CN106544506A - A kind of extractant composition and preparation method and application - Google Patents
A kind of extractant composition and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of extractant composition and preparation method and application.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 is different with D, 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 to, in rare earth metal, the particularly Separation ＆ Purification of cobalt nickel metal, compare with one pack system extractant as extractant, and its extraction ability is more excellent；With two（2,4,4- tri-methyl-amyls）Phosphinic acid are compared, and other synergic reagent components are more easily-synthesized, and reduce the production cost of product.
Description
Technical field
The present invention relates to non-ferrous metal extractive technique field, more particularly to a kind of extractant composition for extract and separate is carried out to metallic element and preparation method and application.
Background technology
Two (2,4,4- tri-methyl-amyl) phosphinic acid, its structure and preparation method patent are American Cyanamid Company earliest（American Cyanamid Company, predecessor of Cytec companies）In United States Patent (USP) 4374780 filed in 14 days Mays in 1981（22 days 2 months nineteen eighty-three is open）, there is additive reaction in the presence of radical initiator with hydrogen phosphide and diisobutylene and generate intermediate product two (2,4,4- tri-methyl-amyl) phosphine alkane, then double (2,4,4- tri-methyl-amyl) phosphinic acid are generated with hydrogen peroxide oxidation.Afterwards, its associated companies has applied widely applying again successively（Such as the US4909939 of nineteen ninety application, the US5639433 of application in 1997）, preparation method and derivant prepare patent（Such as the US20090165598 of application in 2009, the US20140275615 of application in 2014）.The said firm is in dominant position in the field at present, within a very long time is once the product unique manufacturer in the world.
In the last few years, other companies took up to research and develop correlation technique.Rhodia Inc of the U.S.（Rhodia）Mention in patent US7049463 of application in 2006 double (2,4,4- tri-methyl-amyls) phosphinic acid are generated with diisobutylene reaction under 135 DEG C and di-tert-butyl peroxide effect with sodium hypophosphite in acetic acid solution.
China was also quickly grown in recent years in the technology of association area.As domestic main manufacturer, use the new specialization work in Changshu of U.S.'s Cytec company techniques also to apply for many synthetic method patents, mentioned in the Chinese patent 201110057908.2 of application in such as 2011 and under condition of free radical adopt high pressure with diisobutylene with side-product hydrogen phosphide in sodium hypophosphite technique（5-8MPa）Synthesis double (2,4,4- tri-methyl-amyls) phosphine, then Jing hydrogen peroxide oxidations obtain double (2,4,4- tri-methyl-amyls) phosphinic acid, the method is improved in the Chinese patent 201410019641.1 of application in 2014, diisobutylene absorbs hydrogen phosphide under room temperature and certain pressure, then heating absorbs the solution initiation radical reaction of hydrogen phosphide, obtain double (2,4,4- tri-methyl-amyl) phosphorus of intermediate product in high yield.Jing hydrogen peroxide oxidations obtain double (2,4,4- tri-methyl-amyls) phosphinic acid to intermediate product again.Tsing-Hua University is mentioned with sodium hypophosphite in acetic acid solution in patent CN101475588 of application in 2008, uses mixture di-tert-butyl peroxide instead and benzoyl peroxide makees initiator, reacts 10-15 hours, net product is obtained at 120-140 DEG C.Jiangxi Science and Technology Normal College is mentioned with sodium hypophosphite in acetic acid solution in patent CN102020673 of application in 2011, makees initiator with azodiisobutyronitrile, reacts 10 hours prepared products at a reflux temperature.Contain 13.8% 1 substitution product in product；And and applied for a patent CN102268038 and CN1023211117 again at 2011 and 2012 respectively, will be shortened in the response time 5 hours with mixed initiator in same system, in product, a substituent only has 4%.
