CN102557153B - Method for removing calcium-magnesium impurities from nickel sulfate solution - Google Patents
Method for removing calcium-magnesium impurities from nickel sulfate solution Download PDFInfo
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Abstract
The invention discloses a method for removing calcium-magnesium impurities from a nickel sulfate solution. The method comprises the following steps of: (1) heating a nickel sulfate raw material solution, concentrating, cooling and removing a precipitated solid; (2) extracting a filtrate obtained in the step (1) with a phosphorus-containing extracting agent; and adding nickel fluoride into a raffinate obtained in the step (2), heating to 60-90 DEG C for reacting, cooling and filtering to obtain a needed nickel sulfate solution. Due to the adoption of the method, the using amount of a fluorine salt and the discharge of fluorine-containing waste water are greatly reduced, and new impurity irons are not introduced, the nickel yield is high; and the method is particularly suitable for sulfate systems with high calcium content and low magnesium content.
Description
Technical field
The present invention relates in a kind of nickel sulfate solution and go deimpurity method, particularly a kind of method removing calcium magnesium addition from nickel sulfate solution.
Background technology
At present, for the minimizing technology of nickel sulfate solution calcium magnesium addition, the chemical precipitation methods such as Sodium Fluoride, Neutral ammonium fluoride or hydrofluoric acid are generally adopted to remove.Villiaumite precipitator method calcium-magnesium removing is effective, but its drawback is embodied in following four aspects:
1) system that is incorporated as of villiaumite introduces new positively charged ion, as sodium ion, ammonium ion, is difficult to remove, have impact on the quality of nickel sulfate hexahydrate crystal in subsequent handling;
2) fluoride salt consumption amount is large, and price is more expensive, and raw materials cost is high;
3) villiaumite and calcium ions and magnesium ions temperature of reaction high, the time is long, and on the one hand energy consumption is large, and part of nickel also can be precipitated out with the form of nickelous fluoride on the other hand, causes the loss of nickel;
4) because villiaumite excess coefficient is large, in process, a large amount of fluoride wastes can be produced, extremely difficult;
In recent years discloseder new technology adopts two-(2-ethylhexyl) phosphonic acids (to be called for short P
204) and 2-ethylhexyl phosphoric acid-2-(ethyl hexyl) ester (abbreviation P
507) be extraction agent, what reach calcium magnesium and nickel by stepwise solvent extraction is separated object.Chinese patent CN101532094 and CN101148698, to calcium and the high acid nickel of magnesium addition content or copper leach liquor, adopted P before this
204removing calcium with solvent extraction, then adopts P
507stepwise solvent extraction cobalt and magnesium, realize the removal of calcium magnesium.CN1752232 adopts P
507the method of one step extracting and separating nickel, magnesium, cobalt from nickel sulfate solution.P
507extraction agent price is higher, has fabulous selectivity to cobalt, also has certain extractibility to magnesium, if but not containing cobalt in solution, generally do not adopt P
507extract, because P
507raw materials cost is higher.And adopt P simultaneously
204and P
507stepwise solvent extraction calcium and magnesium, whole extraction procedure is tediously long, adds difficulty and the cost of extraction process control.
In addition, for the system that calcium contents in nickel sulfate solution is higher, although it is clean to adopt extraction process calcium magnesium can be removed, but very large problem is there is when back extraction, this solubleness mainly due to calcium sulfate is low, easily separate out in back extraction, form the third phase (solid phase) outside aqueous phase and oil phase, bring very large inconvenience to phase-splitting and follow-up back extraction.
Therefore, in the urgent need to a kind of method removing the energy-conserving and environment-protective of calcium magnesium addition from nickel sulfate solution of efficient, low cost.
Summary of the invention
The present invention is for solving above-mentioned the deficiencies in the prior art, provides a kind of method removing the energy-conserving and environment-protective of calcium magnesium addition from nickel sulfate solution.
