CN107619928A - A kind of extracts composition, extraction system and its application - Google Patents
A kind of extracts composition, extraction system and its application Download PDFInfo
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Abstract
The invention discloses a kind of extracts composition, extraction system and its application.The extracts composition of the present invention includes extractant and the neutral phosphorus oxygen class compound as shown in formula A；Described extractant includes N, N bis- (2 ethylhexyl) 2 methyl propanamides, but does not include N, N bis- (2 ethylhexyl) acetamide.The present invention is extractant by selecting the amides compound of specific structure and the mixture of neutral phosphorus oxygen class compound, and 89.61% is up to the Li of the bittern containing lithium extraction yield；Lithium magnesium distribution coefficient is up to 823；When being stripped lithium with HCl, stripping rate is up to 89.46%, and it extracts the extraction of lithium salts from bittern containing lithium and back extraction performance greatly improves, cost-effective, is more suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of extracts composition, extraction system and its application.
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.
Bittern containing lithium is the valuable source of lithium.China has the abundant lithium resource of bittern containing lithium, 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 bittern containing lithium
The pilot-plant test of lithium, applied in 1987 Chinese invention patent [3. yellow teachers are strong etc., Chinese invention patent,
CN137103431], and authorized.But the extractant employed in the system is tributyl phosphate, to extraction equipment
Corrosivity it is stronger, and the tributyl phosphate not only solution loss in water, and in long-term operating in acid medium easily
Degrade, particularly its serious swelling action to the material for making extraction equipment limit its industrial-scale should
With.
(3) CN103055539A discloses a kind of method that lithium salts is extracted from bittern containing lithium, and it uses co-extraction agent, extraction
Agent and diluent carry out the extraction of lithium, solve first two extraction system and technique and are difficult to industrialization by force to equipment corrosion
Problem, and achieve preferably extraction and back extraction performance.This method is still pure in problems, such as single-stage in industrialization process
Extraction yield is relatively low, influences yield and yield, and extraction series must be increased by wanting acquisition higher yields；The separation of lithium and magnesium, sodium, potassium
Coefficient is not big enough, and the product directly obtained can not reach high-purity requirement, it is necessary to increase washing series or other post processing modes.
Therefore, the extraction that lithium salts is extracted from bittern containing lithium and back extraction performance how are further improved, it is cost-effective, more
Suitable for industrialized production, turn into this area and need technical problems to be solved badly.
The content of the invention
The technical problems to be solved by the invention are to overcome the existing extractor body that lithium salts is extracted from bittern containing lithium
Technique present in system and technique is tediously long, cumbersome, strong to the corrosivity of equipment, extraction yield and back extraction performance are not high enough
Technical problem, and provide a kind of extracts composition, extraction system and its application.Acid amides of the invention by selecting specific structure
The mixture of class compound and neutral phosphorus oxygen class compound is extractant, and 89.61% is up to the Li of the bittern containing lithium extraction yield；
Lithium magnesium distribution coefficient is up to 823；When being stripped lithium with HCl, stripping rate is up to 89.46%, and it extracts lithium from bittern containing lithium
The extraction of salt and back extraction performance greatly improve, cost-effective, are more suitable for industrialized production.
The present invention solves above-mentioned technical problem by following technical proposals.
The invention provides a kind of extracts composition, and it includes extractant and the neutral phosphorus oxygen class compound as shown in formula A；
Described extractant includes N, N- bis- (2- ethylhexyls) -2- methyl propanamides, but does not include N, N- bis- (2- ethylhexyls) second
Acid amides；
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 or 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 preferably independently C1-C8Straight chain or with branch
The alkyl of chain, or C1-C8Straight chain or branched alkoxy；Wherein, described C1-C8Straight chain or branched alkyl are preferred
Methyl, 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, isobutyl oxygen
Base, 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：
In described extracts composition, described extractant and the neutral phosphorus oxygen class compound as shown in formula A
Volume ratio can be the such extraction system conventional proportions in this area.Described extractant and the neutral phosphorus oxygen as shown in formula A
The volume ratio of class compound is preferably 9:1-1:9, more preferably 5:2-2:5 (such as 2:1), more preferably 5:4-2:3 (examples
Such as 1:1).