Cobalt is the important ingredient of high intensity, high-temperature alloy, this Alloyapplication extensively, the engine turbine of such as jet plane, ceramic metal, high-energy battery etc..But cobalt metal is mainly distributed in nickel minerals, content is low to be not readily separated, thus in metallurgical industry all the time separate cobalt metal technique it is more complicated, yield is relatively low, and cost is also higher.Solvent extraction due to good separating effect, disposal ability is big, recovery rate of valuable metals is high, operation is continuous, easily realize automatization, organic reagent reusable edible, low cost and other advantages and be widely used in the extraction and separation of nickel and cobalt ions.With application of the solvent extraction in metallurgy, (2- ethylhexyls) phosphoric acid is successively occurred in that（P204）And di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester（P507）Two kinds of extractant commodity, and obtain extensively application.Two (2,4,4- tri-methyl-amyls) phosphinic acid（Cyanex272）As its succedaneum in terms of cobalt nickel separation, separation improves an order of magnitude again, due to its high separation, can not only reduce extraction series, saves extractant, reduces energy resource consumption, and the solution purity after separating is very high, thus with very high application and promotional value.Separate in cobalt, the solvent extraction technology of nickel ion in sulfuric acid system, the pH of leaching solution that routine acidleach at present and biological dump leaching are produced typically is 1-2, and P204, P507, Cyanex272 are to Ni2+And Co2+Optimal separation pH value be 4.5-5.0.It is thus impossible to directly leachate need to be carried out a certain degree of neutralization with the kind of extractants extract and separate, this can undoubtedly increase extraction cost.Additionally, though Cyanex272 excellent performances, expensive, it is difficult to large-scale industrial application.For this problem, Zhang Pingwei etc.（Zhang Pingwei, Zhu village. cobalt nickel synergistic system [J]. chemical industry metallurgical, 1997,
8(3):282-288.）Research is pointed out, using the cooperative effect of mixed extractant, can separate nickel and cobalt ions under relatively low pH value.In recent years, many synergistic systems are proposed to the numerous studies of nickel and cobalt ions synergic solvent extraction.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.）Research finds that the extraction system of any two composition is to Co in tri- kinds of extractants of Cyanex272, P507, P2042+There is positive Association stripping effect, but it is still higher to the synergic solvent extraction pH value of nickel and cobalt ions.
In prior art, one pack system extractant is expensive, though reducing cost after with the addition of synergic reagent component, corresponding extraction ability can decline, and have impact on the efficiency of extraction.
The content of the invention
In order to overcome the deficiencies in the prior art and defect, the primary and foremost purpose of the present invention is to provide a kind of extractant composition that with the addition of synergic reagent component, be can be widely applied in rare earth metal, the particularly Separation ＆ Purification of cobalt nickel metal, while cost is reduced, its extraction ability is excellent.
It is a further object of the present invention to provide the preparation method 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, alkyl of the R for 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 are different, 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, alkyl of the R for 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 different, 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, 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, alkyl of the R for 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, it is 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%, alkyl of the wherein R for 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, 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, 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 0.01wt%-3wt%, wherein, R6For the alkyl of C1-C8；
And the summation of A, B, C and D component is always 100wt%.
Preferably, R is 2,4,4- 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 described extractant composition, comprises the steps：Prepare after component A is uniformly mixed with component B and/or component C and/or component D respectively.
Wherein, the preparation method of component A, comprises the steps：
a）In the presence of radical initiators, alkene is reacted with hypophosphorous acid source and obtains mixture；
b）Mixture carries out washing purification with the aqueous solution of 0.5wt% ~ 30wt% alkali, obtains the dialkyl phosphinic acid with structure shown in Formulas I after carrying out acidification and concentration with 0.5wt% ~ 50wt% aqueous acids：
Formulas I
Wherein, alkyl of the R for C1-C8.
Preferably, step a）In, reaction temperature is 70 DEG C ~ 160 DEG C, and pressure is 0 ~ 2MPa；Step a）In, in octene, isooctene, butylene, isobutene., amylene, iso-amylene, hexene, dissident's alkene, heptene, iso-heptene, diisobutylene one or more, preferably diisobutylene；Step a）In, the radical initiator is selected from peroxide initiator and/or azo-initiator；The peroxide initiator is preferably one or more in perbenzoic acid, peroxylauric acid, di-tert-butyl peroxide, peroxycarbonates, mistake oxalic acid, tert-butyl hydroperoxide isobutyrate, peroxide -2-ethyl hexanoic acid tert-butyl, the peroxidating pivalic acid tert-butyl ester, peroxidating spy's pentyl ester, Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate；The azo-initiator is selected from azodiisobutyronitrile and/or 2,2'-Azobis(2,4-dimethylvaleronitrile)；Step a）In, the hypophosphorous acid source is hypophosphorous acid and/or hypophosphites, and the hypophosphites are selected from one or more in sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite；Step b）In, the alkali is selected from one or more in sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate；Step b）In, the acid is selected from one or more in sulphuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid.
