CN107441764B - Extraction composition, extraction system and application thereof - Google Patents
Extraction composition, extraction system and application thereof Download PDFInfo
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- CN107441764B CN107441764B CN201610382564.5A CN201610382564A CN107441764B CN 107441764 B CN107441764 B CN 107441764B CN 201610382564 A CN201610382564 A CN 201610382564A CN 107441764 B CN107441764 B CN 107441764B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an extraction composition, an extraction system and application thereof. The invention discloses an extraction composition, which comprises an extracting agent and a neutral phosphorus-oxygen compound shown as a formula A; the extractant comprises N, N-di (2-ethylhexyl) acetamide and N, N-dihexylbenzamide. According to the invention, the amide compound with a specific structure and the neutral phosphorus-oxygen compound are selected as the extracting agents, so that the extraction rate of Li in the lithium-containing brine is more than 80%, for example, 83.21% -92.68%; the distribution coefficient of lithium and magnesium is as high as more than 500, such as 537-688; when HCl is used for stripping lithium, the stripping rate is over 80 percent, such as 84.66 to 93.23 percent; the method has the advantages of greatly improving the extraction and back-extraction performance of extracting the lithium salt from the lithium-containing brine, saving the cost and being 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:6li and7li is an important material for future nuclear fusion reactor fuels and nuclear fission reactions, respectively: it is also increasingly demanded as a battery material. Therefore, lithium is called "energy metal in the 21 st century". The demand for lithium is continuously increasing at home and abroad, and thus research, development and utilization of lithium resources are urgently needed.
Salt lake brine is an important resource of lithium. China has rich lithium resources in salt lake brine, and the storage quantity of the 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); U.S. Pat. No. 3,537,813(1970).]: adding FeC1 into brine3As a co-extraction agent, 80% diisobutyl ketone-20% tributyl phosphate is used as an organic phase, and Li and Fe are used as LiFeC14Form co-extraction is carried out into an organic phase and a large amount of MgC1 is mixed with an aqueous phase2And other metals. The system has high selectivity for Li extraction, but the LiCl and FeC1 are generated by water back extraction3The mixed solution needs to be extracted and separated again by a di (2-ethylhexyl) phosphoric acid-tributyl phosphate system to separate Li and Fe, so 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 of 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 in 1984, a semi-industrial test for extracting lithium from chadan salt lake brine was carried out, and in 1987, a Chinese patent of invention [3. Huangshi Qiang et al, Chinese patent of invention, CN87103431] 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. However, the method still has 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. According to the invention, the amide compound with a specific structure and the neutral phosphorus-oxygen compound are selected as the extracting agents, so that the extraction rate of Li in the lithium-containing brine is more than 80%, for example, 83.21% -92.68%; the distribution coefficient of lithium and magnesium is as high as more than 500, such as 537-688; when HCl is used for stripping lithium, the stripping rate is over 80 percent, such as 84.66 to 93.23 percent; the method has the advantages of greatly improving the extraction and back-extraction performance of extracting the lithium salt from the lithium-containing brine, saving the cost and being more suitable for industrial production.
The invention mainly solves the technical problems through the following technical scheme.
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-di (2-ethylhexyl) acetamide and N, N-dihexylbenzamide;
wherein, in the neutral phosphorus oxygen compound shown as the formula A, R1And 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.
In the neutral phosphorus-oxygen compound shown as the formula A, R1And 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 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 in the formula A is preferably 9:1-1:9 (for example, 3:1, 4:1 or 7:4), more preferably 7:1-1:8, and even more preferably 5:1-1: 1.
In the extractant, the volume ratio of the N, N-bis (2-ethylhexyl) acetamide to the N, N-dihexylbenzamide is preferably 10:1 to 1:10, more preferably 5:1 to 1:6, and even more preferably 4:1 to 1:2 (e.g., 3:1 or 1: 1).
