CN106521153B - The phosphine extractant of neutrality containing amino is used for the purposes and method of extraction and separation uranium - Google Patents

The phosphine extractant of neutrality containing amino is used for the purposes and method of extraction and separation uranium Download PDF

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CN106521153B
CN106521153B CN201611017998.1A CN201611017998A CN106521153B CN 106521153 B CN106521153 B CN 106521153B CN 201611017998 A CN201611017998 A CN 201611017998A CN 106521153 B CN106521153 B CN 106521153B
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uranium
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alkyl
phosphine
extractant
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廖伍平
张志峰
李艳玲
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/382—Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te
    • 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
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents

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Abstract

Purposes and method the present invention relates to the phosphine extractant of neutrality containing amino of following general formula I for extraction and separation uranium,Wherein, R1And R2It is each independently selected from C1‑12Alkyl；R3And R4It is each independently selected from C1‑5Alkyl and hydrogen, R5And R6It is each independently selected from C1‑16Alkyl and hydrogen, and R5And R6At most one is hydrogen.The phosphine of neutrality containing the amino extractant that the present invention uses not only has good extraction and separation ability in different acid mediums to uranium, and synthetic method is simple, industrial chemicals is simple and easy to get used in synthesis, it is of low cost, so as to be effectively reduced the extraction and separation cost of uranium, there is higher industrial application value.The uranium in liquid-liquid extraction separation or liquid-solid extraction separation uranium-bearing raw material is used according to the method for the present invention, the result shows that, the purity of the uranium obtained after extraction, washing, back extraction is 99% or more, and the yield of uranium is 98% or more, effectively realizes the enrichment and purification of uranium.

Description

The phosphine extractant of neutrality containing amino is used for the purposes and method of extraction and separation uranium
Technical field
The invention belongs to the technical field of wet metallurgy of uranium, and in particular to the phosphine extractant of neutrality containing amino is used for extraction and separation The purposes and method of uranium.
Background technology
Currently, the extraction of uranium mainly uses TBP techniques in nitric acid medium.It with tributyl phosphate is extraction that TBP techniques, which are a kind of, Take agent, the method for uranium, thorium and rare earth in extraction and separation solution.Since TBP is high to the separation of the impurity such as uranium and thorium and rare earth, Therefore, which is widely used in technical field of wet metallurgy.But the water solubility of extractant TBP is big and is also only limitted in nitric acid There is preferable uranium thorium separating capacity in system, limits its popularization and application.
Monazite is the precious resources rich in rare earth, thorium, uranium.Monazite concentrate is remaining after caustic digestion Extraction of rare earth to be put Penetrating property acid dissolution slag also contains the ThO of the rare earth oxide (REO) of about 7-18%, 16-28%2, 0.6-1.2% U3O8And not by Zircon, monazite of decomposition etc..
Jan ú bia C.B.S.Amaral et al. (Thorium and uranium extraction from rare earth elements in monazite sulfuric acid liquor through solvent extraction； Minerals Engineering, Vol.23 (6), May 2010, Pages 498-503) have studied Primene JM-T and The mixture of Alamine 336 is the method that extractant extracts thorium and uranium from monazite sulphuric leachate.The result shows that through extraction It takes, be stripped, realize the extracting and enriching of thorium, uranium, the extraction yield of thorium and uranium respectively reaches 99.6% and 99.4%, but not Realize the separation of thorium, uranium.
CN103146938A discloses a kind of extraction separating method of uranium, wherein with two (2- ethyls of 2- ethylhexyls phosphonic acids Oneself) ester is extractant, using the salpeter solution of uranium-bearing as feed liquid, after extracting, being stripped, the purity of uranium reaches 99.0~ 99.7%, yield reaches 98~99%.But extractant used only has good uranium, thorium separation energy in nitric acid medium in the patent Power, separating property is poor in other acid mediums.
Invention content
To solve the above-mentioned problems, the present invention uses the phosphine extractant extraction and separation uranium of neutrality containing amino, achieves good Extraction and separation effect, extractant property used is stable, is readily synthesized.
One aspect of the present invention provides purposes of the phosphine extractant of neutrality containing amino for extraction and separation uranium of general formula I：
Wherein, R1And R2It is each independently selected from C1-12Alkyl, preferably C4-10Alkyl, more preferable C5-9Alkyl, most preferably C6-8Alkyl；
R3And R4It is each independently selected from C1-5Alkyl and hydrogen；
R5And R6It is each independently selected from C1-16Alkyl and hydrogen, and R5And R6At most one is hydrogen.
In the general formula I, R1And R2It is identical or different.Preferably, R1And R2Total carbon atom number be 8 to 20 between it is whole It counts, the integer between preferably 10 to 18.In addition, R1And R2Preferably identical alkyl, more preferably identical C5-9Alkyl.
R3And R4It is identical or different, it is each independently selected from C1-5Alkyl and hydrogen, preferably C1-3Alkyl and hydrogen；Preferably, R3With R4Total carbon atom number be integer between 0 to 10, the integer between preferably 0 to 5.
R5And R6It is identical or different；Preferably, R5Selected from C1-10Alkyl and hydrogen, preferably C1-8Alkyl and hydrogen, R6Selected from C1-14Alkane Base, preferably C1-12Alkyl；Preferably, R5And R6Total carbon atom number be integer between 1 to 16, between preferably 2 to 13 Integer.
Preferably, in the phosphine extractant of neutrality containing amino of the general formula I of the present invention, R1、R2、R3、R4、R5And R6Total carbon it is former Subnumber is 10~46, including be not limited to 10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26, 27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45 and 46 carbon atoms, preferably 13~36, more preferably 15~34.
Preferably, the phosphine extractant of neutrality containing amino of the general formula I is selected from 1- (2- ethylhexylaminos) methylphosphonic acid Two (2- ethylhexyls) esters, 1- (2- ethylhexylaminos) ethylphosphonic acid two (2- ethylhexyls) ester, 1- (2- ethylhexyl ammonia Base) n-propyl phosphonic acids two (2- ethylhexyls) ester, 1- (2- ethylhexylaminos) 1- Methylethyls phosphonic acids two (2- ethylhexyls) Ester, 1- (N, N- dimethylamino)-propyl phosphonous acid two (2- ethylhexyls) ester, 1- (2- ethylhexylaminos) -1- ethyls positive third Base phosphonic acids two (2- ethylhexyls) ester, 1- (N, N- dibutylamino) ethylphosphonic acid two (2- ethylhexyls) ester, 1- (dodecyls Amino) it is one or more in methylphosphonic acid dimethyl esters.
The phosphine extractant of neutrality containing amino of general formula I in the present invention can be commercial product, can also reference It is prepared by method disclosed in CN201610227923.X.
According to another aspect of the present invention, a kind of method of extraction and separation uranium is provided, it is above-mentioned the method includes using The step of phosphine extractant extraction and separation uranium of neutrality containing amino of general formula I.
The method of SEPARATION OF URANIUM according to the present invention may be used solvent-extracted method and carry out, such as the present invention is contained ammonia Base neutrality phosphine extractant is configured to liquid extraction systems use, and the method that can also use liquid-solid extraction carries out, such as this is sent out The use of the solid-states separation material such as extration resin is made in bright nitrogenous neutral phosphorus-dased extractant.
In one embodiment, the method for extraction and separation uranium of the invention may be used solvent-extracted method and carry out, The method includes：The neutral phosphine extraction system of the phosphine extractant of neutrality containing amino comprising general formula I is (hereinafter sometimes referred to organic Phase) it is mixed with the feed liquid of uranium-bearing to carry out that uranium-bearing extract liquor is obtained by extraction and carry uranium tail washings.
After the neutrality phosphine extractant is contacted with the uranium in feed liquid, the extraction complex compound of uranium-bearing is formed, thus by uranium from material It separates and is entered in organic phase in liquid.
The neutrality phosphine extraction system includes the phosphine of neutrality containing the amino extractant of general formula I, nonessential auxiliary extraction agent, non- Required phase modifying agent and diluent.Preferably, the neutral phosphine extraction system is made of mentioned component.
The auxiliary extraction agent mainly plays assistance extraction, can enhance extractibility of the phosphine extractant of neutrality containing amino to uranium Energy.The auxiliary extraction agent can be selected from phosphorus (phosphine) extractant of following general formula II：
Wherein, Z is O or S；
R7Selected from hydrogen, C1-12Alkyl, C1-12Alkoxy ,-SH and be selected from C1-12At least one of alkyl substituent group replaces - NH2Deng being preferably selected from hydrogen, C1-10Alkyl, C1-10Alkoxy ,-SH and be selected from C4-10At least one of alkyl substituent group - the NH of substitution2Deng；It is more preferably selected from C1-10Alkyl and C1-10Alkoxy；
R8And R9It is each independently selected from C4-12Alkyl, C4-12Alkoxy and be selected from C4-12At least one of alkyl replaces - the NH of base substitution2Deng being preferably selected from C4-10Alkyl, C4-10Alkoxy and be selected from C4-10At least one of alkyl substituent group takes - the NH in generation2Deng being more preferably selected from C4-10Alkyl and C4-10Alkoxy.
Suitable auxiliary extraction agent can be selected from：Such as straight chain trialkyl phosphine (Cyanex 923), branch trialkyl Phosphine oxide (Cyanex 925), trioctyl phosphine oxide (TOPO), extraction (P350), 2- ethylhexyl phosphonic acids Neutral phosphor (phosphine) extractant of two (- 2- ethylhexyls) esters, tributyl phosphate (TBP)；Such as two (2,4,4- tri-methyl-amyls) Phosphonodithioic acid (Cyanex 301), two (2,4,4- tri-methyl-amyls) phosphonothiolic acids (Cyanex 302), two (2- ethyl hexyls Base) phosphoric acid (P204), 2- ethylhexyl phosphonic acid mono -2- ethylhexyls (P507), two (2,4,4- tri-methyl-amyls) phosphonic acids Acid phosphorus (phosphine) extractant of (Cyanex 272), two (2- ethylhexyls) phosphonic acids (P227 or P229)；Such as CN 201410409451.0 with neutral phosphamide extractant disclosed in CN201410040023.5, such as three iso-octyl phosphamides, The different octyloxy phosphamide of diisooctyl-, the different octyloxy phosphamide of iso-octyl-two, three (diisobutyl) phosphamides, two (two isobutyls Base)-different octyloxy phosphamide, three decyl phosphamides and two base-decyloxy phosphamides etc.；With the above extractant with arbitrary proportion Mixed mixed extractant.
The phase modifying agent mainly plays a part of to improve extraction physical phenomenon, can be selected from C4-10One kind in alkanol Or it is a variety of, be preferably selected from n-octyl alcohol, isooctanol, 2- isoocanols and above-mentioned three kinds of alcohol arbitrary proportions mixing mixed alcohol and It is a kind of and a variety of in tributyl phosphate；More preferably mixed alcohol or 2- isoocanols.
The diluent is selected from：C5-16Alkane, such as pentane, hexane, heptane, octane, nonane, decane, hendecane, 12 Alkane, tridecane, the tetradecane, pentadecane, hexadecane etc.；Aviation kerosine；Sulfonated kerosene, atoleine, for example (,) it is 250~400 DEG C light Matter lube cut etc.；C5-16Alicyclic alkanes, such as pentamethylene, C1-4Alkyl-substituted pentamethylene, hexamethylene, C1-4Alkyl Substituted hexamethylene, decahydronaphthalene etc.；C6-10Aromatic hydrocarbons, such as benzene,toluene,xylene (including o-, m-, p- dimethylbenzene and mixed Close dimethylbenzene) etc..Preferably, diluent is one or more in aviation kerosine, sulfonated kerosene, heptane and dimethylbenzene.
In the phosphine of neutrality containing the amino extraction system, the phosphine of neutrality containing the amino extractant, nonessential auxiliary extraction The volume ratio of agent, nonessential phase modifying agent and diluent can be：Neutral phosphine extractant：Auxiliary extraction agent：Phase modifying agent：It is dilute Release agent=about 1~60：About 0~40：About 0~20：About 40~99, the more preferably phosphine of neutrality containing amino extractant：Auxiliary extraction agent： Phase modifying agent：Diluent=about 10~40：About 0~20：About 0~20：About 50~90；Also preferably the phosphine of neutrality containing amino extracts Agent：Auxiliary extraction agent：Phase modifying agent：Diluent=about 15~35：About 0~15：About 0~15：About 55~85.
The feed liquid includes uranium and mineral acid and other non-uranium elements.Wherein uranium concentration can be about 0.001~2mol/L, The acidity of feed liquid is indicated with hydrionic molar concentration, is about 0.1~8mol/L, preferably from about the nitric acid of 0.5~4mol/L, The mixed mixed solution of sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid solution or more acid arbitrary proportion.When uranium concentration is excessively high in feed liquid When, uranium easily crystallizes precipitation and solution viscosity is big, influences the progress of extraction.In addition, the acidity of feed liquid is too low or excessively high, can also reduce Extraction ability of the neutral phosphine extraction system to uranium.
In practical applications, the feed liquid can also contain rare earth, alkali metal, alkaline-earth metal, transition metal and nonmetallic The other elements such as element.In the case, method using the present invention can highly selective extraction and separation go out uranium, to it is non- Uranium separation of foreign elements.
For prepare feed liquid raw material there is no limit, as long as wherein contain uranium.Suitable for preparing the raw material packet of feed liquid Include various uranium-bearing raw materials, such as the excellent molten slag of solitary stone ore, monazite, pittinite, oblique Umohoite, chalcolite, iron uranium cloud Mother, rare earth acid dissolution slag etc..Above-mentioned uranium-bearing raw material can anticipate through the methods of physics, chemistry and with sulfuric acid, hydrochloric acid, nitric acid, phosphorus Acid, hydrofluoric acid or more than sour nitration mixture dissolve the feed liquid of suitable the method for the present invention is made.
In the extraction step, it is preferable that extraction series can be 1~20 grade, preferably 3~8 grades.Excessive extraction grade Number, can increase the dosage of separation equipment and extractant etc..
Preferably, the flow-rate ratio of neutral phosphine extraction system and feed liquid can be about 0.1~20：1, preferably from about 0.2~10： 1.The variation of flow-rate ratio mainly changes according to the concentration of uranium in feed liquid, appropriate to increase neutrality when the concentration of uranium in feed liquid is high The flow of phosphine extraction system, to guarantee fully to extract uranium into organic phase.
After obtaining uranium-bearing extract liquor, subsequent processing can be carried out to uranium-bearing extract liquor according to following step.
Solvent extraction method according to the present invention further include not necessarily with cleaning solution (be referred to as washing lotion, wash acid, wash Wash agent) washing uranium-bearing extract liquor the step of.Washing process can further decrease the content of impurity element in uranium-bearing extract liquor, To help to improve the purity of final uranium product.
The cleaning solution can be the mixed solution of the sour arbitrary proportion mixing of nitric acid, sulfuric acid, hydrochloric acid or more.Cleaning solution Acidity is indicated with hydrionic molar concentration, is about 0.2~4mol/L.
It can be 0~15 grade, preferably 0~5 grade to wash series.It is long to wash series, yield and the waste of uranium can be influenced The energy and extractant.
It can be uranium-bearing extract liquor to wash flow-rate ratio：Cleaning solution=about 1：0.1~5, preferably from about 1：0.2~2.Increase washing On the one hand the flow of liquid can improve the purity of uranium product, but on the other hand can also reduce the yield of uranium, and can consume more More washing acid and the required alkali number of these washing acids is neutralized, increases production cost.
Further include being stripped with back washing agent (being referred to as anti-liquid, strip liquor, anti-stripping agent) according to the method for the present invention Uranium in uranium-bearing extract liquor obtains the step of uranium-bearing back extraction product.Organic phase after back extraction can recycle, and be re-used for The extraction and separation uranium from uranium-bearing feed liquid.
The strip liquor is that the mixed acid of the sour arbitrary proportion mixing of acid solution such as hydrochloric acid solution, salpeter solution or more is molten Liquid；Aqueous slkali such as ammonium hydroxide, sodium hydroxide, sodium carbonate；Oxalate solution such as potassium oxalate, sodium oxalate etc..The H of the acid solution+It is dense Degree is 2~10mol/L；Preferably 3~8mol/L；The aqueous slkali is expressed as 0.001~6mol/L with hydroxyl concentration；It is excellent It is selected as 0.1~2mol/L；The oxalate solution oxalate concentration is from 0.01mol/L~saturated solution.
Preferably, in solvent extraction method, back extraction series is 1~10 grade, preferably 2~6 grades；Flow-rate ratio extracts for uranium-bearing Take liquid：Strip liquor=1：0.1~5, preferably 1：0.2~2.
In solvent extraction method according to the present invention, extraction, washing and back extraction may be used as known in the art Liquid distributing device carries out, and is preferably carried out in a series of separatory funnels, mixed settler extractor or centrifugal extractor, more preferably mixed It closes and is carried out in settler extractor or centrifugal extractor.
In solvent extraction method according to the present invention, above-mentioned extraction, washing and back extraction can be carried out intermittently or serially, It is preferred that being carried out continuously.
In another embodiment, the method for extraction and separation uranium of the invention includes containing amino using using general formula I Solid-state separation material made from neutral phosphine extractant carries out isolating and purifying for uranium.More specifically, logical the method includes that will use Solid-state separation material is contacted with the feed liquid of uranium-bearing made from the neutral phosphine extractant of Formulas I, carries out the solid-state point that uranium-bearing is obtained by extraction From material and carry uranium tail washings.
In one embodiment, the liquid-solid extraction method carries out in resin column, wherein solid-state separation material is added Enter in resin column, uranium-bearing feed liquid, which is then added, makes the solid-state separation material contact progress liquid-solid extraction with the feed liquid of uranium-bearing.
The content for carrying uranium in uranium tail washings is not particularly limited, it is preferred that being not greater than about 0.01g/l.
Liquid-solid extraction method is equally applicable to the description of uranium-bearing feed liquid in solvent extraction method, therefore no longer heavy here It is multiple.
The solid-state separation material can be resin, porous silicon ball, the diatomite for the neutral phosphine extractant that load has general formula I Deng.Preferably, the preparation of the conventional method in this field may be used in the solid-state separation material, such as poly- by dipping, original position It closes, the neutral phosphine extractant of general formula I is supported on resin, porous silicon ball, prepared on diatomite by the methods of chemical bonding, preferably logical The methods of dipping, in-situ polymerization is crossed to be made.
In one preferred embodiment, the solid-state separation material is extration resin.To the system of the extration resin Preparation Method is not particularly limited, as long as its load has the phosphine extractant of neutrality containing amino of general formula I.For example, may be used point It dissipates the methods of polymerization, emulsion polymerization, bulk polymerization, suspension polymerisation and first prepares resin particle, then extract the neutral phosphine of general formula I Agent, which is supported on resin particle, is made extration resin, or the neutral phosphine extractant of general formula I is added before polymerization or in polymerization, leads to It crosses in-situ polymerization and extration resin is made.
In one embodiment, extration resin can be by by the neutral phosphine extractant and styrene monomer of general formula I It is prepared by the method for dispersin polymerization with divinylbenzene monomer.For example, by the neutral phosphine extractant and styrene monomer of general formula I It is mixed with divinylbenzene monomer mixture, the initiator of oil phase gross mass 2% is added, oil phase is made；Take 10 times of oil phase volumes Deionized water, be added water phase quality 3% gelatin, 0.5% thiocyanic acid amine, be mixed to prepare water phase；By heated aqueous to 50 DEG C, After equal Gelatins, it is slowly added to oil phase, half an hour is kept the temperature, then heats to 80 DEG C, polymerisation 5 hours；It is warming up to 90 again DEG C solidified resin half an hour, resin is taken out, washing screening resin air-dries and obtains required extration resin.The phenylethylene Monomer can be styrene, methyl styrene, ethyl styrene etc..
In another embodiment, the solid-state separation material is the porous of the neutral phosphine extractant that load has general formula I Silicon ball, diatomite etc..For the method for the supported porous silicon ball of neutral phosphine extractant of general formula I, diatomite etc. is not had special limit System, as long as the neutral phosphine extractant of general formula I can be supported on to porous silicon ball, on diatomite.For example, can be by general formula I Neutral phosphine extractant be dissolved in diluent (such as volatile atent solvent of dichloromethane, chloroform, benzene, toluene), The separation materials such as porous silicon ball, diatomite are added, delay slow-evaporating diluent under stirring condition, the solid-state for being made required detaches material Material.
In one embodiment, liquid-solid extraction method according to the present invention further includes not necessarily being washed to contain with cleaning solution The step of solid-state separation material of uranium.Washing process can further decrease the content of impurity element in uranium-bearing extract liquor, to Help to improve the purity of final uranium product.
Liquid-solid extraction method is equally applicable to the description of cleaning solution in solvent extraction method, therefore no longer heavy here It is multiple.
The cleaning solution after washing is collected, when uranium content is less than 0.01g/l in cleaning solution, stops that cleaning solution is added.
In one embodiment, liquid-solid extraction method according to the present invention further includes being stripped uranium-bearing solid-state with strip liquor The step of uranium in separation material.The strip liquor after back extraction is collected, when uranium content is less than 0.01g/l in strip liquor, Ke Yiting Strip liquor is only added.Solid-state separation material after back extraction can recycle, and be re-used for the extraction and separation uranium from uranium-bearing feed liquid.
Liquid-solid extraction method is equally applicable to the description of strip liquor in solvent extraction method, therefore no longer heavy here It is multiple.
Using the uranium in liquid-liquid extraction separation or leaching separation uranium-bearing raw material, the results showed that, by extracting, washing Wash, be stripped after the obtained purity of uranium be 99% or more, for example, 99.0%~99.9%, the yield of uranium is 98% or more, For example, 98%~99%.
Term
Part term used in the present invention is such as given a definition.
C1-16Alkyl refers to the linear or branched alkyl group containing 1 to 16 carbon atom, for example, with 1,2,3,4,5,6, 7, the linear or branched alkyl group of 8,9,10,11,12,13,14,15 or 16 carbon atoms, without limitation include methyl, ethyl, N-propyl, isopropyl, normal-butyl, tertiary butyl, isobutyl group, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl etc.. C1-3Alkyl, C1-5Alkane Base, C1-8Alkyl, C1-10Alkyl, C1-12Alkyl, C1-14Alkyl, C4-10Alkyl, C5-9Alkyl and C6-8The meaning of alkyl and so on.
C1-12Alkoxy refers to the straight or branched alkoxyl containing 1 to 12 carbon atom, for example, with 1,2,3,4, 5, the straight or branched alkoxyl of 6,7,8,9,10,11 or 12 carbon atoms includes methoxyl group, ethyoxyl, just without limitation Propoxyl group, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentyloxy, neopentyl oxygen, isoamoxy, hexyloxy, Heptan oxygroup, octyloxy, nonyl epoxide, decyloxy, hendecane epoxide, dodecyloxy etc..C1-10Alkoxy, C4-12Alkoxy and C4-10The meaning of alkoxy etc. and so on.
C4-10Alkanol refers to the linear chain or branched chain alkanol containing 4 to 10 carbon atoms, such as with 4,5,6,7,8,9 Or the linear chain or branched chain alkanol of 10 carbon atoms, include n-butanol, the tert-butyl alcohol, isobutanol, n-amyl alcohol, new penta without limitation Alcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol etc..
C5-16Alkane refers to the linear chain or branched chain alkane containing 5 to 16 carbon atoms, have 5,6,7,8,9,10,11, 12, the linear chain or branched chain alkane of 13,14,15 or 16 carbon atoms, such as pentane, hexane, heptane, octane, nonane, decane, ten One alkane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane etc..
C5-16Alicyclic alkanes refer to the saturated rings containing 5 to 16 carbon atoms including the carbon atom number of substituent group Shape alkane, the saturated cyclic alkane can be monocycle or bicyclic, for example, pentamethylene, hexamethylene, cycloheptane, cyclooctane, ring Nonane, cyclodecane, decahydronaphthalene etc., the substituent group can be selected from C1-4One or more substituent groups of alkyl.
C6-10Aromatic hydrocarbons refers to the aromatic hydrocarbons containing 6 to 10 carbon atoms including the carbon atom number of substituent group, such as benzene With with selected from C1-4The benzene of one or more substituent groups substitution of alkyl, such as benzene,toluene,xylene etc..
Unless otherwise indicated, numberical range listed in the present invention includes between endpoint value and endpoint value therein All subranges formed with all point values of the least unit increasing or decreasing of endpoint value and by these point values.
Advantageous effect
The phosphine of neutrality containing the amino extractant that the present invention uses not only has good extraction and separation in different acid mediums to uranium Ability, and synthetic method is simple, and industrial chemicals is simple and easy to get used in synthesis, of low cost, so as to be effectively reduced The extraction and separation cost of uranium has higher industrial application value.
Specific implementation mode
Embodiment
For the scheme that the present invention is further explained, specific embodiments of the present invention are provided to contribute to people in the art Member understands and implements the present invention, but the present invention is not limited to these Examples.
Reagent and source
It is prepared by the phosphine of neutrality containing amino extractant method with reference to disclosed in CN201610227923.X used, title, Structure and characterize data such as following table：
Aviation kerosine, sulfonated kerosene and TBP are purchased from Shanghai Lai Yashi Chemical Co., Ltd.s.
Cyanex 923, P507,2- isoocanol are purchased from Shanghai Qing Te Chemical Co., Ltd.s.
Feed liquid, cleaning solution and back washing agent are made by oneself for laboratory.
Other reagents (such as acid) are ommercially available AR.
Product purity is all made of ICP-OES (instrument models：Optical-8000, manufacturer：Perkin Elmer) it measures.
Nuclear Magnetic Resonance is Varian Mercury 300.
Embodiment 1：
The preparation of organic phase：Take 3L 1- (2- ethylhexylaminos) methylphosphonic acid two (2- ethylhexyls) ester and 7L aviations Kerosene is mixed to prepare organic phase.
Feed liquid is the sulfuric acid solution of 0.05mol/L uranium, acidity 1.5mol/L.
Cleaning solution is the sulfuric acid solution of 0.5mol/L.
Back washing agent is 0.3mol/L ammonia spirits.
Extraction and separation experiment is carried out using 250ml mixing-settler extractor.Carry out 6 stage countercurrent extractions first, organic phase with The flow-rate ratio of feed liquid is 10mL/min：20mL/min obtains uranium-bearing extract liquor and carries uranium tail washings.Then 2 stage countercurrent washings are carried out, The flow-rate ratio of uranium-bearing extract liquor and cleaning solution is 10mL/min：5mL/min.Then carry out 4 stage countercurrent back extraction, uranium-bearing extract liquor with The flow-rate ratio of back washing agent is 10mL/min：3.5mL/min obtains ammonium diuranate precipitation.Wherein, the yield of uranium is 98.4%, uranium Purity be 95.8%.
Embodiment 2：
The preparation of organic phase：Take 3L 1- (2- ethylhexylaminos)-ethylphosphonic acid two (2- ethylhexyls) ester and 7L aviations Kerosene is mixed to prepare organic phase.
Feed liquid is the hydrochloric acid solution of 0.5mol/L uranium, acidity 1.0mol/L.
Cleaning solution is the hydrochloric acid solution of 0.5mol/L.
Back washing agent is 6mol/L hydrochloric acid solutions.
Extraction and separation experiment is carried out using 250ml mixing-settler extractor.Carry out 6 stage countercurrent extractions first, organic phase with The flow-rate ratio of feed liquid is 10mL/min：2mL/min obtains uranium-bearing extract liquor and carries uranium tail washings.Then 2 stage countercurrent washings are carried out, The flow-rate ratio of uranium-bearing extract liquor and cleaning solution is 10mL/min：2mL/min.Then carry out 4 stage countercurrent back extraction, uranium-bearing extract liquor with The flow-rate ratio of back washing agent is 10mL/min：3.5mL/min obtains the strip liquor of uranium-bearing.Gained strip liquor is concentrated, dries, and obtains To uranyl chloride.Wherein, the yield of uranium is 98.0%, and the purity of uranium is 98.9%.
Embodiment 3：
The preparation of organic phase：Take two (2- ethylhexyls) ester of 2L 1- (2- ethylhexylaminos) 1- ethyl diethyldithiocarbamates phosphonic acids, 1L Cyanex 923 is mixed to prepare organic phase with 7L aviation kerosines.
Feed liquid is the salpeter solution of 0.1mol/L uranium, acidity 1.0mol/L.
Cleaning solution is the salpeter solution of 1.0mol/L.
Back washing agent is 0.01mol/L aqueous solution of nitric acid.
Extraction and separation experiment is carried out using 250ml mixing-settler extractor.Carry out 5 stage countercurrent extractions first, organic phase with The flow-rate ratio of feed liquid is 10mL/min：20mL/min obtains uranium-bearing extract liquor and carries uranium tail washings.Then 3 stage countercurrent washings are carried out, The flow-rate ratio of uranium-bearing extract liquor and cleaning solution is 10mL/min：5mL/min.Then 10 stage countercurrent back extraction, uranium-bearing extract liquor are carried out Flow-rate ratio with back washing agent is 10mL/min：5mL/min obtains the strip liquor of uranium-bearing.Gained strip liquor is concentrated, dries, and obtains To uranyl nitrate.Wherein, the yield of uranium is 98.1%, and the purity of uranium is 99.9%.
Embodiment 4：
The preparation of organic phase：Take 2L 1- (N, N- dimethylamino)-propyl phosphonous acid two (2- ethylhexyls) ester, 1L P507,0.5L 2- isoocanols and 6.5L sulfonated kerosenes are mixed to prepare organic phase.
Feed liquid is the hydrochloric acid solution of 0.1mol/L uranium, acidity 1.0mol/L.
Cleaning solution is the hydrochloric acid solution of 1.0mol/L.
Back washing agent is 4.0mol/L sodium hydroxide solutions.
Extraction and separation experiment is carried out using 250ml mixing-settler extractor.Carry out 5 stage countercurrent extractions first, organic phase with The flow-rate ratio of feed liquid is 10mL/min：25mL/min obtains uranium-bearing extract liquor and carries uranium tail washings.Then 3 stage countercurrent washings are carried out, The flow-rate ratio of uranium-bearing extract liquor and cleaning solution is 10mL/min：5mL/min.Then 10 stage countercurrent back extraction, uranium-bearing extract liquor are carried out Flow-rate ratio with back washing agent is 10mL/min：5mL/min obtains sodium diuranate.Wherein, the yield of uranium be 98.6%, uranium it is pure Degree is 97.6%.
Embodiment 5：
The preparation of organic phase：Take 3L 1- (dodecylamino) methylphosphonic acids dimethyl esters, 1L 2- isoocanols and 6L Aviation kerosine is mixed to prepare organic phase.
Feed liquid is 12g/L uranium, 35g/L rare earths, the sulfuric acid solution of 20g/L thoriums, acidity 2.0mol/L.
Cleaning solution is the hydrochloric acid solution of 1.0mol/L.
Back washing agent is 50g/L Potassium Oxalate Solutions.
Extraction and separation experiment is carried out using 250ml mixed settler extractors.Carry out 5 stage countercurrent extractions first, organic phase with The flow-rate ratio of feed liquid is 15mL/min：15mL/min obtains uranium-bearing, thorium extract liquor and carries uranium, thorium tail washings.Then 5 grades of progress is inverse The flow-rate ratio of stream washing, uranium-bearing, thorium extract liquor and cleaning solution is 15mL/min：5mL/min.Then 10 stage countercurrent back extraction are carried out, The flow-rate ratio of uranium-bearing extract liquor and back washing agent is 15mL/min：3.3mL/min obtains uranyl oxalate.Wherein, the yield of uranium is 98.6%, the purity of uranium is 90.3%.
Embodiment 6：
The preparation of organic phase：Take 3L 1- (2- ethylhexylaminos)-n-propyl phosphonic acids two (2- ethylhexyls) ester, 1L TBP is mixed to prepare organic phase with 6L aviation kerosines.
Feed liquid is 12g/L uranium, 35g/L rare earths, the sulfuric acid solution of 20g/L thoriums, acidity 2.0mol/L.
Back washing agent I is the hydrochloric acid solution of 1.0mol/L.
Back washing agent II is 0.3mol/L ammonia spirits.
Extraction and separation experiment is carried out using 250ml centrifugal extractors.5 stage countercurrent extractions, organic phase and feed liquid are carried out first Flow-rate ratio be 15mL/min：15mL/min obtains uranium-bearing, thorium extract liquor and carries uranium tail washings.Then 5 grades are carried out with back washing agent I Countercurrent reextraction takes, and thorium is stripped prior to uranium, obtains the anti-stripping agent of thoriated and uranium-bearing extract liquor, uranium-bearing, thorium extract liquor with The flow-rate ratio of strippant I is 15mL/min：5mL/min.Then 10 stage countercurrent back extraction, uranium-bearing extraction are carried out with back washing agent II again It is 15mL/min to take the flow-rate ratio of liquid and back washing agent II：5mL/min obtains ammonium diuranate precipitation.Wherein, the yield of uranium is 98.2%, the purity of uranium is 91.5%.
Embodiment 7：
(1) preparation of extration resin
Take 50ml 1- (2- ethylhexylaminos)-(2- ethylhexyls) ester of n-propyl phosphonic acids two and 50ml styrene-diethyl Alkene benzene mixed liquor is mixed to prepare oil phase, wherein the volume ratio of styrene and divinylbenzene is 2：1.500ml deionized waters are taken, are added Enter 15g gelatin, 2.5g thiocyanic acid amine is heated to 50 DEG C, after gelatin is completely dissolved, is slowly added to oil phase, stirs half an hour Afterwards, 80 DEG C are warming up to, is reacted 5 hours, is then warming up to 90 DEG C again, cures half an hour.Filtering resin is taken out, is washed, air-dries, obtains To 75g extration resins.
(2) extraction experiments
50 grams of extration resins are weighed in splitter, uranium-bearing feed liquid is added, and (salpeter solution of 0.10mol/L uranium, acidity are 1.5 mol/L), the flow velocity of feed liquid is 2ml/min, every 5 minutes sampling monitorings.When the content for carrying uranium in uranium tail washings is more than 0.01g/ When l, stop feeding liquid.Cleaning solution (salpeter solution of 1.0mol/L) is added with the flow velocity of 2ml/min and washs uranium-bearing extration resin. When the concentration of uranium in eluate is less than 0.1g/L, stop that cleaning solution is added.Secondary water is added with the flow velocity of 2ml/min again.When When the concentration of uranium is less than 0.01g/L in strip liquor, back extraction is completed, and uranium-bearing strip liquor is obtained.Gained uranium-bearing strip liquor is concentrated, Drying, calcining obtain urania solid.Wherein, the yield of uranium is 98.7%, and the purity of uranium is 99.9%.

Claims (66)

1. the phosphine extractant of neutrality containing amino of general formula I is used for the purposes of extraction and separation uranium below：
Wherein,
R1And R2It is each independently selected from C1-12Alkyl；
R3And R4It is each independently selected from C1-5Alkyl and hydrogen；
R5And R6It is each independently selected from C1-16Alkyl and hydrogen, and R5And R6At most one is hydrogen.
2. purposes described in claim 1, wherein R1And R2It is each independently selected from C4-10Alkyl.
3. the purposes described in claim 2, wherein R1And R2It is each independently selected from C5-9Alkyl.
4. the purposes described in claim 3, wherein R1And R2It is each independently selected from C6-8Alkyl.
5. purposes described in claim 1, wherein R1And R2Total carbon atom number be 8 to 20 between integer.
6. the purposes described in claim 5, wherein R1And R2Total carbon atom number be 10 to 18 between integer.
7. purposes described in claim 1, wherein R1And R2For identical alkyl.
8. the purposes described in claim 7, wherein R1And R2For identical C5-9Alkyl.
9. purposes described in claim 1, wherein R3And R4It is each independently selected from C1-3Alkyl and hydrogen.
10. purposes described in claim 1, wherein R3And R4Total carbon atom number be 0 to 10 between integer.
11. purposes according to any one of claims 10, wherein R3And R4Total carbon atom number be 0 to 5 between integer.
12. purposes described in claim 1, wherein R5Selected from C1-10Alkyl and hydrogen.
13. the purposes described in claim 12, wherein R5Selected from C1-8Alkyl and hydrogen.
14. purposes described in claim 1, wherein R6Selected from C1-14Alkyl.
15. the purposes described in claim 14, wherein R6Selected from C1-12Alkyl.
16. purposes described in claim 1, wherein R5And R6Total carbon atom number be 1 to 16 between integer.
17. the purposes described in claim 16, wherein R5And R6Total carbon atom number be 2 to 13 between integer.
18. purposes described in claim 1, wherein in general formula I, R1、R2、R3、R4、R5And R6Total carbon atom number be 10~46.
19. the purposes described in claim 18, wherein in general formula I, R1、R2、R3、R4、R5And R6Total carbon atom number be 13~ 36。
20. the purposes described in claim 19, wherein in general formula I, R1、R2、R3、R4、R5And R6Total carbon atom number be 15~ 34。
21. purposes described in claim 1, wherein the phosphine extractant of neutrality containing amino of the general formula I is selected from 1- (2- ethyls Hexylamino) methylphosphonic acid two (2- ethylhexyls) ester, 1- (2- ethylhexylaminos) ethylphosphonic acid two (2- ethylhexyls) ester, 1- (2- ethylhexylaminos) n-propyl phosphonic acids two (2- ethylhexyls) ester, 1- (2- ethylhexylaminos) 1- Methylethyl phosphonic acids Two (2- ethylhexyls) esters, 1- (N, N- dimethylamino)-propyl phosphonous acid two (2- ethylhexyls) ester, 1- (2- ethylhexyl ammonia Base) -1- ethyl n-propyls phosphonic acids two (2- ethylhexyls) ester, 1- (N, N- dibutylamino) ethylphosphonic acid two (2- ethylhexyls) It is one or more in ester, 1- (dodecylamino) methylphosphonic acid dimethyl esters.
22. a kind of method of extraction and separation uranium, the method includes using the general formula I's described in claim any one of 1-21 The step of phosphine extractant extraction and separation uranium of neutrality containing amino.
23. the method described in claim 22, wherein the method for the extraction and separation uranium is using solvent extraction or liquid-solid extraction Method carries out.
24. according to the method for claim 23, wherein the solvent extraction method includes：Amino will be contained comprising general formula I The neutral phosphine extraction system of neutral phosphine extractant mixes to carry out that uranium-bearing extract liquor is obtained by extraction and carry uranium tail with the feed liquid of uranium-bearing Liquid；
The neutrality phosphine extraction system includes the phosphine of neutrality containing the amino extractant of general formula I, nonessential auxiliary extraction agent, nonessential Phase modifying agent and diluent.
25. according to the method for claim 24, wherein the auxiliary extraction agent is selected from phosphorus or the phosphine extraction of following general formula II Agent：
Wherein,
Z is O or S；
R7Selected from hydrogen, C1-12Alkyl, C1-12Alkoxy ,-SH and be selected from C1-12The substitution of at least one of alkyl substituent group- NH2；
R8And R9It is each independently selected from C4-12Alkyl, C4-12Alkoxy and be selected from C4-12At least one of alkyl substituent group takes - the NH in generation2。
26. according to the method for claim 25, wherein
R7Selected from hydrogen, C1-10Alkyl, C1-10Alkoxy ,-SH and be selected from C4-10The substitution of at least one of alkyl substituent group- NH2；
R8And R9It is each independently selected from C4-10Alkyl, C4-10Alkoxy and be selected from C4-10At least one of alkyl substituent group takes - the NH in generation2。
27. according to the method for claim 26, wherein
R7Selected from C1-10Alkyl and C1-10Alkoxy；
R8And R9It is each independently selected from C4-10Alkyl and C4-10Alkoxy.
28. according to the method for claim 25, wherein the auxiliary extraction agent is selected from：Neutral phosphor or phosphine extractant；It is acid Phosphorus or phosphine extractant；Neutral phosphamide extractant；The mixed extractant mixed with arbitrary proportion with the above extractant.
29. according to the method for claim 28, wherein
The neutral phosphor or phosphine extractant are selected from straight chain trialkyl phosphine, branch trialkyl phosphine, trioctyl phosphine oxide, first Base phosphonic acids diformazan heptyl ester, 2- ethylhexyls phosphonic acids two (- 2- ethylhexyls) ester, tributyl phosphate；
The acid phosphorus or phosphine extractant are selected from two (2,4,4- tri-methyl-amyls) phosphonodithioic acids, two (2,4,4- trimethyls penta Base) phosphonothiolic acid, di-(2-ethylhexyl)phosphoric acid, 2- ethylhexyl phosphonic acid mono -2- ethylhexyls, two (2,4,4- trimethyls Amyl) phosphonic acids, two (2- ethylhexyls) phosphonic acids；
The neutrality phosphamide extractant is selected from three iso-octyl phosphamides, the different octyloxy phosphamide of diisooctyl-, iso-octyl-two Different octyloxy phosphamide, three (diisobutyl) phosphamides, two (diisobutyls)-different octyloxy phosphamide, three decyl phosphamides and Two base-decyloxy phosphamides.
30. according to the method for claim 24, wherein the phase modifying agent is selected from C4-10It is one or more in alkanol.
31. according to the method for claim 24, wherein the phase modifying agent is selected from n-octyl alcohol, isooctanol, 2- methyl heptan One kind and a variety of in alcohol and the mixed alcohol and tributyl phosphate of the mixing of above-mentioned three kinds of alcohol arbitrary proportions.
32. according to the method for claim 31, wherein the phase modifying agent is mixed alcohol or 2- isoocanols.
33. according to the method for claim 24, wherein the diluent is selected from：C5-16Alkane；Aviation kerosine；Sulfonated coal Oil；Atoleine；C5-16Alicyclic alkanes；C6-10Aromatic hydrocarbons.
34. according to the method for claim 33, wherein
The C5-16Alkane be selected from pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, tridecane, the tetradecane, Pentadecane, hexadecane；
The atoleine is 250~400 DEG C of light lubricating oil fractions；
The C5-16Alicyclic alkanes are selected from pentamethylene, C1-4Alkyl-substituted pentamethylene, hexamethylene, C1-4Alkyl-substituted hexamethylene Alkane, decahydronaphthalene；
The C6-10Aromatic hydrocarbons is selected from benzene,toluene,xylene, wherein the dimethylbenzene includes o-, m-, p-xylene and mixing two Toluene.
35. according to the method for claim 33, wherein the diluent be selected from aviation kerosine, sulfonated kerosene, heptane and It is one or more in dimethylbenzene.
36. according to the method for claim 24, wherein described to contain amino in the phosphine of neutrality containing the amino extraction system Neutral phosphine extractant, nonessential auxiliary extraction agent, nonessential phase modifying agent and diluent volume ratio be：Neutral phosphine extraction Agent：Auxiliary extraction agent：Phase modifying agent：Diluent=1~60：0~40：0~20：40~99.
37. according to the method for claim 36, wherein the phosphine extractant of neutrality containing amino：Auxiliary extraction agent：Phase modifying agent： Diluent=10~40：0~20：0~20：50~90.
38. according to the method for claim 36, wherein the phosphine extractant of neutrality containing amino：Auxiliary extraction agent：Phase modifying agent： Diluent=15~35：0~15：0~15：55~85.
39. according to the method for claim 24, wherein in the extraction step, extraction series is 1~20 grade.
40. according to the method for claim 39, wherein extraction series is 3~8 grades.
41. according to the method for claim 24, wherein the flow-rate ratio of neutral phosphine extraction system and feed liquid is 0.1~20：1.
42. according to the method for claim 41, wherein the flow-rate ratio of neutral phosphine extraction system and feed liquid is 0.2~10：1.
43. according to the method for claim 24, further including：
Not necessarily uranium-bearing extract liquor is washed with cleaning solution；
The uranium being stripped in uranium-bearing extract liquor with back washing agent obtains uranium-bearing and is stripped product.
44. according to the method for claim 43, wherein the extraction washs and is stripped in a series of separatory funnels, mixes It closes and is carried out in settler extractor or centrifugal extractor.
45. according to the method for claim 44, wherein the extraction, washing and be stripped in mixed settler extractor or It is carried out in centrifugal extractor.
46. according to the method for claim 43, wherein the extraction, washing and back extraction intermittently or serially carry out.
47. according to the method for claim 46, wherein the extraction, washing and back extraction are carried out continuously.
48. according to the method for claim 43, wherein washing series is 0~15 grade.
49. according to the method for claim 48, wherein washing series is 0~5 grade.
50. according to the method for claim 43, wherein washing flow-rate ratio is uranium-bearing extract liquor：Cleaning solution=1：0.1~5.
51. according to the method for claim 50, wherein washing flow-rate ratio is uranium-bearing extract liquor：Cleaning solution=1：0.2~2.
52. according to the method for claim 43, wherein back extraction series is 1~10 grade.
53. method according to claim 52, wherein back extraction series is 2~6 grades.
54. according to the method for claim 43, wherein back extraction flow-rate ratio is uranium-bearing extract liquor：Strip liquor=1：0.1~ 5。
55. method according to claim 54, wherein back extraction flow-rate ratio is uranium-bearing extract liquor：Strip liquor=1：0.2~ 2。
56. according to the method for claim 23, wherein the liquid-solid extraction method includes that will use the neutral phosphine of general formula I Solid-state separation material made from extractant is contacted with the feed liquid of uranium-bearing, is carried out the solid-state separation material that uranium-bearing is obtained by extraction and is carried uranium Tail washings.
57. method according to claim 56, wherein the liquid-solid extraction method carries out in resin column, wherein will consolidate State separation material is added in resin column, and uranium-bearing feed liquid, which is then added, makes the solid-state separation material contact progress with the feed liquid of uranium-bearing Liquid-solid extraction.
58. method according to claim 56, wherein the solid-state separation material, which is selected from load, the neutral phosphine of general formula I Resin, porous silicon ball, the diatomite of extractant.
59. method according to claim 56, further includes：
The solid-state separation material of uranium-bearing is not necessarily washed with cleaning solution；
It is stripped the uranium in uranium-bearing solid-state separation material with strip liquor.
60. method according to claim 56, further includes：
The solid-state separation material of uranium-bearing is washed with cleaning solution, the cleaning solution after washing is collected, when uranium content is less than in cleaning solution When 0.01g/l, stop that cleaning solution is added；
It is stripped the uranium in uranium-bearing solid-state separation material with strip liquor, the strip liquor after back extraction is collected, when uranium content in strip liquor When less than 0.01g/l, stop that strip liquor is added.
61. according to the method described in claim 43,59 or 60, wherein the cleaning solution is nitric acid, sulfuric acid, hydrochloric acid or more The mixed solution of sour arbitrary proportion mixing.
62. method according to claim 61, wherein the acidity of cleaning solution is indicated with hydrionic molar concentration, is 0.2~4mol/L.
63. according to the method described in claim 43,59 or 60, wherein the strip liquor is acid solution；Aqueous slkali；Oxalates Solution.
64. method according to claim 63, wherein
The acid solution is the mixed acid solution of the sour arbitrary proportion mixing of hydrochloric acid solution, salpeter solution or more；
The aqueous slkali is ammonium hydroxide, sodium hydroxide or sodium carbonate liquor；
The oxalate solution is potassium oxalate or sodium oxalate solution.
65. method according to claim 63, wherein the H of the acid solution+A concentration of 2~10mol/L；The aqueous slkali It is expressed as 0.001~6mol/L with hydroxyl concentration；The oxalate solution oxalate concentration is molten from 0.01mol/L~saturation Liquid.
66. method according to claim 65, wherein the H of the acid solution+A concentration of 3~8mol/L；The aqueous slkali It is expressed as 0.1~2mol/L with hydroxyl concentration.
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