CN105925804B - A kind of nickel method for saponification of acid phosphorus extractant organic phase - Google Patents
A kind of nickel method for saponification of acid phosphorus extractant organic phase Download PDFInfo
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- CN105925804B CN105925804B CN201610319623.4A CN201610319623A CN105925804B CN 105925804 B CN105925804 B CN 105925804B CN 201610319623 A CN201610319623 A CN 201610319623A CN 105925804 B CN105925804 B CN 105925804B
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- saponification
- nickel
- exchange resin
- phosphorus extractant
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/37—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing boron, silicon, selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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Abstract
The present invention discloses a kind of nickel method for saponification of acid phosphorus extractant organic phase, using hydroxyl type strong-basicity styrene anion exchange resin as auxiliary agent, to realize acid phosphorus extractant C272, P507 or P229 nickel saponification.In saponification device, the kerosene or sulfonated kerosene solution, nickel chloride aqueous solution and hydroxyl type strong-basicity styrene anion exchange resin of acidic phosphorus extractant are sequentially added；Stratification after completion of the reaction is sufficiently stirred at room temperature.Upper strata is nickel saponification acidic phosphorus extractant organic phase, and middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Aqueous phase and styrene series anion exchange resin phase are released, the nickel saponification acidic phosphorus extractant organic phase that saponification rate is 30%~40% is obtained.The present invention has the advantages that to improve nickel product purity, reduction production cost, saves energy.
Description
Technical field
The present invention relates to the preparation method of acidic phosphorus extractant saponification organic phase, more particularly to one kind is with hydroxyl type
Strong-basicity styrene anion exchange resin is the nickel method for saponification of the acidic phosphorus extractant of auxiliary agent.The present invention particularly belongs to molten
Agent abstraction technique field.
Background technology
Solvent extraction is to separate one of important method of the non-ferrous metal element such as cobalt and nickel.At present, industrial separation cobalt and
Three kinds of the most frequently used extractants of nickel be respectively two (2,4,4- tri-methyl-amyls) phosphonic acids (often referred to simply as C272 or
Cyanex272), 2-ethylhexyl phosphonic acid mono, 2-ethylhexyl (referred to as P507) and di-(2-ethylhexyl)phosphoric acid (abbreviation
For P204).In order to improve extract and separate efficiency, it is necessary to which these three acidic phosphorus extractants are carried out with soda soap, saponification examination used
Agent is sodium hydroxide.The disadvantage of sodium hydroxide saponification is that some sodium ion therein can enter separation product and trigger
Product stains phenomenon, and this brings very detrimental effect to preparing high-purity nickel product.Therefore, also needed in subsequent technique point
From the sodium impurity in nickel.
In separating technology, the important technology index for evaluating ion exchange resin is effective exchange capacity.Effectively exchange and hold
Measure abbreviation exchange capacity sometimes.Effective exchange capacity of anionic ion-exchange resins refers to that every kg dried resins effectively exchange monovalence
The molal quantity of anion；Now, the unit of effective exchange capacity is mol/kg.Also someone effectively exchanges one using every liter of dried resin
The molal quantity of valency anion；Now, the unit of effective exchange capacity is then mol/L.Although adopting unit mol/kg in mass
It can be converted with unit mol/L by volume.But, for the degree of accuracy of effective exchange capacity, using quality meter unit
Mol/kg is higher than using stereometer unit mol/L.By the way, total exchange capacity of the dried resin of certain mass passes through following
Formula is calculated：
N=m × Q (1)
In formula (1), m is the quality of dried resin, and its unit is kg；Q is effective exchange capacity of resin, and its unit is mol/
kg；N is total exchange capacity, and its unit is mol.From formula (1), maximum when total exchange capacity refers to give resin quality m is effectively
Exchange capacity.In fact, maximum exchange molal quantity when total exchange capacity is exactly given resin quality m, therefore always exchange capacity is also referred to as
It is total to exchange molal quantity.
The content of the invention
The purpose of the present invention is using in saponification reagent sodium hydroxide during sodium hydroxide saponification for acidic phosphorus extractant
Part sodium ion can stain the shortcoming of nickel product, set up it is a kind of without saponification stain acidic phosphorus extractant nickel saponification side
Method.