The extractant can further 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 amount of the other amide compounds used is not particularly limited as long as the extraction and stripping performance of the extractant is not affected. The volume content of the N, N-di (2-ethylhexyl) acetamide and the N, N-dihexyl-2-methylpropionamide in the extractant is 0.01 to 99.9 percent, preferably 10 to 40 percent; the volume ratio of the N, N-di (2-ethylhexyl) acetamide and the N, N-dihexylpropionamide to the other amide compounds is preferably 5:1 to 1:3, and more preferably 4:1 to 2:1 (e.g., 3: 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 diluent is preferably present in the extraction composition in an amount of from 10% to 80%, more preferably from 20% to 60%, most preferably from 30% to 40% (e.g. 20%, 30%, 50% and 70%) by volume, said percentage referring to the volume of diluent as a percentage of the 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 40% to 80%, and most preferably 60% to 70% (volume percent).
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 dosage which is conventional in the field of lithium-containing brine extraction and lithium back extraction, the dosage of the co-extraction agent is preferably calculated by the content of lithium in a substance to be extracted, the substance to be detected is preferably lithium-containing brine, and the dosage of the co-extraction agent is generally that the molar ratio of ferric ions to lithium ions is 1:1-2:1, more preferably 1:1-1.75:1, and even more preferably 1.3:1-1.5: 1.
The extractant preferably consists of N, N-di (2-ethylhexyl) acetamide and N, N-dihexylbenzamide.
The extractant further preferably consists of N, N-di (2-ethylhexyl) acetamide, N-dihexylbenzamide, and N, N-dihexylp-methylbenzamide and/or N, N-dihexyln-butylamide.
The extraction composition preferably consists of the extraction agent and a neutral phosphorus-oxygen compound shown as the formula A.
The extractant further preferably comprises the extractant, a neutral phosphorus-oxygen compound shown as a formula A and a 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 invention also provides the use of an extraction composition as hereinbefore described for extracting and stripping lithium from lithium-containing brines.
The use of said extraction of lithium from a lithium-containing brine preferably comprises the steps of: mixing the extraction composition with lithium-containing brine, oscillating for balancing, and standing for layering.
The use of said stripping of lithium from a 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 step (1) of the extraction of lithium from lithium-containing brine and the extraction of lithium from lithium-containing brine, mass transfer is carried out by shaking. 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 step (1) of the application of extracting lithium from lithium-containing brine and the application of extracting lithium from lithium-containing brine, the volume ratio of the organic phase of the extraction composition to the lithium-containing brine is preferably 1:5 or more, more preferably 1:1 to 10:1, and even more preferably 2:1 to 6:1, and the organic phase of the extraction composition refers to the extraction composition when no co-extractant is contained.
In the application of extracting lithium from lithium-containing brine and the application of back-extracting lithium from lithium-containing brine, the temperature of the organic phase and the aqueous phase in the oscillation equilibrium is preferably 10 ℃ to 50 ℃, and is further preferably 20 ℃ to 40 ℃ (for example 24 ℃ to 25 ℃), namely the oscillation equilibrium operation is carried out at 10 ℃ to 50 ℃ (preferably 20 ℃ to 40 ℃). The period of equilibration of the oscillation may be conventional in the art, preferably 5 to 30 minutes (e.g. 10 minutes).
In the application of the back extraction of lithium from lithium-containing brine, in the step (2), the molar concentration of the aqueous solution of the acid is preferably 0.5-12.0 mol/L, 4-10 mol/L, and more preferably 6-8 mol/L, wherein the molar concentration refers to the ratio of the amount of the substance of the acid to the total volume of the aqueous solution of the acid. The acid in the aqueous acid solution may be an acid conventional in the art, and is preferably an inorganic acid. The inorganic acid is preferably one or more of hydrochloric acid, sulfuric acid and nitric acid, more preferably hydrochloric acid. The volume ratio of the lithium ion-supporting organic phase to the aqueous acid solution may be a volume ratio conventionally used in the art, and is preferably 1:1 to 50:1, more preferably 5:1 to 40:1, and still more preferably 10:1 to 30: 1.
