CN102557153A - 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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- CN102557153A CN102557153A CN2010106083160A CN201010608316A CN102557153A CN 102557153 A CN102557153 A CN 102557153A CN 2010106083160 A CN2010106083160 A CN 2010106083160A CN 201010608316 A CN201010608316 A CN 201010608316A CN 102557153 A CN102557153 A CN 102557153A
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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 to remove in a kind of nickel sulfate solution the method for impurity, particularly a kind of method of from nickel sulfate solution, removing the calcium magnesium addition.
Background technology
At present, for the removal method of nickel sulfate solution calcium magnesium addition, generally adopt chemical precipitation methods such as Sodium Fluoride, Neutral ammonium fluoride or hydrofluoric acid 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 has been introduced new positively charged ion, like sodium ion, ammonium ion, is difficult in the subsequent handling remove, and has influenced the quality of nickel sulfate hexahydrate crystal;
2) the fluoride salt consumption amount is big, and price is more expensive, and raw materials cost is high;
3) villiaumite and calcium ions and magnesium ions temperature of reaction are high, and the time is long, and energy consumption is big on the one hand, 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 the villiaumite excess coefficient is big, can produce a large amount of fluoride wastes in the processing, extremely hard to manage;
In recent years discloseder new technologies adopt 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, reach the purpose of separating of calcium magnesium and nickel through stepwise solvent extraction.Chinese patent CN101532094 and CN101148698 to calcium and high acid nickel or the copper leach liquor of magnesium addition content, adopted P before this
204Removing calcium with solvent extraction adopts P then
507Stepwise solvent extraction cobalt and magnesium are realized the removal of calcium magnesium.CN1752232 adopts P
507The method of one step extracting and separating nickel, magnesium, cobalt from nickel sulfate solution.P
507The extraction agent price is higher, and cobalt is had fabulous selectivity, and magnesium is also had certain extractibility, if but do not contain cobalt in the 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 is tediously long, has increased the difficulty and the cost of extraction process control.
In addition; For the higher system of calcium contents in the nickel sulfate solution,, when back extraction, there is very big problem though it is clean to adopt extraction process can calcium magnesium be removed; This mainly is because the solubleness of calcium sulfate is low; In back extraction, separate out easily, form the third phase (solid phase) outside water and the oil phase, bring very big inconvenience for phase-splitting and follow-up back extraction.
Therefore, press for a kind of method of from nickel sulfate solution, removing the energy-conserving and environment-protective of calcium magnesium addition efficiently, cheaply.
Summary of the invention
The present invention is for solving the deficiency of above-mentioned prior art, a kind of method of from nickel sulfate solution, removing the energy-conserving and environment-protective of calcium magnesium addition being provided.
The present invention is directed to the calcium, the magnesium addition that there are high level in the nickel sulfate solution, adopt and concentrate, extract and put enough way of combining, the calcium magnesium addition is removed the nickel sulfate solution that is purified.Specifically, the present invention's method of from nickel sulfate solution, removing the calcium magnesium addition comprises following step:
1) heating of single nickel salt material solution is concentrated, cools off and remove the solid that is settled out;
2) with the filtrating that obtains in the phosphorus-contained extractant extraction step (1); With
3) add nickelous fluoride in the raffinate that in step (2), obtains, be heated to 60～90 ℃ of reactions after, cooling and filter after obtain required nickel sulfate solution.
Compared with prior art; Method synthesis of the present invention the advantage of extraction and villiaumite calcium-magnesium removing; But significantly reduced the discharging of the consumption and the fluoride waste of villiaumite, and can not introduce new foreign ion, the nickel yield is high; Be particularly useful for the calcic height, contain 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:
One preferred embodiment in, the present invention removes the method for calcium magnesium addition from nickel sulfate solution the 1st step be with the heating of single nickel salt material solution concentrate, cooling and remove the solid that is settled out.One preferred embodiment in, it is 1.4～1.5g/cm that single nickel salt material solution heating is concentrated into density
3
The single nickel salt material solution of handling with the inventive method can be nickel-plating waste water acid liquid concentrator, preferably the sulphuric acid concentration liquid that comprises calcium and magnesium addition; Or the pickling bath liquor of nickel ores raw material, preferably sulfuric acid steeping fluid.The single nickel salt material solution of handling with the inventive method also can be the sulphuric leachate of ni-mh and/or NI-G electrode waste material.It 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 liquid concentrator, steeping fluid or the leach liquor of other acid (being preferably the inorganic acid of nitric acid or hydrochloric acid and so on).
