CN106544506B - A kind of extractant composition and the preparation method and application thereof - Google Patents
A kind of extractant composition and the preparation method and application thereof Download PDFInfo
- Publication number
- CN106544506B CN106544506B CN201510588105.8A CN201510588105A CN106544506B CN 106544506 B CN106544506 B CN 106544506B CN 201510588105 A CN201510588105 A CN 201510588105A CN 106544506 B CN106544506 B CN 106544506B
- Authority
- CN
- China
- Prior art keywords
- component
- tri
- methyl
- amyls
- structure shown
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a kind of extractant compositions and the preparation method and application thereof.By weight percentage, including following component, component A：The dialkyl phosphinic acid with structure shown in Formulas I of 80wt%-99.99wt%；Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-5wt%；Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-10wt%；Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-5wt%；Wherein, it is zero when component B, C and D differences, and the summation of A, B, C and D component is always 100wt%.The extractant composition containing synergic reagent component that the present invention is prepared can be widely applied in rare earth metal, the especially Separation & Purification of cobalt nickel metal compare with one pack system extractant as extractant, and extraction ability is more excellent；With two（2,4,4- tri-methyl-amyls）Phosphinic acids are compared, other synergic reagent components are more easily-synthesized, and reduce the production cost of product.
Description
Technical field
It is the present invention relates to non-ferrous metal extractive technique field, more particularly to a kind of for carrying out extraction and separation to metallic element
Extractant composition and the preparation method and application thereof.
Background technology
Two (2,4,4- tri-methyl-amyl) phosphinic acids, structure and preparation method patent are American earliest
Cyanamid Company（American Cyanamid Company, predecessor of Cytec companies）In United States Patent (USP) filed in 14 days Mays in 1981
4374780（22 days 2 months nineteen eighty-three is open）, it is anti-that addition occurs under the action of radical initiator with diisobutylene with hydrogen phosphide
Intermediate product two (2,4,4- tri-methyl-amyl) phosphine alkane should be generated, then bis- (2,4,4- tri-methyl-amyls) is generated with hydrogen peroxide oxidation
Phosphinic acids.Later, associated companies have applied widely applying successively again（Such as the US4909939 that nineteen ninety applies, apply within 1997
US5639433）, preparation method and derivative prepare patent（Such as the US20090165598 of application in 2009, apply within 2014
US20140275615）.The said firm is in dominant position in the field at present, is once the product within a very long time
Unique manufacturer in the world.
In recent years, other companies take up to research and develop the relevant technologies.Rhodia Inc of the U.S.（Rhodia）In 2006
It mentions in the patent US7049463 of application and being acted in 135 DEG C and di-tert-butyl peroxide in acetic acid solution with sodium hypophosphite
Lower reacted with diisobutylene generates bis- (2,4,4- tri-methyl-amyls) phosphinic acids.
China was also quickly grown in recent years in the technology of related field.As domestic main manufacturer, the U.S. has been used
The new specialization work in Changshu of Cytec company techniques has also applied for more synthetic method patents, the Chinese patent of application in such as 2011
It mentions in 201110057908.2 and being used under condition of free radical with diisobutylene with byproduct hydrogen phosphide in sodium hypophosphite technique
High pressure（5-8MPa）Bis- (2,4, the 4- tri-methyl-amyl) phosphines of synthesis, then obtain bis- (2,4,4- trimethyls penta through hydrogen peroxide oxidation
Base) phosphinic acids, 2014 application Chinese patents 201410019641.1 in the method is improved, diisobutylene is normal
Hydrogen phosphide is absorbed under mild certain pressure, then heating absorbs the solution initiation radical reaction of hydrogen phosphide, obtains high yield
Bis- (2,4,4- tri-methyl-amyls) phosphorus of intermediate product.Intermediate product obtains bis- (2,4,4- tri-methyl-amyls) through hydrogen peroxide oxidation again
Phosphinic acids.It mentions with sodium hypophosphite in acetic acid solution, uses instead in the patent CN101475588 that Tsinghua University applied in 2008
Mixture di-tert-butyl peroxide and benzoyl peroxide make initiator, are reacted 10-15 hours at 120-140 DEG C, are made
Net product.It is mentioned in the patent CN102020673 that Jiangxi Science and Technology Normal College applied in 2011 molten in acetic acid with sodium hypophosphite
In liquid, make initiator with azodiisobutyronitrile, reacts 10 hours obtained products at a reflux temperature.It is taken containing 13.8% 1 in product
For product；And be divided into and do not apply for a patent CN102268038 and CN1023211117 again 2011 and 2012, in same body
It will be shortened in the reaction time 5 hours with mixed initiator in system, a substituent only has 4% in product.