Wherein, the preparation method of component B, comprises the steps：
a）Phosphorus oxychloride generates dialkyl group phosphorus oxychloride with the grignard reagent reaction of twice mole；
b）Dialkyl group chlorethoxyfos are reacted with Lithium Aluminium Hydride and generate the dialkyl group phosphine oxide with structure shown in Formula II：
Formula II
Wherein, R1, R2It is identical or different, it is the alkyl of C1-C8.
Preferably, step a）In, the grignard reagent is selected from branched alkyl magnesium halide, particularly preferably 2,4,4- tri-methyl-amyl magnesium chlorides or 2,4,4- tri-methyl-amyl magnesium bromides.
Wherein, the preparation method of component C, comprises the steps：
a）Phosphorus oxychloride generates dialkyl group chlorethoxyfos with the grignard reagent reaction of twice mole；
b）Dialkyl group chlorethoxyfos are reacted with alcohol and generate the dialkyl phosphinic acid Arrcostab with structure shown in formula III：
Formula III
Wherein, R3, R4, R5It is identical or different, it is the alkyl of C1-C8.
Preferably, step a）In, the grignard reagent is selected from branched alkyl magnesium halide, particularly preferably 2,4,4- tri-methyl-amyl magnesium chlorides or 2,4,4- tri-methyl-amyl magnesium bromides；Step b）In, the alcohol is selected from 2,4,4- trimethylpentanols or 2-Ethylhexyl Alcohol.
Wherein, the preparation method of component D, comprises the steps：
a）Phosphorus oxychloride generates alkyl dichloro phosphorous oxide with the grignard reagent reaction of one times of mole；
b）Alkyl dichloro oxygen phosphorus are reacted with Lithium Aluminium Hydride and generate the monoalkyl phosphine oxide with structure shown in formula IV：
Formula IV
Wherein, R6For the alkyl of C1-C8.
Preferably, step a）In, the grignard reagent is selected from branched alkyl magnesium halide, particularly preferably 2,4,4- tri-methyl-amyl magnesium chlorides or 2,4,4- tri-methyl-amyl magnesium bromides.
Described extractant composition is dissolved in solvent as organic faciess, carries out saponification with aqueous slkali, and the application of extract and separate is carried out with the metal mixed solution as water phase.
Wherein, based on extractant composition organic faciess or its saponification organic faciess gross weight, the mass concentration of the extractant composition is 5wt% ~ 50wt%；The solvent is selected from one or more in petroleum ether, hexane, hexamethylene, heptane, octane, sulfonated kerosene；The aqueous slkali is selected from sodium hydroxide solution and/or potassium hydroxide solution；The saponification degree of the saponification is 8% ~ 50%；The metal mixed solution is the mixture containing rare earth ion；Mixed solution preferably containing cobalt, nickel and/or other metal ions；The described mixed solution containing cobalt, nickel and/or other metal ions can first pass through metal extraction agent P204 and remove other metal ions, after carry out extract and separate with a kind of described extractant composition for metallic element again.
The present invention compared with prior art, has the advantages that：
1）The extractant composition containing synergic reagent component that the present invention is prepared, can be widely applied to rare earth metal as extractant, particularly in the Separation ＆ Purification of cobalt nickel metal, compare with one pack system extractant, and its extraction ability is more excellent.
2）In synthesis two（2,4,4- tri-methyl-amyls）In the technique of the components such as phosphinic acid, substituted using other phosphorus system initiation materials, it is to avoid the use of hydrogen phosphide, improve the safety of production technology.
3）With two（2,4,4- tri-methyl-amyls）Phosphinic acid are compared, and other synergic reagent components are more easily-synthesized, and reduce the production cost of product.