In described extractant, other amides compounds are preferably also can further include；Other described amide-types
Compound is preferably chosen from the one or more in amides compound as follows：
When described extractant further includes other amides compounds as described above, other described amide-types
The dosage of compound can be not especially limited, as long as not influenceing extraction and the back extraction performance of described extractant.It is described
N, N- bis- (2- ethylhexyls) preferred 0.01%-99.9% of the content of -2- methyl propanamides in extractant, more preferably
10%-60%.The volume ratio of described N, N- bis- (2- ethylhexyls) -2- methyl propanamides and other amides compounds is preferred
For 4:1-1:4, more preferably 1:1.
Described extracts composition also can further include diluent.Described diluent can be the conventional dilution in this area
Boiling point is greater than or equal to 100 DEG C of aliphatic hydrocarbon (such as n-dodecane) or aromatic hydrocarbon under agent, preferably normal pressure, or kerosene.
The dosage of described diluent can be not especially limited, as long as not influenceing the extraction ability of extractant.Described diluent
Volume content preferred 10%-80%, most preferably further preferred 10%-50%, 20%-40%, described percentage refers to
The volume of diluent accounts for the percentage of described extracts composition cumulative volume.
It is described when also including other compositions except extractant and neutral phosphorus oxygen class compound in described extracts composition
The preferred 20%-90% of volume content in the extracts composition of extractant and described neutral phosphorous oxides, more preferably
50%-80%, most preferably 60%-70% (percentage by 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 1:1-1.75:1, more preferably 1.3:1-1.5:1.
Described extractant is preferably by N, and the mixture and/or N, N- dihexyl of N- dihexyl propionamides are to toluyl
Amine and N, N- bis- (2- ethylhexyls) -2- methyl propanamides form.
Described extracts composition is preferably as described extractant and the neutral phosphorus oxygen class compound as shown in formula A
Composition.
Neutral phosphorus oxygen class compound and institute of the described extracts composition more preferably as described extractant, as shown in formula A
The diluent composition stated.
Neutral phosphorus oxygen class compound of the described extracts composition further preferably as described extractant, as shown in formula A,
Described diluent and described co-extraction agent composition.
Present invention also offers a kind of extraction system, and it includes foregoing extracts composition and bittern containing lithium.
In described extraction system, the volume ratio of extracts composition organic phase and the bittern containing lithium can be this area
Conventional volume ratio, preferably 1:More than 5, such as 1:2-10:1 (such as 1:1), more preferably 2:1-6:1.It is described in the present invention
Extracts composition organic phase does not include co-extraction agent typically.
Present invention also offers a kind of foregoing extracts composition to extract from bittern containing lithium or be stripped in lithium
Application.
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, balanced oscillations, 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, balanced oscillations, stratification, lithium ion must be loaded
Organic phase；
(2) organic phase of described load lithium ion is mixed with the aqueous solution of acid, balanced oscillations, stratification, 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 extracts composition organic phase and the bittern containing lithium can be the conventional volume ratio in this area, excellent
Select 1:More than 5, such as 1:2-10:1 (such as 1:1), more preferably 2:1-6:1.In the present invention, described extracts composition organic phase
Extracts composition when generally referring to not include co-extraction agent.
The described application extracted from bittern containing lithium is stripped in the applying step (1) of lithium, institute from bittern containing lithium
The temperature of the extracts composition and the bittern containing lithium is preferably 10 DEG C -50 DEG C (such as 25 DEG C -40 during the balanced oscillations stated
DEG C), i.e., the operation of balanced oscillations is carried out at 10 DEG C -50 DEG C.The time of described balanced oscillations can be this area it is conventional when
Between, preferred 5-30 minutes.
