CN107619932B - Extraction composition, extraction system and application thereof - Google Patents
Extraction composition, extraction system and application thereof Download PDFInfo
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Abstract
The invention discloses an extraction composition, an extraction system and application thereof. The extraction composition of the invention comprisesThe extraction method comprises the steps of selecting a mixture of an amide compound with a specific structure and a neutral phosphorus-oxygen compound as an extraction composition, wherein the extraction rate of L i of lithium-containing brine is more than 81%, such as 81.53% -94.69%, the lithium-magnesium distribution coefficient is more than 490, such as 490-987, and when HCl is used for lithium back extraction, the back extraction rate is 87.86% -91.68%, so that the extraction and back extraction performance of extracting lithium salt from the lithium-containing brine is greatly improved, the cost is saved, and the extraction method is more suitable for industrial production.
Description
Technical Field
The invention relates to an extraction composition, an extraction system and application thereof.
Background
Lithium has important applications not only in the defense industry, but also in the national economy, and in particular in the energy field:6l i and7l i is an important material for fuel and nuclear fission reaction of a future nuclear fusion reactor, the demand of which as a battery material is increasing, therefore, lithium is called as energy metal of 21 st century, the demand of lithium is continuously increasing at home and abroad, and the research, development and utilization of lithium resources are urgently needed.
Lithium-containing brines are an important source of lithium. China has abundant lithium-containing brine lithium resources, and the storage quantity of the lithium-containing brine lithium resources is in the forefront of the world. However, since brine contains many kinds of metal ions, the comprehensive utilization thereof and the technology of separating and extracting lithium from brine are important problems to be studied, and particularly, the technology of separating and extracting lithium from brine containing high-concentration magnesium and low-concentration lithium, namely, high magnesium-lithium ratio, is a recognized worldwide technical problem.
The solvent extraction technology is an effective technology for separating and extracting various metals from a solution, has the advantages of high separation efficiency, simple process and equipment, continuous operation, easy realization of automatic control and the like, and is considered to be one of the most promising methods for extracting and separating lithium from brine with a high magnesium-lithium ratio. Since the mid-sixties of the last century, several extraction systems and processes have been proposed at home and abroad, specifically as follows:
(1) in 1967, Nelli J.R. et al invented an extraction system and process [1.Nelli J.R. et al.Fr.1,535,818(1967)；USP3,537,813(1970).]: adding FeCl into brine3As co-extraction agent, using 80% diisobutyl ketone-20% tributyl phosphate as organic phase, using L i and Fe as L iFeCl4Formal co-extraction into the organic phase, with a large amount of MgCl in the aqueous phase2And other metals, the system has higher selectivity for L i extraction, but water back extraction produces L iCl and FeCl3The mixed solution needs to be extracted and separated again L i and Fe by a di (2-ethylhexyl) phosphoric acid-tributyl phosphate system, so that the process is long and the operation is complicated, and the application of the mixed solution in industrial production is not seen so far.
(2) In 1979, the research institute of Qinghai salt lake, Chinese academy of sciences proposed a system and a process for extracting lithium from kerosene solution of tributyl phosphate as a single extractant, thereby simplifying the extraction system, and semi-industrial experiments were conducted in 1984 for extracting lithium from lithium-containing brine of Dachai Dan, and in 1987, a Chinese patent of invention [3. Huangshi Qiang et al, Chinese patent of invention, CN107103431] was applied and granted. However, the extraction agent adopted in the system is tributyl phosphate, which has strong corrosivity to extraction equipment, and tributyl phosphate is not only dissolved and lost in water in long-term operation, but also easily degraded in an acidic medium, and particularly the severe swelling effect of tributyl phosphate on materials for manufacturing the extraction equipment limits the industrial large-scale application of tributyl phosphate.
(3) CN103055539A discloses a method for extracting lithium salt from lithium-containing brine, which adopts a co-extraction agent, an extraction agent and a diluent to extract lithium, solves the problem that the former two extraction systems and processes are highly corrosive to equipment and difficult to industrialize, and obtains better extraction and back-extraction performances. The method is still pure in various problems in the industrial process, such as low single-stage extraction rate, influence on yield and yield, and extraction stages are increased for obtaining high yield; the separation coefficient of lithium from magnesium, sodium and potassium is not large enough, the directly obtained product cannot meet the requirement of high purity, and the washing grade number or other post-treatment modes must be increased.