Specific embodiment
The present invention is further illustrated below by specific embodiment, following examples are not limited by following embodiments for the present invention preferably embodiment, but embodiments of the present invention.
Embodiment
1
：One-component
A
Two（
2,4,4-
Tri-methyl-amyl）The preparation of phosphinic acid
By the hypophosphorous acid of 200g70%; 760g diisobutylene; 4g peroxide -2-ethyl hexanoic acid tert-butyls are put in the enamel reaction still of 2L, under nitrogen protection, are heated to 85 DEG C of beginning stirring reactions; peroxide -2-ethyl hexanoic acid tert-butyl is squeezed into continuously with dosing pump simultaneously; after reaction 12 hours, enclosed system, maintenance system pressure limit is in 0.2-0.4MPa; react after being warming up to 110 DEG C of continuation reactions 48 hours and terminate, lower the temperature.Reactant liquor is moved in separatory funnel, alkali cleaning is carried out with 5% sodium hydroxide solution, then is acidified with 5% hydrochloric acid, after washing, after oil phase concentration, obtain 453g products two（2,4,4- tri-methyl-amyls）Phosphinic acid.
Embodiment
2
：One-component
A
Two（
2,4,4-
Tri-methyl-amyl）The preparation of phosphinic acid
By 225g sodium hypophosphites; 200g acetic acid; 760g diisobutylene, 5g di-tert-butyl peroxides are put in the enamel reaction still of 2L, under nitrogen protection; it is heated to 120 DEG C of beginning stirring reactions; enclosed system, maintenance system pressure limit is in 0.1-0.2MPa, while continuously squeezing into di-tert-butyl peroxide with dosing pump; reaction is reacted after 48 hours and is terminated, and lowers the temperature.Reactant liquor is moved in separatory funnel, is washed with 5% sodium hydroxide solution, then with 5% hydrochloric acid be acidified, after washing, oil phase concentration after obtain 473g products two（2,4,4- tri-methyl-amyls）Phosphinic acid.
Embodiment
3
：One-component
B
Two（
2,4,4-
Tri-methyl-amyl）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, the 2 of 250ml2mol/L under ice bath, is slowly added dropwise; 4; the tetrahydrofuran solution of 4- tri-methyl-amyl magnesium bromides, drips off for about 1 hour, is warming up to backflow continuation reaction and can obtain two in 4 hours（2,4,4- tri-methyl-amyls）Chlorethoxyfos solution.Without any process, under ice bath, continue 5.6 grams of Lithium Aluminium Hydrides of Deca and be dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, be warming up to backflow continuation reaction reaction in 12 hours and terminate, lower the temperature.Ether is added in reactant liquor, is washed with saturated ammonium chloride solution, then extracted three times with saturated aqueous common salt, after organic faciess concentration, be rectifying to obtain 32g products two again（2,4,4- tri-methyl-amyls）Phosphine oxide.
Embodiment
4
：One-component
C
Two（
2,4,4-
Tri-methyl-amyl）Hypophosphorous acid（
2,4,4-
Tri-methyl-amyl）The preparation of ester
38 grams of phosphorus oxychloride and 100ml anhydrous tetrahydro furans are added in 500ml four-hole bottles, under nitrogen protection, the 2 of 250ml2mol/L under ice bath, is slowly added dropwise; 4; the tetrahydrofuran solution of 4- tri-methyl-amyl magnesium bromides, drips off for about 1 hour, is warming up to backflow continuation reaction and can obtain two in 4 hours（2,4,4- tri-methyl-amyls）Chlorethoxyfos solution.Without any process, under ice bath, continue Deca 32.5 gram 2,4,4- trimethylpentanols are dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, be warming up to backflow continuation reaction reaction in 12 hours and terminate, lower the temperature.Ether is added in reactant liquor, is washed with saturated ammonium chloride solution, then extracted three times with saturated aqueous common salt, after organic faciess concentration, obtain 48g products two（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2,4,4- tri-methyl-amyls）Ester.