The present invention is directed in nickel sulfate solution the calcium, the magnesium addition that there is high level, adopt and concentrate, extract and put the way enough combined, calcium magnesium addition is removed, the nickel sulfate solution be purified.Specifically, the method that the present invention removes calcium magnesium addition from nickel sulfate solution comprises following step:
1) heating of single nickel salt material solution is concentrated, cools and remove the solid be settled out;
2) with the filtrate obtained in phosphorus-contained extractant extraction step (1); With
3) add nickelous fluoride in the raffinate obtained in step (2), after being heated to 60 ~ 90 DEG C of reactions, after cooling and filtration, obtain required nickel sulfate solution.
Compared with prior art, the method synthesis of the present invention advantage of extraction and villiaumite calcium-magnesium removing, but greatly reduce the consumption of villiaumite and the discharge of fluoride waste, and new foreign ion can not be introduced, nickel yield is high, be particularly useful for that calcic is high, containing the not high sulfate system of magnesium, Impurity removal is effective.Method of the present invention, can not cause environmental pollution, has the advantage of energy-conserving and environment-protective.
Embodiment:
In one preferred embodiment, the present invention removes the 1st step of the method for calcium magnesium addition from nickel sulfate solution is the heating of single nickel salt material solution concentrated, cool and remove the solid be settled out.In one preferred embodiment, the heating of single nickel salt material solution being concentrated into density is 1.4 ~ 1.5g/cm
3.
Can be the acid concentrated solution of nickel-plating waste water comprising calcium and magnesium addition with the single nickel salt material solution of the inventive method process, preferably sulphuric acid concentration liquid; Or the pickling bath liquor of nickel ores raw material, preferably sulfuric acid steeping fluid.With the sulphuric leachate that the single nickel salt material solution of the inventive method process also can be ni-mh and/or NI-G electrode waste material.Also can be the mixture of above-mentioned solution.Above-mentioned sulphuric acid concentration liquid, sulfuric acid steeping fluid or sulphuric leachate can be transformed by concentrated solution, steeping fluid or the leach liquor of other acid (being preferably the inorganic acid of nitric acid or hydrochloric acid and so on).
In one preferred embodiment, first deironing is carried out to single nickel salt material solution, such as, with hydrolysis and neutralization as known in the art or yellow modumite method, iron ion purification can be removed.
In nickel sulfate solution after deironing, nickel content is usually lower, has to pass through and concentrates and could prepare nickel sulfate hexahydrate crystal.Above-mentioned heating concentrates can be undertaken by method conventional in this area, and such as normal heating is concentrated or heating under reduced pressure is concentrated.By single nickel salt material solution cooling concentrated for heating, be preferably cooled to room temperature (being about 10 ~ 20 DEG C).Now most of calcium sulfate is separated out in solid form, reaches the object of removal after solid-liquid separation, obtains the nickel sulfate solution that calcium content is lower.
Therefore, the present invention concentrates the operation of deliming, not only serves the effect of deliming, and is concentrated by solution in advance, obtains the nickel sulfate solution of high nickel content, decreases the liquid phase volume of follow-up extraction process and the pressure of calcium sulfate generation.No matter adopt which kind of removal of impurities way, concentrating before crystallization is all necessary, and therefore concentrated deliming operation is except having more the step of a step solid-liquid separation, can not bring any extra raw material and energy consumption cost.
The 2nd step that the present invention removes the method for calcium magnesium addition from nickel sulfate solution is the filtrate with obtaining in phosphorus-contained extractant extraction step (1).
In the inventive method the 2nd step, phosphorus-contained extractant used is phosphorus-contained extractant conventional in this area.Preferred phosphorus-contained extractant is that two-(2-ethylhexyl) phosphonic acids (are called for short P
204) and 2-ethylhexyl phosphoric acid-2-(ethyl hexyl) ester (abbreviation P
507).Consider cost, preferred phosphorus-contained extractant is that two-(2-ethylhexyl) phosphonic acids (are called for short P
204).