One preferred embodiment in, earlier the single nickel salt material solution is carried out deironing, for example available hydrolysis neutralisation as known in the art or yellow modumite method purify iron ion and remove.
Nickel content is lower usually in the nickel sulfate solution after the deironing, must could prepare nickel sulfate hexahydrate crystal through concentrating.Above-mentioned heating concentrates and can be undertaken by method conventional in this area, and for example the normal pressure heating concentrates or the decompression heating concentrates.To heat spissated single nickel salt material solution cooling, preferably be cooled to room temperature (being about 10～20 ℃).This moment, most of calcium sulfate was separated out with solid form, after solid-liquid separation, reached the purpose of removal, obtained the lower nickel sulfate solution of calcium content.
Therefore, the present invention concentrates the operation of deliming, has not only played the effect of deliming, and in advance solution has been concentrated, and obtains the nickel sulfate solution of high nickel content, has reduced the liquid phase volume of follow-up extraction process and the pressure that calcium sulfate generates.No matter adopt which kind of removal of impurities way, concentrating before the crystallization all is necessary, therefore concentrates the deliming operation except having more the step of a step solid-liquid separation, can not bring any extra raw material and energy consumption cost.
The present invention removes the method for calcium magnesium addition from nickel sulfate solution the 2nd step is the filtrating that obtains with in the phosphorus-contained extractant extraction step (1).
Used phosphorus-contained extractant was a phosphorus-contained extractant commonly used in this area during the inventive method the 2nd went on foot.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).
One preferred embodiment in, use P
204The filtrating that obtains in the organic phase counter-current extraction step (1), with iron, copper, zinc and not the calcium and the part magnesium of Ex-all be extracted into organic phase, obtain the qualified raffinate of calcic.Organic phase after the extraction is called load organic phases, and phosphorus-contained extractant continues to get into extracting system after dilute sulphuric acid and hydrochloric acid back extraction regeneration.
Above-mentioned P
204Organic phase is by the P as extraction agent
204Constitute P with kerosene as thinner
204Mass ratio in organic phase is 10～20%, and the ratio of organic phase and water is 1: 1.Before the extraction, organic phase should be carried out saponification with sodium hydroxide solution earlier, and saponification degree is 50%, convert the nickel soap again into after, become final extraction agent.During extraction, the pH value of the filtrating that obtains in the controlled step (1) is 3.5～4.5, after the extraction of 4～10 stage countercurrents, obtains qualified raffinate, and the concentration of calcium can drop to below the 5mg/l in the qualified raffinate.
Load organic phases is carried out 4～6 grades with the 0.2N dilute sulphuric acid earlier and is washed nickel, carries out 3～4 grades of anti-copper zinc with 1～2N hydrochloric acid again, carries out 2～3 grades of back extraction iron with 6N hydrochloric acid at last.Organic phase behind the anti-iron is sent to soapmaking again.
Wash in the nickel process, the pH value of control first step feed liquid is 1～1.5, and with the nickel in the abundant recovery organic phase, part copper, zinc, magnesium also get in the anti-nickel liquid in the organic phase at this moment.When the concentration of nickel in the anti-nickel liquid of the first step reached 40～50g/l, the control material liquid PH value was 4～4.5, made the copper, the zinc that get in the anti-nickel liquid get into organic phase again, delivered to system nickel soap after anti-nickel liquid reclaims.
In the anti-copper zinc calcium process, magnesium, calcium are arrived aqueous phase by back extraction together.For reclaiming valuable metal copper wherein, can add sodium hydroxide copper is precipitated recovery.