The nickel saponification of the present invention, is expressed as with chemical equation：
In reaction equation (2), HA represents acidic phosphorus extractant C272, P507 or P204, R4NOH represents hydroxyl type highly basic
Property styrenic anion exchanger resin, R4NCl represents chlorine root type strong-basicity styrene anion exchange resin, and subscript " o " is represented
Organic phase, subscript " a " represents aqueous phase, and subscript " s " represents the resin phase of solid-state.The present invention realizes acid phosphorus by reaction equation (2)
The nickel saponification of kind of extractants.From reaction equation (2), the present invention is by the chlorion in the aqueous solution and hydroxyl type strong basicity
Exchange interaction occurs for the hydroxyl in styrenic anion exchanger resin to promote the saponification of nickel and acidic phosphorus extractant.
A kind of nickel method for saponification of acid phosphorus extractant organic phase of the present invention, with hydroxyl type strong-basicity styrene anion
Exchanger resin realizes the nickel saponification of acid phosphorus extractant organic phase for auxiliary agent.Realized especially by following process program.
The mol ratio for controlling nickel chloride and acidic phosphorus extractant is 0.15:1~0.20:1, hydroxyl type strong basicity benzene second
Alkene anion exchange resin is 4 with respect to total exchange molal quantity of chlorion and the ratio between the molal quantity of nickel chloride:1~6:1；In saponification
In reactor, sequentially add acidic phosphorus extractant concentration be 0.5M~1.5M unsupported extraction organic phase, pH be 2~5 and
Nickel ion concentration is 0.5M~1.5M nickel chloride aqueous solution, and effective exchange capacity with respect to chlorion is 3mol/kg~5mol/
Kg and the hydroxyl type strong-basicity styrene anion exchange resin that average grain diameter is 0.4mm~0.6mm.It is sufficiently stirred at room temperature
After 30min~60min, stratification.Upper strata is nickel saponification acidic phosphorus extractant organic phase, and middle level is aqueous phase, and lower floor is solid
The strong-basicity styrene anion exchange resin phase of state.Aqueous phase and strong-basicity styrene anion exchange resin phase are released, is obtained
Nickel saponification acidic phosphorus extractant organic phase, its saponification rate is 30%~40%.
Described acidic phosphorus extractant is C272 or P507 or P204.
Described unsupported extraction organic phase is C272 or P507 or P204 kerosene or sulfonated kerosene solution.
Advantages of the present invention：Sodium element in saponification agent sodium hydroxide can be eliminated to stain nickel separation product, nickel is improved
The purity of product；The process that sodium impurity in nickel is separated in subsequent technique can be removed from simultaneously, production cost is reduced；Soap at room temperature
Change, save energy.
Embodiment
A kind of nickel method for saponification of acid phosphorus extractant organic phase of the present invention is made with reference to specific embodiment
Further describe.
Embodiment 1
The mol ratio for controlling nickel chloride and acidic phosphorus extractant C227 is 0.18:1, hydroxyl type strong-basicity styrene is cloudy
Ion exchange resin is 5 with respect to the ratio between molal quantity of total exchange molal quantity (i.e. total exchange capacity) and the nickel chloride of chlorion:1,
It is 3 and nickel ion concentration is that C227 sulfonated kerosene solution 500L, pH that concentration is 1.0M are sequentially added in 1000L saponification devices
1.0M nickel chloride aqueous solution 90L, effective exchange capacity with respect to chlorion is 4mol/kg and hydrogen that average grain diameter is 0.5mm
Oxygen root type strong-basicity styrene anion exchange resin 112.5kg (dry weight).It is sufficiently stirred at room temperature after 45min, stratification.
Upper strata is nickel saponification C227 organic phases, and middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Put
Go out aqueous phase and strong-basicity styrene anion exchange resin, obtain nickel saponification C227 organic phases, its saponification rate is 36%.