In one preferred embodiment, P is used
204the filtrate obtained in organic phase counter-current extraction step (1), is extracted into organic phase by the calcium of iron, copper, zinc and non-Ex-all and part magnesium, obtains the raffinate that calcic is qualified.Organic phase after extraction is called load organic phases, and phosphorus-contained extractant, after dilute sulphuric acid and hydrochloric acid back extraction regeneration, continues to enter extracting system.
Above-mentioned P
204organic phase is by the P as extraction agent
204form with the kerosene as thinner, P
204mass ratio in organic phase is 10 ~ 20%, and the ratio of organic phase and aqueous phase is 1: 1.Before extraction, organic phase first should carry out saponification with sodium hydroxide solution, and saponification degree is 50%, then after being converted to nickel soap, becomes final extraction agent.During extraction, the pH value of the filtrate obtained in rate-determining steps (1) is 3.5 ~ 4.5, and after 4 ~ 10 stage countercurrent extractions, obtain qualified raffinate, in qualified raffinate, the concentration of calcium can drop to below 5mg/l.
Load organic phases, first carries out 4 ~ 6 grades with 0.2N dilute sulphuric acid and washes nickel, then carries out 3 ~ 4 grades of anti-copper zinc with 1 ~ 2N hydrochloric acid, finally carries out 2 ~ 3 grades of back extraction iron with 6N hydrochloric acid.Organic phase after anti-iron sends to soapmaking again.
Wash in nickel process, the pH value controlling first step feed liquid is 1 ~ 1.5, and fully to reclaim the nickel in organic phase, now in organic phase, part copper, zinc, magnesium also enter in anti-nickel liquid.When in the anti-nickel liquid of the first step, the concentration of nickel reaches 40 ~ 50g/l, controlling material liquid PH value is 4 ~ 4.5, and make to enter the copper in anti-nickel liquid, zinc reenters organic phase, anti-nickel liquid delivers to nickel soap processed after reclaiming.
In anti-copper zinc calcium process, magnesium, calcium together by back extraction in aqueous phase.For reclaiming valuable metal copper wherein, sodium hydroxide can be added precipitation recovery is carried out to copper.
The 3rd step that the present invention removes the method for calcium magnesium addition from nickel sulfate solution adds nickelous fluoride in the raffinate obtained in step (2), after being heated to 60 ~ 90 DEG C of reactions, obtains required nickel sulfate solution after cooling and filtration.In one preferred embodiment, 70 ~ 80 DEG C of reactions are heated to.The time of reacting by heating is generally 20 minutes to 1 hour, is preferably 20 ~ 40 minutes, is more preferably about 30 minutes.
Because the clearance of magnesium in removal of impurities in early stage operation is limited, still containing higher magnesium in raffinate, need to remove.In order to not introduce new metallic impurity, the present invention adopts nickelous fluoride to replace magnesium, concrete grammar is, nickelous fluoride pressed powder is added in the raffinate obtained in the 2nd step under stirring, be heated to 70 ~ 80 DEG C of reactions after 20 minutes to 1 hour, after preferred reaction half an hour, the magnesium in solution is with magnesium fluoride Precipitation, filter, obtain the nickel sulfate solution that calcium magnesium addition content is qualified.
Nickelous fluoride pressed powder used in the inventive method is commercially available product, the nickelous fluoride pressed powder preferably more than chemical pure.The consumption of nickelous fluoride pressed powder is depending on the content of magnesium remaining in raffinate.Usually, in the raffinate of 100 weight parts, add the nickelous fluoride pressed powder of 0.1 ~ 10 weight part, preferably add 0.5 ~ 5 weight part nickelous fluoride pressed powder.
Although do not want by concrete theoretical constraint, but the present inventor unexpectedly finds, add enough nickelous fluoride pressed powders in the raffinate obtained in the 2nd step, and after reacting by heating certain hour, effectively can reduce the content of calcium-magnesium ratio compound impurity in nickel sulfate solution.
