CN109097570A

CN109097570A - The phosphine extractant of acidity containing amino is used for the purposes and method of extraction and separation cobalt and nickel

Info

Publication number: CN109097570A
Application number: CN201811119533.6A
Authority: CN
Inventors: 廖伍平; 王永姣; 李艳玲; 邝圣庭; 张志峰; 吴国龙
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2018-09-25
Filing date: 2018-09-25
Publication date: 2018-12-28
Anticipated expiration: 2038-09-25
Also published as: CN109097570B

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

Application and method of amino-containing acidic phosphine extraction agent for extracting and separating cobalt and nickel

Technical Field

The invention relates to a method for extracting and separating cobalt and nickel, in particular to an application of an amino acid-containing phosphine extracting agent for extracting and separating cobalt and nickel and a method thereof.

Background

Nickel and cobalt are important strategic metals and have the characteristics of corrosion resistance, oxidation resistance, high strength, good ductility and the like. Cobalt is used as an important raw material for manufacturing lithium batteries, alloys and catalysts, and is widely applied to the high-tech fields of national defense, electronics, aerospace and the like; nickel is an important component of nickel-cadmium batteries and stainless steel, and is widely applied to the fields of aviation, chemical engineering, telecommunication and the like.

In recent years, the consumption of nickel and cobalt has been kept on the rise, and the purity of nickel and cobalt is required to be higher in modern industries, so that the separation of nickel and cobalt is an important problem in nickel and cobalt refining technology. However, because the atomic numbers of nickel and cobalt are adjacent, the nickel and cobalt are also group VIII elements in the fourth period, and have many similar physicochemical properties, and are often symbiotic and associated in various ore deposits and waste residues.

For many years, metallurgical workers have paid much attention to nickel and cobalt separation technology, and the current nickel and cobalt separation methods include a chemical precipitation method and a solvent extraction method. The product obtained by the chemical precipitation method is not pure and is not suitable for the solution with approximately equivalent cobalt and nickel concentration; the solvent extraction method has the advantages of high selectivity, high recovery rate, continuous operation, low cost and the like, has better economic benefit and social benefit, and has become a main industrial method for separating nickel and cobalt.

Currently, the more mature extractants used for separating cobalt and nickel are: 2-ethylhexyl phosphate (D2EHPA or P204), 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507 or PC-88A), bis (2,4, 4-trimethylpentyl) phosphonic acid (Cyanex272), and the like.

CN107287420A discloses a method for preparing 5N-grade cobalt chloride by P507 fractional extraction, which takes high-cobalt low-nickel industrial hydrochloride solution as feed liquid and 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507) as an extracting agent to realize the separation of nickel and metal elements such as cobalt, magnesium, calcium, sodium and the like, and directly prepare 5N-grade cobalt chloride with the yield of cobalt as high as 95-97%.

CN103805782A discloses a purification method of nickel-containing solution, which uses di (2,4, 4-trimethyl amyl) phosphonic acid (Cyanex272) as an extracting agent, and carries out countercurrent extraction on saponified organic phase and the nickel-containing solution to be purified in a mixer-settler, so that the contents of iron, zinc, copper and cobalt in the nickel-containing solution are reduced together, and the nickel-containing solution is rapidly and deeply purified.

However, the separation coefficient of P507 to cobalt and nickel is small, the separation of sulfate solution with high nickel and low cobalt is difficult, and P507 has certain extraction to calcium and magnesium, and calcium sulfate precipitation is generated during back extraction to influence normal operation; cyanex272 is superior to P507 in cobalt separation effect, can reduce extraction stages, but is very expensive, has an import price of about 40 ten thousand per ton, and has large loss of an extracting agent in the cobalt-nickel separation process.

Therefore, the search for an extraction system which can efficiently extract and separate cobalt and nickel and has low cost and stability is of great significance to the nickel-cobalt refining technology.

Disclosure of Invention

In order to solve the problems in the separation technology of cobalt and nickel, the invention adopts an amino acid-containing phosphine extraction agent to extract and separate cobalt and nickel, and obtains good separation effect. The extractant is easy to synthesize, has stable properties, and reduces the separation cost. The invention has the remarkable characteristics that in the extraction process of the extractant, nickel is preferentially extracted to enter the extraction liquid, and cobalt is left in the water phase, so that the separation of nickel and cobalt is realized; compared with the conventional cobalt-nickel separation extracting agent (such as P507 and Cyanex272), the cobalt is preferentially extracted into the extraction liquid, and the nickel is remained in the water phase, so that the investment of the extracting agent and the consumption of chemical raw materials in the extraction process can be saved due to the small amount of nickel to be extracted when the low-nickel high-cobalt feed liquid is treated, and the economical efficiency of the separation process is improved, therefore, the method has remarkable advantages when the low-nickel high-cobalt feed liquid is separated.

One aspect of the present invention provides the use of an amino acid phosphine-containing extractant of the general formula I below for the extractive separation of nickel from a feed solution comprising cobalt and nickel:

wherein,

R₁is selected from C₁～C₁₂Alkyl, preferably C₄～C₁₀Alkyl, more preferably C₅～C₉Alkyl, most preferably C₆～C₈An alkyl group;

R₂is selected from C₁～C₁₄Alkyl, preferably C₁～C₁₂An alkyl group.

In another aspect of the invention there is provided a process for the separation of nickel and cobalt which comprises the step of extracting nickel from a feed solution comprising cobalt and nickel using an amino acid phosphine extractant of general formula I.