Therefore, how to further improve the extraction and back-extraction performance of lithium salt from lithium-containing brine, save cost, and be more suitable for industrial production becomes a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to solve the technical problems of long process, complex operation, strong corrosion to equipment, insufficient extraction rate and back-extraction performance and the like in the conventional extraction system and process for extracting lithium salt from lithium-containing brine, and provides an extraction composition, an extraction system and application thereof.
The invention provides an extraction composition, which comprises an extracting agent and a neutral phosphorus-oxygen compound shown as a formula A; the extractant comprises N, N-dihexylbenzamide, but does not comprise N, N-bis (2-ethylhexyl) acetamide:
wherein, in the neutral phosphorus oxygen compound shown as the formula A, R1Or R2Independently is C1-C12Straight-chain or branched alkyl, C1-C12Linear or branched alkoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, thienyl, pyridyl or naphthyl; said substituent of said substituted phenyl or said substituted phenoxy is one or more of the following groups: halogen, C1-C6Alkyl, hydroxy, C1-C6Alkoxy, trifluoromethyl, trifluoromethoxy, phenoxy, piperidinyl, morpholinyl, pyrrolyl, tetrahydropyrrolyl, nitro or amino; when the substituent is plural, the substituents may be the same or different.
The neutral phosphorus oxygen shown as the formula AIn the class of compounds, R1Or R2Preferably C1-C8Straight-chain or branched alkyl, or C1-C8Linear or branched alkoxy; wherein, said C1-C8The linear or branched alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-methyl-heptyl or 2-ethyl-hexyl. Said C1-C8The linear or branched alkoxy group is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 1-methyl-heptoxy or 2-ethyl-hexyloxy.
The neutral phosphorus-oxygen compound shown in the formula A is preferably selected from one or more of the following compounds:
in the extraction composition, the volume ratio of the extraction agent to the neutral phosphorus-oxygen compound shown as the formula A is preferably 9:1-1:9, more preferably 6: 1-1: 2.5, and further preferably 5: 1-1.5: 1.
The extractant can also comprise other amide compounds, and the other amide compounds are preferably N, N-dihexyl-p-methylbenzamide and/or N, N-dihexyl-N-butylamide:
when the extractant contains other amide compounds, the dosage of the other amide compounds is not particularly limited as long as the extraction and back-extraction performance of the extractant is not affected; the content of the N, N-dihexylpropionamide in the extractant is preferably 0.01% -99.9% (83%), and more preferably 50% -80%. The volume ratio of the N, N-dihexylpropionamide to the other amide compounds is preferably 5:1 to 1:5, and more preferably 4:1 to 1: 1.
The extraction composition may further comprise a diluent. The diluent can be any diluent conventional in the art, preferably an aliphatic hydrocarbon (for example n-dodecane) or an aromatic hydrocarbon with a boiling point greater than or equal to 100 ℃ at atmospheric pressure, and can also be kerosene. The amount of the diluent to be used is not particularly limited as long as the extraction performance of the extractant is not affected. The volume content of the diluent is preferably 10% -80%, more preferably 20% -50%, and even more preferably 30% -40%, and the percentage refers to the volume percentage of the diluent in the total volume of the extraction composition.
When the extraction composition contains other components in addition to the extractant and the neutral phosphorus oxy-compound, the extractant and the neutral phosphorus oxide are preferably present in the extraction composition in an amount of 20% to 90%, more preferably 50% to 80%, and most preferably 60% to 70% by volume.
The extraction composition may further comprise a co-extractant. The co-extractant can be dissolved in the water phase firstly during extraction, and can also be stabilized in the organic phase firstly. The co-extractant generally refers to ferric salt capable of obviously improving the extraction rate of lithium, and can be one or more of ferric trichloride, ferric sulfate, ferric nitrate and ferric phosphate, and preferably is ferric trichloride. The dosage of the co-extraction agent can be the conventional dosage in the field of extracting and back-extracting lithium, and is generally calculated according to the content of lithium in a substance to be extracted, and the substance to be extracted is preferably lithium-containing brine; the amount of the co-extractant used is generally such that the molar ratio of ferric ions to lithium ions is from 1:1 to 2:1, more preferably from 1:1 to 1.75:1, and still more preferably from 1.3:1 to 1.5: 1.
The extractant is preferably N, N-dihexylbenzamide.