Cobalt is the important component part of high intensity, high-temperature alloy, and this Alloyapplication is extensive, such as jet plane
Engine turbine, cermet, high-energy battery etc..However cobalt metal is mainly distributed in nickel minerals, content is low to be not readily separated, therefore one
The technique of separation cobalt metal is more complex in metallurgical industry since straight, and yield is relatively low, and cost is also higher.Solvent extraction is imitated due to separation
Fruit is good, processing capacity is big, recovery rate of valuable metals is high, operation is continuous, it is can be recycled easily to realize automation, organic reagent, at
This low advantage and the extraction and separation for being widely used in nickel and cobalt ions.With application of the solvent extraction in metallurgy, first
Occurs (2- ethylhexyls) phosphoric acid afterwards（P204）And di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester（P507）Two kinds of extractants
Commodity, and obtain extensive use.Two (2,4,4- tri-methyl-amyls) phosphinic acids（Cyanex272）As it in terms of cobalt nickel separation
Substitute, separation improves an order of magnitude again, due to its high separation, can not only reduce extraction series,
It saves extractant, reduce energy consumption, and the solution purity after separation is very high, thus there is very high application and promotional value.
In the solvent extraction technology that sulfuric acid system detaches cobalt, nickel ion, the leachate pH of routine acidleach at present and biological dump leaching generation
Value is generally 1-2, and P204, P507, Cyanex272 are to Ni2+And Co2+Optimal separation pH value be 4.5-5.0.Therefore,
Need to leachate cannot be subjected to a degree of neutralization directly with the kind of extractants extraction and separation, this can undoubtedly increase extraction at
This.It is expensive in addition, though Cyanex272 is had excellent performance, it is difficult to large-scale industrial application.For this problem, Zhang Ping
It is big etc.（Zhang Pingwei, Zhu collect cobalt nickel synergistic systems;J]Chemical industry metallurgical, 1997,8 (3):282-288.）Research refers to
Go out, using the synergistic effect of mixed extractant, nickel and cobalt ions can be detached under relatively low pH value.In recent years, to nickel, cobalt from
The numerous studies of sub- synergic solvent extraction propose many synergistic systems.Devi etc.（Devi N B, Nathsarma K C,
Chakravortty V. Separation and Recovery of Cobalt(II) and Nickle(II) from
Sulphate Solutions Using Sodium Salts of D2EHPA, PC 88A and Cyanex272 [J].
Hydrometallurgy, 1998, 52(49): 47-61.）The study found that tri- kinds of extractants of Cyanex272, P507, P204
The extraction system of middle any two composition is to Co2+Have a positive Association stripping effect, but to the synergic solvent extraction pH value of nickel and cobalt ions still compared with
It is high.
One pack system extractant is expensive in the prior art, though cost is reduced after being added to synergic reagent component, it is corresponding
Extraction ability can be declined, affect the efficiency of extraction.
Invention content
For overcome the deficiencies in the prior art with defect, the primary purpose of the present invention is that provide one kind being added to synergic reagent
The extractant composition of component can be widely applied in rare earth metal, the especially Separation & Purification of cobalt nickel metal, reduce
While cost, extraction ability is excellent.
It is a further object of the present invention to provide the preparation methods of above-mentioned extractant composition.
Another object of the present invention is to provide the application of above-mentioned extractant composition.
The present invention is achieved by the following technical solutions：
A kind of extractant composition, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 80wt%-99.99wt%：
Formulas I
Wherein, R is the alkyl of C1-C8；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-5wt%：
Formula II
Wherein, R1, R2It is identical or different, it is the alkyl of C1-C8；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-10wt%：
Formula III
Wherein, R3, R4, R5It is identical or different, it is the alkyl of C1-C8；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-5wt%：
Formula IV
Wherein, R6For the alkyl of C1-C8；
It is 0wt% when component B, C, D difference, and the summation of A, B, C and D component is always 100wt%.
Preferably, a kind of extractant composition, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%, wherein R is the alkyl of C1-C8；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0.01wt%-4wt%, wherein R1, R2It is identical or not
Together, it is the alkyl of C1-C8；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-8wt%, wherein R3, R4, R5Phase
It is same or different, it is the alkyl of C1-C8；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-3wt%, wherein R6For the alkyl of C1-C8；
And the summation of A, B, C and D component is always 100wt%.
Preferably, a kind of extractant composition, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%, wherein R is the alkyl of C1-C8；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-4wt%, wherein R1, R2It is identical or different,
For the alkyl of C1-C8；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0.01wt%-8wt%, wherein R3, R4,
R5It is identical or different, it is the alkyl of C1-C8；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-3wt%, wherein R6For the alkyl of C1-C8；
And the summation of A, B, C and D component is always 100wt%.
Preferably, a kind of extractant composition, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%, wherein R are the alkyl of C1-C8；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-4wt%, wherein R1, R2It is identical or different,
For the alkyl of C1-C8；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-8wt%, wherein R3, R4, R5Phase
It is same or different, it is the alkyl of C1-C8；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0.01wt%-3wt%, wherein R6For the alkane of C1-C8
Base；
And the summation of A, B, C and D component is always 100wt%.
Preferably, 2 R, 4,4- tri-methyl-amyls.
Preferably, R1, R2It is identical, it is 2,4,4- tri-methyl-amyls.
Preferably, R3, R4It is identical, it is 2,4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls.
Preferably, R6For 2,4,4- tri-methyl-amyls.