Described is stripped in the applying step (2) of lithium from bittern containing lithium, the molar concentration of the described sour aqueous solution
Preferably 0.5mol/L-12.0mol/L, more preferably 4mol/L-10mol/L, more preferably 6mol/L-8mol/L, it is described
Molar concentration refer to acid material amount account for acid aqueous solution cumulative volume ratio.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 in this area, and the present invention preferably contains high Mg/Li ratio
Bittern containing lithium, Mg/Li ratio preferably 2~30 (such as 16) in described high Mg/Li ratio.Described bittern containing lithium preferably comprises：
0.02mol/L-2.0mol/L (such as 0.144mol/L, 0.29mol/L) Li+, 2.0mol/L-5.0mol/L (such as 4mol/
L, 4.32mol/L, 4.64mol/L) Mg2+, 0mol/L-0.5mol/L (0.05mol/L, 0.1mol/L, 0.4mol/L) Na+, 0mol/L-0.5mol/L (such as 0.02mol/L, 0.4mol/L) K+, >=6mol/L (such as 9.2mol/L, 9.8mol/L,
Cl 10.7mol/L)-, 0mol/L-0.90mol/L (0.01mol/L, 0.1mol/L) B2O3And 0.001mol/L-0.5mol/
L (such as 0.04mol/L, 0.05mol/L, 0.3mol/L) H+(bittern acidity), remaining is water.
In the present invention, described normal pressure refers to 1 atmospheric pressure, i.e. 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 can also use the operation such as stirring, and its purpose is to organic phase is mixed with water conjunction
Uniformly.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：Amides compound and neutral phosphor of the invention by selecting specific structure
The mixture of oxygen class compound is extractant, and 89.61% is up to the Li of the bittern containing lithium extraction yield；Lithium magnesium distribution coefficient is up to
823；When being stripped lithium with HCl, stripping rate is up to 89.46%, and it extracts the extraction and back extraction of lithium salts from bittern containing lithium
Performance greatly improves, cost-effective, is more suitable for industrialized 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.Unless otherwise instructed, the number being related in the following example refers both to volume parts.
In following embodiments, compare, the basic conception of distribution ratio, extraction yield and extract and separate factor etc. it is as follows：
(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,
The ratio between total concentration of the material in extraction organic phase (O) and total concentration in feed liquid phase (A) are extracted, is 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.
1~embodiment of embodiment 7
Organic phase：Extractant+neutral phosphorus oxygen class compound+diluent
Aqueous phase：Bittern containing lithium
Compared to (O:A organic phase and aqueous phase volume ratio) are represented.
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 -30 minutes 5 minutes), stratification (organic phase and aqueous phase containing lithium ion after being balanced).Respectively
Measure Li in balance aqueous phase and organic phase+、Na+、K+And Mg2+Concentration, thus calculate Li extraction yield, Li+、Mg2+、Na+With
K+Distribution ratio, Li/Mg, Li/Na and Li/K separation.
Embodiment 8
Organic phase：Extractant+neutral phosphorous oxides+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 organic phase, then adds aqueous phase, balanced oscillations (duration of oscillation
For 30 minutes), stratification, aqueous phase and the organic phase containing lithium ion must be balanced.Li in balance aqueous phase and organic phase is measured respectively+、Na+、K+And Mg2+Concentration, thus calculate Li extraction yield, Li+、Mg2+、Na+And K+Distribution ratio, Li/Mg, Li/Na,
With Li/K separation.
The experimental implementation of comparative example 1~4 is the same as embodiment 1.
Embodiment 1-8 and comparative example 1-4 details are as shown in Table 1, 2 and 3.
The composition of the bittern containing lithium and concrete content (mol/L) in the embodiment 1-8 of table 1 and comparative example 1-4
Extraction conditions and operating parameter in the embodiment 1-8 of table 2 and comparative example 1-4
The embodiment 1-8 of table 3 and comparative example 1-4 extraction results
Note：In addition to being in three-phase after the extraction of comparative example 2, other embodiment and comparative example split-phase effect are good, and aqueous phase is colourless, and two
Boundary is clear.
Embodiment 11
One effective extraction system, excellent extraction ability is not only required, and to have good back extraction
Energy.
Organic phase：The organic phase containing lithium obtained in embodiment 2,7 and comparative example 5,6；
Aqueous phase：6mol/L aqueous hydrochloric acid solution；
Compared to (O/A)=30:1；
It is respectively that the organic phase containing lithium after extraction equilibrium in 30 parts of above-described embodiments 2,7 and 1 part of 6mol/L hydrochloric acid is water-soluble
Liquid mixes, and vibrates 10 minutes, is stripped, stratification at 25 DEG C.Determine lithium concentration in stripping equilibria two-phase.
Design parameter and result see below list 4.
Extracts composition is 20%N wherein in comparative example 5, and N- bis- (2- ethylhexyls) acetamide+30%TBP+ kerosene is right
Extracts composition is 80%TBP+ kerosene in ratio 6, and its organic phase lithium concentration each loaded sees below list 4.(referring to
Patent CN103055539 A)
The back extraction result of the embodiment 2,7 of table 4 and comparative example 5,6
Preparation example 1：The preparation of extractant
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- bis- (2- ethylhexyls) acetamide, yield:90%；138~
143℃/9×10-2mba；1H NMR(400MHz,CDCl3)δ3.13-3.34(m,2H),3.14(d,2H),2.09(s,1H),
1.59-1.68(m,2H),1.23-1.39(m,16H),0.85-0.91(m,12H)；13CNMR(100MHz,CDCl3)δ
170.903,52.095,48.311,38.284,36.898,30.561,30.473,28.752,28.716,23.859,
23.764,23.035,22.991,21.970,14.022,13.985,10.806,10.638；IR(thin film):2961,
2929,2873,2857,1651,1463,1379,1234,1185,1037cm-1；MS(ESI):284.7(M++1),306.3(M++
Na)；EA:calcd.for C18H37NO:C,76.26；H,13.14；N,4.94,Found:C,76.29；H,13.19；N,4.91.
12H)；13CNMR(100MHz,CDCl3)δ177.789,51.422,49.091,38.950,37.083,30.529,30.459,
30.250,28.771,28.716,23.851,23.720,23.053,23.007,19.575,14.036,14.005,10.868,
10.651；IR(thin film):2960,2929,2873,1647,1467,1430,1380,1220,1126,1085cm-1；MS
(ESI):312.7(M++1),334.3(M++Na)；EA:calcd.for C20H41NO:C,77.10；H,13.27；N,4.50,
Found:C,76.98；H,13.59；N,4.76.
δ
3.28-3.30(m,4H),1.60-1.63(m,2H),1.18-1.32(m,25H),0.85-0.89(m,12H)；13CNMR
(100MHz,CDCl3)δ178.355,39.492,30.545,29.220,29.166,29.096,28.988,28.895,
23.875,23.053,14.036,11.077,11.030,10.984；IR(thin film):2959,2929,2873,1633,
1464,1412,1379,1364,1187,1120cm-1；MS(ESI):326.7(M++1)；EA:calcd.for C21H43NO:C,
77.47；H,13.31；N,4.30,Found:C,77.54；H,13.38；N,4.49.
N, N- dihexyl acetamide, yield:97%；130~142 DEG C/6 ×
10-2mba；1H NMR(400 MHz,CDCl3)δ3.27(t,2H),3.14(t,2H),2.07(s,3H),1.50-1.53(m,
4H),1.27-1.28(m,12H),0.85-0.88(m,6H)；13CNMR(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.
3.13-3.35(m,2H),2.33(dd,2H),1.14-1.16(m,4H),1.20-1.35(m,12H),1.13(t,3H),0.81-
0.91(m,6H)；13CNMR(100MHz,CDCl3)δ173.373,47.913,45.992,31.544,31.464,29.003,
27.702,26.609,22.558,13.966,9.682；IR(thin film):2957,2929,2858,1651,1465,
1425,1375,1193,1074cm-1；MS(ESI):242.7(M++1),264.3(M++Na)；EA:calcd.for C15H31NO:
C,74.63；H,12.94；N,5.80,Found:C,74.05；H,13.48；N,5.98.
3.19-3.30(m,4H),2.69-2.76(m,1H),1.46-1.55(m,4H),1.21-1.35(m,12H),1.11(s,3H),
1.09(s,3H),0.83-0.91(m,6H)；13CNMR(100MHz,CDCl3)δ176.821,31.544,30.119,26.571,
22.558,19.699,13.966；IR(thin film):2959,2929,2858,1644,1470,1425,1378,1135,
1085cm-1；MS(ESI):256.7(M++1),278.3(M++Na)；EA:calcd.for C16H33NO:C,75.23；H,13.02；
N,5.48,Found:C,74.88；H,13.40；N,5.87.
1.48-1.63(m,4H),1.00-1.48(m,12H),0.61-0.74(m,6H)；13CNMR(100MHz, CDCl3)δ
171.638,137.296,134.523,130.549,128.992,128.860,128.829,128.310,128.155,
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.
3.30-3.48(m,2H),3.19-3.29(m,2H),2.36(s,3H),1.42-1.65(m,4H),1.00-1.39(m,12H),
0.75-0.91(m,6H)；13CNMR(100MHz,CDCl3)δ171.832,138.970,134.322,130.611,129.550,
128.891,126.505,49.021,48.959,44.900,44.791,44.737,44.698,31.451,31.226,
28.585,28.476,28.438,28.414,28.391,28.329,27.616,27.562,27.500,27.477,27.407,
26.811,26.656,26.540,26.540,26.501,26.346,26.299,26.121,22.511,21.318,13.959；
IR(thin film):2956,2928,2858,1636,1466,1422,1378,1180,1105,1020cm-1；MS(ESI):
304.7(M++1),326.3(M++Na)；EA:calcd.for C20H33NO:C,79.15；H,10.96；N,4.62,Found:C,
78.95；H,11.04；N,4.61.
(m,4H),1.20-1.35(m,12H),0.88-1.02(m,9H)；13CNMR(100MHz,CDCl3)δ172.599,47.991,
47.952,45.907,34.953,31.529,29.081,27.717,26.671,26.547,22.558,18.924,13.966；
IR(thin film):2958,2929,2858,1647,1465,1423,1378,1297,1250,1191,1145,1093cm-1；
MS(ESI):304.7(M++1),326.3(M++Na)；EA:calcd.for C16H33NO:C,75.23；H,13.02；N,5.48,
Found:C,74.68；H,13.31；N, 5.60.
Acetoxy acetyl chloride 25g (0.183mol) 30mL dichloromethane solutions, two octodrines are added dropwise at 0 DEG C
In 52mL (0.183mol), triethylamine 31mL (0.222mol) and 150mL dichloromethane reaction bulb, reacted at room temperature after finishing
Night.Isometric water is added by the solid dissolving of generation and separates organic phase, and is done with watery hydrochloric acid, water washing, anhydrous sodium sulfate
Desolvation obtains crude product after dry.Gained crude product and 11g (0.262mol) Lithium hydroxide monohydrate are dissolved in 180mL methanol and 30mL water
In be stirred at room temperature reaction 1 hour.After most of methanol is removed in rotation, extracted with dichloromethane, watery hydrochloric acid washing, anhydrous sodium sulfate is done
Desolvation after dry, it is evaporated under reduced pressure.
1.57-1.60(m,1H),1.66-1.69(m,1H),1.22-1.27(m,16H),0.85-0.90(m,12H)；13CNMR
(100MHz,CDCl3)δ172.033,59.905,49.044,48.587,37.610,36.641,30.475,28.763,
28.631,23.797,23.774,23.015,22.945,14.021,13.990,10.821,10.573；IR(thin film):
3411,2959,2929,2873,2859,1648,1464,1404,1380,1278,1087cm-1；MS(ESI):300.8(M++
1),322.4(M++Na)；EA:calcd.for C18H37NO2:C,72.19；H,12.45；N,4.68,Found:C,72.10；H,
12.67；N,4.90.
Ethoxyacetic acid 40mL (0.423mol) is placed in 250mL flasks, add 38mL (0.443mol) oxalyl chlorides and
A few drop pyridines are used as catalyst, after 80 DEG C of back flow reactions 2 hours, revolve after removing excessive oxalyl chloride, are made into 50% dichloromethane
Alkane solution is placed in dropping funel, and two octodrine 100mL (0.333mol), triethylamine 51mL are added dropwise at 0 DEG C
In the reaction bulb of (0.368mol) and 250mL dichloromethane, reacted at room temperature overnight after finishing.Isometric water is added by generation
Solid dissolving simultaneously separates organic phase, and with watery hydrochloric acid, water washing, desolvation obtains crude product after anhydrous sodium sulfate drying, and decompression is steamed
Evaporate.
2H),3.12(d,2H),1.65-1.67(m,1H),1.55-1.57(m,1H),1.20-1.26(m,19H),0.75-0.91(m,
12H)；13C NMR(100MHz,CDCl3)δ169.864,69.775,66.777,50.594,50.570,50.067,47.983,
37.904,36.603,35.456,35.441,30.498,30.359,28.794,28.685,28.224,28.221,23.782,
23.658,23.642,23.022,22.976,22.821,15.035,14.021,13.990,10.868,10.597,10.132,
10.101；IR(thin film):2959,2929,2873,1647,1459,1379,1276,1229,1112,1030cm-1；MS
(ESI):304.7(M++1),326.3(M++Na)；EA:calcd.for C20H41NO2:C,73.34；H,12.62；N,4.28,
Found:C,72.53；H,12.92；N,4.50. .
Claims (12)
1. a kind of extracts composition, it is characterised in that it includes extractant and the neutral phosphorus oxygen class compound as shown in formula A；Institute
The extractant stated includes N, N- bis- (2- ethylhexyls) -2- methyl propanamides, but does not include N, N- bis- (2- ethylhexyls) acetyl
Amine；
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 or 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 neutral phosphorus oxygen class chemical combination as shown in formula A
In thing, R1And R2It independently is 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 third
Epoxide, isopropoxy, n-butoxy, isobutoxy, 1- methyl-heptan epoxide or 2- ethyls-hexyloxy.
3. extracts composition as claimed in claim 1 or 2, it is characterised in that the neutral phosphorus oxygen class as shown in formula A
Compound is the one or more in following compounds：
4. extracts composition as claimed in claim 1, it is characterised in that in described extracts composition, described extractant
Volume ratio with the neutral phosphorus oxygen class compound as shown in formula A is 9:1-1:9, preferably 5:2-2:5, more preferably 5:
4-2:3。
5. extracts composition as claimed in claim 1, it is characterised in that other amide-types are also included in described extractant
Compound, other described amides compounds are preferably chosen from the one or more in following amides compounds：
6. extracts composition as claimed in claim 5, it is characterised in that when described extractant also includes other amide-types
During compound, content of (2- the ethylhexyls) -2- methyl propanamides of described N, N- bis- in extractant is 0.01%-99.9%,
It is preferred that 10%-60%；The volume ratio of (2- the ethylhexyls) -2- methyl propanamides of described N, N- bis- and other amides compounds
For 4:1-1:4, preferably 1:1.
7. the extracts composition as described in claim 1 or 5, it is characterised in that described extracts composition further comprises
Diluent；Aliphatic hydrocarbon of the boiling point greater than or equal to 100 DEG C under the preferred normal pressure of described diluent, boiling point is greater than or equal under normal pressure
One or more in 100 DEG C of aromatic hydrocarbon and kerosene；The preferred 10%-80% of volume content of described diluent, more preferably
10%-50%, further preferred 20%-40%, described percentage refer to that the volume of diluent accounts for described extracts composition
The percentage of cumulative volume；When in described extracts composition except extractant and neutral phosphorus oxygen class compound also include other compositions
When, the preferred 20%-90% of volume content of described extractant and described neutral phosphorous oxides in the extracts composition,
More preferably 50%-80%, further preferred 60%-70%.
8. the extracts composition as described in claim 1,5 or 7, it is characterised in that also further in described extracts composition
Include co-extraction agent；One or more in the described preferred ferric trichloride of co-extraction agent, ferric sulfate, ferric nitrate and ferric phosphate；It is described
Co-extraction agent dosage with the content meter of lithium in material to be extracted, described thing to be extracted preferably bittern containing lithium；Described co-extraction agent
Dosage preferably makes the mol ratio of ferric ion and lithium ion be 1:1-2:1, more preferably 1:1-1.75:1, further preferred 1.3:
1-1.5:1。
9. a kind of extraction system, it includes the extracts composition as described in claim any one of 1-8 and bittern containing lithium.
10. a kind of extracts composition as described in claim any one of 1-8 is being extracted from bittern containing lithium or is being stripped in lithium
Application.
11. application as claimed in claim 10, it is characterised in that：
The described application that lithium is extracted from bittern containing lithium comprises the following steps：Described extracts composition and bittern containing lithium are mixed
Close, balanced oscillations, stratification, you can；
The described application that lithium is stripped from bittern containing lithium comprises the following steps：(1) by described extracts composition and containing lithium
Bittern mixes, balanced oscillations, stratification, must load the organic phase of lithium ion；(2) by the organic phase of described load lithium ion
Mixed with the aqueous solution of acid, balanced oscillations, stratification, you can.
12. application as claimed in claim 11, it is characterised in that the application or described that lithium is extracted from bittern containing lithium
From bittern containing lithium be stripped lithium applying step (1) in, described extracts composition organic phase and described bittern containing lithium
Volume ratio be 1:More than 5, preferably 1:2-10:1, more preferably 2:1-6:1；Described extracts composition organic phase does not include co-extraction
Agent；
And/or the application extracted from bittern containing lithium or from bittern containing lithium be stripped lithium applying step (1) in,
The temperature of the extracts composition and the bittern containing lithium is 10 DEG C -50 DEG C, preferably 25 DEG C -40 DEG C during described balanced oscillations；
And/or the application extracted from bittern containing lithium or from bittern containing lithium be stripped lithium applying step (1) in,
The time of described balanced oscillations is 5-30 minutes；
And/or it is described be stripped from bittern containing lithium in the applying step (2) of lithium, the described sour aqueous solution it is mole dense
Spend for 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 applying step (2) of the back extraction lithium from bittern containing lithium, the acid in the described sour aqueous solution is
Inorganic acid；One or more in the preferred hydrochloric acid of described inorganic acid, sulfuric acid and nitric acid；
And/or in the applying step (2) of the back extraction lithium from bittern containing lithium, the organic phase of described load lithium ion
Volume ratio with the aqueous solution of acid is 1:1-50:1, preferably 5:1-40:1, more preferably 10:1-30:1；
And/or in the application that lithium is extracted from bittern containing lithium or the application of the back extraction lithium from bittern containing lithium,
Mg/Li ratio is 2~30, preferably 16 in described bittern containing lithium；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
For water；Described Li+The preferred 0.144mol/L-0.29mol/L of concentration；Described Mg2+The preferred 4mol/L- of concentration
4.64mol/L, more preferably 4.32mol/L；Described Na+Concentration preferred 0.05mol/L-0.4mol/L, more preferably 0.1mol/
L；Described K+The preferred 0.02mol/L-0.4mol/L of concentration；Described Cl-The preferred 9.2mol/L-10.7mol/L of concentration,
More preferably 9.8mol/L；Described B2O3The preferred 0.01mol/L-0.1mol/L of concentration；Described H+Concentration it is preferred
0.05mol/L-0.3mol/L。
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