In the application and the method, the amino acid-containing phosphine extracting agent with the general formula I can selectively extract nickel from feed liquid containing cobalt and nickel.

The feed liquid is an aqueous solution containing nickel and cobalt in the form of divalent ions, wherein the concentration of nickel and the concentration of cobalt can be 0.001-2 mol/L, such as 0.005-1 mol/L, independently.

In some embodiments, the molar ratio of cobalt to nickel in the feed solution can be 500:1 to 1:500, such as 100:1 to 1:100, or 50:1 to 1: 50.

In some embodiments, the molar concentration of cobalt in the feed solution is not less than the molar concentration of nickel, for example, the molar ratio of cobalt to nickel may be 1:1 to 100:1, for example, 1:1 to 50:1, and more preferably 1:1 to 30: 1.

In some embodiments, the pH of the feed solution may be about 4 to less than 6, preferably 4.5 to 5.8.

In some embodiments, the feed solution is a nickel and cobalt sulfate, chloride, nitrate, or mixed solution thereof.

There is no limitation on the raw materials for preparing the feed liquid as long as cobalt and nickel are contained therein. Suitable materials for preparing the feed solution include various materials containing cobalt and nickel, such as, for example, thiocobalite, nickel skutterudite, pentlandite, and the like. The raw material can be pretreated by physical or chemical methods and dissolved by sulfuric acid, hydrochloric acid, nitric acid or the mixed acid of the above acids to prepare the feed liquid suitable for the invention.

In one embodiment, in the amino acid phosphine-containing extractant of formula I, R is₁And R₂The total number of carbon atoms of (a) is an integer between 5 and 24, including but 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, preferably an integer between 6 and 21.

In one embodiment, the amino acid-containing phosphine extractant of formula I may be selected from the group consisting of mono- (2-ethylhexyl) 1- (2-ethylhexyl amino) methylphosphonic acid, mono- (2-ethylhexyl) 1- (2-methylhexylamino) methylphosphonic acid, mono- (2-ethylhexyl) 1- (2-propylpentylamino) methylphosphonic acid, mono- (2-ethylhexyl) 1- (2-propylhexylamino) methylphosphonic acid, mono- (2-methylhexyl) 1- (2-methylhexylamino) methylphosphonic acid, mono- (2-methylhexyl) 1- (2-ethylhexylamino) methylphosphonic acid, mono- (2-methylhexyl) 1- (2-propylpentylamino) methylphosphonic acid, mono- (2-ethylhexyl) 1- (2-propylpentylamino) methylphosphonic acid, mono- (2, 1- (2-propylpentylamino) methylphosphonic acid mono (2-methylhexyl) ester and 1- (2-propylhexylamino) methylphosphonic acid mono (2-methylhexyl) ester.

The amino acid phosphine-containing extractant of formula I can be synthesized according to methods disclosed in the prior art (e.g., Zhao, q.et.al., solvent.extr.ion exchange,2018, doi:10.1080/07366299.2018.1431079, etc.).

In one embodiment, the amino acid-containing phosphine extractant of formula I may be obtained by subjecting compound II, compound III, and compound IV to an aminomethylation reaction to obtain an amino group-containing neutral phosphine extractant of formula I, as shown in reaction formula 1:

wherein R is₁And R₂The definitions of (A) are the same as in formula I.

Compound III can be a commercially available product or synthesized according to methods known in the art.

The reaction conditions of the aminomethylation reaction (also referred to as Mannich reaction) are not particularly limited as long as the reaction can be carried out. For example, the aminomethylation reaction may be carried out with or without a catalyst, and with or without a solvent. The solvent may be, for example, benzene, toluene, xylene, tetrahydrofuran, dichloromethane, chloroform, and the catalyst may be, for example, hydrochloric acid, p-toluenesulfonic acid, InCl₃、SnCl₂、SnCl₄、ZnCl₂、MgBr₂、BF₃·Et₂And Lewis acids such as O. The reaction time can be 25min to 72h, and the reaction temperature can be room temperature to 150 ℃.

In another embodiment, the amino acid-containing phosphine extractant of general formula I can be obtained by subjecting compound V to hydrolysis to give an amino group-containing neutral phosphine extractant of general formula I, as shown in reaction scheme 2:

wherein R is₁And R₂Is as defined in formula I, R₃Definition of (A) and R₁The same is true.

Compound V can be a commercially available product or synthesized according to methods disclosed in the prior art (e.g. CN 105734289A).

In one embodiment, the method for separating cobalt from nickel of the present invention comprises the steps of:

(1) mixing an acidic phosphine extraction system containing an amino acid phosphine extraction agent with a feed liquid containing nickel and cobalt to extract to obtain nickel-containing extraction liquid and cobalt-containing raffinate;

(2) optionally washing the nickel-containing extract with a washing liquid;

(3) and (3) back-extracting the nickel in the nickel-containing extract by using a back-extractant to obtain a nickel-containing back-extraction product.

In the step (1), the acidic phosphine extraction system comprises an amino acid-containing phosphine extraction agent with a general formula I, an optional auxiliary extraction agent, an optional phase modifier and a diluent. In some embodiments, the acidic phosphine extraction system consists essentially of an amino acid-containing phosphine extractant of formula I, an optional co-extractant, an optional phase modifier, and a diluent. By "consisting essentially of … …," it is meant that the above components constitute greater than 95 wt%, greater than 97 wt%, or, in some aspects, greater than 99 wt% of the acidic phosphine extraction system. In some embodiments, the acidic phosphine extraction system consists of the components described above.

