby obtain single nickel salt product.
2. the separating and purifying method of rough nickel hydroxide according to claim 1, it is characterized in that, in step (1.1), rough nickel hydroxide is joined in NaOH solution, stir 2.0-2.5 hour temperature 70-90 DEG C of making beating, continue to stir 1.5-2.0 hour at temperature 20-25 DEG C again, to react fully.
3. the separating and purifying method of rough nickel hydroxide according to claim 1 and 2, is characterized in that, in step (1.2), filter cake is joined in NaOH solution, carries out agitator treating 2.0-2.5 hour at 25-30 DEG C.
4. according to the separating and purifying method of the rough nickel hydroxide described in claim 1-3 any one, it is characterized in that, the filter cake that step (1.2) obtains is entering before ammonia treatment operation, first using deionized water to carry out heat to filter cake according to the ratio of every liter of deionized water 300-350 gram filter cake washes, preferably, wash 2 times each 2 hours 60-70 DEG C of heat.
5. according to the separating and purifying method of the rough nickel hydroxide described in claim 1-4 any one, it is characterized in that, in step (2.1), after sufficient reacting, carry out the filter cake 1.2-2.0mol/LNH that solid-liquid separation obtains
4oH solution washing, and then solid-liquid separation, carry out the filtrate that solid-liquid separation obtains and together enter step (2.2) after the filtrate obtaining and sufficient reacting.
6. according to the separating and purifying method of the rough nickel hydroxide described in claim 1-5 any one, it is characterized in that, in step (2.2), add H
2siF
6after, stirring at normal temperature processing, preferably treatment 1.5-2.0 hour.
7. according to the separating and purifying method of the rough nickel hydroxide described in claim 1-6 any one, it is characterized in that, in step (3.1), add after oxalic acid, control 45-50 DEG C of stir process of temperature, preferably treatment 1.5-2 hour.
8. according to the separating and purifying method of the rough nickel hydroxide described in claim 1-7 any one, it is characterized in that, in step (3.2), in solution, add after hydrogen peroxide heated and boiled, preferably maintain gentle boil 30 minutes; With Ba (OH)
2solution is neutralized to pH value for 6-6.5, and stir process, preferably stir process 30 minutes.
9. according to the separating and purifying method of the rough nickel hydroxide described in claim 1-8 any one, it is characterized in that nickel recovery >=96.32% (weight).
10. the product that prepared by the separating and purifying method of the rough nickel hydroxide described in employing claim 1-9 any one, is characterized in that nickel sulfate content >=99.90% (weight).
11. products according to claim 10, it is characterized in that, 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.
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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 |
| JP2006027913A (en) * | 2004-07-12 | 2006-02-02 | Kazumitsu Kato | High purity metal hydroxide, its refining method and production method, hydroxide and oxide obtained by their methods, and synthetic resin composition and synthetic resin molded article |
| 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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|---|---|---|---|---|
| CN87103814A (en) * | 1987-05-23 | 1988-12-14 | 张铨 | Electrolytic process is POV nickel from the nickel plating waste residue |
| JP2006027913A (en) * | 2004-07-12 | 2006-02-02 | Kazumitsu Kato | High purity metal hydroxide, its refining method and production method, hydroxide and oxide obtained by their methods, and synthetic resin composition and synthetic resin molded article |
| 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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