The extractant further preferably consists of N, N-dihexylbenzamide, and N, N-dihexylp-methylbenzamide and/or N, N-dihexyln-butylamide.
The extraction composition preferably consists of the extraction agent and the neutral phosphorus-oxygen compound shown as the formula A.
The extraction composition further preferably comprises the extractant, the neutral phosphorus oxygen compound shown in the formula A and the diluent.
The extraction composition more preferably consists of the extractant, the neutral phosphorus oxygen compound shown in the formula A, the diluent and the co-extractant.
The invention also provides an extraction system comprising an extraction composition as described above and a lithium-containing brine.
The volume ratio of the organic phase of the extraction composition to the lithium-containing brine in the extraction system can be any volume ratio conventional in the art, preferably 1:5 or more, for example 1:2 to 10:1 (e.g., 1:1), more preferably 2:1 to 6: 1. In the present invention, the organic phase of the extraction composition generally refers to the extraction composition when no co-extractant is included.
The extraction system refers to a system before oscillation equilibrium.
The invention also provides the use of an extraction composition as hereinbefore described for extracting or stripping lithium from lithium-containing brines.
The application of extracting lithium from lithium-containing brine preferably comprises the following steps: mixing the extraction composition with lithium-containing brine, oscillating for balancing, and standing for layering.
The use of stripping lithium from lithium-containing brine preferably comprises the steps of:
(1) mixing the extraction composition with lithium-containing brine, oscillating for balancing, standing for layering to obtain an organic phase loaded with lithium ions;
(2) and mixing the lithium ion loaded organic phase with an acid aqueous solution, oscillating for balancing, and standing for layering.
In the application of extracting lithium from lithium-containing brine or the application of back-extracting lithium from lithium-containing brine, mass transfer is carried out by oscillation. In addition, the mass transfer and phase separation process can be completed by means of extraction equipment such as a centrifugal extractor, a mixing and clarifying tank, an extraction tower and the like. The centrifugal extractor, the mixer-settler and the extraction tower can be conventional extraction equipment in the field, and the using conditions and the method can refer to the conventional using conditions and the method for extracting lithium from the lithium-containing aqueous solution.
In the application of extracting lithium from lithium-containing brine or the application step (1) of extracting lithium from lithium-containing brine, the volume ratio of the organic phase of the extraction composition to the lithium-containing brine can be a volume ratio conventional in the art, and is preferably 1:5 or more, for example, 1:2 to 10:1 (e.g., 1:1), and more preferably 2:1 to 6: 1. In the present invention, the organic phase of the extraction composition generally refers to the extraction composition when no co-extractant is included.
In the step (1) of extracting from lithium-containing brine or extracting lithium from lithium-containing brine, the temperature of the extraction composition and the lithium-containing brine is preferably 10 ℃ to 50 ℃ (for example, 25 ℃ to 40 ℃) during the oscillating equilibrium, that is, the oscillating equilibrium is performed at 10 ℃ to 50 ℃. The period of equilibration of the oscillation may be conventional in the art, preferably 5 to 30 minutes.
In the step (2) of applying the lithium back-extraction from the lithium-containing brine, the molar concentration of the aqueous acid solution is preferably 0.5 mol/L-12.0 mol/L, more preferably 4 mol/L-10 mol/L, more preferably 6 mol/L-8 mol/L, and the molar concentration refers to the ratio of the amount of the substance of the acid to the total volume of the aqueous acid solution.
In the invention, the lithium-containing brine can be conventional lithium-containing brine in the field, the invention preferably selects the lithium-containing brine with high magnesium-lithium ratio, the magnesium-lithium ratio in the high magnesium-lithium ratio is preferably 2-30 (such as 16), and the lithium-containing brine preferably comprises L i with 0.02 mol/L-2.0 mol/L (such as 0.144 mol/L and 0.29 mol/L)+2.0 mol/L-5.0 mol/L (e.g. 4 mol/L, 4.32 mol/L, 4.64 mol/L) of Mg2+0 mol/L-0.5 mol/L (0.05 mol/L, 0.1 mol/L, 0.4 mol/L) of Na+K of 0 mol/L-0.5 mol/L (e.g. 0.02 mol/L, 0.4 mol/L)+And ≧ 6 mol/L (e.g., 9.2 mol/L, 9.8 mol/L, 10.7 mol/L) Cl-0 mol/L-0.90 mol/L (0.01 mol/L, 0.1 mol/L) of B2O3And H from 0.001 mol/L to 0.5 mol/L (e.g., 0.04 mol/L, 0.05 mol/L, 0.3 mol/L)+(acidity of brine), and the balance of water.