The preparation method of the extractant composition, includes the following steps：By component A respectively with component B and/or component
C and/or component D are prepared after evenly mixing.
Wherein, the preparation method of the component A, includes the following steps：
a）In the presence of radical initiators, alkene reacts to obtain mixture with hypophosphorous acid source；
b）Mixture carries out washing purification with the aqueous solution of 0.5wt% ~ 30wt% alkali, with the aqueous solution of 0.5wt% ~ 50wt% acid
The dialkyl phosphinic acid with structure shown in Formulas I is obtained after carrying out acidification and concentration：
Formulas I
Wherein, R is the alkyl of C1-C8.
Preferably, step a）In, reaction temperature is 70 DEG C ~ 160 DEG C, and pressure is 0 ~ 2MPa；Step a）In, it is octene, different pungent
It is one or more of in alkene, butylene, isobutene, amylene, iso-amylene, hexene, dissident's alkene, heptene, iso-heptene, diisobutylene, preferably
For diisobutylene；Step a）In, the radical initiator is selected from peroxide initiator and/or azo-initiator；It is described
Peroxide initiator be preferably perbenzoic acid, peroxylauric acid, di-tert-butyl peroxide, peroxycarbonates,
Cross oxalic acid, tert-butyl hydroperoxide isobutyrate, peroxide -2-ethyl hexanoic acid tert-butyl, the peroxidating pivalic acid tert-butyl ester, peroxide
Change one or more of in special pentyl ester, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate；It is different that the azo-initiator is selected from azo two
Butyronitrile and/or azobisisoheptonitrile；Step a）In, the hypophosphorous acid source is hypophosphorous acid and/or hypophosphites, the hypophosphites
It is one or more of in sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite；Step b）In, the alkali is selected from hydroxide
It is one or more of in sodium, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate；Step b）In, it is described acid selected from sulfuric acid, hydrochloric acid, phosphoric acid,
It is one or more of in acetic acid, formic acid.
Wherein, the preparation method of the component B, includes the following steps：
a）Phosphorus oxychloride is reacted with the grignard reagent of twice of mole generates dialkyl group phosphorus oxychloride；
b）Dialkyl group chlorethoxyfos react the dialkyl group phosphine oxide for generating and having structure shown in Formula II with Lithium Aluminium Hydride：
Formula II
Wherein, R1, R2It is identical or different, it is the alkyl of C1-C8.
Preferably, step a）In, the grignard reagent be selected from branched alkyl magnesium halide, particularly preferably 2,4,4- trimethyls
Amyl magnesium chloride or 2,4,4- tri-methyl-amyl magnesium bromides.
Wherein, the preparation method of the component C, includes the following steps：
a）Phosphorus oxychloride is reacted with the grignard reagent of twice of mole generates dialkyl group chlorethoxyfos；
b）Dialkyl group chlorethoxyfos react the dialkyl phosphinic acid Arrcostab for generating and having structure shown in formula III with alcohol：
Formula III
Wherein, R3, R4, R5It is identical or different, it is the alkyl of C1-C8.
Preferably, step a）In, the grignard reagent be selected from branched alkyl magnesium halide, particularly preferably 2,4,4- trimethyls
Amyl magnesium chloride or 2,4,4- tri-methyl-amyl magnesium bromides；Step b）In, the alcohol is selected from 2,4,4- trimethylpentanols or 2- second
Base hexanol.
Wherein, the preparation method of the component D, includes the following steps：
a）Phosphorus oxychloride is reacted with the grignard reagent of one times of mole generates alkyl dichloro phosphorous oxide；
b）Alkyl dichloro oxygen phosphorus reacts the monoalkyl phosphine oxide for generating and having structure shown in formula IV with Lithium Aluminium Hydride：
Formula IV
Wherein, R6For the alkyl of C1-C8.
Preferably, step a）In, the grignard reagent be selected from branched alkyl magnesium halide, particularly preferably 2,4,4- trimethyls
Amyl magnesium chloride or 2,4,4- tri-methyl-amyl magnesium bromides.
The extractant composition is dissolved in solvent as organic phase, and saponification is carried out with aqueous slkali, with the gold as water phase
Belong to the application that mixed solution carries out extraction and separation.
Wherein, based on the organic phase of extractant composition or its saponification organic phase total weight, the extractant composition
Mass concentration is 5wt% ~ 50wt%；The solvent in petroleum ether, hexane, hexamethylene, heptane, octane, sulfonated kerosene one
Kind is several；The aqueous slkali is selected from sodium hydroxide solution and/or potassium hydroxide solution；The saponification degree of the saponification be 8% ~
50%；The metal mixed solution is the mixture containing rare earth ion；Preferably contain cobalt, nickel and/or other metals from
The mixed solution of son；The mixed solution containing cobalt, nickel and/or other metal ions can first pass through metal extraction agent
P204 removes other metal ions, after carry out extraction and separation with a kind of described extractant composition for metallic element again.
Compared with prior art, the present invention having the advantages that：
1）The extractant composition containing synergic reagent component that the present invention is prepared, can be widely applied to as extractant
Rare earth metal is especially compared in the Separation & Purification of cobalt nickel metal with one pack system extractant, and extraction ability is more excellent
It is different.