Embodiment
5
：One-component
C
Two（
2,4,4-
Tri-methyl-amyl）Hypophosphorous acid（
2-
Ethylhexyl）The preparation of ester
38 grams of phosphorus oxychloride and 100ml anhydrous tetrahydro furans are added in 500ml four-hole bottles, under nitrogen protection, the 2 of 250ml2mol/L under ice bath, is slowly added dropwise; 4; the tetrahydrofuran solution of 4- tri-methyl-amyl magnesium bromides, drips off for about 1 hour, is warming up to backflow continuation reaction and can obtain two in 4 hours（2,4,4- tri-methyl-amyls）Chlorethoxyfos solution.Without any process, under ice bath, continue 32.5 grams of 2-Ethylhexyl Alcohols of Deca and be dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, be warming up to backflow continuation reaction reaction in 12 hours and terminate, lower the temperature.Ether is added in reactant liquor, is washed with saturated ammonium chloride solution, then extracted three times with saturated aqueous common salt, after organic faciess concentration, obtain 48g products two（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2- ethylhexyls）Ester.
Embodiment
6
：One-component
D
（
2,4,4-
Tri-methyl-amyl）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, the 2 of 125ml2mol/L under ice bath, is slowly added dropwise; 4; the tetrahydrofuran solution of 4- tri-methyl-amyl magnesium bromides, drips off for about 1 hour, is warming up to backflow continuation reaction and can obtain for 4 hours（2,4,4- tri-methyl-amyls）Dichloro oxygen phosphorus solution.Without any process, under ice bath, continue Deca 2.8g Lithium Aluminium Hydride and be dissolved in 100ml anhydrous tetrahydro furans, drip off within about 1 hour, be warming up to backflow continuation reaction reaction in 12 hours and terminate, lower the temperature.Ether is added in reactant liquor, is washed with saturated ammonium chloride solution, then extracted three times with saturated aqueous common salt, after organic faciess concentration, be rectifying to obtain 17g products again（2,4,4- tri-methyl-amyls）Phosphine oxide.
Embodiment
7
：Component
A+
Component
B+
Component
C+
Component
D
Preparation
By 80g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 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 uniformly mixed, and obtains 100g compositionss.
Embodiment
8
：Component
A+
Component
B+
Component
C+
Component
D
Preparation
By 85g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 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 obtains 100g compositionss.
Embodiment
9
：Component
A+
Component
B
Preparation
By 97g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 3g bis-（2,4,4- tri-methyl-amyls）Phosphine oxide is uniformly mixed, and obtains 100g compositionss.
Embodiment
10
：Component
A +
Component
C
Preparation
By 94g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 6g bis-（2,4,4- tri-methyl-amyls）Hypophosphorous acid（2,4,4- tri-methyl-amyls）Ester is uniformly mixed, and obtains 100g compositionss.
Embodiment
11
：Component
A+
Component
D
Preparation
By 98g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 2g（2,4,4- tri-methyl-amyls）Phosphine oxide is uniformly mixed, and obtains 100g compositionss.
Embodiment
12
：Component
A+
Component
B+
Component
C
Preparation
By 90g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 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 compositionss.
Embodiment
13
：Component
A+
Component
B+
Component
D
Preparation
By 95g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 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 compositionss.
Embodiment
14
：Component
A+
Component
C+
Component
D
Preparation
By 89g bis-（2,4,4- tri-methyl-amyls）Phosphinic acid, 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 obtains 100g compositionss.
Comparative example
1
：
The extractant 20ml that embodiment 2 is obtained is dissolved in 180ml sulfonated kerosenes as organic faciess, and saponification, saponification degree 50%, water 600ml cobalt nickel mixing sulfuric acid solutions mutually to prepare are carried out with sodium hydroxide solution（Wherein, cobalt content 4g/L, nickel content 80g/L, pH value are 5）, the two mixing is placed in separatory funnel, temperature constant is maintained at 40 DEG C, extracted 5 minutes with the velocity fluctuation of 200r/min in an oscillator and stopped, testing the content of cobalt and nickel in water phase and oil phase respectively.（Ni2+Use murexide complexometric titration, Co2+Nitroso R salt spectrophotometry is used, 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 faciess, and saponification, saponification degree 50%, water 600ml cobalt nickel mixing sulfuric acid solutions mutually to prepare are carried out with sodium hydroxide solution（Wherein, cobalt content 4g/L, nickel content 80g/L, pH value are 5）, the two mixing is placed in separatory funnel, temperature constant is maintained at 40 DEG C, extracted 5 minutes with the velocity fluctuation of 200r/min in an oscillator and stopped, testing the content of cobalt and nickel in water phase and oil phase respectively.（Ni2+Use murexide complexometric titration, Co2+Nitroso R salt spectrophotometry is used, instrument is 722 grating spectrophotometers）
Table 1
Can be obtained by the experimental data of table 1, with the addition of synergic reagent component B in component A, C, the extractant composition that D is prepared, compared with single component A, in the Separation ＆ Purification of cobalt nickel metal, its extraction ability is more excellent.