Calcium contents in the nickel sulfate solution that step (3) processes can be reduced to below 5mg/l, and the content of magnesium can be reduced to below 0.5g/l, preferably can be reduced to below 0.4g/l.
Due to meeting residual minim organism in raffinate, in order to obtain the nickel sulfate hexahydrate crystal of high-quality, need to use gac oil removing.Nickelous fluoride of the present invention preferably adds together with gac, reaches the double effects of demagging oil removing, is not only conducive to the simplification of flow process, can also save energy and reduce the cost.
Gac used in the inventive method is gac conventional in this area.The consumption of gac is depending on organic amount remaining in raffinate.Usually, in the raffinate of 100 weight parts, add the gac of below 5 weight parts, preferably add 1 ~ 3 parts by weight of activated carbon.
The present invention's displacement is except magnesium method, and can not increase any equipment, the nickel added in nickelous fluoride obtains recovery with single nickel salt form, remaining unreacted fluorion, because amount is very little, continues to stay in mother liquor after crystallisation, delivers to nickel soap processed or extraction procedure.
Effect of the present invention is: (1) concentrates, extract and replace the calcium magnesium addition of high-content in three-step approach sulfuric acid nickel solution, calcium contents in nickel sulfate solution before crystallization can be dropped to below 5mg/l, the content of magnesium is dropped to below 0.5g/l, obtains high-grade nickel sulfate hexahydrate crystal; (2) calcium-magnesium removing method of the present invention, combines the advantage of extraction and villiaumite calcium-magnesium removing technique.On the one hand, make use of P
204to calcium and the good advantage of copper zinc impurity selectivity, and eliminate P
507extraction demagging operation, simplifies and shortens extraction procedure, saved cost; On the other hand, have employed nickelous fluoride is raw material demagging, new foreign ion can not be introduced, nickel in nickelous fluoride can also reclaim, simultaneously because nickelous fluoride excess coefficient is little, therefore the fluoride waste produced greatly reduces, and compared with common villiaumite calcium-magnesium removing technique, calcium magnesium of the present invention is removed technique and had better economy and the feature of environmental protection; (3) the present invention goes the method for calcium-magnesium removing, is specially adapted to calcium contents higher, and the system that Mg content is not too high, does not increase extra operation, equipment and cost of investment little, operation is simple and feasible, and nickel yield is high.
Embodiment
Below by embodiment the inventive method be further explained and illustrate, but should notice that these embodiments are only illustrative, and can not be used for limiting the scope of the invention.
Embodiment 1 concentrates deliming
Be 1.12g/cm by 10L density
3deironing after nickel sulfate solution heating to be concentrated into density be 1.42g/cm
3, after cooling, have calcium sulphate solid to separate out.Filter, obtain single nickel salt filtrate 2.86L, the changing conditions of impurity in analytical solution, find that the clearance of calcium reaches 86.6%.
Embodiment 2-3 concentrates deliming
Above embodiment is undertaken by the step and method of embodiment 1, and difference is the density of solution and the clearance of calcium, and detailed results is listed in table 1.
Table 1 concentrates the effect table look-up of deliming
Embodiment 4 removing calcium with solvent extraction magnesium
The 2.86L single nickel salt filtrate pH value that embodiment 1 obtains controls 4.1, and organic phase is by the P as extraction agent
204form with the kerosene as thinner, wherein P
204mass ratio in organic phase is 10%, saponification degree is 50%, the ratio of organic phase and aqueous phase is after 1: 1,7 stage countercurrent contact extractions, obtains the qualified raffinate of 2.85L, load organic phases 0.2N sulfuric acid carries out 5 grades and washes nickel, make nickel enter aqueous phase, 2N hydrochloric acid carries out 3 grades of anti-copper zinc, makes copper zinc calcium magnesium enter aqueous phase, 6N hydrochloric acid carries out 2 grades of anti-iron, by the iron back extraction in organic phase out.Result shows, in raffinate, the content of magnesium is down to 2.12g/l, and clearance is 13.1%, and the content of calcium is down to 3.04mg/l, and clearance is 98.6%.