2）In synthesis two（2,4,4- tri-methyl-amyls）In the technique of the components such as phosphinic acids, using other phosphorus system starting materials
It is substituted, avoids the use of hydrogen phosphide, improve the safety of production technology.
3）With two（2,4,4- tri-methyl-amyls）Phosphinic acids are compared, other synergic reagent components are more easily-synthesized, and reduce production
The production cost of product.
Specific implementation mode
It is further illustrated the present invention below by specific implementation mode, following embodiment is the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1：One-component A bis-（2,4,4- tri-methyl-amyls）The preparation of phosphinic acids
By the hypophosphorous acid of 200g70%, 760g diisobutylene, 4g peroxide -2-ethyl hexanoic acid tert-butyls put into warding off for 2L
In porcelain reaction kettle, under nitrogen protection, it is heated to 85 DEG C and starts to be stirred to react, while continuously squeezing into peroxidating -2- second with metering pump
Base hecanoic acid t-butyl ester, after reaction 12 hours, enclosed system, maintenance system pressure limit in 0.2-0.4MPa, be warming up to 110 DEG C after
Continuous reaction is reacted after 48 hours to be terminated, and is cooled down.Reaction solution is moved in separatory funnel, alkali is carried out with 5% sodium hydroxide solution
It washes, then is acidified with 5% hydrochloric acid, after washing, 453g products two are obtained after oil phase concentration（2,4,4- tri-methyl-amyls）Phosphinic acids.
Embodiment 2：One-component A bis-（2,4,4- tri-methyl-amyls）The preparation of phosphinic acids
By 225g sodium hypophosphites, 200g acetic acid, 760g diisobutylene, 5g di-tert-butyl peroxides put into warding off for 2L
In porcelain reaction kettle, under nitrogen protection, it is heated to 120 DEG C and starts to be stirred to react, enclosed system, maintenance system pressure limit is in 0.1-
0.2MPa, while di-tert-butyl peroxide is continuously squeezed into metering pump, reaction is reacted after 48 hours to be terminated, and is cooled down.It will reaction
Liquid moves in separatory funnel, is washed with 5% sodium hydroxide solution, then is acidified with 5% hydrochloric acid, after washing, oil phase concentration
After obtain 473g products two（2,4,4- tri-methyl-amyls）Phosphinic acids.
Embodiment 3：One-component B bis-（2,4,4- tri-methyl-amyls）The preparation of phosphine oxide
38 grams of phosphorus oxychloride and 100ml anhydrous tetrahydro furans are added in 500ml four-hole bottles, under nitrogen protection, under ice bath
The tetrahydrofuran solution of the 2 of 250ml2mol/L, 4,4- tri-methyl-amyl magnesium bromides is slowly added dropwise, drips off within about 1 hour, is warming up to
Flowing back, the reaction was continued 4 hours can obtain two（2,4,4- tri-methyl-amyls）Chlorethoxyfos solution.Without any processing, under ice bath, continue
5.6 grams of Lithium Aluminium Hydrides are added dropwise and are dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, be warming up to reflux the reaction was continued 12 hours it is anti-
It should terminate, cool down.Ether is added into reaction solution, is washed with saturated ammonium chloride solution, then three times with saturated salt solution extraction, is had
Machine is rectifying to obtain 32g products two again after mutually concentrating（2,4,4- tri-methyl-amyls）Phosphine oxide.
Embodiment 4：One-component C bis-（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2,4,4- tri-methyl-amyls）The preparation of ester
38 grams of phosphorus oxychloride and 100ml anhydrous tetrahydro furans are added in 500ml four-hole bottles, under nitrogen protection, under ice bath
The tetrahydrofuran solution of the 2 of 250ml2mol/L, 4,4- tri-methyl-amyl magnesium bromides is slowly added dropwise, drips off within about 1 hour, is warming up to
Flowing back, the reaction was continued 4 hours can obtain two（2,4,4- tri-methyl-amyls）Chlorethoxyfos solution.Without any processing, under ice bath, continue
It is added dropwise 32.5 gram 2,4,4- trimethylpentanols are dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, are warming up to reflux and continue instead
It answers reaction in 12 hours to terminate, cools down.Ether is added into reaction solution, is washed with saturated ammonium chloride solution, then uses saturated salt solution
Extraction three times, 48g products two is obtained after organic phase concentration（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2,4,4- tri-methyl-amyls）
Ester.
Embodiment 5：One-component C bis-（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2- ethylhexyls）The preparation of ester
38 grams of phosphorus oxychloride and 100ml anhydrous tetrahydro furans are added in 500ml four-hole bottles, under nitrogen protection, under ice bath
The tetrahydrofuran solution of the 2 of 250ml2mol/L, 4,4- tri-methyl-amyl magnesium bromides is slowly added dropwise, drips off within about 1 hour, is warming up to
Flowing back, the reaction was continued 4 hours can obtain two（2,4,4- tri-methyl-amyls）Chlorethoxyfos solution.Without any processing, under ice bath, continue
32.5 grams of 2-Ethylhexyl Alcohols are added dropwise and are dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, is warming up to reflux the reaction was continued and is 12 small
Shi Fanying terminates, cooling.Ether is added into reaction solution, is washed with saturated ammonium chloride solution, then extracts three with saturated salt solution
It is secondary, obtain 48g products two after organic phase concentration（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2- ethylhexyls）Ester.