Comparative example
2
：
The extractant 20ml that embodiment 2 is obtained is dissolved in 180ml hexamethylene as organic faciess, and saponification, saponification degree 30%, respectively with the 600mlLu for preparing are carried out with potassium hydroxide solution3+, Yb3+, Tm3+, Er3+Chloride solution（Wherein, metal ion content is 0.01mol/L, and pH value is 5）Mixing is placed in separatory funnel, maintains temperature constant at 50 DEG C, is extracted 5 minutes with the velocity fluctuation of 300r/min in an oscillator and is stopped, test the concentration of metal ion in water phase and oil phase respectively with EDTA titrimetrys, 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 hexamethylene as organic faciess, and saponification, saponification degree 30%, respectively with the 600mlLu for preparing are carried out with potassium hydroxide solution3+, Yb3+, Tm3+, Er3+Chloride solution（Wherein, metal ion content is 0.01mol/L, and pH value is 5）Mixing is placed in separatory funnel, maintains temperature constant at 50 DEG C, is extracted 5 minutes with the velocity fluctuation of 300r/min in an oscillator and is stopped, test the concentration of metal ion in water phase and oil phase respectively with EDTA titrimetrys, and calculate the separation factor between different ions pair.
Table 2
Can be obtained by the experimental data of table 2, with the addition of synergic reagent component B in component A, C, the extractant composition that D is prepared, compared with single component A, in the Separation ＆ Purification of other rare earth elements, its extraction ability also increases.
Claims (18)
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 80wt%-99.99wt%：
Formulas I
Wherein, alkyl of the R for 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 are different, 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, alkyl of the R for 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 different, 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, 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%.
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, alkyl of the R for 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, it is 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%.
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%, alkyl of the wherein R for 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, 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, 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 0.01wt%-3wt%, wherein, R6For the alkyl of C1-C8；
And the summation of A, B, C and D component is always 100wt%.
5. the extractant composition according to any one of claim 1-4, it is characterised in that R is 2,4,4- tri-methyl-amyls.
6. the extractant composition according to any one of claim 1-4, it is characterised in that R1, R2It is identical, it is 2,4,4- tri-methyl-amyls.
7. the extractant composition according to any one of claim 1-4, it is characterised in that R3, R4It is identical, it is 2,4,4- tri-methyl-amyls, R5For 2,4,4- tri-methyl-amyls or 2- ethylhexyls.
8. the extractant composition according to any one of claim 1-4, it is characterised in that R6For 2,4,4- tri-methyl-amyls.
9. the preparation method of the extractant composition as described in any one of claim 1-8, comprises the steps：Prepare after component A is uniformly mixed with component B and/or component C and/or component D respectively.
10. the preparation method of extractant composition according to claim 9, it is characterised in that：The preparation method of component A, comprises the steps：
a）In the presence of radical initiators, alkene is reacted with hypophosphorous acid source and obtains mixture；
b）Mixture carries out washing purification with the aqueous solution of 0.5wt% ~ 30wt% alkali, obtains the dialkyl phosphinic acid with structure shown in Formulas I after carrying out acidification and concentration with 0.5wt% ~ 50wt% aqueous acids：
Formulas I
Wherein, alkyl of the R for C1-C8.
The preparation method of 11. extractant compositions according to claim 10, it is characterised in that：Step a）In, reaction temperature is 70 DEG C ~ 160 DEG C, and pressure is 0 ~ 2MPa；Step a）In, the alkene is selected from one or more in octene, isooctene, butylene, isobutene., amylene, iso-amylene, hexene, dissident's alkene, heptene, iso-heptene, diisobutylene, preferably diisobutylene；Step a）In, the radical initiator is selected from peroxide initiator and/or azo-initiator；The peroxide initiator is preferably one or more in perbenzoic acid, peroxylauric acid, di-tert-butyl peroxide, peroxycarbonates, mistake oxalic acid, tert-butyl hydroperoxide isobutyrate, peroxide -2-ethyl hexanoic acid tert-butyl, the peroxidating pivalic acid tert-butyl ester, peroxidating spy's pentyl ester, Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate；The azo-initiator is selected from azodiisobutyronitrile and/or 2,2'-Azobis(2,4-dimethylvaleronitrile)；Step a）In, the hypophosphorous acid source is hypophosphorous acid and/or hypophosphites, and the hypophosphites are selected from one or more in sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite；Step b）In, the alkali is selected from one or more in sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate；Step b）In, the acid is selected from one or more in sulphuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid.
The preparation method of 12. extractant compositions according to claim 9, it is characterised in that：The preparation method of component B, comprises the steps：
a）Phosphorus oxychloride generates dialkyl group phosphorus oxychloride with the grignard reagent reaction of twice mole；
b）Dialkyl group chlorethoxyfos are reacted with Lithium Aluminium Hydride and generate the dialkyl group phosphine oxide with structure shown in Formula II：
Formula II
Wherein, R1, R2It is identical or different, it is the alkyl of C1-C8.
The preparation method of 13. extractant compositions according to claim 12, it is characterised in that：Step a）In, the grignard reagent is selected from branched alkyl magnesium halide, preferably 2,4,4- tri-methyl-amyl magnesium chlorides or 2,4,4- tri-methyl-amyl magnesium bromides.
The preparation method of 14. extractant compositions according to claim 9, it is characterised in that：The preparation method of component C, comprises the steps：
a）Phosphorus oxychloride generates dialkyl group chlorethoxyfos with the grignard reagent reaction of twice mole；
b）Dialkyl group chlorethoxyfos are reacted with alcohol and generate the dialkyl phosphinic acid Arrcostab with structure shown in formula III：
Formula III
Wherein, R3, R4, R5It is identical or different, it is the alkyl of C1-C8.
The preparation method of 15. extractant compositions according to claim 14, it is characterised in that step a）In, the grignard reagent is selected from branched alkyl magnesium halide, preferably 2,4,4- tri-methyl-amyl magnesium chlorides or 2,4,4- tri-methyl-amyl magnesium bromides；Step b）In, the alcohol is selected from 2,4,4- trimethylpentanols or 2-Ethylhexyl Alcohol.
The preparation method of 16. extractant compositions according to claim 9, it is characterised in that：The preparation method of component D, comprises the steps：
a）Phosphorus oxychloride generates alkyl dichloro phosphorous oxide with the grignard reagent reaction of one times of mole；
b）Alkyl dichloro oxygen phosphorus are reacted with Lithium Aluminium Hydride and generate the monoalkyl phosphine oxide with structure shown in formula IV：
Formula IV
Wherein, R6For the alkyl of C1-C8.
The preparation method of 17. extractant compositions according to claim 16, it is characterised in that：Step a）In, the grignard reagent is selected from branched alkyl magnesium halide, preferably 2,4,4- tri-methyl-amyl magnesium chlorides or 2,4,4- tri-methyl-amyl magnesium bromides.
18. extractant compositions as described in any one of claim 1-8 are dissolved in solvent as organic faciess, carry out saponification with aqueous slkali, and the application of extract and separate is carried out with the metal mixed solution as water phase；
Wherein, based on extractant composition organic faciess or its saponification organic faciess gross weight, the mass concentration of the extractant composition is 5wt% ~ 50wt%；The solvent is selected from one or more in petroleum ether, hexane, hexamethylene, heptane, octane, sulfonated kerosene；The aqueous slkali is selected from sodium hydroxide solution and/or potassium hydroxide solution；The saponification degree of the saponification is 8% ~ 50%；The metal mixed solution is the mixture containing rare earth ion；Mixed solution preferably containing cobalt, nickel and/or other metal ions.
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