The present invention removes the method for calcium magnesium addition from nickel sulfate solution the 3rd step is to add nickelous fluoride in the raffinate that in step (2), obtains, be heated to 60～90 ℃ of reactions after, cooling and filter after obtain required nickel sulfate solution.One preferred embodiment in, be heated to 70～80 ℃ of reactions.The time of reacting by heating was generally 20 minutes to 1 hour, was preferably 20～40 minutes, more preferably about 30 minutes.
Because the clearance of magnesium in removal of impurities in early stage operation is limited, still contains higher magnesium in the raffinate, need to remove.In order not introduce new metallic impurity, the present invention adopts nickelous fluoride displacement magnesium, and concrete grammar is; Stir in the raffinate that in the 2nd step, obtains down and add the nickelous fluoride pressed powder; Be heated to 70～80 ℃ and react 20 minutes after 1 hour, preferred reaction is after half a hour, and the magnesium in the solution is separated out with the Sellaite deposition; Filter, obtain the qualified nickel sulfate solution of calcium magnesium addition content.
Used nickelous fluoride pressed powder is commercially available product in the inventive method, preferably the above nickelous fluoride pressed powder of CP.The consumption of nickelous fluoride pressed powder is looked the content of remaining magnesium in the raffinate and is decided.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.
Though do not want to receive concrete theoretical constraint; But the inventor unexpectedly finds; Add the nickelous fluoride pressed powder of capacity in the raffinate that in the 2nd step, obtains, and behind the reacting by heating certain hour, can reduce the content of calcium-magnesium ratio compound impurity in the nickel sulfate solution effectively.
Calcium contents in the nickel sulfate solution that step (3) is handled can be reduced to below the 5mg/l, and the content of magnesium can be reduced to below the 0.5g/l, preferably can be reduced to below the 0.4g/l.
Because meeting residual minim organism in order to obtain high-quality nickel sulfate hexahydrate crystal, needs use the gac oil removing in the raffinate.Nickelous fluoride of the present invention preferably adds with gac, reaches the double effects of demagging oil removing, not only helps the simplification of flow process, can also save energy and reduce the cost.
Used gac is a gac commonly used in this area in the inventive method.The consumption of gac is looked remaining organic amount in the raffinate and is decided.Usually, in the raffinate of 100 weight parts, add the gac below 5 weight parts, preferably add 1～3 weight part gac.
The present invention displacement removes magnesium method, can not increase any equipment, and the nickel that adds in the nickelous fluoride has obtained recovery with the single nickel salt form, and remaining unreacted fluorion because amount is very little, continues to stay in the mother liquor after the crystallization, delivers to system nickel soap or extraction.
Effect of the present invention is: (1) concentrates, extracts and the displacement three-step approach is removed high-load calcium magnesium addition in the sulfuric acid nickel solution; Can calcium contents in the nickel sulfate solution before the crystallization be dropped to below the 5mg/l; The content of magnesium is dropped to below the 0.5g/l, obtain high-grade nickel sulfate hexahydrate crystal; (2) calcium-magnesium removing method of the present invention combines the extraction and the advantage of villiaumite calcium-magnesium removing technology.On the one hand, utilized P
204To calcium and the good advantage of copper zinc impurity selectivity, and save P
507Extraction demagging operation is simplified and has been shortened extraction, has practiced thrift cost; On the other hand; Having adopted nickelous fluoride is the raw material demagging, can not introduce new foreign ion, and the nickel in the nickelous fluoride can also reclaim; Simultaneously because the nickelous fluoride excess coefficient is little; Therefore the fluoride waste that produces significantly reduces, and compares with common villiaumite calcium-magnesium removing technology, and calcium magnesium of the present invention is removed technology and had the better economy and the feature of environmental protection; (3) the present invention goes the method for calcium-magnesium removing, and it is higher to be specially adapted to calcium contents, and the not too high system of Mg content does not increase extra procedure, and equipment and cost of investment are little, and operation is simple and feasible, and the nickel yield is high.
Embodiment
Through embodiment the inventive method is done further to explain and explanation below, but should notice that these embodiment only are illustrative, and can not be used to limit protection scope of the present invention.