In the extraction and stripping processes, the extraction composition preferably comprises the extractant, the neutral phosphine oxide, the diluent and the co-extractant.
In the invention, the lithium-containing brine can be in the fieldConventional lithium-ion-containing lithium-containing brines, lithium-containing brines with high magnesium-to-lithium ratios are preferred in the present invention. The molar ratio of Mg/Li in the lithium-containing brine with high Mg/Li ratio is preferably 2-30 (for example, 16). The lithium-containing brine preferably comprises the following components in percentage by weight: 0.02mol/L-2.0mol/L Li+(e.g., 0.144mol/L-2mol/L), 2.0mol/L-5.0mol/L Mg2+(e.g., 4mol/L-4.64mol/L), 0mol/L-0.5mol/L of Na+(e.g., 0.05mol/L-0.4mol/L), 0mol/L-0.5mol/L of K+(e.g., 0.02mol/L-0.4mol/L) and Cl ≧ 6mol/L-(e.g., 9.2mol/L-10.4mol/L), 0mol/L-0.90mol/L of B2O3(e.g., 0-0.1mol/L) and 0.001mol/L-0.5mol/L of H+(e.g., 0.04mol/L-0.3mol/L) (brine acidity), and the balance water.
H in the lithium-containing brine+The concentration of (B) is preferably 0.04mol/L to 0.05 mol/L.
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.
In the invention, the normal pressure refers to 1 atmosphere and 101.325 kPa.
In the present invention, the volume ratio or volume fraction refers to the volume ratio or volume fraction of each substance at room temperature.
In the present invention, room temperature means 10 ℃ to 30 ℃.
In the present invention, the shaking operation may be performed by stirring or the like, and the purpose thereof is to uniformly mix the organic phase and the aqueous phase.
The positive progress effects of the invention are as follows:
according to the invention, the amide compound with a specific structure and the neutral phosphorus-oxygen compound are selected as the extracting agents, so that the extraction rate of Li in the lithium-containing brine is more than 80%, for example, 83.21% -92.68%; the distribution coefficient of lithium and magnesium is as high as more than 500, such as 537-688; when HCl is used for stripping lithium, the stripping rate is over 80 percent, such as 84.66 to 93.23 percent; the method has the advantages of greatly improving the extraction and back-extraction performance of extracting the lithium salt from the lithium-containing brine, saving the cost and being more suitable for industrial production.
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 preparation of the extractant referred to in the following examples is as follows:
general procedure of the experiment: in a 2L three-necked flask equipped with a thermometer, a dropping funnel having a constant pressure, and mechanical stirring, 1mol of dialkylamine, 400mL of methylene chloride, and 153mL (1.1mol) of triethylamine were charged, respectively, stirring was turned on, and the system was cooled to 0 ℃ while placing 1.05mol of acid chloride and about 200mL of a methylene chloride solution in the dropping funnel and starting the dropwise addition while keeping the temperature of the system at 15 ℃ or less, and the dropwise addition was completed in about 30 minutes. The ice bath was removed and the reaction was allowed to proceed overnight at room temperature. Adding water with the same volume to dissolve the generated solid, separating by a separating funnel, washing the organic phase by dilute hydrochloric acid and saturated saline solution, drying by anhydrous sodium sulfate, removing the solvent, and distilling under reduced pressure.
Wherein Yield is Yield, IR (thin film) is infrared (thin film method), EA is elementary analysis, calcd.
N, N-di (2-ethylhexyl) 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)；13C NMR(100MHz,CDCl3)δ170.903,52.095,48.311,38.284,36.898,30.561,30.473,28.752,28.716,23.859,23.764,23.035,22.991,21.970,14.022,13.985,10.806,10.638；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.
N, N-dihexylbenzamide
Yield:95％；138～148℃/7×10-2mba；1H NMR(400MHz,CDCl3)δ7.34-7.37(m,5H),3.35-3.54(m,2H),3.07-3.30(m,2H),1.48-1.63(m,4H),1.00-1.48(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.