In some embodiments, the acidic phosphine extraction system may comprise an amino acid-containing phosphine extractant of formula I, an optional co-extractant, an optional phase modifier, and a diluent in a volume ratio of: the amino acid-containing phosphine extractant of the general formula I comprises an auxiliary extractant, a phase modifier and a diluent, wherein the diluent comprises about 1-80: about 0-20: about 20-99, and more preferably the amino acid-containing phosphine extractant of the general formula I comprises an auxiliary extractant, a phase modifier and a diluent comprises about 25-75: about 0-15: about 25-75; also preferred are amino acid-containing extractants of formula I, auxiliary extractants, phase modifiers, diluents, and the like in a ratio of about 30-60: 0:0: about 40-70.

The auxiliary extracting agent mainly plays a role in assisting extraction and can enhance the extraction performance of the amino acid-containing phosphine extracting agent on nickel and cobalt. The auxiliary extractant may be selected from the group consisting of linear trialkylphosphine oxides (Cyanex 923), branched trialkylphosphine oxides (Cyanex 925), trioctylphosphine oxide (TOPO), dimethylheptyl methylphosphonate (P350), di (-2-ethylhexyl) 2-ethylhexylphosphonate, tributyl phosphate (TBP) neutral phosphorus (phosphine) extractants (sometimes also referred to as neutral phosphorus or phosphine extractants, i.e. neutral phosphorus extractants or neutral phosphine extractants); acidic phosphorus (phosphine) extractants (sometimes also referred to as acidic phosphorus or phosphine extractants, i.e., acidic phosphorus extractants or acidic phosphine extractants) such as bis (2,4, 4-trimethylpentyl) dithiophosphinic acid (Cyanex 301), bis (2,4, 4-trimethylpentyl) thiophosphonic acid (Cyanex 302), bis (2-ethylhexyl) phosphonic acid (P227 or P229); neutral phosphoramide extractants such as triisooctylphosphoramide, diisooctyl-isooctyloxyphosphoramide, isooctyl-diisooctyloxyphosphoramidate, tri (diisobutyl) phosphoramide, di (diisobutyl) -isooctyloxyphosphoramide, tridecylphosphamide, and dihexyl-decyloxyphosphamide and the like as disclosed in CN201410409451.0 and CN 201410040023.5; and the mixed extractant mixed with the extractant in any proportion.

The phase modifier, which mainly acts to modify the physical phenomena of extraction, may be selected from C₄～C₁₀One or more of alkanol and tributyl phosphate. In some embodiments, the phase modifier is one or more selected from the group consisting of n-octanol, isooctanol, 2-methylheptanol, and mixed alcohols and tributyl phosphate mixed in any proportion of the three; in other embodiments, is a mixed alcohol or 2-methylheptanol.

The diluent is selected from: c₅～C₁₆Alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, etc.; aviation kerosene; sulfonated kerosene, liquid paraffin, for example, light lubricating oil fraction at 250 to 400 ℃ and the like; c₅～C₁₆Alicyclic alkanes, e.g. cyclopentane, C₁～C₄Alkyl-substituted cyclopentanes, cyclohexanes, C₁～C₄Alkyl-substituted cyclohexane, decahydronaphthalene, and the like; c₆～C₁₀Aromatic hydrocarbons such as benzene, toluene, xylenes (including ortho-, meta-, para-xylene and mixed xylenes), and the like. In some embodiments, the diluent is one or more selected from the group consisting of jet fuel, sulfonated kerosene, heptane.

In some embodiments, the acidic phosphine extraction system is prepared as follows: mixing the amino acid-containing phosphine extracting agent with a non-essential auxiliary extracting agent, a non-essential phase modifying agent and a diluting agent, and then adding a saponifying agent to carry out saponification to obtain an acidic phosphine extracting system.

In the present invention, the acidic phosphine extraction system is sometimes referred to as an organic phase.

The saponifier may be one or more selected from the group consisting of aqueous ammonia and alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), preferably sodium hydroxide. In some embodiments, the saponifier may be formulated for use in the form of an aqueous solution.

The saponification temperature at which the saponification treatment is carried out is not particularly limited as long as the saponification reaction can be carried out without affecting the properties of the components in the extraction system. In some embodiments, the saponification temperature is 10-40 ℃.

The saponification degree of the acidic phosphine extraction system can be 1-60%, and preferably 20-40%. Since the extraction mechanism is a cation exchange mechanism, if a saponification process is not performed, one nickel ion is extracted into an organic phase in the extraction process, and two hydrogen ions are replaced into an aqueous phase, so that the acidity of the aqueous phase is increased, and the subsequent extraction reaction is influenced, therefore, the acidic phosphine extraction system is preferably saponified by adding alkali into the acidic phosphine extraction system before extraction, and the saponification degree is calculated as follows:

the saponification degree% is the molar amount of the base/the molar amount of the acidic phosphine extractant × 100.

Wherein the acidic phosphine extractant refers to the addition of the amino acid-containing phosphine extractant and the acidic phosphine extractant (if present) in the auxiliary extractant;

in some embodiments, in step (1), the volume ratio of the acidic phosphine extraction system to the feed liquid can be (0.1-20): 1, and preferably 0.2-5: 1.

The extraction stage number of the extraction can be 1-20 stages, and preferably 1-10 stages.