The volume ratio or volume fraction in the present invention refers to the volume ratio or volume fraction of each of the above substances at room temperature.
In the present invention, room temperature generally means 10 ℃ to 30 ℃.
In the invention, the oscillation operation can also be stirring operation and the like, and the action of the oscillation operation can be to uniformly mix the organic phase and the water phase.
In the invention, the normal pressure refers to 1 atmosphere and 101.325 kPa.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The invention has the positive effects that the extraction rate of L i of lithium-containing brine is more than 81 percent, such as 81.53-94.69 percent, the lithium-magnesium distribution coefficient is more than 490, such as 490-987 percent, and the back extraction rate is 87.86-91.68 percent when HCl is used for back extraction of lithium, thereby greatly improving the extraction and back extraction performance of lithium salt from the lithium-containing brine, saving the cost and being more suitable for industrial production by selecting the mixture of the amide compound with a specific structure and the neutral phosphorus-oxygen compound as the extraction composition.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The parts referred to in the following examples are parts by volume
In the following examples, basic concepts of phase comparison, distribution ratio, extraction separation factor, and the like.
(1) Compare
For a batch extraction process, the volume of organic phase extracted, V (m)3) And feed liquid water phase L (m)3) The ratio of the two is called the phase ratio; for a continuous extraction process, the extract phase volume flow rate V (m)3S) and liquid phase volume flow rate L (m)3The ratio/s), also referred to as phase ratio or two-phase flow ratio, is herein collectively referred to as O/A for two-phase volume or flow. Compared with the formula shown by R:
in the formula: voVolume of the extract phase, VaIs the volume of the feed liquid phase
(2) Extraction rate
The extraction rate is the percentage of the extracted material transferred from the feed liquid phase to the extraction phase in the extraction process to the total amount of the extracted material in the feed liquid phase, and represents the degree of extraction separation. The formula for calculating the extraction rate E (%) is:
in the formula: n isaN is the amount of extracted material in the feed solutionoThe amount of extracted material in the raffinate.
(3) Distribution ratio
The distribution ratio is also called the distribution coefficient. The partitioning behavior of extracted substance a in the two phases can be understood as the overall effect of a partitioning of a in the two phases in the various forms a1, a 2. In general, the experimentally determined values represent the total concentration of the various forms of extracted material present in each phase. The system partition coefficient is defined as the ratio of the total concentration of extracted substances in the extraction organic phase (O) to the total concentration in the feed liquid phase (A) under certain conditions when the system reaches equilibrium, and is represented by D:
the partition ratio represents the actual partition ratio of the extracted substances in the two phases after the extraction system reaches equilibrium and is generally determined experimentally. The larger the distribution ratio of the extracted substance is, the easier the substance is to be extracted, and the distribution ratio is related to the extraction conditions, such as the concentration and acidity of the extracted substance in the aqueous phase, other coexisting substances, the type and concentration of the extractant in the organic substance, the type of the diluent, the temperature during extraction, and the like.
(4) Separation factor
When extraction separation is performed under certain conditions, the ratio of the extraction distribution ratio of two substances to be separated between two phases, which is called extraction separation factor, also called extraction separation coefficient, is usually represented by β, if A, B represents two substances to be separated respectively, there are:
in the formula: dAIs the distribution ratio of A substance, DBThe distribution ratio of the B substance is shown.
The extraction separation coefficient quantitatively shows the difficulty of separating two substances in a liquid phase of a certain extraction system, when the β value is 1, the two substances cannot be separated, and the larger or smaller the β value is, the better the separation effect is, namely, the higher the separation selectivity of the extractant is.
Example 1 to example 7:
organic phase: extracting agent, neutral phosphorus-oxygen compound and diluent
Water phase: lithium-containing brine
The ratio (O: A) represents the volume ratio of the organic phase to the aqueous phase.
The specific operation is as follows:
adding a certain amount of FeCl3Adding the (co-extraction agent) into lithium-containing brine, shaking to dissolve, adding the organic phase, oscillating for balancing (oscillation time is 5-30 min), standing for layering (obtaining a balanced organic phase containing lithium ions and a balanced aqueous phase), and respectively measuring L i in the balanced aqueous phase and the balanced organic phase+、Na+、K+And Mg2+The extraction rate of L i, L i, was calculated from the concentration of (b)+、Mg2+、Na+And K+Partition ratio of L i/Mg, L i/Na, and L i/K.
Example 8
Organic phase: extracting agent, neutral phosphorus oxide and diluent;
water phase: a lithium-containing brine;
comparison (O: A): refers to the volume ratio of the organic phase to the aqueous phase;
the specific operation is as follows:
adding a certain amount of FeCl3Adding the co-extraction agent into the organic phase, adding the aqueous phase, oscillating for balancing (oscillation time is 30 min), standing for layering to obtain balanced aqueous phase and lithium ion-containing organic phase, and measuring L i in the balanced aqueous phase and the organic phase respectively+、Na+、K+And Mg2+The extraction rate of L i, L i, was calculated from the concentration of (b)+、Mg2+、Na+And K+Partition ratio of L i/Mg, L i/Na, and L i/K.
The experimental procedures of comparative examples 1 to 4 were the same as those of example 8.
The lithium-containing brine parameters in examples 1 to 8 and comparative examples 1 to 4 are shown in Table 1:
TABLE 1 content of ions in lithium-containing brines (mol/L)
| Li+ | Mg2+ | Na+ | K+ | Cl- | B2O3 | H+ | |
| Example 1 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Example 2 | 0.144 | 4.32 | 0.05 | 0.4 | 9.2 | 0.1 | 0.05 |
| Example 3 | 2 | 4.00 | 0.4 | 0.02 | 10.7 | 0 | 0.3 |
| Example 4 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Example 5 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Example 6 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Example 7 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Example 8 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Comparative example 1 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Comparative example 2 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Comparative example 3 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
| Comparative example 4 | 0.29 | 4.64 | 0.1 | 0.02 | 9.8 | 0.01 | 0.05 |
The reaction conditions and parameters of examples 1 to 8 and comparative examples 1 to 4 are shown in Table 2:
TABLE 2 reaction conditions and parameters
The reaction results of examples 1 to 8 and comparative examples 1 to 4 are shown in Table 3:
TABLE 3 reaction results
Example 9 Back extraction
Adding a certain amount of FeCl3(Co-extraction agent) 60 parts by volume of lithium-containing brine (FeCl) was added3The amounts and the contents of the components in the lithium-containing brine are shown in examples 2, 4, 9 and comparative example 4), after shaking to dissolve them, 30 parts by volume of the organic phase in examples 2, 4, 9 and comparative example 4 was added, shaking was carried out for 10 minutes to extract and obtain a lithium ion-loaded organic phase, 30 parts by volume of the lithium ion-loaded organic phase was mixed with 1 part by volume of 6 mol/L aqueous hydrochloric acid solution, shaking was carried out for 10 minutes at 25 ℃ to carry out back extraction, and the layer was left to stand and separate, and L i of the two phases in the back extraction equilibrium was measured+And (4) concentration. Specific parameters are shown in table 4 below.
FeCl in comparative example 53The amounts and contents of the components in the lithium-containing brine were the same as in comparative example 4.
TABLE 4 stripping conditions
Example 10 preparation of extractant:
general procedure for the experiments dialkylamine 1mol, 400m L dichloromethane and 153m L (1.1mol) triethylamine were added to a three-necked flask equipped with thermometer, constant pressure dropping funnel, mechanically stirred 2L, stirring was turned on and the system was cooled to 0 ℃ while a solution of 1.05mol of acid chloride and about 200m L dichloromethane was placed in the dropping funnel and dropping was started, the temperature of the system was maintained at 15 ℃ and dropping was completed for about 30 minutes, the ice bath was removed and the reaction was allowed to proceed overnight at room temperature, an equal volume of water was added to dissolve the resulting solid, the separating funnel was layered and the organic phase was washed with dilute hydrochloric acid and saturated brine, dried over anhydrous sodium sulfate and, after removal of the solvent, distilled under reduced pressure, where Yield is Yield, ir (thin film method), analysis is EA is elementary analysis, calcd.
The compound N, N-di (2-ethylhexyl) acetamide
90 percent of N, N-di (2-ethylhexyl) acetamide YIeld, 138-143 ℃/9 × 10-2mba；1H NMR(400MHz,CDCl3)3.13-3.34(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)；13C NMR(100MHz,CDCl3)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.