N, N-dihexyl p-methylbenzamide
Yield:96％；150～170℃/7×10-2mba；1H NMR(400MHz,CDCl3)δ7.16-7.18(m,2H),7.19-7.26(m,2H),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)；13C NMR(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.
N, N-dihexyl N-butylamide
Yield:93％；126～136℃/6×10-2mba；1H NMR(400MHz,CDCl3)δ3.12-3.27(m,4H),2.26(t,2H),1.60-1.71(m,2H),1.42-1.55(m,4H),1.20-1.35(m,12H),0.88-1.02(m,9H)；13C NMR(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.
N, N-di (2-ethylhexyl) tert-butyramide
N, N-bis (2-ethylhexyl) -2-hydroxyacetamide
A solution of acetoxyacetyl chloride (25 g, 0.183mol) in methylene chloride (30 mL) was added dropwise to a reaction flask containing diisooctylamine (52 mL, 0.183mol), triethylamine (31 mL, 0.222mol) and methylene chloride (150 mL) at 0 ℃ and then the mixture was reacted at room temperature overnight. Adding water with the same volume to dissolve the generated solid and separating out an organic phase, washing with dilute hydrochloric acid and water, drying with anhydrous sodium sulfate, and removing the solvent to obtain a crude product. The crude product obtained is reacted with 11g (0.262mol) of lithium hydroxide monohydrate dissolved in 180mL of methanol and 30mL of water with stirring at room temperature for 1 hour. Most of methanol is removed by rotation, and then dichloromethane is used for extraction, diluted hydrochloric acid is used for washing, anhydrous sodium sulfate is used for drying, then the solvent is removed, and reduced pressure distillation is carried out.
N, N-di (2-ethylhexyl) -2-ethoxyacetamide
40mL (0.423mol) of ethoxyacetic acid was placed in a 250mL flask, 38mL (0.443mol) of oxalyl chloride and several drops of pyridine were added as a catalyst, the mixture was refluxed at 80 ℃ for 2 hours, and then excess oxalyl chloride was removed to prepare a 50% dichloromethane solution, which was then placed in a dropping funnel, added dropwise to a reaction flask containing 100mL (0.333mol) of diisooctylamine, 51mL (0.368mol) of triethylamine and 250mL of dichloromethane at 0 ℃ and reacted overnight at room temperature after the addition. Adding water with the same volume to dissolve the generated solid and separating out an organic phase, washing with dilute hydrochloric acid and water, drying with anhydrous sodium sulfate, removing the solvent to obtain a crude product, and distilling under reduced pressure.
Yield:81％；165～172℃/7×10-2mba；1H NMR(400MHz,CDCl3)δ4.12(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)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.
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 aqueous 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 volume flow L (m) of the feed liquid phase3The 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 is called extraction separation factor, also called extraction separation coefficient, and is usually expressed by beta. If A, B represents two substances to be separated, respectively, then 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 represents the difficulty of a certain extraction system in separating two substances in a feed liquid phase. When the beta value is 1, the two substances cannot be separated, and the larger or smaller the beta value is, the better the separation effect is, namely, the higher the separation selectivity of the extractant is.
Examples 1 to 9
Organic phase: extracting agent, neutral phosphine 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 lithium-containing brine, shaking to dissolve the lithium-containing brine, adding an organic phase, oscillating for balancing (oscillation time is 5-30 minutes), standing for layering to obtain a balanced aqueous phase and an organic phase containing loaded lithium ions. Separately measuring Li in equilibrium aqueous phase and organic phase+、Na+、K+And Mg2+From the concentration of (b), the extraction rate of Li, was calculated+、Mg2+、Na+And K+Partition ratio of (A), separation coefficient of Li/Mg, Li/Na, and Li/K.