Embodiment 6：One-component D（2,4,4- tri-methyl-amyls）The preparation of phosphine oxide
38 grams of phosphorus oxychloride and 100ml anhydrous tetrahydro furans are added in 500ml four-hole bottles, under nitrogen protection, under ice bath
The tetrahydrofuran solution of the 2 of 125ml2mol/L, 4,4- tri-methyl-amyl magnesium bromides is slowly added dropwise, drips off within about 1 hour, is warming up to
Flowing back, the reaction was continued 4 hours to obtain（2,4,4- tri-methyl-amyls）Dichloro oxygen phosphorus solution.Without any processing, under ice bath, continue
2.8g Lithium Aluminium Hydrides are added dropwise and are dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, be warming up to reflux the reaction was continued 12 hours it is anti-
It should terminate, cool down.Ether is added into reaction solution, is washed with saturated ammonium chloride solution, then three times with saturated salt solution extraction, is had
Machine is rectifying to obtain 17g products again after mutually concentrating（2,4,4- tri-methyl-amyls）Phosphine oxide.
Embodiment 7：The preparation of component A+ components B+ component Cs+component D
By 80g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 5g bis-（2,4,4- tri-methyl-amyls）Phosphine oxide, 10g bis-（2,
4,4- tri-methyl-amyls）Hypophosphorous acid（2,4,4- tri-methyl-amyls）Ester, 5g（2,4,4- tri-methyl-amyls）Phosphine oxide is stirred
Uniformly, 100g compositions are obtained.
Embodiment 8：The preparation of component A+ components B+ component Cs+component D
By 85g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 4g bis-（2,4,4- tri-methyl-amyls）Phosphine oxide, 8g bis-（2,
4,4- tri-methyl-amyls）Hypophosphorous acid（2- ethylhexyls）Ester, 3g（2,4,4- tri-methyl-amyls）Phosphine oxide is uniformly mixed, and is obtained
To 100g compositions.
Embodiment 9：The preparation of component A+ components B
By 97g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 3g bis-（2,4,4- tri-methyl-amyls）Phosphine oxide is stirred
Uniformly, 100g compositions are obtained.
Embodiment 10：The preparation of component A+component C
By 94g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 6g bis-（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2,4,4- tri-
Methyl amyl）Ester is uniformly mixed, and obtains 100g compositions.
Embodiment 11：The preparation of component A+ components D
By 98g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 2g（2,4,4- tri-methyl-amyls）Phosphine oxide is stirred
It is even, obtain 100g compositions.
Embodiment 12：The preparation of component A+ component B+ component Cs
By 90g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 3g bis-（2,4,4- tri-methyl-amyls）Phosphine oxide, 7g bis-（2,
4,4- tri-methyl-amyls）Hypophosphorous acid（2- ethylhexyls）Ester is uniformly mixed, and obtains 100g compositions.
Embodiment 13：The preparation of component A+ component B+ components D
By 95g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 2g bis-（2,4,4- tri-methyl-amyls）Phosphine oxide, 3g（2,4,
4- tri-methyl-amyls）Phosphine oxide is uniformly mixed, and obtains 100g compositions.
Embodiment 14：The preparation of component A+ component Cs+component D
By 89g bis-（2,4,4- tri-methyl-amyls）Phosphinic acids, 8g bis-（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2- ethyl hexyls
Base）Ester, 3g（2,4,4- tri-methyl-amyls）Phosphine oxide is uniformly mixed, and obtains 100g compositions.
Comparative example 1：
The extractant 20ml that embodiment 2 obtains is dissolved in 180ml sulfonated kerosenes as organic phase, with sodium hydroxide solution into
Row saponification, saponification degree 50%, water phase are prepared 600ml cobalts nickel mixing sulfuric acid solution（Wherein, cobalt content 4g/L, nickel content
80g/L, pH value 5）, the two is mixed and is placed in separatory funnel, maintains temperature constant at 40 DEG C, in an oscillator with 200r/
The velocity fluctuation of min, which extracts 5 minutes, to be stopped, and tests the content of cobalt and nickel in water phase and oil phase respectively.（Ni2+With murexide network
Close titration measuring, Co2+It is measured with Nitroso R salt spectrophotometry, instrument is 722 grating spectrophotometers）,
Embodiment 15-22：Application of the extracts composition in the Separation & Purification of cobalt nickel metallic element
The extractant composition 20ml that embodiment 7-14 is obtained is dissolved in 180ml sulfonated kerosenes as organic phase, uses hydrogen-oxygen
Change sodium solution and carry out saponification, saponification degree 50%, water phase is prepared 600ml cobalts nickel mixing sulfuric acid solution（Wherein, cobalt content 4g/
L, nickel content 80g/L, pH value 5）, the two is mixed and is placed in separatory funnel, maintains temperature constant at 40 DEG C, in an oscillator
It is extracted 5 minutes and is stopped with the velocity fluctuation of 200r/min, test the content of cobalt and nickel in water phase and oil phase respectively.（Ni2+With purple urea
Sour ammonium complexometric titration, Co2+It is measured with Nitroso R salt spectrophotometry, instrument is 722 grating spectrophotometers）
Table 1
It can be obtained by the experimental data of table 1, synergic reagent component B, the extractant group that C, D are prepared are added in component A
Object is closed, compared with single component A, in the Separation & Purification of cobalt nickel metal, extraction ability is more excellent.