Embodiment 2
The mol ratio for controlling nickel chloride and acidic phosphorus extractant C227 is 0.15:1, hydroxyl type strong-basicity styrene is cloudy
Ion exchange resin is 4 with respect to the ratio between molal quantity of total exchange molal quantity (i.e. total exchange capacity) and the nickel chloride of chlorion:1；
It is 2 and nickel ion concentration is 1.5M that C227 kerosins 500L, pH that concentration is 1.5M are sequentially added in 1000L saponification devices
Nickel chloride aqueous solution 75L, effective exchange capacity with respect to chlorion is 5mol/kg and hydroxyl that average grain diameter is 0.4mm
Type strong-basicity styrene anion exchange resin 90kg (dry weight).It is sufficiently stirred at room temperature after 30min, stratification；Upper strata is
Nickel saponification C227 organic phases, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase
With strong-basicity styrene anion exchange resin, nickel saponification C227 organic phases are obtained, its saponification rate is 30%.
Embodiment 3
The mol ratio for controlling nickel chloride and acidic phosphorus extractant P507 is 0.18:1, hydroxyl type strong-basicity styrene is cloudy
Ion exchange resin is 5 with respect to the ratio between molal quantity of total exchange molal quantity (i.e. total exchange capacity) and the nickel chloride of chlorion:1；
It is 4 and nickel ion concentration is that P507 sulfonated kerosene solution 500L, pH that concentration is 1.0M are sequentially added in 1000L saponification devices
1.0M nickel chloride aqueous solution 90L, effective exchange capacity with respect to chlorion is 4mol/kg and hydrogen that average grain diameter is 0.5mm
Oxygen root type strong-basicity styrene anion exchange resin 112.5kg (dry weight).It is sufficiently stirred at room temperature after 45min, stratification.
Upper strata is nickel saponification P507 organic phases, and middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Put
Go out aqueous phase and strong-basicity styrene anion exchange resin, obtain nickel saponification P507 organic phases, its saponification rate is 36%.
Embodiment 4
The mol ratio for controlling nickel chloride and acidic phosphorus extractant P507 is 0.20:1, hydroxyl type strong-basicity styrene is cloudy
Ion exchange resin is 6 with respect to the ratio between molal quantity of total exchange molal quantity (i.e. total exchange capacity) and the nickel chloride of chlorion:1；
It is 5 and nickel ion concentration is 0.5M that P507 kerosins 500L, pH that concentration is 0.5M are sequentially added in 1000L saponification devices
Nickel chloride aqueous solution 100L, effective exchange capacity with respect to chlorion is 3mol/kg and hydroxyl that average grain diameter is 0.6mm
Type strong-basicity styrene anion exchange resin 100kg (dry weight).It is sufficiently stirred at room temperature after 60min, stratification；Upper strata is
Nickel saponification P507 organic phases, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase
With strong-basicity styrene anion exchange resin, nickel saponification P507 organic phases are obtained, its saponification rate is 40%.
Embodiment 5
The mol ratio for controlling nickel chloride and acidic phosphorus extractant P204 is 0.18:1, hydroxyl type strong-basicity styrene is cloudy
Ion exchange resin is 5 with respect to the ratio between molal quantity of total exchange molal quantity (i.e. total exchange capacity) and the nickel chloride of chlorion:1；
It is 3 and nickel ion concentration is that P204 sulfonated kerosene solution 500L, pH that concentration is 1.0M are sequentially added in 1000L saponification devices
1.0M nickel chloride aqueous solution 90L, effective exchange capacity with respect to chlorion is 4mol/kg and hydrogen that average grain diameter is 0.4mm
Oxygen root type strong-basicity styrene anion exchange resin 112.5kg (dry weight)；It is sufficiently stirred at room temperature after 45min, stratification；
Upper strata is nickel saponification P204 organic phases, and middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Put
Go out aqueous phase and strong-basicity styrene anion exchange resin, obtain nickel saponification P204 organic phases, its saponification rate is 36%.