Example 10
Organic phase: extractant + neutral phosphine oxide;
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 FeCl3(Co-extractant) is added to the organic phase, followed by additionAdding into water phase, oscillating for balancing (oscillation time is 30 min), standing for layering to obtain balanced water phase and organic phase loaded with lithium ions. Separately measuring Li in equilibrium aqueous phase and organic phase+、Na+、K+And Mg2+From the concentration of (b), the extraction rate of Li, was calculated+、Mg2+、Na+And K+Partition ratio of (A), separation coefficient of Li/Mg, Li/Na, and Li/K.
The parameters of the lithium-containing brine in examples 1 to 10 are shown in Table 1:
TABLE 1 compositions and contents (mol/L) of lithium-containing brine in examples 1 to 10
Examples 1-10 extraction conditions and parameters are shown in table 2:
the organic phases of examples 1 to 10 are, in each case, the following:
1. 25% N, N-bis (2-ethylhexyl) acetamide + 5% N, N-dihexylbenzamide + 30% TBP + 40% kerosene
2. 10% N, N-di (2-ethylhexyl) acetamide + 60% N, N-dihexylbenzamide + 10% TBP + 20% kerosene
3. 5% N, N-bis (2-ethylhexyl) acetamide + 5% N, N-dihexylbenzamide + 80% TBP + 10% kerosene
4. 25% N, N-bis (2-ethylhexyl) acetamide + 25% N, N-dihexylbenzamide + 10% TOP + 40% kerosene
5. 10% of N, N-di (2-ethylhexyl) acetamide, 10% of N, N-dihexylbenzamide, 20% of dibutyl butyl phosphate and 60% of kerosene
6. 30% N, N-di (2-ethylhexyl) acetamide + 30% N, N-dihexylbenzamide + 20% DBBP + 20% kerosene solution
7. 20% N, N-di (2-ethylhexyl) acetamide + 10% N, N-dihexylbenzamide + 10% P350+ 60% kerosene solution
8. 30% of N, N-di (2-ethylhexyl) acetamide, 10% of N, N-dihexylbenzamide, 10% of N, N-dihexylp-methylbenzamide, 10% of TBP and 40% of kerosene
9. 10% N, N-bis (2-ethylhexyl) acetamide + 20% N, N-dihexylbenzamide + 10% N, N-dihexyln-butylamide + 10% TBP + 50% kerosene
10. 30% N, N-bis (2-ethylhexyl) acetamide + 30% N, N-dihexylbenzamide + 40% TBP
TABLE 2 extraction conditions and parameters from example 1 to example 10
The results of the extraction of examples 1 to 10 are shown in table 3:
TABLE 3 extraction results of examples 1 to 10
Comparative examples 1 to 3
The organic phase was replaced with kerosene solution of N, N-bis (2-ethylhexyl) acetamide + N, N-bis (2-ethylhexyl) -2-hydroxyacetamide + TBP, kerosene solution of N, N-bis (2-ethylhexyl) acetamide + N, N-bis (2-ethylhexyl) tert-butylamide + TBP, kerosene solution of N, N-bis (2-ethylhexyl) acetamide + N, N-bis (2-ethylhexyl) -2-ethoxyacetamide + TBP, respectively, and the remaining operations and conditions were the same as in example 1. The results of the experiments are shown in Table 4 below.
TABLE 4 results of the extraction of comparative examples 1 to 3
Example 11
Adding a certain amount of FeCl3(Co-extraction agent) 60 parts by volume of lithium-containing brine (FeCl) was added3The dosage and the content of each component in the lithium-containing brine are shown in examples 2, 7 and 8), after shaking to dissolve, 30 parts of the organic phase in examples 2, 7 and 8 is added, and shaking is carried out for 10 minutes to extract, thus obtaining the lithium ion-loaded organic phase. Mixing 30 parts (volume) of organic phase loaded with lithium ions and 1 part (volume) of 6mol/L hydrochloric acid aqueous solution, oscillating for 10 minutes at 24 ℃, carrying out back extraction, standing for layering, and measuring Li in two phases of back extraction equilibrium+And (4) concentration. The specific experimental results are shown in table 5 below.