Comparative example 2：
The extractant 20ml that embodiment 2 obtains is dissolved in 180ml hexamethylenes as organic phase, is carried out with potassium hydroxide solution
Saponification, saponification degree 30%, respectively with prepared 600mlLu3+, Yb3+, Tm3+, Er3+Chloride solution（Wherein, metal ion
Content is 0.01mol/L, pH value 5）, mix and be placed in separatory funnel, maintain temperature constant at 50 DEG C, in an oscillator
It is extracted 5 minutes and is stopped with the velocity fluctuation of 300r/min, use metal ion in EDTA titrations test water phase and oil phase respectively
Concentration, and calculate the separation factor between different ions pair.
Embodiment 23-30：Application of the extracts composition in the Separation & Purification of other rare earth elements
The extractant 20ml that embodiment 7-14 is obtained is dissolved in 180ml hexamethylenes as organic phase, uses potassium hydroxide solution
Carry out saponification, saponification degree 30%, respectively with prepared 600mlLu3+, Yb3+, Tm3+, Er3+Chloride solution（Wherein, metal
Ion concentration is 0.01mol/L, pH value 5）, mix and be placed in separatory funnel, maintain temperature constant at 50 DEG C, vibrating
In device with the velocity fluctuation of 300r/min extract 5 minutes stop, respectively use EDTA titrations test water phase and oil phase in metal from
The concentration of son, and calculate the separation factor between different ions pair.
Table 2
It can be obtained by the experimental data of table 2, synergic reagent component B, the extractant group that C, D are prepared are added in component A
Object is closed, compared with single component A, in the Separation & Purification of other rare earth elements, extraction ability also increases.
Claims (15)
1. a kind of extractant composition, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%：
Formulas I
Wherein, 2 R, 4,4- tri-methyl-amyls；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-5wt%：
Formula II
Wherein, R1, R2It is identical, it is 2,4,4- tri-methyl-amyls；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-10wt%：
Formula III
Wherein, R3, R4It is identical, it is 2,4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-5wt%：
Formula IV
Wherein, R6For 2,4,4- tri-methyl-amyls；
It is 0wt% when component B, C, D difference, and the summation of A, B, C and D component is always 100wt%.
2. extractant composition according to claim 1, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%, wherein R 2,4,4- trimethyl penta
Base；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0.01wt%-4wt%, wherein R1, R2It is identical, it is 2,4,4-
Tri-methyl-amyl；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-8wt%, wherein R3, R4It is identical, it is 2,
4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-3wt%, wherein R6For 2,4,4- tri-methyl-amyls；
And the summation of A, B, C and D component is always 100wt%.
3. extractant composition according to claim 1, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%, wherein R 2,4,4- trimethyl penta
Base；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-4wt%, wherein R1, R2It is identical, it is 2,4,4- tri-
Methyl amyl；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0.01wt%-8wt%, wherein R3, R4It is identical,
It is 2,4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0wt%-3wt%, wherein R6For 2,4,4- tri-methyl-amyls；
And the summation of A, B, C and D component is always 100wt%.
4. extractant composition according to claim 1, by weight percentage, including following component：
Component A：The dialkyl phosphinic acid with structure shown in Formulas I of 85wt%-98wt%, wherein R are 2,4,4- tri-methyl-amyls；
Component B：The dialkyl group phosphine oxide with structure shown in Formula II of 0wt%-4wt%, wherein R1, R2It is identical, it is 2,4,4- tri-
Methyl amyl；
Component C：The dialkyl phosphinic acid Arrcostab with structure shown in formula III of 0wt%-8wt%, wherein R3, R4It is identical, it is 2,
4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls；
Component D：The monoalkyl phosphine oxide with structure shown in formula IV of 0.01wt%-3wt%, wherein R6For 2,4,4- trimethyls penta
Base；
And the summation of A, B, C and D component is always 100wt%.
5. the preparation method of extractant composition according to any one of claims 1-4, includes the following steps：By component A points
It is not prepared after evenly mixing with component B and/or component C and/or component D.
6. the preparation method of extractant composition according to claim 5, it is characterised in that：The preparation side of the component A
Method includes the following steps：
a）In the presence of radical initiators, diisobutylene reacts to obtain mixture with hypophosphorous acid source；
b）Mixture carries out washing purification with the aqueous solution of 0.5wt% ~ 30wt% alkali, is carried out with the aqueous solution of 0.5wt% ~ 50wt% acid
The dialkyl phosphinic acid with structure shown in Formulas I is obtained after acidification and concentration：
Formulas I
Wherein, 2 R, 4,4- tri-methyl-amyls.