Compound N, N-dihexylbenzamide
Compound N, N-dihexyl p-methylbenzamide
Compound N, N-dihexyl N-butylamide
The compound N, N-di (2-ethylhexyl) tert-butyramide
The compound N, N-bis (2-ethylhexyl) -2-hydroxyacetamide
Acetoxyacetyl chloride 25g (0.183mol) in dichloromethane 30m L is added dropwise into a reaction bottle containing diisooctylamine 52m L (0.183mol), triethylamine 31m L (0.222mol) and dichloromethane 150m L at 0 ℃, after the addition is finished, the reaction is carried out at room temperature overnight, equal volume of water is added to dissolve the generated solid and separate out an organic phase, diluted hydrochloric acid and water are used for washing, anhydrous sodium sulfate is used for drying and then the solvent is removed to obtain a crude product, the obtained crude product and 11g (0.262mol) of lithium hydroxide monohydrate are dissolved in methanol 180m L and water 30m L for stirring reaction at room temperature for 1 hour, most of the methanol is removed by rotation, the extraction is carried out by dichloromethane, diluted hydrochloric acid is used for washing, the anhydrous sodium sulfate is used for drying and then the solvent is removed, and reduced pressure distillation is carried out.
The compound N, N-di (2-ethylhexyl) -2-ethoxyacetamide
Ethoxyacetic acid 40m L (0.423mol) is placed in a 250m L flask, 38m L (0.443mol) oxalyl chloride and a few drops of pyridine are added as catalysts, after reflux reaction is carried out for 2 hours at 80 ℃, excessive oxalyl chloride is removed, a 50% dichloromethane solution is prepared and placed in a dropping funnel, the solution is dropwise added into a reaction bottle of diisooctylamine 100m L (0.333mol), triethylamine 51m L (0.368mol) and 250m L dichloromethane at 0 ℃, reaction is carried out at room temperature overnight after the addition is finished, equal volume of water is added to dissolve generated solid and separate out an organic phase, diluted hydrochloric acid and water are used for washing, anhydrous sodium sulfate is dried, a solvent is removed to obtain a crude product, and reduced pressure distillation is carried out.
Yield:81％；165～172℃/7×10-2mba；1H NMR(400MHz,CDCl3)4.12(s,2H),3.55(dd,2H),3.20-3.31(m,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)169.864,69.775，66.777,50.594，50.570，50.067，47.983,37.904,36.603,35.456，35.441，30.498,30.359,28.794,28.685,28.224，28.221，23.782,23.658,23.642,23.022，22.976,22.821,15.035，14.021,13.990,10.868,10.597，10.132，10.101；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 (26)
1. An extraction composition is characterized by comprising an extracting agent and a neutral phosphorus-oxygen compound shown as a formula A; the extractant comprises N, N-dihexylbenzamide, but does not comprise N, N-bis (2-ethylhexyl) acetamide:
wherein, in the neutral phosphorus oxygen compound shown as the formula A, R1Or R2Independently is C1-C12Straight-chain or branched alkyl, C1-C12Linear or branched alkoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, thienyl, pyridyl or naphthyl; said substituent of said substituted phenyl or said substituted phenoxy is one or more of the following groups: halogen, C1-C6Alkyl, hydroxy, C1-C6Alkoxy, trifluoromethyl, trifluoromethoxy, phenoxy, piperidinyl, morpholinyl, pyrrolyl, tetrahydropyrrolyl, nitro or amino; when the substituent is plural, the substituents may be the same or different.
2. The extraction composition of claim 1, wherein R is the neutral phosphorus oxygen compound of formula A1Or R2Is C1-C8Straight-chain or branched alkyl, or C1-C8Linear or branched alkoxy.
3. The extraction composition of claim 2, wherein R is1Or R2In (b), the C1-C8Straight-chain or branched alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-methyl-heptyl or 2-ethyl-hexyl; said C1-C8Straight-chain or branched alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 1-methyl-heptyloxy or 2-ethyl-hexyloxy.
4. The extraction composition according to any one of claims 1 to 3,
the neutral phosphorus-oxygen compound shown in the formula A is one or more of the following compounds:
5. the extraction composition of claim 1,
the volume ratio of the extracting agent to the neutral phosphorus-oxygen compound shown as the formula A is 9:1-1: 9.