TABLE 5
Claims (24)
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-di (2-ethylhexyl) acetamide and N, N-dihexylbenzamide;
wherein, in the neutral phosphorus oxygen compound shown as the formula A, R1And R2Independently is C1-C12Straight-chain or branched alkyl, C1-C12Linear or branched alkoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, thienyl, pyridyl or naphthyl; said substituted phenyl or said substitutedThe substituents in phenoxy are 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 A1And R2Is C1-C8Straight-chain or branched alkyl, or C1-C8Linear or branched alkoxy.
3. The extraction composition of claim 2, wherein R is1And 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;
and/or, 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, wherein the neutral phosphorus oxygen compound of formula A is one or more of the following compounds:
5. the extraction composition according to any one of claims 1 to 3,
in the extraction composition, the volume ratio of the extracting agent to the neutral phosphorus-oxygen compound shown as the formula A is 9:1-1: 9;
and/or in the extracting agent, the volume ratio of the N, N-di (2-ethylhexyl) acetamide to the N, N-dihexylbenzamide is 10:1-1: 10.
6. The extraction composition of claim 5,
the volume ratio of the extracting agent to the neutral phosphorus-oxygen compound shown as the formula A is 7:1-1: 8;
and/or the volume ratio of the N, N-di (2-ethylhexyl) acetamide to the N, N-dihexylbenzamide is 5:1-1: 6.
7. The extraction composition of claim 6,
the volume ratio of the extracting agent to the neutral phosphorus-oxygen compound shown as the formula A is 5:1-1: 1;
and/or the volume ratio of the N, N-di (2-ethylhexyl) acetamide to the N, N-dihexylbenzamide is 4:1-1: 2.
8. The extraction composition of claim 1, wherein the extractant further comprises other amide compounds.
9. The extraction composition according to claim 8, wherein the other amide compound is N, N-dihexyl-p-methylbenzamide and/or N, N-dihexyl-N-butylamide
10. The extraction composition according to claim 8 or 9, wherein the extraction agent, when containing other amide compounds, contains N, N-bis (2-ethylhexyl) acetamide and N, N-dihexyl-2-methylpropanamide in an amount of 0.01% to 99.9% by volume;
and/or the volume ratio of the N, N-di (2-ethylhexyl) acetamide to the N, N-dihexylpropionamide to other amide compounds is 5:1-1: 3.
11. The extraction composition as claimed in claim 10, wherein the extraction agent, when containing other amide compounds, contains N, N-bis (2-ethylhexyl) acetamide and N, N-dihexyl-2-methylpropanamide in an amount of 10% to 40% by volume;
and/or the volume ratio of the N, N-di (2-ethylhexyl) acetamide to the N, N-dihexylpropionamide to other amide compounds is 4:1-2: 1.
12. The extraction composition of claim 1, wherein the extraction composition further comprises 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 in the extraction composition is 10-80%, and the percentage refers to the volume percentage of the diluent in the volume of the extraction composition;
and/or, when the extraction composition comprises other components besides the extractant and the neutral phosphorus oxygen compound, the volume content of the extractant and the neutral phosphorus oxide in the extraction composition is 20-90%.
14. The extraction composition of claim 13 wherein said diluent comprises from about 20% to about 60% by volume of said extraction composition, said percentages being based on the volume of diluent in the extraction composition;
and/or, when the extraction composition comprises other components besides the extractant and the neutral phosphorus oxygen compound, the volume content of the extractant and the neutral phosphorus oxide in the extraction composition is 40-80%.
15. The extraction composition of claim 14, wherein said diluent comprises from about 30% to about 40% by volume of said extraction composition, said percentages being based on the volume of diluent in the extraction composition;
and/or, when the extraction composition comprises other components besides the extractant and the neutral phosphorus oxide compound, the volume content of the extractant and the neutral phosphorus oxide in the extraction composition is 60-70%.
16. The extraction composition of any one of claims 1, 8-9, or 12-15, 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 dosage of the co-extraction agent is calculated by the content of lithium in the material to be extracted;
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 based on the amount of lithium in the material to be extracted, and the material to be extracted is a lithium-containing brine;
and/or the dosage of the co-extraction agent is that the molar ratio of ferric ions to lithium ions is 1:1-1.75: 1.
19. An extraction system comprising an extraction composition of any one of claims 1 to 18 and a lithium-containing brine.
20. Use of an extraction composition according to any one of claims 1 to 18 for extracting and stripping lithium from a lithium-containing brine.
21. The use of claim 20, wherein the use of extracting lithium from a lithium-containing brine comprises the steps of: mixing the extraction composition of any of claims 1-18 with a lithium-containing brine, equilibrating with shaking, and layering by standing;
and/or, the use of stripping lithium from lithium-containing brine comprises the steps of: (1) mixing the extraction composition of any of claims 1-18 with a lithium-containing brine, equilibrating by shaking, and layering by standing to obtain a lithium ion-loaded organic phase; (2) and mixing the lithium ion loaded organic phase with an acid aqueous solution, oscillating for balancing, and standing for layering.
22. The use according to claim 21,
in the application of extracting lithium from lithium-containing brine and the application step (1) of back-extracting lithium from lithium-containing brine, the volume ratio of an extraction composition organic phase to the lithium-containing brine is more than 1: 5;
and/or, the organic phase of the extraction composition refers to the extraction composition without the co-extractant;
and/or, in said application of extracting lithium from lithium-containing brine or said application 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 extracting lithium from lithium-containing brine or the application of back-extracting lithium from lithium-containing brine, the oscillation and equilibrium time is 5-30 minutes;
and/or, in the application of back extracting lithium from lithium-containing brine, in the step (2), the molar concentration of the acid aqueous solution is 0.5-12.0 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 of back extracting lithium from lithium-containing brine, in the step (2), the acid in the acid aqueous solution is inorganic acid;
and/or in the application of back extracting lithium from the lithium-containing brine, in the step (2), 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 molar ratio of Mg/Li in the lithium-containing brine is 2-30.
23. The use according to claim 22,
in the application of extracting lithium from lithium-containing brine and the application step (1) of back-extracting lithium from lithium-containing brine, the volume ratio of an organic phase of an extraction composition to the lithium-containing brine is 1:1-10:1, and the organic phase of the extraction composition refers to the extraction composition when no co-extractant is contained;
and/or, in the application of back extracting lithium from lithium-containing brine, in the step (2), the molar concentration of the acid aqueous solution is 4mol/L-10mol/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 of back-extracting lithium from lithium-containing brine, in the step (2), the acid in the acid aqueous solution is an inorganic acid, and the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid;
and/or in the application of back extracting lithium from the lithium-containing brine, in the step (2), the volume ratio of the lithium ion-loaded organic phase to the acid aqueous solution is 5:1-40: 1;
and/or, the lithium-containing brine comprises the following components in percentage by weight: 0.02mol/L-2.0mol/L Li+2.0mol/L to 5.0mol/L of Mg2+0mol/L to 0.5mol/L of Na+0mol/L to 0.5mol/L of K+Cl of not less than 6mol/L-0mol/L to 0.90mol/L of B2O3And 0.001mol/L to 0.5mol/L of H+Which isThe balance being water.
24. The use according to claim 23,
in the application of extracting lithium from lithium-containing brine and the application step (1) of back extracting lithium from lithium-containing brine, the volume ratio of the organic phase of the extraction composition to the lithium-containing brine is 2:1-6: 1; the organic phase of the extraction composition refers to the extraction composition without the co-extractant;
and/or, in the application of back extracting lithium from lithium-containing brine, in the step (2), the molar concentration of the acid aqueous solution is 6mol/L-8mol/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 of back extracting lithium from the lithium-containing brine, in the step (2), the volume ratio of the lithium ion-loaded organic phase to the acid aqueous solution is 10:1-30: 1.
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