Embodiment 5
The 2.55L single nickel salt filtrate pH value that embodiment 2 obtains controls 3.8, and organic phase is by the P as extraction agent
204form with the kerosene as thinner, wherein P
204mass ratio in organic phase is 15%, saponification degree is 50%, the ratio of organic phase and aqueous phase is after 1: 1,5 stage countercurrent contact extractions, obtains the qualified raffinate of 2.53L, load organic phases 0.2N sulfuric acid carries out 5 grades and washes nickel, make nickel enter aqueous phase, 2N hydrochloric acid carries out 3 grades of anti-copper zinc, makes copper zinc calcium magnesium enter aqueous phase, 6N hydrochloric acid carries out 2 grades of anti-iron, by the iron back extraction in organic phase out.Result shows, in raffinate, the content of magnesium is down to 4.71g/l, and clearance is 7.11%, and the content of calcium is down to 1.14mg/l, and clearance is 99.6%.
Embodiment 6
The 2.61L single nickel salt filtrate pH value that embodiment 3 obtains controls 4.3, and organic phase is by the P as extraction agent
204form with the kerosene as thinner, wherein P
204mass ratio in organic phase is 20%, saponification degree is 50%, organic phase is 1 with the ratio of aqueous phase: after Isosorbide-5-Nitrae stage countercurrent contacts and extracts, and obtains the qualified raffinate of 2.6L, load organic phases 0.2N sulfuric acid carries out 5 grades and washes nickel, make nickel enter aqueous phase, 2N hydrochloric acid carries out 3 grades of anti-copper zinc, makes copper zinc calcium magnesium enter aqueous phase, 6N hydrochloric acid carries out 2 grades of anti-iron, by the iron back extraction in organic phase out.Result shows, in raffinate, the content of magnesium is down to 3.38g/l, and clearance is 18.2%, and the content of calcium is down to 0.73mg/l, and clearance is 99.7%.
The effect table look-up of table 2 removing calcium with solvent extraction magnesium
Embodiment 7 replaces demagging
Get the raffinate that 2.85L embodiment 4 obtains, under stirring, add powdery four water nickelous fluoride solid 32 grams, be heated to 80 DEG C of reactions 0.5 hour, filtered while hot, obtain the qualified nickel sulfate solution of 2.5L purification.After tested, in qualified single nickel salt liquid, the concentration of magnesium is 0.32g/l, and the clearance of magnesium is 86.4%.
Embodiment 8
Get the raffinate that 2.53L embodiment 5 obtains, under stirring, add powdery four water nickelous fluoride solid 70 grams, be heated to 80 DEG C of reactions 0.5 hour, filtered while hot, obtain the qualified nickel sulfate solution of 2.38L purification.After tested, in qualified single nickel salt liquid, the concentration of magnesium is 0.48mg/l, and the clearance of magnesium is 90.4%.
Embodiment 9
Get the raffinate that 2.6L embodiment 4 obtains, under stirring, add powdery four water nickelous fluoride solid 52 grams, be heated to 80 DEG C of reactions 0.5 hour, filtered while hot, obtain the qualified nickel sulfate solution of 2.42L purification.After tested, in qualified single nickel salt liquid, the concentration of magnesium is 0.29g/l, and the clearance of magnesium is 91.8%.
The effect table look-up of demagging replaced by table 3
As can be seen from the above embodiments, employing concentrates, extract and displacement three steps go the effect of calcium-magnesium removing fine, not only nickel content is high for final nickel sulfate solution, directly can carry out crystallization, and calcium-magnesium content is low, the nickel sulfate hexahydrate crystal obtained to reach in the People's Republic of China's chemical industry standard premium grads standard in HG/T2824-1997.