Embodiment 1 concentrates deliming
With 10L density is 1.12g/cm
3Deironing after nickel sulfate solution heating to be concentrated into density be 1.42g/cm
3, have calcium sulphate solid to separate out after the cooling.Filter, get single nickel salt filtrating 2.86L, the changing conditions of impurity in the analytical solution finds that the clearance of calcium reaches 86.6%.
Embodiment 2-3 concentrates deliming
Above embodiment is undertaken by step and the method for embodiment 1, and different is the density of solution and the clearance of calcium, and detailed results is listed in the 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 filtrating pH value that embodiment 1 obtains is controlled at 4.1, and organic phase is by the P as extraction agent
204Constitute with kerosene, wherein P as thinner
204Mass ratio in organic phase is 10%, and saponification degree is 50%, and the ratio of organic phase and water is 1: 1; After the 7 stage countercurrents contact extraction, obtain the qualified raffinate of 2.85L, load organic phases is carried out 5 grades with 0.2N sulfuric acid and is washed nickel; Make nickel get into water, 2N hydrochloric acid carries out 3 grades of anti-copper zinc, makes copper zinc calcium magnesium get into water; 6N hydrochloric acid carries out 2 grades of anti-iron, and the iron back extraction in the organic phase is come out.The result shows that the content of magnesium is reduced to 2.12g/l in the raffinate, and clearance is 13.1%, and the content of calcium is reduced to 3.04mg/l, and clearance is 98.6%.
Embodiment 5
The 2.55L single nickel salt filtrating pH value that embodiment 2 obtains is controlled at 3.8, and organic phase is by the P as extraction agent
204Constitute with kerosene, wherein P as thinner
204Mass ratio in organic phase is 15%, and saponification degree is 50%, and the ratio of organic phase and water is 1: 1; After the 5 stage countercurrents contact extraction, obtain the qualified raffinate of 2.53L, load organic phases is carried out 5 grades with 0.2N sulfuric acid and is washed nickel; Make nickel get into water, 2N hydrochloric acid carries out 3 grades of anti-copper zinc, makes copper zinc calcium magnesium get into water; 6N hydrochloric acid carries out 2 grades of anti-iron, and the iron back extraction in the organic phase is come out.The result shows that the content of magnesium is reduced to 4.71g/l in the raffinate, and clearance is 7.11%, and the content of calcium is reduced to 1.14mg/l, and clearance is 99.6%.
Embodiment 6
The 2.61L single nickel salt filtrating pH value that embodiment 3 obtains is controlled at 4.3, and organic phase is by the P as extraction agent
204Constitute with kerosene, wherein P as thinner
204Mass ratio in organic phase is 20%, and saponification degree is 50%, and the ratio of organic phase and water is 1: 1; After the 4 stage countercurrents contact extraction, obtain the qualified raffinate of 2.6L, load organic phases is carried out 5 grades with 0.2N sulfuric acid and is washed nickel; Make nickel get into water, 2N hydrochloric acid carries out 3 grades of anti-copper zinc, makes copper zinc calcium magnesium get into water; 6N hydrochloric acid carries out 2 grades of anti-iron, and the iron back extraction in the organic phase is come out.The result shows that the content of magnesium is reduced to 3.38g/l in the raffinate, and clearance is 18.2%, and the content of calcium is reduced 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 displacement demaggings
Get the raffinate that 2.85L embodiment 4 obtains, stir adding powdery four water nickelous fluoride solids 32 grams down, be heated to 80 ℃ of reactions 0.5 hour, filtered while hot obtains the qualified nickel sulfate solution that 2.5L purifies.Through test, the concentration of magnesium is 0.32g/l in the qualified single nickel salt liquid, and the clearance of magnesium is 86.4%.
Embodiment 8
Get the raffinate that 2.53L embodiment 5 obtains, stir adding powdery four water nickelous fluoride solids 70 grams down, be heated to 80 ℃ of reactions 0.5 hour, filtered while hot obtains the qualified nickel sulfate solution that 2.38L purifies.Through test, the concentration of magnesium is 0.48mg/l in the qualified single nickel salt liquid, and the clearance of magnesium is 90.4%.
Embodiment 9
Get the raffinate that 2.6L embodiment 4 obtains, stir adding powdery four water nickelous fluoride solids 52 grams down, be heated to 80 ℃ of reactions 0.5 hour, filtered while hot obtains the qualified nickel sulfate solution that 2.42L purifies.Through test, the concentration of magnesium is 0.29g/l in the qualified single nickel salt liquid, and the clearance of magnesium is 91.8%.
The effect table look-up of table 3 displacement demagging
Can find out by above embodiment; Employing concentrates, extracts and replace three steps and goes the effect of calcium-magnesium removing fine; Final nickel sulfate solution not only nickel content is high; Can directly carry out crystallization, and calcium-magnesium content is low, the nickel sulfate hexahydrate crystal that obtains reaches in the People's Republic of China's chemical industry standard premium grads standard among the HG/T2824-1997.
Claims (10)
1. method of from nickel sulfate solution, removing the calcium magnesium addition, it comprises the steps:
(1) heating of single nickel salt material solution is concentrated, cools off and remove the solid that is settled out;
(2) with the filtrating that obtains in the phosphorus-contained extractant extraction step (1); With
(3) add nickelous fluoride in the raffinate that in step (2), obtains, be heated to 60～90 ℃ of reactions after, cooling and filter after obtain required nickel sulfate solution.
2. the method for claim 1; It is characterized in that described single nickel salt material solution is the nickel-plating waste water liquid concentrator that comprises calcium and magnesium addition, sulfuric acid steeping fluid, ni-mh and/or the sulphuric leachate of NI-G electrode waste material or their mixture of nickel ores raw 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. like each described method among the claim 1-3, it is characterized in that described phosphorus-contained extractant is two-(2-ethylhexyl) phosphonic acids or 2-ethylhexyl phosphoric acid-2-(ethyl hexyl) ester.
5. method as claimed in claim 4 is characterized in that, the extraction in the step (2) is carried out in kerosene, and phosphorus-contained extractant continues to get into extracting system after sulfuric acid and hydrochloric acid back extraction regeneration.
6. like each described method among the claim 1-3, it is characterized in that being reflected at 70～80 ℃ and carrying out 20 minutes to 1 hour in the step (3).
7. like each described method among the claim 1-3, it is characterized in that, add the nickelous fluoride pressed powder in the step (3).
8. method as claimed in claim 7 is characterized in that, adds the nickelous fluoride pressed powder of 0.1～10 weight part in per 100 weight part raffinates.
9. method as claimed in claim 8 is characterized in that, adds the nickelous fluoride pressed powder of 0.5～5 weight part in per 100 weight part raffinates.
10. method as claimed in claim 7 is characterized in that, adds the following gac of 5 weight parts in per 100 weight part raffinates.
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Cited By (9)
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| CN104591304A (en) * | 2015-01-13 | 2015-05-06 | 江西赣锋锂业股份有限公司 | Method for treating waste material containing nickel sulfate |
| 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 |
| CN108117105A (en) * | 2017-12-29 | 2018-06-05 | 江西瑞林稀贵金属科技有限公司 | A kind of process for purification 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 |
| CN109706328A (en) * | 2019-01-31 | 2019-05-03 | 金驰能源材料有限公司 | A kind of method of metallic nickel acid dissoluting liquid back extraction load nickel cobalt manganese organic phase preparation ternary feed liquid |
| 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 |
| 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 |
| CN113249593A (en) * | 2021-07-06 | 2021-08-13 | 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591304A (en) * | 2015-01-13 | 2015-05-06 | 江西赣锋锂业股份有限公司 | Method for treating waste material containing nickel sulfate |
| 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 |
| CN108117105A (en) * | 2017-12-29 | 2018-06-05 | 江西瑞林稀贵金属科技有限公司 | A kind of process for purification 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 |
| CN109706328A (en) * | 2019-01-31 | 2019-05-03 | 金驰能源材料有限公司 | A kind of method of metallic nickel acid dissoluting liquid back extraction load nickel cobalt manganese organic phase preparation ternary feed liquid |
| 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 |
| 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 |
| CN113249593A (en) * | 2021-07-06 | 2021-08-13 | 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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