CN109097570A - The phosphine extractant of acidity containing amino is used for the purposes and method of extraction and separation cobalt and nickel - Google Patents
The phosphine extractant of acidity containing amino is used for the purposes and method of extraction and separation cobalt and nickel Download PDFInfo
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- CN109097570A CN109097570A CN201811119533.6A CN201811119533A CN109097570A CN 109097570 A CN109097570 A CN 109097570A CN 201811119533 A CN201811119533 A CN 201811119533A CN 109097570 A CN109097570 A CN 109097570A
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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
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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Abstract
The present invention relates to purposes and method that the phosphine extractant of acidity containing amino of following general formula I is used for extraction and separation cobalt and nickel, wherein R1Selected from C1~C12Alkyl, R2Selected from C1~C14Alkyl.The method includes use the acidity containing amino of general formula I phosphine extractant from include cobalt and nickel feed liquid in extraction and separation go out nickel the step of.Method of the invention can preferential extraction of nickel, to realize the separation of nickel cobalt, therefore there is significant advantage when separating the feed liquid of the low high cobalt of nickel.In addition, the phosphine of acidity containing amino extractant of the present invention not only can separate cobalt and nickel in different acid mediums, there is good extraction and separation ability, and synthetic method is simple, and low in cost, property is stablized, easily realize industrialization, industrial application value with higher.
Description
Technical field
The present invention relates to the methods of extraction and separation cobalt and nickel, use in particular to a kind of phosphine extractant of acidity containing amino
In the purposes and method of extraction and separation cobalt and nickel.
Background technique
Nickel and cobalt are important strategy metal, have the characteristics that corrosion resistance, anti-oxidant, high-intensitive, ductility is good.Cobalt is made
For the important raw material of manufacture lithium battery, alloy and catalyst, have widely in high-tech areas such as national defence, electronics, space flight
Using；Nickel is the important component of nickel-cadmium cell and stainless steel, is widely used in aviation, chemical industry and telecommunication etc..
In recent years, the consumption figure of nickel and cobalt is always maintained at biggish growing trend, and modern industry requires the pure of nickel cobalt
Spend relatively high, therefore the separation of nickel and cobalt is a major issue in nickel cobalt refining techniques.But due to the atom of nickel and cobalt
Ordinal number is adjacent, is all the VIIIth race's element of period 4, has many similar physicochemical properties, in various mineral deposits, waste residue
Chang Gongsheng, association.
For many years, metallargist very pays close attention to the isolation technics of nickel and cobalt, and the separation method of nickel and cobalt has chemistry at present
The precipitation method and solvent extraction.The product that chemical precipitation method obtains is impure, the roughly the same solution of unsuitable cobalt nickel concentration；It is molten
Agent extraction has many advantages, such as highly selective, high-recovery, operates serialization, is low in cost, there is preferable economic benefit and society
Meeting benefit, has become the key industry method of Separation of nickel and cobalt.
Comparative maturity has for separating cobalt and the extractant of nickel at present: ethylhexyl dihydrogen phosphate (D2EHPA or
P204), 2- ethylhexyl phosphonic acid mono (2- ethylhexyl) ester (P507 or PC-88A), two (2,4,4- tri-methyl-amyl) phosphonic acids
(Cyanex272) etc..
CN107287420A discloses a kind of 5N grades of cobalt chloride methods of P507 fractional extraction preparation, and this method is with the low nickel of high cobalt
Technical hydrochloric acid salting liquid is feed liquid, and 2- ethylhexyl phosphonic acid mono (2- ethylhexyl) ester (P507) is extractant, realize nickel and cobalt,
The separation of the metallic elements such as magnesium, calcium, sodium, directly prepares 5N grades of cobalt chlorides, and the yield of cobalt is up to 95%~97%.
CN103805782A discloses a kind of purification method of solution containing nickel, and this method is with two (2,4,4- tri-methyl-amyls)
Phosphonic acids (Cyanex272) is extractant, will be saponified organic phase in mixer-settler and solution containing nickel to be clean carries out adverse current
Extraction, reduces the iron in solution containing nickel, zinc, copper, cobalt content jointly, realizes the quick and deep purifying of solution containing nickel.
But P507 is to the smaller of the separation of cobalt, nickel, the sulfate liquor of nickelic low cobalt is separated it is difficult, and
And P507 has certain extraction to calcium, magnesium, when back extraction, will generate calcium sulfate precipitation and influence normal operating；Although Cyanex272
The effect for separating cobalt is better than P507, can be reduced extraction series, but the price is very expensive, and import price is about 400,000/ton, in cobalt nickel point
The loss of extractant is big from during.
Therefore, find it is a kind of can efficiently extraction and separation cobalt and nickel, low in cost and stable extraction system for nickel cobalt essence
Refining technology has great importance.
Summary of the invention
In order to solve the above problem present on the isolation technics of cobalt and nickel, the present invention is using a kind of phosphine of acidity containing amino extraction
Agent extraction and separation cobalt and nickel are taken, good separating effect is achieved.The extractant is readily synthesized, and property is stablized, and is reduced point
From cost.Distinguishing feature of the invention is that extractant has in extraction process, and preferential extraction of nickel enters in extract liquor, and cobalt is stayed in water
Xiang Zhong, to realize the separation of nickel and cobalt；With conventional cobalt nickel extraction agent (such as P507, Cyanex272) preferentially by cobalt extract into
Extract liquor, and nickel is stayed in into difference in water phase, when handling the feed liquid of the low high cobalt of nickel, since the amount for the nickel for needing to extract is few, from
And the consumption of chemical raw material in the investment and extraction process of extractant can be saved, so that the economy of separation process is improved,
Therefore, the present invention has significant advantage when separating the feed liquid of the low high cobalt of nickel.