In some embodiments, the extraction is performed as a counter current extraction.

A small amount of cobalt may be entrained in the nickel-containing extract. In general, in a nickel-containing extract, the amount of cobalt can be controlled to be 10% or less, normally 5% or less, based on the total molar amount of cobalt and nickel; the nickel content is above 90%, normally above 95%.

In some embodiments, in step (2), the washing solution may be water or a mixture solution of hydrochloric acid, nitric acid, sulfuric acid or the above acids at any ratio. The acidity of the washing solution, expressed as the molar concentration of hydrogen ions, was 1 × 10^-8～1mol/L。

The washing grade number of the washing can be 0-10 grade, and preferably 0-5 grade. Too long washing stages can affect the yield of nickel and waste extractant.

In some embodiments, the washing is performed as a counter current wash.

The cobalt content of the nickel-containing extract can be further reduced by washing. Generally, after washing, the cobalt content in the nickel-containing extract may be up to 5% or less, normally 2% or less, based on the total molar amount of cobalt and nickel; the nickel content is above 95%, normally above 98%. In order to increase the yield of nickel and cobalt, the obtained washing liquid can be recycled to the extraction section to carry out the separation of nickel and cobalt again.

In some embodiments, in step (3), the volume ratio of the nickel-containing extraction liquid to the stripping agent may be (0.1-20): 1, and preferably 1-10: 1.

The extraction stage number of the back extraction can be 1-10 stages, and preferably 3-5 stages.

In some embodiments, the back-extraction is performed as a counter current back-extraction.

In some embodiments, the stripping agent may be selected from: hydrochloric acid, nitric acid, sulfuric acid solution or mixed solution of the above acids in any proportion. The concentration of the acid in the stripping agent can be 0.3-6 mol/L, preferably 0.5-2 mol/L, based on the concentration of the hydrogen ions.

The nickel-containing strip product obtained in step (3) can be further processed, such as evaporation crystallization to obtain corresponding nickel salt or alkali precipitation to obtain corresponding basic salt precipitation, so as to obtain different nickel products.

The process for the separation of nickel and cobalt according to the invention may also include a step of recovering cobalt from the cobalt-containing raffinate.

The step of recovering cobalt from the cobalt-containing raffinate is not particularly limited and any method of recovering cobalt known in the art may be employed. For example, in an embodiment, the method for recovering cobalt can be performed by the method disclosed in patent CN 201710904948.3.

In the solvent extraction method according to the present invention, the extraction and the back-extraction may be performed using a separatory apparatus well known in the art, preferably in a series of separatory funnels, mixed-clarifying extraction tanks, or centrifugal extractors, more preferably in a mixed-clarifying extraction tank or centrifugal extractor.

In the solvent extraction process according to the present invention, the extraction and the back-extraction may be carried out batchwise or continuously, preferably continuously.

The result shows that the yield of the obtained nickel is more than 98 percent and the purity of the nickel is more than 90 percent after extraction separation, thereby effectively realizing the separation of the cobalt and the nickel.

In addition, through the step of recovering cobalt, the yield of the obtained cobalt is more than 95%, and the purity of the cobalt is more than 99%.

Term(s) for

In the context of the present invention, "extractive separation of nickel and cobalt" means that nickel (II) (i.e. the divalent nickel ion Ni) is separated by extraction² ⁺) And cobalt (II) (i.e. divalent cobalt ion Co)²⁺) And (4) separating.

The term C as used in the present invention₁～C₁₄Alkyl refers to a straight or branched chain alkyl group containing 1 to 14 carbon atoms, such as a straight or branched chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms, including, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and the like. C₁～C₁₂Alkyl radical, C₄～C₁₀Alkyl radical, C₅～C₉Alkyl and C₆～C₈The meaning of alkyl is analogized.

The term C as used in the present invention₄～C₁₀By alkanol is meant a straight or branched chain alkanol containing from 4 to 10 carbon atoms, such as straight or branched chain alkanols having 4, 5, 6, 7, 8, 9 or 10 carbon atoms, including without limitation n-butanol, t-butanol, isobutanol, n-pentanol, neopentanol, isopentanol, hexanol, heptanol, octanol, nonanol, decanol, and the like.

The term C as used in the present invention₅～C₁₆Alicyclic alkane refers to saturated cyclic alkane containing 5 to 16 carbon atoms including the number of carbon atoms of the substituent which may be selected from C, which may be monocyclic or bicyclic, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decahydronaphthalene, etc₁～C₄One or more substituents of an alkyl group.

Used in the present inventionTerm C₆～C₁₀The aromatic hydrocarbon means an aromatic hydrocarbon containing 6 to 10 carbon atoms inclusive of the number of carbon atoms of the substituent, such as benzene and C₁～C₄Benzene substituted with one or more substituents of alkyl, such as benzene, toluene, xylene, and the like.

Unless otherwise indicated, all numerical ranges recited herein include the endpoints thereof, and all values between the endpoints that are incremented or decremented by the minimum unit of the endpoint, and all subranges subsumed therein.

Unless expressly stated otherwise, numerical values throughout this specification represent approximate measures or limitations to the extent that such deviations from the given values, as well as embodiments having approximately the stated values and having the exact values stated, are included. Other than in the detailed description of the last-provided embodiments, all numbers expressing, for example, quantities or conditions of parameters (e.g., quantities or conditions) used in this specification including the appended claims are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the number. "about" means that the numerical value so stated is allowed to be somewhat imprecise (with some approach to exactness in that value; about or reasonably close to that value; approximately). As used herein, "about" refers to at least variations that can be produced by ordinary methods of measuring and using such parameters, provided that the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" can include less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5% variation, and in some aspects, less than or equal to 0.1% variation.

The present invention has been described above in detail, but the present invention is not limited to the above.

Advantageous effects

The method has the obvious characteristic of preferentially extracting nickel so as to realize the separation of nickel and cobalt, and has obvious advantages when separating low-nickel high-cobalt feed liquid, unlike the prior cobalt-nickel separation extracting agent (such as P507 and Cyanex272) which preferentially extracts cobalt. The amino acid-containing phosphine extracting agent adopted by the invention can separate cobalt from nickel in different acid media (sulfuric acid, nitric acid and hydrochloric acid), has good extraction and separation capabilities, is simple in synthesis method, low in synthesis cost, easy to realize industrialization and has high industrial application value.

Detailed Description

To further illustrate aspects of the present invention, specific examples of the present invention are provided to assist those skilled in the art in understanding and practicing the present invention, but the present invention is not limited to these examples.

Examples

Reagents and sources

Aviation kerosene and TBP were purchased from Laiyaxi chemical Co., Ltd, Shanghai; sulfonated kerosene was purchased from the Ontada chemical Co., Ltd, Luoyang; methylheptanol, Cyanex 923 was purchased from Shanghai Cyanox Chemicals Ltd; the feed liquid and the stripping agent are prepared by laboratories; other reagents (e.g., acids, etc.) were commercially available analytical grade reagents, and the product purity was determined by ICP-OES (Instrument model: Optical-8000, manufacturer: Perkin Elmer).

Preparation examples Synthesis of amino acid phosphine-containing extractant

The amino acid-containing phosphine extractants listed in Table 1 below were synthesized by the method disclosed in ZHao, Q.et.al, solvent.Extr.ion exchange,2018, doi:10.1080/07366299.2018.1431079, using the appropriate starting compounds (synthesized according to the method disclosed in CN 105734289A).

Example 1

Preparation of organic phase: 3L of 1- (2-ethylhexyl amino) methyl phosphonic acid mono (2-ethylhexyl) ester was mixed with 7L of sulfonated kerosene, and then saponified by adding sodium hydroxide solid at a saponification degree of 40% to obtain an organic phase.

The feed liquid is a mixed solution of cobalt chloride and nickel, wherein the concentration of cobalt is 0.2mol/L, and the concentration of nickel is 0.2 mol/L; the pH of the feed solution was 5.0.

The washing solution is 0.2mol/L hydrochloric acid solution.

The stripping agent is 1.0mol/L hydrochloric acid solution.

And mixing the organic phase and the feed liquid according to the volume ratio of 1:1, and performing 10-stage countercurrent extraction to obtain nickel-containing extract and cobalt-containing raffinate water phase. Then mixing the nickel-containing extract liquor with a washing liquid according to the volume ratio of 10:1 for 2-stage countercurrent washing, and recycling the obtained washing liquid to the extraction section for extraction and separation of nickel and cobalt again. Then mixing the nickel-containing extraction liquid with a stripping agent according to the volume ratio of 2:1 to perform 3-stage countercurrent stripping to obtain a nickel-containing aqueous solution.

The obtained nickel-containing aqueous solution is subjected to elemental analysis, and the result shows that the back extraction rate of nickel is more than 99%. The yield of nickel was 98.3% and the purity was 91.7%.

And (3) extracting and recovering cobalt:

preparation of organic phase: 3L of Cyanex272 was mixed with 7L of sulfonated kerosene, followed by saponification by adding sodium hydroxide solid at a saponification degree of 40% to obtain an organic phase.

The feed liquid is cobalt-containing raffinate water phase;

the stripping agent is 3mol/L hydrochloric acid solution;

mixing the cobalt-containing raffinate water phase with the organic phase according to the volume ratio of 2:1 for 7-grade extraction, and then carrying out 3-grade back extraction on the cobalt-containing extract and the back extractant according to the volume ratio of 1:4 to obtain a cobalt-containing aqueous solution. Wherein the purity of the cobalt is 99.6 percent, and the yield is 95.2 percent.

Example 2

3L of 1- (2-methylhexylamino) methylphosphonic acid mono (2-ethylhexyl) ester, 1L of methylheptanol and 6L of aviation kerosene were mixed, and then NaOH was added according to a saponification degree of 30% to carry out saponification, thereby obtaining an organic phase.

The feed liquid is a mixed solution of cobalt sulfate and nickel sulfate, wherein the concentration of cobalt is 0.5mol/L, and the concentration of nickel is 0.1 mol/L; the feed solution had a pH of 5.5.

The detergent is water.

The stripping agent is [ H ]₂SO₄]1.0mol/L sulfuric acid solution.

And mixing the organic phase and the feed liquid according to the volume ratio of 1:2, and performing 20-stage countercurrent extraction to obtain nickel-containing extract and cobalt-containing raffinate water phase. Then mixing the nickel-containing extract liquor with a washing liquid according to the volume ratio of 6:1 for 10-stage countercurrent washing, and recycling the obtained washing liquid to the extraction section for extraction and separation of nickel and cobalt again. Then mixing the nickel-containing extraction liquid with a stripping agent according to the volume ratio of 2:1 to perform 10-stage counter-current stripping to obtain a nickel-containing aqueous solution.

Elemental analysis of the obtained nickel-containing aqueous solution showed that the back extraction rate of nickel was 99.9%. The yield of nickel was 98.5% and the purity was 95.2%.

And (3) extracting and recovering cobalt:

The feed liquid is cobalt-containing raffinate water phase;

the stripping agent is 3mol/L hydrochloric acid solution;

mixing the cobalt-containing raffinate water phase with the organic phase according to the volume ratio of 5:1 for 7-grade extraction, and then carrying out 3-grade back extraction on the cobalt-containing extract and the back extractant according to the volume ratio of 1:4 to obtain a cobalt-containing aqueous solution. Wherein the purity of the cobalt is 99.3 percent, and the yield is 96.8 percent.

Example 3

3L of 1- (2-propylpentylamino) methylphosphonic acid mono (2-ethylhexyl) ester and 7L of aviation kerosene were mixed, and then sodium hydroxide was added according to a saponification degree of 25% to carry out saponification, thereby obtaining an organic phase.

The feed liquid is a mixed solution of cobalt and nickel nitrate, wherein the concentration of cobalt is 0.05mol/L, and the concentration of nickel is 0.5 mol/L; the feed solution pH was 4.8.

The stripping agent is 0.5mol/L nitric acid solution.

And mixing the organic phase and the feed liquid in a volume ratio of 3:1 to perform 1-stage countercurrent extraction to obtain nickel-containing extract liquid and cobalt-containing raffinate water phase. Then directly carrying out 5-stage countercurrent back extraction on the nickel-containing extraction liquid and a back extractant according to the volume ratio of 20:1 to obtain the nickel-containing aqueous solution.

Elemental analysis of the obtained nickel-containing aqueous solution showed that the back extraction rate of nickel was 97.8%. The yield of nickel is 98.7%, and the purity is more than 91.5%.

And (3) extracting and recovering cobalt:

The feed liquid is cobalt-containing raffinate water phase;

the stripping agent is 3mol/L hydrochloric acid solution;

mixing the cobalt-containing raffinate water phase with the organic phase according to the volume ratio of 1:2 for 7-grade extraction, and then carrying out 3-grade back extraction on the cobalt-containing extract and the back extractant according to the volume ratio of 1:4 to obtain a cobalt-containing aqueous solution. Wherein the purity of the cobalt is 99.9 percent, and the yield is 91.1 percent.

Example 4

5L of 1- (2-methylhexylamino) methylphosphonic acid mono (2-methylhexyl) ester, 1LCyanex 923 and 4L of sulfonated kerosene were mixed, and then sodium hydroxide solid was added in an amount of 30% of the saponification degree to saponify the mixture, thereby obtaining an organic phase.

The feed liquid is a mixed solution of cobalt sulfate and nickel sulfate, wherein the concentration of cobalt is 0.5mol/L, and the concentration of nickel is 0.05 mol/L; the pH value of the feed liquid is 5.0;

the washing solution is [ H ]₂SO₄]0.15mol/L sulfuric acid solution.

The stripping agent is a mixed solution of hydrochloric acid, nitric acid and sulfuric acid with hydrogen ion concentration of 6mol/L, and the ratio of the hydrochloric acid to the nitric acid to the sulfuric acid is 2mol/L to 1 mol/L.

And mixing the organic phase and the feed liquid in a volume ratio of 1:5 to perform 8-stage countercurrent extraction to obtain nickel-containing extract liquid and cobalt-containing raffinate water phase. Then mixing the nickel-containing extract liquor with a washing liquid according to the volume ratio of 10:1 for 4-stage countercurrent washing, and recycling the obtained washing liquid to the extraction section for extraction and separation of nickel and cobalt again. And then carrying out 3-stage countercurrent back extraction on the nickel-containing extraction liquid and the back extractant according to the volume ratio of 10:1 to obtain a nickel-containing aqueous solution.

Elemental analysis of the obtained nickel-containing aqueous solution showed that the stripping rate of nickel was 99.4%, the yield of nickel was 99.2%, and the purity was 94.8%.

And (3) extracting and recovering cobalt:

The feed liquid is cobalt-containing raffinate water phase;

the stripping agent is 3mol/L hydrochloric acid solution;

mixing the cobalt-containing raffinate water phase with the organic phase according to the volume ratio of 5:1 for 7-grade extraction, and then carrying out 3-grade back extraction on the cobalt-containing extract and the back extractant according to the volume ratio of 1:4 to obtain a cobalt-containing aqueous solution. Wherein the purity of the cobalt is 99.8 percent, and the yield is 95.9 percent.

Example 5

5L of 1- (2-propylhexylamino) methylphosphonic acid mono (2-ethylhexyl) ester, 1L of methylheptanol and 4L of sulfonated kerosene were mixed, and then solid sodium hydroxide was added in an amount of 30% of the degree of saponification to saponify the mixture, thereby obtaining an organic phase.

The feed liquid is a mixed solution of cobalt and nickel sulfate, wherein the concentration of nickel is 0.5mol/L, and the concentration of cobalt is 0.1 mol/L; the pH value of the feed liquid is 5.0;

the detergent is [ H ]₂SO₄]0.1mol/L sulfuric acid solution;

the stripping agent is 0.5mol/L nitric acid solution.

And mixing the organic phase and the feed liquid in a volume ratio of 2:1, and performing 10-stage countercurrent extraction to obtain nickel-containing extract liquid and cobalt-containing raffinate water phase. Then mixing the nickel-containing extract liquor with a washing liquid according to the volume ratio of 8:1 for 3-stage countercurrent washing, and recycling the obtained washing liquid to the extraction section for extraction and separation of nickel and cobalt again. And then carrying out 8-stage countercurrent back extraction on the nickel-containing extraction liquid and the back extractant according to the volume ratio of 10:1 to obtain a nickel-containing aqueous solution.

Elemental analysis of the obtained nickel-containing aqueous solution showed that the stripping rate of nickel was 95.9%, the yield of nickel was 98.7%, and the purity was 96.7%.

And (3) extracting and recovering cobalt:

The feed liquid is cobalt-containing raffinate water phase;

the stripping agent is 3mol/L hydrochloric acid solution;

mixing the cobalt-containing raffinate water phase with the organic phase according to the volume ratio of 2:1 for 7-grade extraction, and then carrying out 3-grade back extraction on the cobalt-containing extract and the back extractant according to the volume ratio of 1:4 to obtain a cobalt-containing aqueous solution. Wherein the purity of the cobalt is 99.2 percent, and the yield is 96.7 percent.

Example 6

0.1L of 1- (2-ethylhexyl amino) methyl phosphonic acid mono (2-methyl hexyl) ester, 1L of TBP and 8.9L of aviation kerosene were mixed, and then sodium hydroxide solid was added at a saponification degree of 60% to carry out saponification, to obtain an organic phase.

The feed liquid is a mixed solution of cobalt and nickel hydrochloride, wherein the concentration of cobalt is 0.025mol/L, and the concentration of nickel is 0.001 mol/L; the pH value of the feed liquid is 5.2;

the detergent is 0.3mol/L hydrochloric acid solution;

the stripping agent is [ H ]₂SO₄]+[HCl]1.0mol/L hydrochloric acid and sulfuric acid solution, wherein the molar ratio of hydrochloric acid to sulfuric acid is 1: 1.

And mixing the organic phase and the feed liquid in a volume ratio of 2:1, and performing 10-stage countercurrent extraction to obtain nickel-containing extract liquid and cobalt-containing raffinate water phase. Then mixing the nickel-containing extract liquor with a washing liquid according to the volume ratio of 10:1 for 5-stage countercurrent washing, and recycling the obtained washing liquid to the extraction section for extraction and separation of nickel and cobalt again. Then mixing the nickel-containing extraction liquid with a stripping agent according to the volume ratio of 3:1 to perform 5-stage counter-current stripping to obtain a nickel-containing aqueous solution.

Elemental analysis of the obtained nickel-containing aqueous solution showed that the back extraction rate of nickel was 98.3%. The yield of nickel was 99.7% and the purity was 93.6%.

And (3) extracting and recovering cobalt:

The feed liquid is cobalt-containing raffinate water phase;

the stripping agent is 3mol/L hydrochloric acid solution;

mixing the cobalt-containing raffinate water phase with the organic phase according to the volume ratio of 1:4 to perform 7-level extraction, and then performing 3-level back extraction on the cobalt-containing extract and the back extractant according to the volume ratio of 1:4 to obtain a cobalt-containing aqueous solution. Wherein the purity of the cobalt is 99.9 percent, and the yield is 96.9 percent.

Claims

1. Use of an acidic phosphine extractant containing amino groups of the general formula I below for the extraction of nickel from a feed solution comprising cobalt and nickel:

wherein,

2. A process for the separation of nickel and cobalt comprising the step of extracting nickel from a feed solution comprising cobalt and nickel using an amino acid phosphine extractant of the general formula I as defined in claim 1.

3. The use according to claim 1 or the process according to claim 2, wherein in the feed liquid comprising cobalt and nickel, the concentration of nickel and the concentration of cobalt are each independently 0.001-2 mol/L, such as 0.005-1 mol/L; and/or the molar ratio of cobalt to nickel is 500:1 to 1:500, for example 100:1 to 1:100, or 50:1 to 1: 50; and/or the molar ratio of cobalt to nickel is 1:1 to 100:1, for example 1:1 to 50:1, preferably 1:1 to 30: 1; and/or the pH of the feed solution is 4 to less than 6, preferably 4.5 to 5.8; and/or the feed liquid is a nickel and cobalt sulfate, hydrochloride, nitrate solution or a mixed solution thereof; and/or

In the amino acid-containing phosphine extractant of the general formula I, R₁And R₂The total number of carbon atoms of (a) is an integer between 5 and 24, preferably an integer between 6 and 21; and/or the amino acid-containing phosphine extractant of the general formula I is selected from the group consisting of 1- (2-ethylhexylamino) methylphosphonic acid mono (2-ethylhexyl) ester, 1- (2-methylhexylamino) methylphosphonic acid mono (2-ethylhexyl) ester, 1- (2-propylpentylamino) methylphosphonic acid mono (2-ethylhexyl) ester, 1- (2-propylhexylamino) methylphosphonic acid mono (2-ethylhexyl) ester, 1- (2-methylhexylamino) methylphosphonic acid mono (2-methylhexyl) ester, 1- (2-ethylhexylamino) methylphosphonic acid mono (2-methylhexyl) ester, 1- (2-propylpentylamino) methylphosphonic acid mono (2-methylhexyl) ester and 1- (2-propylpentylamino) methylphosphonic acid mono (2-methylhexyl) ester One or more of (2-propylhexylamino) methyl phosphonic acid mono (2-methylhexyl) ester.

4. A method according to claim 2 or 3, comprising the steps of:

(2) optionally washing the nickel-containing extract with a washing liquid;

5. The process of claim 4, wherein the acidic phosphine extraction system comprises an amino acid-containing phosphine extractant of formula I, an optional co-extractant, an optional phase modifier, and a diluent;

preferably, in the acidic phosphine extraction system, the volume ratio of the amino acid-containing phosphine extraction agent with the general formula I, the optional auxiliary extraction agent, the optional phase modifier and the diluent is as follows: the amino acid-containing phosphine extractant of the general formula I comprises 1-80: 0-20: 20-99 of a phase modifier, preferably the amino acid-containing phosphine extractant of the general formula I comprises 25-75: 0-15: 25-75 of a phase modifier; also preferably, the amino acid-containing extractant is represented by the general formula I, the auxiliary extractant is a phase modifier, and the diluent is 30-60: 0:0: 40-70;

preferably, the auxiliary extractant is selected from a neutral phosphorus or phosphine extractant, an acidic phosphorus or phosphine extractant, a neutral phosphoramide extractant and a mixed extractant of the extractants in any proportion; and/or

The neutral phosphorus or phosphine extraction agent comprises linear trialkyl phosphine oxide, branched trialkyl phosphine oxide, trioctyl phosphine oxide, dimethylheptyl methylphosphonate, di- (2-ethylhexyl) 2-ethylhexyl phosphonate, tributyl phosphate; the acidic phosphorus or phosphine extractant comprises bis (2,4, 4-trimethylpentyl) dithiophosphinic acid, bis (2,4, 4-trimethylpentyl) thiophosphonic acid, bis (2-ethylhexyl) phosphonic acid; the neutral phosphoramide extractant comprises triisooctylphosphoramide, diisooctyl-isooctyloxyphosphoramide, isooctyl-diisooctyloxyphosphoramidate, tri (diisobutyl) phosphoramide, di (diisobutyl) -isooctyloxyphosphoramide, tridecylphosphamide and dihexyl-decyloxyphosphamide; and/or

The phase modifier is selected from C₄～C₁₀One or more of alkanol and tributyl phosphate; for example, the phase modifier is one or more selected from n-octanol, isooctanol, 2-methylheptanol, mixed alcohol of the three alcohols in any proportion, and tributyl phosphate; or, a mixed alcohol or 2-methylheptanol; and/or

The diluent is selected from: c₅～C₁₆Alkanes, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane; aviation kerosene; sulfonated kerosene; liquid paraffin, such as 250-400 ℃ light lubricating oil fraction; c₅～C₁₆Alicyclic alkanes, e.g. cyclopentane, C₁～C₄Alkyl-substituted cyclopentanes, cyclohexanes, C₁～C₄Alkyl substituted cyclohexane, decahydronaphthalene; c₆～C₁₀Aromatic hydrocarbons such as benzene, toluene, xylene; in particular, the diluent is one or more selected from aviation kerosene, sulfonated kerosene and heptane.

6. The process of claim 5, wherein the acidic phosphine extraction system is prepared by: mixing the amino acid-containing phosphine extracting agent with a general formula I, an unnecessary auxiliary extracting agent, an unnecessary phase modifying agent and a diluting agent, and then adding a saponifying agent to carry out saponification to obtain an acidic phosphine extracting system;

preferably, the saponifier is one or more selected from the group consisting of ammonia and alkali metal hydroxide, preferably sodium hydroxide;

preferably, the saponification temperature is 10-40 ℃;

preferably, the saponification degree of the acidic phosphine extraction system is 1-60%, preferably 20-40%.

7. The method of claim 4, wherein,

in the step (1), the volume ratio of the acidic phosphine extraction system to the feed liquid is (0.1-20) to 1, preferably 0.2-5: 1; and/or the extraction stage number of the extraction is 1-20, preferably 1-10; and/or, the extraction is carried out in a counter-current extraction mode; and/or

In the step (2), the washing liquid is water or a mixed solution of hydrochloric acid, nitric acid, sulfuric acid or the above acids in any proportion; and/or the acidity of the washing liquid, expressed as the molar concentration of hydrogen ions, is 1x10^-8-1 mol/L; and/or the washing grade number of the washing is 0-10 grade, preferably 0-5 grade; and/or, the washing is carried out in a counter current washing mode; and/or

Preferably, the method also comprises the step of recycling the obtained washing liquid to the extraction section for separating nickel and cobalt again; and/or

In the step (3), the volume ratio of the nickel-containing extraction liquid to the stripping agent is (0.1-20) to 1, preferably 1-10: 1; and/or the extraction stage number of the back extraction is 1-10, preferably 3-5; and/or, the back extraction is carried out in a counter-current back extraction mode; and/or, the stripping agent is selected from: hydrochloric acid, nitric acid, sulfuric acid solution or mixed solution of the above acids in any proportion; and/or the concentration of acid in the stripping agent is 0.3-6 mol/L, preferably 0.5-2 mol/L, calculated by the concentration of hydrogen ions.

8. The process according to claim 4, further comprising the step of further processing the resulting nickel containing strip product to obtain a different nickel product.

9. The process of claim 4, further comprising the step of recovering cobalt from the cobalt-containing raffinate.

10. The process according to claim 4, wherein the extraction and back-extraction is carried out in a series of separatory funnels, mixed-clarification extraction tanks or centrifugal extractors, preferably in mixed-clarification extraction tanks or centrifugal extractors.