Embodiment 6
The mol ratio for controlling nickel chloride and acidic phosphorus extractant P204 is 0.20:1, hydroxyl type strong-basicity styrene is cloudy
Ion exchange resin is 6 with respect to the ratio between molal quantity of total exchange molal quantity (i.e. total exchange capacity) and the nickel chloride of chlorion:1；
It is 5 and nickel ion concentration is 0.5M that P204 kerosins 500L, pH that concentration is 0.5M are sequentially added in 1000L saponification devices
Nickel chloride aqueous solution 100L, effective exchange capacity with respect to chlorion is 3mol/kg and hydroxyl that average grain diameter is 0.6mm
Type strong-basicity styrene anion exchange resin 100kg (dry weight).It is sufficiently stirred at room temperature after 60min, stratification；Upper strata is
Nickel saponification P204 organic phases, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Release aqueous phase
With strong-basicity styrene anion exchange resin, nickel saponification P204 organic phases are obtained, its saponification rate is 40%.
Claims (1)
1. a kind of nickel method for saponification of acid phosphorus extractant organic phase, it is characterised in that：The nickel method for saponification is with hydroxyl type
Strong-basicity styrene anion exchange resin realizes the nickel saponification of acid phosphorus extractant organic phase for auxiliary agent；Specific control chlorination
The mol ratio of nickel and acidic phosphorus extractant is 0.15:1~0.20:1, hydroxyl type strong-basicity styrene anion exchange resin
It is 4 with respect to total exchange molal quantity of chlorion and the ratio between the molal quantity of nickel chloride:1~6:1；In saponification device, add successively
Enter unsupported extraction organic phase of the acidic phosphorus extractant concentration for the M of 0.5 M~1.5, pH is 2~5 and nickel ion concentration is
The M of 0.5 M~1.5 nickel chloride aqueous solution, effective exchange capacity with respect to chlorion is the mol/kg of 3 mol/kg~5 and flat
Equal particle diameter is the mm of 0.4 mm~0.6 hydroxyl type strong-basicity styrene anion exchange resin；30 are sufficiently stirred at room temperature
After the min of min~60, stratification；Upper strata is nickel saponification acidic phosphorus extractant organic phase, and middle level is aqueous phase, and lower floor is solid-state
Strong-basicity styrene anion exchange resin phase；Aqueous phase and strong-basicity styrene anion exchange resin phase are released, nickel is obtained
Saponification acidic phosphorus extractant organic phase, its saponification rate is 30%~40%；
Described acidic phosphorus extractant is C272 or P507 or P204；
Described unsupported extraction organic phase is C272 or P507 or P204 kerosene or sulfonated kerosene solution.
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Citations (6)
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|---|---|---|---|---|
| JPH03291332A (en) * | 1990-04-09 | 1991-12-20 | Unitika Ltd | Separation of rare earth element |
| CN1084896A (en) * | 1992-09-30 | 1994-04-06 | 中国科学技术大学 | A kind of resin substitution extration chromatography for preparing high purity nickel salt |
| CN102627333A (en) * | 2012-04-24 | 2012-08-08 | 中南大学 | Method for refined nickel sulfate |
| CN103205572A (en) * | 2013-04-25 | 2013-07-17 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
| CN104073635A (en) * | 2014-06-12 | 2014-10-01 | 金川集团股份有限公司 | Method of removing impurities out of nickel chloride leachate |
| CN104073633A (en) * | 2014-06-12 | 2014-10-01 | 金川集团股份有限公司 | Purification method of cobalt nickel hydroxide hydrochloric acid leaching solution |
-
2016
- 2016-05-13 CN CN201610319623.4A patent/CN105925804B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03291332A (en) * | 1990-04-09 | 1991-12-20 | Unitika Ltd | Separation of rare earth element |
| CN1084896A (en) * | 1992-09-30 | 1994-04-06 | 中国科学技术大学 | A kind of resin substitution extration chromatography for preparing high purity nickel salt |
| CN102627333A (en) * | 2012-04-24 | 2012-08-08 | 中南大学 | Method for refined nickel sulfate |
| CN103205572A (en) * | 2013-04-25 | 2013-07-17 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
| CN104073635A (en) * | 2014-06-12 | 2014-10-01 | 金川集团股份有限公司 | Method of removing impurities out of nickel chloride leachate |
| CN104073633A (en) * | 2014-06-12 | 2014-10-01 | 金川集团股份有限公司 | Purification method of cobalt nickel hydroxide hydrochloric acid leaching solution |
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