The phosphine extractant of acidity containing amino that one aspect of the present invention provides following general formula I is used for from the material comprising cobalt and nickel
Extraction and separation go out the purposes of nickel in liquid:
Wherein,
R1Selected from C1~C12Alkyl, preferably C4~C10Alkyl, more preferable C5~C9Alkyl, most preferably C6~C8Alkyl；
R2Selected from C1~C14Alkyl, preferably C1~C12Alkyl.
Another aspect of the present invention provides a kind of method for separating nickel and cobalt, and the method includes using containing for general formula I
Amino acidity phosphine extractant from include cobalt and nickel feed liquid in extraction and separation go out nickel the step of.
In such use and method, the phosphine extractant of acidity containing the amino property of can choose of the general formula I by nickel from packet
It is extracted in feed liquid containing cobalt and nickel.
The feed liquid is the aqueous solution of the nickel comprising divalent ion form and cobalt, wherein the concentration of nickel and the concentration of cobalt can
To be each independently 0.001~2mol/L, such as 0.005~1mol/L.
In some embodiments, in feed liquid the molar ratio of cobalt and nickel can be 500:1~1:500, for example, 100:1~
1:100 or 50:1~1:50.
In some embodiments, the molar concentration of cobalt is not less than the molar concentration of nickel in feed liquid, for example, cobalt and nickel rub
You are than that can be 1:1~100:1, for example, 1:1~50:1, more preferably 1:1~30:1.
In some embodiments, the pH of feed liquid can be about 4 to less than 6, preferably 4.5-5.8.
In some embodiments, the feed liquid is that sulfate, hydrochloride, nitrate solution or its mixing of nickel and cobalt are molten
Liquid.
For prepare feed liquid raw material there is no limit, as long as wherein contain cobalt and nickel.Suitable for preparing the original of feed liquid
Material includes various raw materials containing cobalt and nickel, such as sulphur nickel cobalt mine, nickel-skutterudite, pentlandite etc..Raw material can be through physics, chemistry etc.
Method pre-process and with sulfuric acid, hydrochloric acid, nitric acid or more than sour nitration mixture dissolution be suitble to feed liquid of the invention to be made.
In one embodiment, in the phosphine extractant of acidity containing amino of the general formula I, R1And R2Total carbon atom number be 5
Integer between to 24, including be not limited to 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,
23 and 24 carbon atoms, the integer between preferably 6 to 21.
In one embodiment, the phosphine of acidity containing the amino extractant of the general formula I can be for selected from 1- (2- ethylhexyl
Amino) methylphosphonic acid list (2- ethylhexyl) ester, 1- (2- methylhexyl amino) methylphosphonic acid list (2- ethylhexyl) ester, 1-
(2- propylpentyl amino) methylphosphonic acid list (2- ethylhexyl) ester, 1- (2- propyl hexylamino) methylphosphonic acid list (2- ethyl
Hexyl) ester, 1- (2- methylhexyl amino) methylphosphonic acid list (2- methylhexyl) ester, 1- (2- ethylhexylamino) methylphosphonic acid
Single (2- methylhexyl) ester, 1- (2- propylpentyl amino) methylphosphonic acid list (2- methylhexyl) ester, 1- (2- propylpentyl ammonia
Base) in methylphosphonic acid list (2- methylhexyl) ester and 1- (2- propyl hexylamino) methylphosphonic acid list (2- methylhexyl) ester one
Kind is a variety of.
The phosphine of acidity containing the amino extractant of general formula I can according to the prior art (such as Zhao, Q.et.Al.,
Solvent.Extr.Ion exchange, 2018, doi:10.1080/07366299.2018.1431079 etc.) side disclosed in
Method synthesis.
In one embodiment, the phosphine of acidity containing the amino extractant of general formula I can be by making compound II, compound
III and compound IV obtains the phosphine extractant of neutrality containing amino of general formula I through Mannich reaction, as shown in reaction equation 1:
Wherein, R1And R2Definition it is identical with general formula I.
Compound III can be commercial product or be synthesized according to known method in the prior art.
The reaction condition of the Mannich reaction (also referred to as Mannich (Mannich) reacts) is not specifically limited, as long as
It is able to carry out reaction.For example, Mannich reaction can be carried out with or without catalyst with or without under conditions of solvent.
The solvent for example can be benzene,toluene,xylene, tetrahydrofuran, methylene chloride, chloroform, and the catalyst for example can be
Hydrochloric acid, p-methyl benzenesulfonic acid, InCl3、SnCl2、SnCl4、ZnCl2、MgBr2、BF3·Et2The Lewis such as O acid.Reaction time can be with
For 25min to 72h, reaction temperature can be room temperature to 150 DEG C.
In another embodiment, the phosphine of acidity containing the amino extractant of general formula I can be by making compound V through hydrolyzing
To the phosphine extractant of neutrality containing amino of general formula I, as shown in reaction equation 2:
Wherein, R1And R2Definition and identical, R in general formula I3Definition and R1It is identical.
Compound V can be commercial product or the method according to disclosed in the prior art (such as CN105734289A) is closed
At.
In one embodiment, the method for separation cobalt of the invention and nickel includes the following steps:
(1) the acid phosphine extraction system of the phosphine extractant of acidity containing amino comprising general formula I is mixed with nickeliferous and cobalt feed liquid
It closes to carry out that nickeliferous extract liquor and raffinate containing cobalt is obtained by extraction；
(2) the nickeliferous extract liquor not necessarily is washed with cleaning solution；
(3) nickeliferous back extraction product is obtained with the nickel that stripping agent is stripped in nickeliferous extract liquor.
In step (1), the acidity phosphine extraction system includes the phosphine of acidity containing the amino extractant, nonessential auxiliary of general formula I
Help extractant, nonessential phase modifying agent and diluent.In some embodiments, the acid phosphine extraction system substantially by
The phosphine of acidity containing amino extractant, nonessential auxiliary extraction agent, nonessential phase modifying agent and the diluent composition of general formula I.This
In, " substantially by ... form " indicates that said components account for 95wt% or more, the 97wt% or more of acid phosphine extraction system, or
In some aspects, 99wt% or more.In some embodiments, the acid phosphine extraction system is made of said components.
In some embodiments, in the acid phosphine extraction system, the phosphine of acidity containing the amino extractant of general formula I, it is non-must
The volume ratio of the auxiliary extraction agent, nonessential phase modifying agent and diluent that need can be with are as follows: the phosphine of acidity containing the amino extraction of general formula I
Agent: auxiliary extraction agent: phase modifying agent: diluent=about 1~80: about 0~20: about 0~20: about 20~99, more preferably general formula I
The phosphine extractant of acidity containing amino: auxiliary extraction agent: phase modifying agent: diluent=about 25~75: about 0~15: about 0~15: about
25~75；The also preferably acidic extractant containing amino of general formula I: auxiliary extraction agent: phase modifying agent: diluent=about 30~60:
0:0: about 40~70.
The auxiliary extraction agent mainly plays assistance extraction, can enhance the phosphine extractant of acidity containing amino to the extraction of nickel and cobalt
Take performance.The auxiliary extraction agent can be selected from straight chain trialkyl phosphine (Cyanex 923), branch trialkyl phosphine
(Cyanex 925), trioctyl phosphine oxide (TOPO), extraction (P350), two (- 2- second of 2- ethylhexyl phosphonic acids
Base hexyl) ester, tributyl phosphate (TBP) neutral phosphor (phosphine) extractant (otherwise referred to as neutral phosphor or phosphine extractant, i.e., it is neutral
Phosphorus extractant or neutral phosphine extractant)；Such as two (2,4,4- tri-methyl-amyl) phosphonodithioic acids (Cyanex 301), two (2,
4,4- tri-methyl-amyl) phosphonothiolic acid (Cyanex 302), two (2- ethylhexyl) phosphonic acids (P227 or P229) acid phosphorus
(phosphine) extractant (otherwise referred to as acid phosphorus or phosphine extractant, i.e. acid phosphorus extractant or acid phosphine extractant)；Such as
Neutrality phosphamide extractant disclosed in CN201410409451.0 and CN201410040023.5, such as three iso-octyl phosphinylidynes
The different octyloxy phosphamide of amine, diisooctyl-, the different octyloxy phosphamide of iso-octyl-two, three (diisobutyl) phosphamides, two (two is different
Butyl)-different octyloxy phosphamide, three decyl phosphamides and two base-decyloxy phosphamides etc.；With the above extractant arbitrarily to compare
The mixed extractant of example mixing.
The phase modifying agent mainly plays a part of to improve extraction physical phenomenon, can be for selected from C4~C10Alkanol and phosphoric acid
One of tributyl is a variety of.In some embodiments, the phase modifying agent is selected from n-octyl alcohol, isooctanol, 2- methyl
Mixed alcohol and one of tributyl phosphate of enanthol and the mixing of above-mentioned three kinds of alcohol arbitrary proportions and a variety of；In other implementations
It is mixed alcohol or 2- isoocanol in mode.
The diluent is selected from: C5~C16Alkane, such as pentane, hexane, heptane, octane, nonane, decane, hendecane, ten
Dioxane, tridecane, the tetradecane, pentadecane, hexadecane etc.；Aviation kerosine；Sulfonated kerosene, atoleine, such as 250~400 DEG C
Light lubricating oil fractions etc.；C5~C16Alicyclic alkanes, such as pentamethylene, C1~C4Alkyl-substituted pentamethylene, hexamethylene, C1
~C4Alkyl-substituted hexamethylene, decahydronaphthalene etc.；C6~C10Aromatic hydrocarbons, such as benzene,toluene,xylene (including o-, m-, p- two
Toluene and mixed xylenes) etc..In some embodiments, the diluent is in aviation kerosine, sulfonated kerosene, heptane
It is one or more.
In some embodiments, the acid phosphine extraction system is prepared as follows: the phosphine of acidity containing amino of general formula I is extracted
Agent is mixed with nonessential auxiliary extraction agent, nonessential phase modifying agent and diluent, then, saponification agent is added and is saponified
Processing obtains acid phosphine extraction system.
In the present invention, acid phosphine extraction system is sometimes referred to as organic phase.
The saponification agent can be one kind selected from ammonium hydroxide and alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide)
Or a variety of, preferably sodium hydroxide.In some embodiments, the saponification agent can be formulated into the use of aqueous solution form.
The saponification temperature for carrying out saponification process is not particularly limited, as long as being able to carry out saponification and not influencing to extract
The property of each component in system.In some modes, saponification temperature is 10-40 DEG C.
The saponification degree of the acidity phosphine extraction system can be 1~60%, preferably 20~40%.Due to extracting reaction mechanism
It is extracted in reaction process, a nickel ion is extracted into organic for cation exchange mechanism if not carrying out saponification process
Phase is just displaced in water phase there are two hydrogen ion, so that aqueous phase acidity be made to increase, influences the progress of subsequent extraction reaction, because
This, is preferably added alkali before extraction and carries out saponification process, the saponification to acid phosphine extraction system in oxytropism phosphine extraction system
Degree is following to be calculated:
The mole of saponification degree %=alkali/acidity phosphine extractant mole × 100.
Wherein, acid phosphine extractant refers to the acid phosphine extractant in the phosphine extractant of acidity containing amino and auxiliary extraction agent (such as
Fruit exist if) adduction；
In some embodiments, in step (1), the volume ratio of acid phosphine extraction system and feed liquid can for (0.1~
20): 1, preferably 0.2~5:1.
The extraction series of the extraction can be 1~20 grade, preferably 1~10 grade.
In some embodiments, the extraction is carried out in a manner of counter-current extraction.
A small amount of cobalt can be carried secretly in nickeliferous extract liquor.In general, in nickeliferous extract liquor, always rubbing based on cobalt and nickel
You measure, and the content of cobalt may be controlled to 10% hereinafter, being normally 5% or less；The content of nickel is 90% or more, it is normal for 95% with
On.
In some embodiments, in step (2), the cleaning solution can be water or hydrochloric acid, nitric acid, sulfuric acid or more
The mixed solution of sour arbitrary proportion.The acidity of cleaning solution is indicated with hydrionic molar concentration, is 1x10-8~1mol/L.
The washing series of the washing can be 0~10 grade, preferably 0~5 grade.It is too long to wash series, will affect the receipts of nickel
Rate and waste extractant.
In some embodiments, the washing is carried out with countercurrent washing regime.
By the content for washing the cobalt that can be further reduced in nickeliferous extract liquor.In general, after washed, nickeliferous
In extract liquor, the integral molar quantity based on cobalt and nickel, the content of cobalt can achieve 5%. hereinafter, being normally 2% or less；The content of nickel
It is 95% or more, normal is 98% or more.In order to increase the yield of nickel and cobalt, resulting cleaning solution can be recycled back to extraction section again
The secondary separation for carrying out nickel, cobalt.
In some embodiments, in step (3), the volume ratio of nickeliferous extract liquor and stripping agent can be (0.1~20):
1, preferably 1~10:1.
The extraction series of the back extraction can be 1~10 grade, preferably 3~5.
In some embodiments, the back extraction is carried out in a manner of countercurrent reextraction.
In some embodiments, the stripping agent can be selected from: hydrochloric acid, nitric acid, sulfuric acid solution or the above acid are with any
The mixed solution of ratio mixing.Sour concentration in stripping agent can be 0.3~6mol/L, preferably by pH-meter
0.5~2mol/L.
Nickeliferous back extraction product obtained by step (3) can be further processed, such as evaporative crystallization obtains corresponding nickel
Salt or alkaline chemical precipitation obtain corresponding basic salt precipitating, to obtain different nickel products.
The method of separation nickel and cobalt according to the present invention can also be included the steps that from the Call Provision of raffinate containing cobalt.
It is not particularly limited from the step of Call Provision of raffinate containing cobalt, any recycling well known in the prior art can be used
The method of cobalt.For example, in embodiments, the method for the Call Provision can be public using institute in patent CN201710904948.3
The method shown carries out.
In solvent extraction method according to the present invention, extraction and back extraction can be filled using liquid separation as known in the art
Progress is set, is preferably carried out in a series of separatory funnels, mixed settler extractor or centrifugal extractor, is more preferably clarified in mixing
It is carried out in extraction tank or centrifugal extractor.
In solvent extraction method according to the present invention, extraction and back extraction can be carried out intermittently or serially, preferably continuously
It carries out.
The result shows that the yield of gained nickel is greater than 98%, and the purity of nickel is greater than 90% through extraction and separation, effectively realize
The separation of cobalt and nickel.
In addition, the step of passing through Call Provision, the yield of gained cobalt is greater than 95%, and the purity of cobalt is greater than 99%.
Term
In the present invention, " extraction and separation nickel and cobalt " is referred to nickel (II) (i.e. bivalent nickel ion Ni through the method for extraction2 +) and cobalt (II) (i.e. divalent cobalt ion Co2+) separate.
Term C used in the present invention1~C14Alkyl refers to the linear or branched alkyl group containing 1 to 14 carbon atom,
Such as the linear or branched alkyl group with 1,2,3,4,5,6,7,8,9,10,11,12,13 or 14 carbon atom, without limitation
Including methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, isobutyl group, n-pentyl, neopentyl, isopentyl, hexyl, heptan
Base, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl etc..C1~C12Alkyl, C4~C10Alkane
Base, C5~C9Alkyl and C6~C8Meaning of alkyl and so on.
Term C used in the present invention4~C10Alkanol refers to the linear chain or branched chain alkanol containing 4 to 10 carbon atoms,
Such as the linear chain or branched chain alkanol with 4,5,6,7,8,9 or 10 carbon atoms, without limitation include n-butanol, the tert-butyl alcohol,
Isobutanol, n-amyl alcohol, neopentyl alcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol etc..
Term C used in the present invention5~C16Alicyclic alkanes refer to containing 5 including the carbon atom number of substituent group
To the saturated cyclic alkane of 16 carbon atoms, the saturated cyclic alkane can be monocycle or bicyclic, for example, pentamethylene, hexamethylene
Alkane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decahydronaphthalene etc., the substituent group can be selected from C1~C4One or more of alkyl
A substituent group.
Term C used in the present invention6~C10Aromatic hydrocarbons refers to containing 6 to 10 including the carbon atom number of substituent group
The aromatic hydrocarbons of carbon atom, for example, benzene and be selected from C1~C4The benzene that one or more substituent groups of alkyl replace, such as benzene, toluene, two
Toluene etc..
Unless otherwise indicated, numberical range listed in the present invention includes between endpoint value and endpoint value therein
With all point values of the minimum unit increasing or decreasing of endpoint value and all subranges being made of these point values.
Unless expressly stated otherwise, numerical value in entire application documents indicate to include with the little deviation of given value with
And the approximate measure or limitation of the range with about mentioned value and the embodiment with mentioned exact value.It removes
Except the embodiment that detailed description finally provides, the parameter in present specification (including appended claims) is (for example, number
Amount or condition) all numerical value shall be construed as being modified by term " about " in all cases, regardless of whether " about " real
Border appears in front of the numerical value." about " indicate that the numerical value allows slightly inaccurately (to have at this value some close to accurate；
Approximately or reasonably close to the value；It is approximate).If " about " inexactness provided is not contained commonly with this in the art
Justice understands, then " about " used herein at least indicates to generate by measuring and using the commonsense method of these parameters
Variation.For example, " about " may include being less than or equal to 10%, it is less than or equal to 5%, is less than or equal to 4%, is less than or equal to
3%, less than or equal to 2%, the variation less than or equal to 1% or less than or equal to 0.5%, and in some aspects, it is less than
Or the variation equal to 0.1%.
The present invention is described in detail above, but the present invention is not limited to above contents.
Beneficial effect
Distinguishing feature of the invention is preferential extraction of nickel, so that the separation of nickel cobalt is realized, with conventional cobalt nickel extraction agent
(such as P507, Cyanex272) preferentially extraction cobalt is different, and the present invention has significant advantage when separating the feed liquid of the low high cobalt of nickel.This
The phosphine of acidity containing amino extractant used by inventing not only in different acid mediums (sulfuric acid, nitric acid, hydrochloric acid) can by cobalt and
Nickel separates, and has good extraction and separation ability, and synthetic method is simple, and synthesis cost is cheap, easily realizes industrialization, tool
There is higher industrial application value.
Specific embodiment
For the scheme that the present invention is further explained, specific embodiments of the present invention are provided to facilitate those skilled in the art
Member understands and implements the present invention, but the present invention is not limited to these Examples.
Embodiment
Reagent and source
Aviation kerosine and TBP are purchased from Shanghai Lai Yashi Chemical Co., Ltd.；Sulfonated kerosene is limited up to chemical industry purchased from Luoyang Austria
Company；First enanthol, Cyanex 923 are purchased from Shanghai Qing Te Chemical Co., Ltd.；Feed liquid and stripping agent are laboratory self-control；Other
Reagent (such as acid) is ommercially available AR, and product purity is all made of ICP-OES (instrument model: Optical-8000, system
Make quotient: Perkin Elmer) measurement.
Prepare the synthesis of embodiment acidity containing amino phosphine extractant
Referring to Zhao, Q.et.al., Solvent.Extr.Ion exchange, 2018, doi:10.1080/
07366299.2018.1431079 the initial compounds appropriate of method selection disclosed in are (according to disclosed in CN105734289A
Method synthesis) synthesize the phosphine extractant of acidity containing amino listed in the following table 1.
Embodiment 1
The preparation of organic phase: by 3L 1- (2- ethylhexylamino) methylphosphonic acid list (2- ethylhexyl) ester and 7L sulfonation
Then kerosene mixing is added sodium hydrate solid with saponification degree 40% and is saponified, organic phase is made.
Feed liquid is the mixed solution of cobalt chloride nickel, and wherein the concentration of cobalt is 0.2mol/L, and the concentration of nickel is 0.2mol/L；Material
Liquid pH=5.0.
Cleaning solution is the hydrochloric acid solution of 0.2mol/L.
Stripping agent is the hydrochloric acid solution of 1.0mol/L.
By organic phase and feed liquid by volume 1:1 ratio mix carry out 10 stage countercurrent extractions, obtain nickeliferous extract liquor and
The water phase of raffinate containing cobalt.Then by nickeliferous extract liquor, 10:1 mixes 2 stage countercurrent washings of progress by volume with cleaning solution, resulting to wash
It washs liquid and is recycled back to the extraction and separation that extraction section carries out nickel cobalt again.Then by nickeliferous extract liquor and stripping agent 2:1 by volume
Mixing carries out 3 stage countercurrent back extraction, obtains nickeliferous aqueous solution.
Elemental analysis is carried out to the nickeliferous aqueous solution of gained, the results showed that, the back extraction ratio of nickel is greater than 99%.The yield of nickel is
98.3%, purity 91.7%.
The extraction and recovery of cobalt:
The preparation of organic phase: 3L Cyanex272 is mixed with 7L sulfonated kerosene, and hydrogen-oxygen then is added with saponification degree 40%
Change sodium solid to be saponified, organic phase is made.
Feed liquid is the water phase of raffinate containing cobalt；
Stripping agent is the hydrochloric acid solution of 3mol/L；
By the water phase of raffinate containing cobalt and organic phase by volume 2:1 mix carry out 7 grades of extractions, then to containing cobalt extract liquor with
1:4 carries out 3 grades of back extraction to stripping agent by volume, obtains the aqueous solution containing cobalt.Wherein the purity of cobalt is 99.6%, and yield is
95.2%.
Embodiment 2
By 3L 1- (2- methylhexyl amino) methylphosphonic acid list (2- ethylhexyl) ester, 1L first enanthol and 6L aviation kerosine
Then mixing is added NaOH according to saponification degree 30% and is saponified, organic phase is made.
Feed liquid is the mixed solution of cobaltous sulfate nickel, and wherein the concentration of cobalt is 0.5mol/L, and the concentration of nickel is 0.1mol/L；Material
Liquid pH=5.5.
Detergent is water.
Stripping agent is [H2SO4The sulfuric acid solution of]=1.0mol/L.
By organic phase and feed liquid by volume 1:2 ratio mix carry out 20 stage countercurrent extractions, obtain nickeliferous extract liquor and
The water phase of raffinate containing cobalt.Then by nickeliferous extract liquor, 6:1 mixes 10 stage countercurrent washings of progress by volume with cleaning solution, resulting to wash
It washs liquid and is recycled back to the extraction and separation that extraction section carries out nickel cobalt again.Then by nickeliferous extract liquor and stripping agent 2:1 by volume
Mixing carries out 10 stage countercurrent back extraction, obtains nickeliferous aqueous solution.
Elemental analysis is carried out to the nickeliferous aqueous solution of gained, the results showed that, the back extraction ratio of nickel is 99.9%.The yield of nickel is
98.5%, purity 95.2%.
The extraction and recovery of cobalt:
The preparation of organic phase: 3L Cyanex272 is mixed with 7L sulfonated kerosene, and hydrogen-oxygen then is added with saponification degree 40%
Change sodium solid to be saponified, organic phase is made.
Feed liquid is the water phase of raffinate containing cobalt；
Stripping agent is the hydrochloric acid solution of 3mol/L；
By the water phase of raffinate containing cobalt and organic phase by volume 5:1 mix carry out 7 grades of extractions, then to containing cobalt extract liquor with
1:4 carries out 3 grades of back extraction to stripping agent by volume, obtains the aqueous solution containing cobalt.Wherein the purity of cobalt is 99.3%, and yield is
96.8%.
Embodiment 3
3L 1- (2- propylpentyl amino) methylphosphonic acid list (2- ethylhexyl) ester is mixed with 7L aviation kerosine, then
Sodium hydroxide is added according to saponification degree 25% to be saponified, organic phase is made.
Feed liquid is the mixed solution of cobalt nitrate nickel, and wherein the concentration of cobalt is 0.05mol/L, and the concentration of nickel is 0.5mol/L；
Material liquid pH=4.8.
Stripping agent is 0.5mol/L nitric acid solution.
Organic phase and the ratio of material liquid volume ratio 3:1 are mixed and carry out 1 stage countercurrent extraction, obtains nickeliferous extract liquor and containing cobalt
Raffinate water phase.Then directly by nickeliferous extract liquor and stripping agent, 20:1 carries out 5 stage countercurrent back extraction by volume, obtains nickeliferous water-soluble
Liquid.
Elemental analysis is carried out to the nickeliferous aqueous solution of gained, the results showed that, the back extraction ratio of nickel is 97.8%.The yield of nickel is
98.7%, purity is greater than 91.5%.
The extraction and recovery of cobalt:
The preparation of organic phase: 3L Cyanex272 is mixed with 7L sulfonated kerosene, and hydrogen-oxygen then is added with saponification degree 40%
Change sodium solid to be saponified, organic phase is made.
Feed liquid is the water phase of raffinate containing cobalt；
Stripping agent is the hydrochloric acid solution of 3mol/L；
By the water phase of raffinate containing cobalt and organic phase by volume 1:2 mix carry out 7 grades of extractions, then to containing cobalt extract liquor with
1:4 carries out 3 grades of back extraction to stripping agent by volume, obtains the aqueous solution containing cobalt.Wherein the purity of cobalt is 99.9%, and yield is
91.1%.
Embodiment 4
By 5L 1- (2- methylhexyl amino) methylphosphonic acid list (2- methylhexyl) ester, 1LCyanex 923 and 4L sulfonation
Then kerosene mixing is added sodium hydrate solid according to saponification degree 30% and is saponified, organic phase is made.
Feed liquid is the mixed solution of cobaltous sulfate nickel, and wherein the concentration of cobalt is 0.5mol/L, and the concentration of nickel is 0.05mol/L；
Material liquid pH=5.0；
Cleaning solution is [H2SO4]=0.15mol/L sulfuric acid solution.
Stripping agent be hydrogen ion concentration be 6mol/L hydrochloric acid, nitric acid, sulfuric acid mixed solution, its ratio be hydrochloric acid: nitre
Acid: sulfuric acid=2mol/L:2mol/L:1mol/L.
Organic phase and the ratio of material liquid volume ratio 1:5 are mixed and carry out 8 stage countercurrent extractions, obtains nickeliferous extract liquor and containing cobalt
Raffinate water phase.Then by nickeliferous extract liquor, 10:1 mixes 4 stage countercurrent washings of progress, resulting cleaning solution by volume with cleaning solution
It is recycled back to the extraction and separation that extraction section carries out nickel cobalt again.Then by nickeliferous extract liquor and stripping agent, 10:1 is carried out by volume
The back extraction of 3 stage countercurrents, obtains nickeliferous aqueous solution.
Elemental analysis is carried out to the nickeliferous aqueous solution of gained, the results showed that, the back extraction ratio of nickel is 99.4%, and the yield of nickel is
99.2%, purity 94.8%.
The extraction and recovery of cobalt:
The preparation of organic phase: 3L Cyanex272 is mixed with 7L sulfonated kerosene, and hydrogen-oxygen then is added with saponification degree 40%
Change sodium solid to be saponified, organic phase is made.
Feed liquid is the water phase of raffinate containing cobalt；
Stripping agent is the hydrochloric acid solution of 3mol/L；
By the water phase of raffinate containing cobalt and organic phase by volume 5:1 mix carry out 7 grades of extractions, then to containing cobalt extract liquor with
1:4 carries out 3 grades of back extraction to stripping agent by volume, obtains the aqueous solution containing cobalt.Wherein the purity of cobalt is 99.8%, and yield is
95.9%.
Embodiment 5
By 5L 1- (2- propyl hexylamino) methylphosphonic acid list (2- ethylhexyl) ester, 1L first enanthol and 4L sulfonated kerosene
Then mixing is added sodium hydrate solid according to saponification degree 30% and is saponified, organic phase is made.
Feed liquid is the mixed solution of cobaltous sulfate nickel, and wherein the concentration of nickel is 0.5mol/L, and the concentration of cobalt is 0.1mol/L；Material
Liquid pH=5.0；
Detergent is [H2SO4]=0.1mol/L sulfuric acid solution；
Stripping agent is 0.5mol/L nitric acid solution.
Organic phase and the ratio of material liquid volume ratio 2:1 are mixed and carry out 10 stage countercurrent extractions, nickeliferous extract liquor is obtained and contains
Cobalt raffinate water phase.Then by nickeliferous extract liquor, 8:1 mixes 3 stage countercurrent washings of progress, resulting washing by volume with cleaning solution
Liquid is recycled back to the extraction and separation that extraction section carries out nickel cobalt again.Then by nickeliferous extract liquor and stripping agent by volume 10:1 into
The back extraction of 8 stage countercurrent of row, obtains nickeliferous aqueous solution.
Elemental analysis is carried out to the nickeliferous aqueous solution of gained, the results showed that, the back extraction ratio of nickel is 95.9%, and the yield of nickel is
98.7%, purity 96.7%.
The extraction and recovery of cobalt:
The preparation of organic phase: 3L Cyanex272 is mixed with 7L sulfonated kerosene, and hydrogen-oxygen then is added with saponification degree 40%
Change sodium solid to be saponified, organic phase is made.
Feed liquid is the water phase of raffinate containing cobalt；
Stripping agent is the hydrochloric acid solution of 3mol/L；
By the water phase of raffinate containing cobalt and organic phase by volume 2:1 mix carry out 7 grades of extractions, then to containing cobalt extract liquor with
1:4 carries out 3 grades of back extraction to stripping agent by volume, obtains the aqueous solution containing cobalt.Wherein the purity of cobalt is 99.2%, and yield is
96.7%.
Embodiment 6
By 0.1L 1- (2- ethylhexylamino) methylphosphonic acid list (2- methylhexyl) ester, 1L TBP and 8.9L aviation coal
Then oil mixing is added sodium hydrate solid with saponification degree 60% and is saponified, organic phase is made.
Feed liquid is the mixed solution of hydrochloric acid cobalt nickel, and wherein the concentration of cobalt is 0.025mol/L, and the concentration of nickel is 0.001mol/
L；Material liquid pH=5.2；
Detergent is 0.3mol/L hydrochloric acid solution；
Stripping agent is [H2SO4]+[HCl]=1.0mol/L hydrochloric acid and sulfuric acid solution, the wherein molar ratio of hydrochloric acid and sulfuric acid
For 1:1.
Organic phase and the ratio of material liquid volume ratio 2:1 are mixed and carry out 10 stage countercurrent extractions, nickeliferous extract liquor is obtained and contains
Cobalt raffinate water phase.Then by nickeliferous extract liquor, 10:1 mixes 5 stage countercurrent washings of progress, resulting washing by volume with cleaning solution
Liquid is recycled back to the extraction and separation that extraction section carries out nickel cobalt again.Then by nickeliferous extract liquor, 3:1 is mixed by volume with stripping agent
It closes and carries out 5 stage countercurrent back extraction, obtain nickeliferous aqueous solution.
Elemental analysis is carried out to the nickeliferous aqueous solution of gained, the results showed that, the back extraction ratio of nickel is 98.3%.The yield of nickel is
99.7%, purity 93.6%.
The extraction and recovery of cobalt:
The preparation of organic phase: 3L Cyanex272 is mixed with 7L sulfonated kerosene, and hydrogen-oxygen then is added with saponification degree 40%
Change sodium solid to be saponified, organic phase is made.
Feed liquid is the water phase of raffinate containing cobalt；
Stripping agent is the hydrochloric acid solution of 3mol/L；
By the water phase of raffinate containing cobalt and organic phase by volume 1:4 mix carry out 7 grades of extractions, then to containing cobalt extract liquor with
1:4 carries out 3 grades of back extraction to stripping agent by volume, obtains the aqueous solution containing cobalt.Wherein the purity of cobalt is 99.9%, and yield is
96.9%.
Claims (10)
1. the phosphine extractant of acidity containing amino of following general formula I is used for the use that the extraction and separation from the feed liquid comprising cobalt and nickel go out nickel
On the way:
Wherein,
R1Selected from C1~C12Alkyl, preferably C4~C10Alkyl, more preferable C5~C9Alkyl, most preferably C6~C8Alkyl；
R2Selected from C1~C14Alkyl, preferably C1~C12Alkyl.
2. a kind of method for separating nickel and cobalt, the method includes using general formula I's described in claim 1 to contain amino acidity
Phosphine extractant from include cobalt and nickel feed liquid in extraction and separation go out nickel the step of.
3. purposes according to claim 1 or method as claimed in claim 2, wherein in the feed liquid comprising cobalt and nickel,
The concentration of nickel and the concentration of cobalt are each independently 0.001~2mol/L, such as 0.005~1mol/L；And/or cobalt and nickel
Molar ratio is 500:1~1:500, for example, 100:1~1:100 or 50:1~1:50；And/or the molar ratio of cobalt and nickel is 1:
1~100:1, for example, 1:1~50:1, preferably 1:1~30:1；And/or the pH of feed liquid is 4 to less than 6, preferably 4.5-
5.8；And/or the feed liquid is sulfate, hydrochloride, nitrate solution or its mixed solution of nickel and cobalt；And/or
In the phosphine extractant of acidity containing amino of the general formula I, R1And R2Total carbon atom number be 5 to 24 between integer, preferably
Integer between 6 to 21；And/or the phosphine extractant of acidity containing amino of the general formula I is selected from 1- (2- ethylhexylamino) first
Base phosphonic acids list (2- ethylhexyl) ester, 1- (2- methylhexyl amino) methylphosphonic acid list (2- ethylhexyl) ester, 1- (2- propyl penta
Base amino) methylphosphonic acid list (2- ethylhexyl) ester, 1- (2- propyl hexylamino) methylphosphonic acid list (2- ethylhexyl) ester, 1-
(2- methylhexyl amino) methylphosphonic acid list (2- methylhexyl) ester, 1- (2- ethylhexylamino) methylphosphonic acid list (2- methyl
Hexyl) ester, 1- (2- propylpentyl amino) methylphosphonic acid list (2- methylhexyl) ester, 1- (2- propylpentyl amino) methylphosphonic acid
Single one of (2- methylhexyl) ester and 1- (2- propyl hexylamino) methylphosphonic acid list (2- methylhexyl) ester or a variety of.
4. according to the method in claim 2 or 3 comprising following steps:
(1) the acid phosphine extraction system of the phosphine extractant of acidity containing amino comprising general formula I is mixed to come with nickeliferous and cobalt feed liquid
It carries out that nickeliferous extract liquor and raffinate containing cobalt is obtained by extraction；
(2) the nickeliferous extract liquor not necessarily is washed with cleaning solution；
(3) nickeliferous back extraction product is obtained with the nickel that stripping agent is stripped in nickeliferous extract liquor.
5. according to the method described in claim 4, wherein, the acidity phosphine extraction system includes the phosphine of acidity containing amino of general formula I
Extractant, nonessential auxiliary extraction agent, nonessential phase modifying agent and diluent；
Preferably, in the acid phosphine extraction system, the phosphine of acidity containing the amino extractant of general formula I, nonessential auxiliary extraction agent,
The volume ratio of nonessential phase modifying agent and diluent are as follows: the phosphine extractant of acidity containing amino of general formula I: auxiliary extraction agent: mutually change
Good dose: diluent=1~80:0~20:0~20:20~99, the phosphine extractant of acidity containing amino of preferably general formula I: auxiliary extraction
Take agent: phase modifying agent: diluent=25~75:0~15:0~15:25~75；The also preferably acid extract containing amino of general formula I
Agent: auxiliary extraction agent: phase modifying agent: diluent=30~60:0:0:40~70；
Preferably, the auxiliary extraction agent is selected from neutral phosphor or phosphine extractant, acid phosphorus or phosphine extractant, neutral phosphamide extraction
The mixed extractant that agent and the above extractant are mixed with arbitrary proportion；And/or
The neutral phosphor or phosphine extractant include straight chain trialkyl phosphine, branch trialkyl phosphine, trioctyl phosphine oxide, first
Base phosphonic acids diformazan heptyl ester, 2- ethylhexyl phosphonic acids two (- 2- ethylhexyl) ester, tributyl phosphate；The acid phosphorus or phosphine extraction
Agent includes two (2,4,4- tri-methyl-amyl) phosphonodithioic acids, two (2,4,4- tri-methyl-amyl) phosphonothiolic acids, two (2- ethyl hexyls
Base) phosphonic acids；The neutrality phosphamide extractant includes three iso-octyl phosphamides, the different octyloxy phosphamide of diisooctyl-, different pungent
The different octyloxy phosphamide of base-two, three (diisobutyl) phosphamides, two (diisobutyls)-different octyloxy phosphamide, three decyl phosphinylidynes
Amine and two base-decyloxy phosphamides；And/or
The phase modifying agent is selected from C4~C10One of alkanol and tributyl phosphate are a variety of；For example, the phase modifying agent
For in the mixed alcohol and tributyl phosphate that n-octyl alcohol, isooctanol, 2- isoocanol and above-mentioned three kinds of alcohol arbitrary proportions mix
One kind and it is a variety of；Alternatively, being mixed alcohol or 2- isoocanol；And/or
The diluent is selected from: C5~C16Alkane, such as pentane, hexane, heptane, octane, nonane, decane, hendecane, 12
Alkane, tridecane, the tetradecane, pentadecane, hexadecane；Aviation kerosine；Sulfonated kerosene；Atoleine, such as 250~400 DEG C of lightweights
Lube cut；C5~C16Alicyclic alkanes, such as pentamethylene, C1~C4Alkyl-substituted pentamethylene, hexamethylene, C1~C4Alkane
Hexamethylene, the decahydronaphthalene of base substitution；C6~C10Aromatic hydrocarbons, such as benzene,toluene,xylene；Particularly, the diluent is selected from boat
One of empty kerosene, sulfonated kerosene, heptane are a variety of.
6. according to the method described in claim 5, wherein, the acidity phosphine extraction system is prepared as follows: by general formula I containing amino
Acid phosphine extractant is mixed with nonessential auxiliary extraction agent, nonessential phase modifying agent and diluent, then, saponification is added
Agent carries out saponification process and obtains acid phosphine extraction system；
Preferably, the saponification agent is one or more selected from ammonium hydroxide and alkali metal hydroxide, preferably sodium hydroxide；
Preferably, saponification temperature is 10-40 DEG C；
Preferably, the saponification degree of the acid phosphine extraction system is 1~60%, preferably 20~40%.
7. according to the method described in claim 4, wherein,
In step (1), the volume ratio of acid phosphine extraction system and feed liquid is (0.1~20): 1, preferably 0.2~5:1；And/or
The extraction series of the extraction is 1~20 grade, preferably 1~10 grade；And/or the extraction is carried out in a manner of counter-current extraction；
And/or
In step (2), the cleaning solution be water or hydrochloric acid, nitric acid, sulfuric acid or more than sour arbitrary proportion mixed solution；With/
Or, the acidity of cleaning solution, is indicated with hydrionic molar concentration, it is 1x10-8~1mol/L；And/or the scrubbing stage of the washing
Number is 0~10 grade, preferably 0~5 grade；And/or the washing is carried out with countercurrent washing regime；And/or
Preferably, the method also includes gained cleaning solution is recycled back to the step of extraction section carries out the separation of nickel, cobalt again；
And/or
In step (3), the volume ratio of nickeliferous extract liquor and stripping agent is (0.1~20): 1, preferably 1~10:1；And/or institute
State back extraction extraction series be 1~10 grade, preferably 3~5；And/or the back extraction is carried out in a manner of countercurrent reextraction；With/
Or, the stripping agent is selected from: the mixed solution that hydrochloric acid, nitric acid, sulfuric acid solution or the above acid are mixed with arbitrary proportion；And/or instead
Extract concentration sour in agent, is 0.3~6mol/L, preferably 0.5~2mol/L by pH-meter.
8. according to the method described in claim 4, it further includes the nickeliferous back extraction product of gained being further processed to obtain
The step of to different nickel products.
9. according to the method described in claim 4, it further includes the steps that from the Call Provision of raffinate containing cobalt.
10. according to the method described in claim 4, wherein, extraction and back extraction are in a series of separatory funnels, mixing clarification extraction
It carries out in slot or centrifugal extractor, is preferably carried out in mixed settler extractor or centrifugal extractor.
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