7. the preparation method of extractant composition according to claim 6, it is characterised in that：Step a）In, reaction temperature
It it is 70 DEG C ~ 160 DEG C, pressure is 0 ~ 2MPa；Step a）In, the radical initiator is selected from peroxide initiator and/or idol
Nitrogen class initiator；Step a）In, the hypophosphorous acid source is hypophosphorous acid and/or hypophosphites；Step b）In, the alkali is selected from hydrogen-oxygen
Change one or more of in sodium, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate；Step b）In, the acid is selected from sulfuric acid, hydrochloric acid, phosphorus
It is one or more of in acid, acetic acid, formic acid.
8. the preparation method of extractant composition according to claim 7, it is characterised in that：Step a）In, the peroxide
Compound initiator is preferably perbenzoic acid, peroxylauric acid, di-tert-butyl peroxide, peroxycarbonates, crosses two
Acetic acid, tert-butyl hydroperoxide isobutyrate, peroxide -2-ethyl hexanoic acid tert-butyl, the peroxidating pivalic acid tert-butyl ester, peroxidating are special
It is one or more of in pentyl ester, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate.
9. the preparation method of extractant composition according to claim 7, it is characterised in that：Step a）In, the azo
Class initiator is selected from azodiisobutyronitrile and/or azobisisoheptonitrile.
10. the preparation method of extractant composition according to claim 7, it is characterised in that：Step a）In, the secondary phosphorus
Hydrochlorate is one or more of in sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite.
11. the preparation method of extractant composition according to claim 5, it is characterised in that：The preparation side of the component B
Method includes the following steps：
a）The 2,4,4- tri-methyl-amyls magnesium chloride or 2,4,4- tri-methyl-amyl magnesium bromides of phosphorus oxychloride and twice mole are anti-
Dialkyl group chlorethoxyfos should be generated；
b）Dialkyl group chlorethoxyfos react the dialkyl group phosphine oxide for generating and having structure shown in Formula II with Lithium Aluminium Hydride：
Formula II
Wherein, R1, R2It is identical, it is 2,4,4- tri-methyl-amyls.
12. the preparation method of extractant composition according to claim 5, it is characterised in that：The preparation side of the component C
Method includes the following steps：
a）The 2,4,4- tri-methyl-amyls magnesium chloride or 2,4,4- tri-methyl-amyl magnesium bromides of phosphorus oxychloride and twice mole are anti-
Dialkyl group chlorethoxyfos should be generated；
b）Dialkyl group chlorethoxyfos, which react to generate with 2,4,4- trimethylpentanols or 2-Ethylhexyl Alcohol, has two of structure shown in formula III
Alkyl phosphinic acid Arrcostab：
Formula III
Wherein, R3, R4It is identical, it is 2,4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls.
13. the preparation method of extractant composition according to claim 5, it is characterised in that：The preparation side of the component D
Method includes the following steps：
a）The 2,4,4- tri-methyl-amyls magnesium chloride or 2,4,4- tri-methyl-amyl magnesium bromides of phosphorus oxychloride and one times of mole are anti-
Dialkyl group chlorethoxyfos should be generated；
b）Dialkyl group chlorethoxyfos react the monoalkyl phosphine oxide for generating and having structure shown in formula IV with Lithium Aluminium Hydride：
Formula IV
Wherein, R6For 2,4,4- tri-methyl-amyls.
14. extractant composition according to any one of claims 1-4 is dissolved in solvent as organic phase, soap is carried out with aqueous slkali
Change, with the application for carrying out extraction and separation as the metal mixed solution of water phase；
Wherein, based on the organic phase of extractant composition or its saponification organic phase total weight, the quality of the extractant composition
A concentration of 5wt% ~ 50wt%；One kind in petroleum ether, hexane, hexamethylene, heptane, octane, sulfonated kerosene of the solvent or
It is several；The aqueous slkali is selected from sodium hydroxide solution and/or potassium hydroxide solution；The saponification degree of the saponification is 8% ~ 50%；Institute
It is the mixture containing rare earth ion to state metal mixed solution.