Claims (9)
1. from nickel sulfate solution, remove a method for calcium magnesium addition, it comprises the steps:
(1) heating of single nickel salt material solution is concentrated, cools and remove the solid be settled out;
(2) with the filtrate obtained in phosphorus-contained extractant extraction step (1); With
(3) nickelous fluoride is added in the raffinate obtained in step (2), after being heated to 60 ~ 90 DEG C of reactions, obtain required nickel sulfate solution after cooling and filtration, wherein said phosphorus-contained extractant is two-(2-ethylhexyl) phosphonic acids or 2-ethylhexyl phosphoric acid-2-(ethyl hexyl) ester.
2. the method for claim 1, it is characterized in that, described single nickel salt material solution is the sulphuric leachate or their mixture that comprise the nickel-plating waste water concentrated solution of calcium and magnesium addition, the sulfuric acid steeping fluid of nickel ores raw material, ni-mh and/or NI-G electrode waste material.
3. the method for claim 1, is characterized in that, it is 1.4 ~ 1.5g/cm that the heating of single nickel salt material solution is concentrated into density
3.
4. the method for claim 1, is characterized in that, the extraction in step (2) is carried out in kerosene, and phosphorus-contained extractant, after sulfuric acid and hydrochloric acid back extraction regeneration, continues to enter extracting system.
5. the method according to any one of claim 1-3, is characterized in that, the reaction in step (3) carries out 20 minutes to 1 hour at 70 ~ 80 DEG C.
6. the method according to any one of claim 1-3, is characterized in that, step adds nickelous fluoride pressed powder in (3).
7. method as claimed in claim 6, is characterized in that, add the nickelous fluoride pressed powder of 0.1 ~ 10 weight part in every 100 weight part raffinates.
8. method as claimed in claim 7, is characterized in that, add the nickelous fluoride pressed powder of 0.5 ~ 5 weight part in every 100 weight part raffinates.
9. method as claimed in claim 6, is characterized in that, add the following gac of 5 weight part in every 100 weight part raffinates.
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| CN104591304B (en) * | 2015-01-13 | 2016-04-27 | 江西赣锋锂业股份有限公司 | A kind for the treatment of process of sulfur acid nickel waste material |
| CN105712383A (en) * | 2016-04-22 | 2016-06-29 | 四川天齐锂业股份有限公司 | Method for removing calcium and magnesium impurities in lithium-rich solution by extraction process |
| CN108117105B (en) * | 2017-12-29 | 2019-11-29 | 江西华赣瑞林稀贵金属科技有限公司 | A kind of refining methd of Copper making by-product crude nickle sulphate |
| CN108751267A (en) * | 2018-06-30 | 2018-11-06 | 贵州中伟资源循环产业发展有限公司 | A kind of method of refined sulfuric acid nickel |
| CN109336194A (en) * | 2018-12-13 | 2019-02-15 | 怀化恒安石化有限公司 | A kind of process of the waste nitric acid nickel solution through removing chloride production nickel nitrate product |
| CN109706328B (en) * | 2019-01-31 | 2020-11-06 | 金驰能源材料有限公司 | Method for preparing ternary feed liquid by back-extracting nickel-cobalt-manganese-loaded organic phase with metal nickel acid dissolving solution |
| CN111455174A (en) * | 2020-06-09 | 2020-07-28 | 矿冶科技集团有限公司 | Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt |
| CN111455175A (en) * | 2020-06-09 | 2020-07-28 | 矿冶科技集团有限公司 | Method for removing calcium and magnesium from nickel-cobalt-manganese solution |
| CN113249593B (en) * | 2021-07-06 | 2021-10-15 | 金驰能源材料有限公司 | Two-stage process for removing calcium and magnesium from solutions containing nickel, cobalt, manganese and lithium |
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