6. The extraction composition of claim 5, wherein the volume ratio of the extraction agent to the neutral phosphorus oxygen compound shown in formula A is 6: 1-1: 2.5.
7. The extraction composition of claim 6, wherein the volume ratio of the extraction agent to the neutral phosphorus oxygen compound of formula A is 5:1 to 1.5: 1.
8. The extraction composition of claim 1,
the extractant also comprises other amide compounds, wherein the other amide compounds are N, N-dihexyl-p-methylbenzamide and/or N, N-dihexyl-N-butylamide:
9. the extraction composition of claim 8,
when the extractant contains other amide compounds, the content of the N, N-dihexylpropionamide in the extractant is 0.01-99.9%.
10. The extraction composition of claim 9, wherein the N, N-dihexylpropionamide is present in the extractant in an amount of 50% to 80%;
and/or the volume ratio of the N, N-dihexylpropionamide to the other amide compounds is 5: 1-1: 5.
11. The extraction composition according to claim 10, wherein the volume ratio of the N, N-dihexylpropionamide to the other amide compounds is 4:1 to 1: 1.
12. The extraction composition of claim 1 or 8, further comprising a diluent.
13. The extraction composition of claim 12, wherein the diluent is one or more of an aliphatic hydrocarbon having a boiling point at atmospheric pressure of 100 ℃ or higher, an aromatic hydrocarbon having a boiling point at atmospheric pressure of 100 ℃ or higher, and kerosene;
and/or, the volume content of the diluent is 10-80%, and the percentage refers to the percentage of the volume of the diluent in the total volume of the extraction composition;
and/or the volume content of the extracting agent and the neutral phosphorus oxide in the extracting composition is 20-90%.
14. The extraction composition of claim 13, wherein the diluent comprises about 20% to about 50% by volume of the total extraction composition, wherein the percentages are based on the volume of the diluent;
and/or the volume content of the extractant and the neutral phosphorus oxide in the extraction composition is 50-80%.
15. The extraction composition of claim 14, wherein the diluent comprises from 30% to 40% by volume, wherein the percentage is the volume of diluent to the total volume of the extraction composition;
and/or the volume content of the extractant and the neutral phosphorus oxide in the extraction composition is 60-70%.
16. The extraction composition of claim 1, 8 or 12, further comprising a co-extractant.
17. The extraction composition of claim 16, wherein the co-extractant is one or more of ferric chloride, ferric sulfate, ferric nitrate, and ferric phosphate;
and/or, the co-extraction agent is calculated by the content of lithium in the material to be extracted, and the material to be extracted is lithium-containing brine;
and/or the dosage of the co-extraction agent is that the molar ratio of ferric ions to lithium ions is 1:1-2: 1.
18. The extraction composition of claim 17, wherein the co-extractant is used in an amount such that the molar ratio of ferric ion to lithium ion is from 1:1 to 1.75: 1.
19. The extraction composition of claim 18, wherein the co-extractant is used in an amount such that the molar ratio of ferric ion to lithium ion is from 1.3:1 to 1.5: 1.
20. An extraction system comprising the extraction composition of any one of claims 1-19 and a lithium-containing brine.
21. Use of an extraction composition according to any one of claims 1 to 19 for extracting or stripping lithium from lithium-containing brine.
22. The use of claim 21, wherein said use for extracting lithium from lithium-containing brine comprises the steps of: mixing the extraction composition with lithium-containing brine, oscillating for balancing, and standing for layering;
the application of the lithium stripping from the lithium-containing brine comprises the following steps:
(1) mixing the extraction composition with lithium-containing brine, oscillating for balancing, standing for layering to obtain an organic phase loaded with lithium ions;
(2) and mixing the lithium ion loaded organic phase with an acid aqueous solution, oscillating for balancing, and standing for layering.
23. The use of claim 22, wherein in said use of extracting lithium from a lithium-containing brine or said use of back-extracting lithium from a lithium-containing brine step (1), the volume ratio of the organic phase of the extraction composition to said lithium-containing brine is 1:5 or more; the organic phase of the extraction composition refers to the extraction composition without the co-extractant;
and/or, in said application of extraction from lithium-containing brine or application step (1) of back-extracting lithium from lithium-containing brine, the temperature of said extraction composition and said lithium-containing brine at said oscillating equilibrium is between 10 ℃ and 50 ℃;
and/or, in the application of extraction from lithium-containing brine or the application step (1) of stripping lithium from lithium-containing brine, the time of the oscillation equilibrium is 5 to 30 minutes;
and/or in the application step (2) for stripping lithium from lithium-containing brine, the molar concentration of the acid aqueous solution is 0.5 mol/L-12.0 mol/L, and the molar concentration refers to the ratio of the amount of acid substances to the total volume of the acid aqueous solution;
and/or, in the application step (2) for stripping lithium from lithium-containing brine, the acid in the acid aqueous solution is an inorganic acid; and/or in the application step (2) for back-extracting lithium from lithium-containing brine, the volume ratio of the lithium ion-loaded organic phase to the acid aqueous solution is 1:1-50: 1;
and/or in the application of extracting lithium from the lithium-containing brine or the application of back extracting lithium from the lithium-containing brine, the ratio of magnesium to lithium in the lithium-containing brine is 2-30.
24. The use of claim 23, wherein in said use of extracting lithium from a lithium-containing brine or said use of extracting lithium from a lithium-containing brine in step (1), the volume ratio of the organic phase of the extraction composition to said lithium-containing brine is from 1:2 to 10: 1;
and/or, in said application of extraction from lithium-containing brine or application step (1) of back-extracting lithium from lithium-containing brine, the temperature of said extraction composition and said lithium-containing brine at said oscillating equilibrium is between 25 ℃ and 40 ℃;
and/or in the application step (2) for stripping lithium from lithium-containing brine, the molar concentration of the aqueous acid solution is 4 mol/L-10 mol/L, and the molar concentration refers to the ratio of the amount of acid substances to the total volume of the aqueous acid solution;
and/or, in the application step (2) of the back extraction of lithium from the lithium-containing brine, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid;
and/or in the application step (2) for stripping lithium from lithium-containing brine, the volume ratio of the lithium ion-loaded organic phase to the acid aqueous solution is 5:1-40: 1;
and/or in the application of extracting lithium from the lithium-containing brine or the application of back-extracting lithium from the lithium-containing brine, the ratio of magnesium to lithium in the lithium-containing brine is 16;
and/or the lithium-containing brine comprises L i in an amount of 0.02 mol/L-2.0 mol/L+2.0 mol/L-5.0 mol/L of Mg2+0 mol/L-0.5 mol/L of Na+K of 0 mol/L-0.5 mol/L+And Cl of not less than 6 mol/L-0 mol/L-0.90 mol/L of B2O3And 0.001 mol/L-0.5 mol/L of H+And the balance of water.
25. The use of claim 24, wherein in said use of extracting lithium from a lithium-containing brine or said use of extracting lithium from a lithium-containing brine in step (1), the volume ratio of the organic phase of the extraction composition to said lithium-containing brine is from 2:1 to 6: 1;
and/or in the application step (2) for stripping lithium from lithium-containing brine, the molar concentration of the aqueous acid solution is 6 mol/L-8 mol/L, and the molar concentration refers to the ratio of the amount of acid substances to the total volume of the aqueous acid solution;
and/or in the application step (2) for stripping lithium from lithium-containing brine, the volume ratio of the lithium ion-loaded organic phase to the acid aqueous solution is 10:1-30: 1;
and/or, said lithium-containing brine, said L i+The concentration of (A) is 0.144 mol/L-0.29 mol/L;
and/or, said lithium-containing brine, said Mg2+The concentration of (A) is 4 mol/L-4.64 mol/L;
and/or, the lithium-containing brine, the Na+The concentration of (A) is 0.05 mol/L-0.4 mol/L;
and/or, said lithium-containing brine, said K+The concentration of (A) is 0.02 mol/L-0.4 mol/L;
and/or, said lithium-containing brine, said Cl-The concentration of (A) is 9.2 mol/L-10.7 mol/L;
and/or, said lithium-containing brine, said B2O3The concentration of (A) is 0.01 mol/L-0.1 mol/L;
and/or, said lithium-containing brine, said H+The concentration of (A) is 0.05 mol/L-0.3 mol/L.
26. The use according to claim 25, wherein said Mg is present2+Has a concentration of 4.32 mol/L;
and/or, the lithium-containing brine, the Na+The concentration of (A) is 0.1 mol/L;
and/or, said lithium-containing brine, said Cl-The concentration of (b) was 9.8 mol/L.
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