15. application according to claim 14, it is characterised in that：The metal mixed solution be containing cobalt, nickel and/or its
The mixed solution of his metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510588105.8A CN106544506B (en) | 2015-09-16 | 2015-09-16 | A kind of extractant composition and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510588105.8A CN106544506B (en) | 2015-09-16 | 2015-09-16 | A kind of extractant composition and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106544506A CN106544506A (en) | 2017-03-29 |
| CN106544506B true CN106544506B (en) | 2018-10-26 |
Family
ID=58361452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510588105.8A Active CN106544506B (en) | 2015-09-16 | 2015-09-16 | A kind of extractant composition and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106544506B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110331286B (en) * | 2019-07-10 | 2021-05-04 | 青海柴达木兴华锂盐有限公司 | Application of alkyl phosphine oxide compound and method for extracting lithium from salt lake brine |
| CN113604687B (en) * | 2021-08-18 | 2022-12-23 | 鞍山昊旻稀土科技有限公司 | Method for removing aluminum from rare earth feed liquid by using extracting agent containing pivalic acid |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2562059B1 (en) * | 1984-04-02 | 1989-12-01 | Rhone Poulenc Spec Chim | PROCESS FOR SEPARATING RARE EARTH BY LIQUID-LIQUID EXTRACTION |
| US4900522A (en) * | 1986-07-22 | 1990-02-13 | Amax Inc. | Separation of nickel and cobalt from sulfate solutions by solvent extraction |
| US5622679A (en) * | 1995-12-13 | 1997-04-22 | Cytec Technology Corp. | Extraction of rare earth elements using alkyl phosphinic acid or salt/tetraalkylammonium salt as extractant |
| KR100712301B1 (en) * | 2005-08-11 | 2007-04-30 | 한국과학기술연구원 | Solvent extraction method for separation of cobalt and nickel |
| CN101624401B (en) * | 2008-12-05 | 2013-08-21 | 清华大学 | Synthesis method of dialkyl phosphinic acid extractant |
| CN101475588B (en) * | 2008-12-25 | 2012-01-04 | 清华大学 | Method for synthesizing dialkyl hypophosphorous acid |
| CN103184337A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Separation and extraction method for nickel and cobalt in low-grade sulfide mineral bioleaching agent through synergistic extraction |
| RU2540257C1 (en) * | 2013-10-18 | 2015-02-10 | Федеральное Государственное Бюджетное Учреждение Науки Институт Химии И Химической Технологии Сибирского Отделения Российской Академии Наук (Иххт Со Ран) | Cobalt and nickel separation method |
| CN104195335B (en) * | 2014-09-19 | 2017-02-15 | 厦门稀土材料研究所 | Extraction separation method for heavy rare earth elements |
-
2015
- 2015-09-16 CN CN201510588105.8A patent/CN106544506B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106544506A (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Toward greener comprehensive utilization of bastnaesite: Simultaneous recovery of cerium, fluorine, and thorium from bastnaesite leach liquor using HEH (EHP) | |
| CN107815542B (en) | A kind of synergic reagent and method for nickel selective extraction in acid solution | |
| CN104470936B (en) | The new difunctional compound that can be used as uranium (VI) ligand, synthesizes its method and application thereof | |
| CN101475588B (en) | Method for synthesizing dialkyl hypophosphorous acid | |
| Ma et al. | Cobalt recovery from cobalt-bearing waste in sulphuric and citric acid systems | |
| CN109097570A (en) | The phosphine extractant of acidity containing amino is used for the purposes and method of extraction and separation cobalt and nickel | |
| CN106544506B (en) | A kind of extractant composition and the preparation method and application thereof | |
| Wang et al. | Synthesis of novel nonsymmetric dialkylphosphinic acid extractants and studies on their extraction–separation performance for heavy rare earths | |
| Guan et al. | Recovery of cobalt and nickel in the presence of magnesium and calcium from sulfate solutions by Versatic 10 and mixtures of Versatic 10 and Cyanex 301 | |
| Zheng et al. | A novel strategy of lithium recycling from spent lithium-ion batteries using imidazolium ionic liquid | |
| CN108642283A (en) | A kind of nickel cobalt synergic reagent and its method detached with impurity extraction for nickel cobalt | |
| Zhou et al. | Recovery of Ga (III) from chloride solutions by solvent extraction with Cextrant 230 | |
| CN106544505B (en) | A kind of extractant composition and the preparation method and application thereof | |
| Wang et al. | Extractant (2-ethylhexyl)(2, 4, 4′-trimethylpentyl) phosphinic acid (USTB-1): Synthesis and its extraction and separation behaviors for rare earths from chloride media | |
| CN103694273B (en) | Preparation method and application of dialkyl phosphinate compounds and salts thereof | |
| Hu et al. | The separation of Ni (II) over base metal ions in acidic polymetallic medium: Synergistic extraction and structural evidence | |
| Li et al. | Efficient zinc extraction with novel phenyl phosphate ptopp in sulfuric acid system | |
| CN105944768B (en) | A kind of method that rhodium catalyst is recycled in the waste water phase from rhodium-containing | |
| Li et al. | Dialkyl phosphinic acids: Synthesis and applications as extractant for nickel and cobalt separation | |
| Li et al. | Separation of valuable metals from mixed cathode materials of spent lithium-ion batteries by single-stage extraction | |
| CN102643299B (en) | Method for preparing aliphatic boric acid by ethylene diamine tetraacetic acid (EDTA) trisodium salt | |
| CN108866352A (en) | The technique that Phosphate Ionic Liquids extract the lithium production lithium carbonate in salt lake bittern | |
| CN113736995A (en) | Application of carboxylic acid compound as extracting agent and metal ion extraction method | |
| CN107674974B (en) | The purposes and method of the phosphine extractant extraction and recovery copper of neutrality containing amino | |
| CN103496668B (en) | Method for preparing sodium hydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |