CN107619927A - The application of amides compound, containing its extracts composition and extraction system - Google Patents
The application of amides compound, containing its extracts composition and extraction system Download PDFInfo
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Abstract
The invention discloses a kind of application of amides compound, containing its extracts composition and extraction system.The extracts composition of the present invention, it includes N, N dihexyls benzamide and diluent, but not comprising the neutral phosphorous oxides as shown in formula A；The amides compound of the present invention can extract and be stripped lithium from bittern containing lithium containing its extracts composition, to the Li of the bittern containing lithium extraction yield more than 84.8%；Lithium magnesium distribution coefficient is up to more than 617；When being stripped lithium with HCl, stripping rate is small to equipment corrosion more than 86.41%, and is required suitable for industrialization running.
Description
Technical field
The present invention relates to a kind of application of amides compound, containing its extracts composition and extraction system.
Background technology
Lithium not only has important application in national defense industry, and its importance in national economy is also increasingly shown, especially
It is in energy field：6Li and7Li be respectively following fusion reactor fuel and nuclear fission reaction used in important materials：It makees
It is also growing for the demand of battery material.Therefore, lithium has the title of " energy metal of 21 century ".Both at home and abroad to the demand of lithium
Sustainable growth, therefore the research and development to lithium resource utilizes and seems extremely urgent.
Salt lake bittern is the valuable source of lithium.China has abundant salt lake bittern lithium resource, before its reserves occupies the world
Row.But due to containing various metals ion in bittern, it is comprehensively utilized and the technology of separation and Extraction lithium is desirable from bittern
The important topic of research, especially for containing high concentration magnesium, low concentration lithium so-called " high Mg/Li ratio " bittern in separation and Extraction
Lithium, it is generally acknowledged worldwide technological puzzle.
Solvent extraction technology is the effective technology of the various metals of separation and Extraction from solution, and it has separative efficiency height, work
Skill and equipment are simple, operate serialization, are easily achieved the advantages that automatically controlling, it is considered to be are extracted from " high Mg/Li ratio " bittern
One of most promising method of separating Li.Since last century middle nineteen sixties, oneself proposes some extractor bodies both at home and abroad
System and technique, it is specific as follows：
(1) 1967 year, Nelli J.R. etc. invented a kind of extraction system and technique [1.Nelli J.R.etal.Fr.1,
535,818(1967)；USP3,537,813(1970).]：FeC1 is added in bittern3As co-extraction agent, with 80% 2 isobutyl
The tributyl phosphate of ketone -20% is as organic phase, by Li and Fe with LiFeC14Form coextraction enters big in organic phase, with aqueous phase
Measure MgC12And other metals separation.Though extraction of the system to Li has higher selectivity, be stripped with water produce LiCl and
FeC13Mixed liquor, di-(2-ethylhexyl)phosphoric acid-tributyl phosphate system extract and separate Li and Fe again must be used, causes technique
Tediously long, cumbersome, so far there are no, and it is used for industrial production.
(2) 1979 years, Qinghai Salt Lake research institute of the Chinese Academy of Sciences proposed the kerosin with single extractant tributyl phosphate
The system and technique of lithium are extracted, so as to simplify extraction system, and in 1984 extract from big bavin denier salt lake bittern
The pilot-plant test of lithium, applied in 1987 Chinese invention patent [3. yellow teachers are strong etc., Chinese invention patent,
CN87103431], and authorized.But the extractant employed in the system is tributyl phosphate (TBP), to extraction
The corrosivity of equipment is stronger, and the tributyl phosphate not only solution loss in water, and in acid medium in long-term operating
Easily degrade, particularly its serious swelling action to the material for making extraction equipment limits its industrial-scale
Using.
(3) since 2010, Qinghai Yanhu Inst., Chinese Academy of Sciences is studied with Chinese Academy of Sciences Shanghai organic chemistry
Cooperated, have developed a kind of can reduce to the corrosivity of equipment and be adapted to commercial Application extract lithium salts from bittern containing lithium jointly
Technology and method, its use amides compound or amides compound and the mixture of neutral phosphorus oxygen class compound for extraction
The extraction that agent, ferric trichloride are co-extraction agent and aliphatic hydrocarbon or aromatic hydrocarbon is diluent progress lithium.Chinese invention is applied within 2011
Patent [Yuan Chengye etc., Chinese invention patent, CN103055539A], and authorized.And lithium is extracted to the kind of extractants
Performance has carried out system research, completes the process test research of amide-type and neutral phosphorus oxygen class mixed system, it is determined that technique
The optimum process condition of flow.Complete the process test research of N523-TBP- sulfonated kerosene extraction systems, it is determined that flow
Optimum process condition, but this method exposes problems in industrialization process, it is water-soluble big such as because TBP is present,
It is strong to equipment corrosion.To solve TBP water solubility problems, both increased in the outlet of raffinate, strip liquor and each aqueous phase substantial amounts of
TBP retracting devices and aqueous phase deoiler, make technological process lengthen significantly, increase production cost.Asked to solve TBP corrosivity
Topic, the material of nucleus equipment have very harsh requirement, have selected the equipment of a large amount of Hastelloy and fluoroplastics materials, equipment
Infusion of financial resources is very huge.Further, since being hybrid extraction system, TBP water solubilitys are bigger than N523, have after a period of time is run
Extractant TBP amounts significantly reduce in machine phase, cause technique unstable, it is necessary to often add TBP.TBP presence also influences subsequently
The purifying of product, often the phosphorus content in product is higher.
The content of the invention
The technical problems to be solved by the invention are, in order to overcome the existing extraction that lithium salts is extracted from bittern containing lithium
The shortcomings of taking technique present in system and technique tediously long, cumbersome, strong to the corrosivity of equipment, the molten damage of extractant is big, and
A kind of application of amides compound is provided, containing its extracts composition and extraction system.Using the amide-type of the present invention
Compound can extract and be stripped lithium from bittern containing lithium, and lithium extraction yield and back extraction ratio height, lithium and sodium potassium magnesium separation factor are big, right
Equipment corrosion is small, and is required suitable for industrialization running.
The present invention mainly solves above-mentioned technical problem by the following technical programs.
The invention provides a kind of extracts composition, it is characterised in that it includes N, N- dihexyls benzamide and dilution
Agent, but do not include the neutral phosphorous oxides as shown in formula A,
Wherein, in the neutral phosphorus oxygen class compound as shown in formula A, R1And R2It independently is C1-C12Straight chain or branched alkane
Base, C1-C12Straight chain or branched alkoxy, phenyl, the phenyl of substitution, phenoxy group, the phenoxy group of substitution, thienyl, pyridine
Base or naphthyl；Substituent described in described substituted phenyl or described substituted phenoxy group is one in following groups
It is or multiple：Halogen, C1-C6Alkyl, hydroxyl, C1-C6Alkoxy, trifluoromethyl, trifluoromethoxy, phenoxy group, piperidyl, morpholine
Base, pyrrole radicals, nafoxidine base, nitro and amino；When described substituent for it is multiple when, described substituent is identical or not
Together.
In the described neutral phosphorus oxygen class compound as shown in formula A, R1And R2It is preferred that C1-C8Straight chain or branched alkyl,
Or C1-C8Straight chain or branched alkoxy；Wherein, described C1-C8Straight chain or the preferred methyl of branched alkyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 1- methyl-heptyls or 2- ethyl hexyls.Described C1-C8Straight chain or
The preferred methoxyl group of branched alkoxy, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, 1- methyl-heptan
Epoxide or 2- ethyls-hexyloxy.
One or more in the described neutral preferred following compounds of phosphorus oxygen class compound as shown in formula A：
Described diluent can be the conventional diluent in this area, and boiling point is greater than or equal to 100 DEG C of fat preferably under normal pressure
Fat hydrocarbon (such as n-dodecane) or aromatic hydrocarbon, or kerosene.The dosage of described diluent can be not especially limited, as long as
The extraction ability of extractant is not influenceed.The volume content preferred 5%-95% of described diluent, further preferred 20%
~95%, described percentage refers to that the volume of diluent accounts for the percentage of described extracts composition cumulative volume.
Co-extraction agent is also can further include in described extracts composition.Described co-extraction agent can first be dissolved in extraction
In aqueous phase, first it can also stabilize it in organic phase.Described co-extraction agent refers generally to significantly improve positive the three of lithium extraction yield
The molysite of valency, can be the one or more in ferric trichloride, ferric sulfate, ferric nitrate and ferric phosphate, preferably ferric trichloride.It is described
The dosage of co-extraction agent can be that bittern containing lithium extracts and be stripped the conventional dosage in lithium field, typically contained with lithium in material to be extracted
Gauge, described thing to be extracted preferably bittern containing lithium；The dosage of described co-extraction agent typically makes rubbing for ferric ion and lithium ion
You are than being 1:1-2:1, further preferred 1.1:1-1.7:1, more preferably 1.1:1-1.3:1.
The invention provides a kind of extracts composition as previously described to extract or be stripped answering in lithium from bittern containing lithium
With.
The described application that lithium is extracted from bittern containing lithium, preferably includes the following steps：By described extracts composition with
Bittern containing lithium mixes, vibration or stirring balance, stratification, you can.
The described application that lithium is stripped from bittern containing lithium, preferably includes the following steps：
(1) described extracts composition and bittern containing lithium are mixed, vibration or stirring balance, stratification, obtains load lithium
The organic phase of ion；
(2) organic phase of described load lithium ion is mixed with the aqueous solution of acid, vibration or stirring balance, standing point
Layer, you can.
In the described application that lithium is extracted from bittern containing lithium or the application of the back extraction lithium from bittern containing lithium, lead to
Cross vibration mass transfer.In addition, mass transfer and split-phase can also be completed by extraction equipments such as centrifugal extractor, mixer-settler, extraction towers
Process.Described centrifugal extractor, mixer-settler, extraction tower can be the conventional extraction equipment of this area, its use condition
The normal service condition and method that lithium is extracted from the aqueous solution containing lithium are can refer to method.
The described application that lithium is extracted from bittern containing lithium or the applying step that lithium is stripped from bittern containing lithium
(1) in, the volume ratio of described extraction organic phase and the bittern containing lithium can be the conventional volume ratio in this area, preferably 1:5-
10:1, more preferably 2:1-6:1；In the present invention, described extracts composition organic phase generally refers to extract when not including co-extraction agent
Composition.
In the described application that lithium is extracted from bittern containing lithium or the application of the back extraction lithium from bittern containing lithium, institute
The extracts composition and the temperature of the bittern containing lithium stated are preferably 10 DEG C -50 DEG C, further preferred 20 DEG C -40 DEG C (such as
24-25 DEG C), i.e., the operation of balance is vibrated or stirred under 10 DEG C -50 DEG C (preferably 20 DEG C -40 DEG C).Described vibration or
The time for stirring balance can be this area conventional time, preferably 5-30 minutes.(such as 10 minutes)
It is described to be stripped from bittern containing lithium in the application of lithium, in step (2), the described sour aqueous solution it is mole dense
Degree preferably 0.5mol/L-12.0mol/L, more preferably more preferably 4mol/L-10mol/L, 6mol/L-8mol/L, institute
The molar concentration stated refers to that the amount of the material of acid accounts for the ratio of the aqueous solution cumulative volume of acid.Acid in the described sour aqueous solution can be
The conventional acid in this area, preferably inorganic acid.Described inorganic acid is preferably one kind or more in hydrochloric acid, sulfuric acid and nitric acid
Kind, it is more preferably hydrochloric acid.The organic phase of described load lithium ion can be that this area is conventional with the volume ratio of the aqueous solution of acid
Volume ratio, preferably 1:1-50:1, further preferred 5:1-40:1, more preferably 10:1-30:1.
In the present invention, the bittern containing lithium can be the conventional bittern containing lithium containing lithium ion in this area, and the present invention is preferably
Bittern containing lithium containing high Mg/Li ratio.Preferred 1.5-240 (the examples of Mg/Li molar ratio in the bittern containing lithium of described high Mg/Li ratio
As 16).Described bittern containing lithium preferably comprises the component of following content：0.02mol/L-2.0mol/L Li+、2.0mol/L-
5.0mol/L Mg2+, 0mol/L-0.5mol/L Na+, 0mol/L-0.5mol/L K+, >=6mol/L Cl-、0mol/L-
0.90mol/L B2O3With 0.001mol/L-0.5mol/L H+, remaining is water.
H in described bittern containing lithium+The preferred 0.005mol/L-0.5mol/L of concentration.
The invention provides a kind of amides compound from bittern containing lithium extract or be stripped lithium in application, it is described
Amides compound be N, N- dihexyl benzamides.
The described application that lithium is extracted from bittern containing lithium, preferably includes the following steps：By N, N- dihexyl benzamides
Mixed with bittern containing lithium, vibration or stirring balance, stratification, you can.
The described application that lithium is stripped from bittern containing lithium, preferably includes the following steps：
(1) N, N- dihexyls benzamide and the mixing of bittern containing lithium, vibration or stirring are balanced, stratification, must loaded
The organic phase of lithium ion；
(2) organic phase of described load lithium ion is mixed with the aqueous solution of acid, vibration or stirring balance, standing point
Layer, you can.
In the described application that lithium is extracted from bittern containing lithium or the application of the back extraction lithium from bittern containing lithium, lead to
Cross vibration mass transfer.In addition, mass transfer and split-phase can also be completed by extraction equipments such as centrifugal extractor, mixer-settler, extraction towers
Process.Described centrifugal extractor, mixer-settler, extraction tower can be the conventional extraction equipment of this area, its use condition
The normal service condition and method that lithium is extracted from the aqueous solution containing lithium are can refer to method.
The described application that lithium is extracted from bittern containing lithium or the applying step that lithium is stripped from bittern containing lithium
(1) in, by N, the volume ratio of N- dihexyls benzamide and the bittern containing lithium can be the conventional volume ratio in this area, preferably
1:5-10:1, more preferably 2:1-6:1.
In the described application that lithium is extracted from bittern containing lithium or the application of the back extraction lithium from bittern containing lithium, institute
The temperature of N when the vibration stated or stirring balance, N- dihexyls benzamide and the bittern containing lithium is preferably 10 DEG C -50 DEG C,
Further preferred 20 DEG C -40 DEG C (such as 24-25 DEG C), i.e., vibrated or stirred under 10 DEG C -50 DEG C (preferably 20 DEG C -40 DEG C)
The operation of balance.Described vibration or the time of stirring balance can be this area conventional time, preferably 5-30 minutes.(such as
10 minutes)
Described is stripped in the application of lithium from bittern containing lithium, in step (2), mole of the described sour aqueous solution
Concentration is preferably 0.5mol/L-12.0mol/L, more preferably 4mol/L-10mol/L, more preferably 6mol/L-8mol/L,
Described molar concentration refers to that the amount of the material of acid accounts for the ratio of the aqueous solution cumulative volume of acid.Acid in the described sour aqueous solution can
For the conventional acid in this area, preferably inorganic acid.Described inorganic acid be preferably one kind in hydrochloric acid, sulfuric acid and nitric acid or
It is a variety of, it is more preferably hydrochloric acid.The organic phase of described load lithium ion can be that this area is conventional with the volume ratio of the aqueous solution of acid
Volume ratio, preferably 1:1-50:1, further preferred 5:1-40:1, more preferably 10:1-30:1.
In the present invention, the bittern containing lithium can be the conventional bittern containing lithium containing lithium ion in this area, and the present invention is preferably
Bittern containing lithium containing high Mg/Li ratio.Preferred 1.5-240 (the examples of Mg/Li molar ratio in the bittern containing lithium of described high Mg/Li ratio
As 16).Described bittern containing lithium preferably comprises the component of following content：0.02mol/L-2.0mol/L Li+、2.0mol/L-
5.0mol/L Mg2+, 0mol/L-0.5mol/L Na+, 0mol/L-0.5mol/L K+, >=6mol/L Cl-、0mol/L-
0.90mol/L B2O3With 0.001mol/L-0.5mol/L H+, remaining is water.
H in described bittern containing lithium+The preferred 0.005mol/L-0.5mol/L of concentration.
Present invention also offers a kind of extraction system, and it includes bittern containing lithium and N, N- dihexyl benzamide；Or containing lithium
Bittern and extracts composition.
Wherein, the volume ratio of N, N- dihexyl benzamide and the bittern containing lithium can be the conventional volume ratio in this area, preferably
1:5-10:1, more preferably 2:1-6:1；Described extracts composition and the volume ratio of the bittern containing lithium can be that this area is conventional
Volume ratio, preferably 1:5-10:1, more preferably 2:1-6:1.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can be combined, and it is each preferably to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
In the present invention, described normal pressure refers to 1 atmospheric pressure, 101.325kPa.
In the present invention, described volume ratio or volume fraction each mean the volume ratio or volume of each material at ambient temperature
Fraction.
In the present invention, room temperature refers to 10 DEG C -30 DEG C.
In the present invention, the operation of vibration or stirring can also use the operation such as stirring, and its purpose is to make organic phase and water
Mix uniformly.
The positive effect of the present invention is：Extractant of the present invention, extraction system are to the Li of salt lithium bittern
Extraction yield more than 84.8%, reach as high as 92.55%；Separation of Li and Mg factor reaches as high as 1041 more than 617.With dense
When HCl is stripped lithium, for stripping rate more than 86.41%, it extracts the extraction of lithium salts and back extraction performance from bittern containing lithium
Greatly improve, avoid TBP use, extractant is water-soluble and corrosivity substantially reduces, cost-effective, is more suitable for industrializing
Production.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
In following embodiments, compare, the basic conception of distribution ratio, extraction yield and extract and separate factor.
(1) compare
For interrupted extraction process, organic phase volume V (m are extracted3) and feed liquid aqueous phase L (m3) the ratio between be referred to as comparing；For even
Continuous extraction process, extraction phase volume flow V (m3/ s) and feed liquid phase volume flow L (m3/ s) the ratio between also referred to as compare or two phase flow
Than unified herein to represent two-phase volume or flow with O/A.Represented compared to R：
In formula：VoFor the volume of extraction phase, VaFor the volume of feed liquid phase
(2) extraction yield
Extraction yield, which represents to be extracted material in extraction process the amount of extraction phase is mutually transferred to by feed liquid, to be accounted for and is extracted material in original
The percentage of total amount in feed liquid phase, it represents the degree of extract and separate.Extraction yield E (%) calculation formula is：
In formula：naTo be extracted the amount of material, n in feed liquidoTo be extracted the amount of material in extraction raffinate.
(3) distribution ratio
Distribution ratio is also known as distribution coefficient.It is extracted distribution behavior of the substance A in two-phase and can be understood as A in two-phase
The gross effect of existing variform A1, A2 ..., An distribution.Under normal conditions, measured value of experiment is extracted in representing per phase
Take the total concentration of a variety of existing forms of material.System distribution coefficient is defined as under certain condition, when system reaches balance, quilt
The ratio between total concentration of the extracting substance in extraction organic phase (O) and total concentration in feed liquid phase (A), are represented with D：
Distribution ratio represents that extraction system is extracted actual allocation proportion of the material in two-phase after reaching balance, typically by reality
Test is determined.It is bigger by the distribution ratio of extraction thing, show that the material is more easily extracted, while the size of distribution ratio except with by extraction thing
Property has outside the Pass, also relevant with extraction conditions, as by extraction thing concentration, acidity, the other materials coexisted, extracted in aqueous phase in organic matter
Take the species and concentration of agent, temperature when species of diluent and extraction etc. is relevant.
(4) separation factor
Under certain condition carry out extract and separate when, two kinds of materials to be separated two alternate distribution coefficients ratio,
Referred to as extract and separate factor, also known as extract and separate coefficient, commonly use β and represent.If A, B represents two kinds of materials to be separated respectively, have：
In formula：DAFor the distribution ratio of A materials, DBFor the distribution ratio of B substance.
Extract and separate quantifies illustrate the complexity of two kinds of materials in some extraction system separating material liquid phase.β value
For 1 when both materials can not be separated, β value is bigger or smaller, and separating effect is better, i.e. the separation selectivity of extractant is got over
It is high.
Embodiment 1-3
Organic phase：N, N- dihexyl benzamide+diluent
Aqueous phase：Bittern containing lithium；
Compared to (O:A)：Refer to the volume ratio of organic phase and aqueous phase；
Concrete operations are as follows：
By a certain amount of FeCl3(co-extraction agent) is added in bittern containing lithium, after shake is allowed to dissolving, adds organic phase, vibration
Balance (duration of oscillation is -30 minutes 5 minutes), stratification, must balance aqueous phase and the organic phase of the lithium ion containing load.Survey respectively
Go out to balance Li in aqueous phase and organic phase+、Na+、K+And Mg2+Concentration, thus calculate Li extraction yield, Li+、Mg2+、Na+And K+
Distribution ratio, Li/Mg, Li/Na and Li/K separation.
Embodiment 4
Organic phase：N, N- dihexyl benzamide
Aqueous phase：Bittern containing lithium；
Compared to (O:A)：Refer to the volume ratio of organic phase and aqueous phase；
Concrete operations are as follows：
By a certain amount of FeCl3(co-extraction agent) is added in bittern containing lithium, after shake is allowed to dissolving, adds organic phase, vibration
Balance 30 minutes, stratification, aqueous phase and the organic phase of the lithium ion containing load must be balanced.Balance aqueous phase and organic phase are measured respectively
Middle Li+、Na+、K+And Mg2+Concentration, thus calculate Li extraction yield, Li+、Mg2+、Na+And K+Distribution ratio, Li/Mg, Li/
Na and Li/K separation.
The content of each ion is as shown in table 1 in bittern containing lithium in above-described embodiment 1~4：
In the embodiment 1~4 of table 1. in bittern containing lithium each ion content (mol/L)
| Numbering | Li+ | Mg2+ | Na+ | K+ | Cl- | B2O3 | H+ | Mg/Li ratio |
| 1 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.037 | 16 |
| 2 | 0.02 | 4.8 | 0.1 | 0.4 | 10.2 | 0.1 | 0.005 | 240 |
| 3 | 2 | 3 | 0.4 | 0.02 | 9.0 | 0 | 0.5 | 1.5 |
| 4 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.037 | 16 |
Wherein, the extraction conditions of 1~embodiment of embodiment 4 and parameter are as shown in table 2：
1st, the kerosene of 50%N, N- dihexyl benzamide -50%
2nd, the n-dodecane of 5%N, N- dihexyl benzamide -95%
3rd, the kerosene of 80%N, N- dihexyl benzamide -20%
4th, 100%N, N- dihexyl benzamide
The extraction conditions of 2. embodiment of table 1~4 and parameter
| Numbering | Extraction phase compares O/A | Fe/Li mol ratios | Extraction temperature (DEG C) |
| 1 | 2 | 1.3 | 25 |
| 2 | 5 | 1.1 | 10 |
| 3 | 10 | 1.75 | 40 |
| 4 | 2 | 1.3 | 25 |
The extraction results of 1~embodiment of embodiment 4 are as shown in table 3：
The extraction results of 3. embodiment of table 1~4
Comparative example 1
Organic phase is replaced with into N respectively, N- dihexyls acetamide+kerosene, remaining operation and condition are the same as embodiment 1.Experiment
As a result it is as shown in table 4.
The extraction results of 4 comparative example of table 1
Embodiment 5
By a certain amount of FeCl3(co-extraction agent) adds 60 parts of (volume) bittern containing lithium (FeCl3It is each in dosage and bittern containing lithium
Component and content see embodiment 1,4) in, shake be allowed to dissolving after, add 30 parts of (volume) embodiments 1,4 in organic phase, shake
Swing 10 minutes, extracted, the organic phase of lithium ion must be loaded.The organic phase 30 parts (volumes) and 6mol/ of lithium ion will be loaded
L 1 part of aqueous hydrochloric acid solution (volume) mixing, 24 DEG C vibrate 10 minutes, are stripped, stratification, determine stripping equilibria two
Li in phase+Concentration.Design parameter sees below list 5, and the actual conditions and parameter of the back extraction of comparative example 2,3 refer to patent
CN103055539A。
Table 5. is stripped result data table
The preparation method for the extractant being related in the example is as follows：
Test general operation：Equipped with thermometer, constant pressure funnel, churned mechanically 2L three-necked bottle in, respectively
Dialkylamine 1mol, 400mL dichloromethane and 153mL (1.1mol) triethylamine are added, opens stirring, and system is cooled to 0
DEG C, while the dichloromethane solution of 1.05mol acyl chlorides and about 200mL is placed in dropping funel and starts to be added dropwise, keeping body
It is that temperature is no more than 15 DEG C, is added dropwise within about 30 minutes.Ice bath is removed, room temperature reaction is overnight.Add isometric water dissolving life
Into solid, after separatory funnel layering, organic phase watery hydrochloric acid and saturated common salt water washing, and with anhydrous sodium sulfate drying are de-
After solvent, it is evaporated under reduced pressure.
Wherein, Yield refers to yield, and IR (thin film) refers to infrared (membrane process), and EA refers to elementary analysis, and calcd.For refers to
Calculated value, Found refer to actual value.
N, N- dihexyl acetamide
(s,3H),1.50-1.53(m,4H),1.27-1.28(m,12H),0.85-0.88(m,6H)；13C NMR(100MHz,CDCl3)
δ170.174,48.866,45.829,31.606,31.490,28.856,27.678,26.679,26.516,22.550,
21.404,13.998,13.951；IR(thin film):2957,2929,2873,2858,1648,1458,1422,1378,
1260,1108cm-1；MS(ESI):228.6(M++1),250.3(M++Na)；EA:calcd.for C14H29NO:C,73.95；
H,12.86；N,6.16,Found:C,73.00；H,12.87；N,6.15.
N, N- dihexyl benzamide
(m,12H),0.61-0.74(m,6H)；
13C NMR(100MHz,CDCl3)δ171.638,137.296,134.523,130.549,128.992,128.860,
128.829,128.310,128.155,126.428,126.304,126.265,48.998,48.874,44.729,44.636,
31.598,31.498,31.288,31.157,28.554,28.430,27.585,27.469,27.376,26.780,26.679,
26.524,26.253,26.206,22.496,13.959；IR(thin film):2956,2929,2857,1636,1466,
1423,1379,1300,1267,1107,1074cm-1；MS(ESI):290.6(M++1),312.3(M++Na)；EA:
calcd.for C19H31NO:C,78.84；H,10.80；N,4.84,Found:C,78.35；H,10.62；N,4.96.
Claims (12)
1. a kind of extracts composition, it is characterised in that it includes extractant N, N- dihexyl benzamide and diluent, but does not wrap
Containing the neutral phosphorous oxides as shown in formula A；
Wherein, in the neutral phosphorus oxygen class compound as shown in formula A, R1And R2It independently is C1-C12Straight chain or branched alkyl,
C1-C12Straight chain or branched alkoxy, phenyl, the phenyl of substitution, phenoxy group, the phenoxy group of substitution, thienyl, pyridine radicals or
Naphthyl；Substituent described in described substituted phenyl or described substituted phenoxy group is one or more in following groups
It is individual：Halogen, C1-C6Alkyl, hydroxyl, C1-C6Alkoxy, trifluoromethyl, trifluoromethoxy, phenoxy group, piperidyl, morpholinyl, pyrrole
Cough up base, nafoxidine base, nitro and amino；When described substituent is multiple, described substituent is identical or different.
2. extracts composition as claimed in claim 1, it is characterised in that the diluent is that boiling point is greater than or equal under normal pressure
One or more under 100 DEG C of aliphatic hydrocarbon, normal pressure in aromatic hydrocarbon and kerosene of the boiling point greater than or equal to 100 DEG C, preferably kerosene
And/or n-dodecane.
3. extracts composition as claimed in claim 1, it is characterised in that the volume content of described diluent is 5%-
95%, preferably 20%~95%, described percentage refer to that the volume of diluent accounts for the hundred of described extracts composition cumulative volume
Divide ratio.
4. the extracts composition as described in claim any one of 1-3, it is characterised in that the extracts composition also further wraps
Agent containing co-extraction.
5. extracts composition as claimed in claim 4, it is characterised in that described co-extraction agent is ferric trichloride, ferric sulfate, nitre
One or more in sour iron and ferric phosphate, preferably ferric trichloride；The dosage of described co-extraction agent is contained with lithium in material to be extracted
Gauge, described thing to be extracted are bittern containing lithium；The dosage of described co-extraction agent makes the mol ratio of ferric ion and lithium ion be
1:1-2:1, preferably 1:1-1.75:1.
6. a kind of extracts composition or N, N- dihexyl benzamide as described in claim any one of 1-5 is from bittern containing lithium
Middle extraction lithium or the application being stripped in lithium.
7. application as claimed in claim 6, it is characterised in that the application that lithium is extracted from bittern containing lithium includes following
Step：By the extracts composition as described in claim any one of 1-5 or N, N- dihexyl benzamide, mixed with bittern containing lithium
Close, vibration or stirring balance, stratification, you can.
8. application as claimed in claim 6, it is characterised in that under the application that lithium is stripped from bittern containing lithium includes
Row step：
(1) will as described in claim any one of 1-5 extracts composition or N, N- dihexyl benzamide, and bittern containing lithium mixes
Close, vibration or stirring balance, stratification, the organic phase of lithium ion must be loaded；
(2) organic phase of described load lithium ion is mixed with the aqueous solution of acid, vibration or stirring balance, stratification, i.e.,
Can.
9. application as claimed in claim 7 or 8, it is characterised in that it is described to extract lithium from bittern containing lithium, or it is described from
It is stripped in bittern containing lithium in the applying step (1) of lithium, N, N- dihexyls benzamide or extracts composition organic phase, and it is described
The bittern containing lithium volume ratio be 1:5-10:1, preferably 2:1-6:1；Described extracts composition organic phase refers to not include co-extraction
Extracts composition during agent.
10. application as claimed in claim 8, it is characterised in that be stripped from bittern containing lithium in the application of lithium, its feature exists
In step (2), the molar concentration of the described sour aqueous solution is 0.5mol/L-12.0mol/L, preferably 4mol/L-10mol/
L, more preferably 6mol/L-8mol/L, described molar concentration refer to that the amount of the material of acid accounts for the ratio of the aqueous solution cumulative volume of acid；
And/or in the application of the back extraction lithium from bittern containing lithium, in step (2), the acid in the described sour aqueous solution
For inorganic acid；Described inorganic acid is preferably the one or more in hydrochloric acid, sulfuric acid and nitric acid；
And/or in the application of the back extraction lithium from bittern containing lithium, in step (2), described loads the organic of lithium ion
It is mutually 1 with the volume ratio of the aqueous solution of acid:1-50:1, preferably 5:1-40:1, more preferably 10:1-30:1.
11. application as claimed in claim 7 or 8, it is characterised in that extract lithium from bittern containing lithium or be stripped the application of lithium
In, extracts composition or N, N- dihexyl benzamide and described bittern containing lithium described in when described vibration or stirring balance
Temperature be 10 DEG C -50 DEG C；
And/or it is described from bittern containing lithium extract lithium or be stripped lithium application in, described vibration or stirring balance when
Between be 5-30 minutes；
And/or in the application that lithium or back extraction lithium are extracted from bittern containing lithium, Mg/Li molar ratio is 1.5-
240；Described bittern containing lithium includes the component of following content：0.02mol/L-2.0mol/L Li+、2.0mol/L-5.0mol/
L Mg2+, 0mol/L-0.5mol/L Na+, 0mol/L-0.5mol/L K+, >=6mol/L Cl-、0mol/L-0.90mol/L
B2O3With 0.001mol/L-0.5mol/L H+, remaining is water；Described bittern containing lithium preferably comprises the component of following content：
0.02mol/L-2.0mol/L Li+, 3mol/L-4.8mol/L Mg2+, 0.1mol/L-0.4mol/L Na+、0.02mol/
L-0.4mol/L K+, 9.0mol/L-10.2mol/L Cl-, 0-0.1mol/L B2O3With 0.005mol/L-0.5mol/L's
H+, remaining is water.
12. a kind of extraction system, it includes bittern containing lithium and the extracts composition as described in claim any one of 1-5；Or containing lithium
Bittern and N, N- dihexyl benzamide.
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| CN113061722A (en) * | 2021-03-22 | 2021-07-02 | 湘潭大学 | Extraction method for separating calcium from low-temperature calcium-containing brine to extract lithium and application of extraction method |
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