WO2021088285A1 - Extraction system and extraction method for extracting lithium and boron by separating calcium from calcium-containing brine with secondary amide/alkyl alcohol composite solvent, and use of extraction method - Google Patents
Extraction system and extraction method for extracting lithium and boron by separating calcium from calcium-containing brine with secondary amide/alkyl alcohol composite solvent, and use of extraction method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a method for extracting lithium and boron from calcium-containing brine, in particular to an extraction system, an extraction method and its application for separating calcium from calcium-containing brine using a composite solvent to extract lithium and boron.
- Yu Xiaoping first adopts acid method to precipitate boron and adopts extraction or adsorption method to deeply recover boron, then uses sodium carbonate to precipitate calcium and most of magnesium, and separates and recovers sodium chloride and/ by evaporative crystallization and/or cooling crystallization. Or potassium chloride, lithium-containing concentrated solution adopts sodium carbonate precipitation method to recover lithium carbonate (CN108264064A).
- the solvent extraction method is considered to be the most promising method for extracting lithium from salt lake brine with high magnesium-lithium ratio [Song JF, Nghiem LD, Li XM, He T..Environ.Sci.:Water Res.Technol .,2017,3(4),593–597], this method may also be applied to high calcium-to-lithium ratio oilfield brines.
- This method may also be applied to high calcium-to-lithium ratio oilfield brines.
- Alkyl alcohol as an effective neutral solvent for extracting boron from brine, may be combined with other effective ingredients to form a new high-efficiency extraction system.
- the basic chemical products such as lithium carbonate, lithium chloride and lithium hydroxide can be produced, and the brine can also be purified and enriched.
- Boron elements produce boric acid products.
- the purpose of the present invention is to provide an economical and effective extraction system, extraction method and application for extracting lithium and boron from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent to solve the deficiencies in the prior art methods. .
- An extraction system for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron.
- the extraction system contains two types of substances A and B; the type A substance is a single compound or two secondary amides. It is composed of a mixture of more than one species; wherein, a single compound has a structure as shown in formula (I):
- R 1 is selected from a C1-C12 alkyl group or a C3-C12 cycloalkyl group containing a monocyclic structure
- R 2 is selected from a C1-C11 alkyl group or a C3-C11 cycloalkyl group containing a monocyclic structure
- alkyl or cycloalkyl includes various isomers (because R 1 and R 2 can be changed, when When R 1 and R 2 are uniquely determined, the Type A substance is a single compound, and the mixture refers to a substance formed by mixing two or more compounds produced with the change of R 1 and R 2 );
- type B substances are alkyl alcohols consisting of a single compound or a mixture of two or more; among them, a single compound has a structure as shown in formula (II):
- R 3 is selected from C8 to C20 alkyl groups, where the alkyl groups include linear or branched various isomers (because R 3 can be changed, when R 3 is uniquely determined, B
- the class substance is a single compound, and the mixture refers to a substance formed by mixing two or more compounds produced with the change of R 3);
- the freezing point of an extraction system containing two types of substances A and B is less than 0°C (the freezing point of a single component constituting the extraction system may be less than, equal to, or greater than 0°C.
- the freezing point of a single component may be less than, equal to, or greater than 0°C.
- the conditions of the extraction system when the freezing point of a single component is greater than or equal to 0°C, it may be mixed with other components with a freezing point less than 0°C, dissolve and finally form a mixture with a freezing point less than 0°C).
- the type A substance mainly plays the role of extracting lithium.
- the volume percentage in the entire organic phase is 0-100%, excluding the two endpoints (when the volume percentage of the type A substance is high, there is Facilitate the extraction of lithium from calcium-containing brine);
- the B-type substances mainly play the role of extracting boron.
- the volume percentage in the entire organic phase is 0-100%, excluding the two endpoints (when B When the volume percentage of such substances is high, it is beneficial to extract boron from calcium-containing brine).
- the volume percentage of the A substance in the entire organic phase is 50-90%, and the B substance in the entire organic phase The volume percentage is 10-50% (when the volume percentages of the two types of substances A and B are relatively large, it is beneficial to extract lithium and boron from the calcium-containing brine at the same time).
- the diluent 260# solvent oil, 300# solvent oil or sulfonated kerosene is also included.
- the extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron includes the following steps:
- the calcium-containing brine is used as the pre-extraction brine phase; wherein, in the calcium-containing brine, the concentration of lithium ions is 0.09-24g/L, the concentration of calcium ions is 145-277g/L, and the concentration of chloride ions is 271 ⁇ 517g/L, the mass ratio of calcium to lithium is 7.5 ⁇ 1900:1, the total concentration of boric acid and its borate ion is 0.5 ⁇ 17g/L based on B 2 O 3 , and the brine density is 1.30 ⁇ 1.56g/cm at 20°C 3.
- Use hydrochloric acid or sulfuric acid to adjust the pH value of brine between 0-7;
- the calcium-containing brine also contains one or more of sodium ion, potassium ion, magnesium ion, iron ion or ferrous ion.
- the calcium-containing brine includes oilfield brine or underground brine containing lithium and boron, but is not limited to this kind of brine.
- the extraction temperature is 0-50°C; the two-phase mixing is performed by stirring, and the two-phase separation after extraction is performed by centrifugal separation or clarification and sedimentation.
- the method further includes the following steps:
- stripping ratio that is, the ratio of the stripping agent to the volume of the loaded organic phase is 1:1-20. After phase separation, a back-extracted organic phase and a back-extracted aqueous phase are obtained;
- step S5. Return the organic phase after the stripping to step S2 to realize the recycling use of the extraction system.
- the stripping temperature is 0-50°C; the two-phase mixing is carried out by stirring, and the two-phase separation after stripping is carried out by centrifugal separation or clarification and sedimentation.
- the application of the extraction method for separating calcium and extracting lithium and boron from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent in obtaining boron product boric acid, after the step S4, further includes the following steps:
- the application of the extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol compound solvent to extract lithium and boron in obtaining the lithium product lithium chloride, after the step S4, further includes the following steps:
- an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution;
- the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;
- the refined lithium chloride solution is concentrated, crystallized, separated and dried to obtain a lithium chloride product.
- the application of the extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron in obtaining the lithium product lithium carbonate, after the step S4, further includes the following steps:
- an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution;
- the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;
- an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution;
- the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;
- the method further includes the following steps:
- the source of the secondary amide compound used in the examples of the present invention is synthesized by reacting organic acid chlorides or acid anhydrides with primary amines in a stoichiometric ratio, and then washed with water and purified by vacuum distillation, using the Agilent 7890A/5975C GC/MS instrument. Test evaluation is obtained.
- the source of the alkyl alcohol compound used in the examples of the present invention is purchased from a chemical product company on the market.
- the secondary amide as the A substance in the extraction system has a simple molecular structure, easy to obtain and easy to produce. It is used as an extractant for lithium. It is a new type of special component for separating calcium and extracting lithium from calcium-containing brine.
- the secondary amide functional group It is the key part of lithium-calcium separation and extraction of lithium.
- the hydrogen atom on N–H shifts to a low field in the 1 H NMR spectrum before and after extraction, which plays a key role in the extraction of Li +.
- Alkyl alcohol as the B substance in the extraction system is used as an extractant for boron in brine, which can effectively improve the physical properties of the composite solvent such as the viscosity and freezing point, increase the mixing entropy of the system, and produce a synergistic co-extraction effect.
- Fig. 1 is an extraction system, an extraction method and a process flow diagram of its application for separating calcium from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent to extract lithium and boron according to the present invention.
- Table 19 shows the common names, corresponding standardized names and codes of the secondary amides of substance A involved in the examples of the present invention.
- Table 20 shows the common names, corresponding normative names and CAS numbers of substance B alkyl alcohols involved in the examples of the present invention.
- a calcium brines Li +, Ca 2+ B 2 O 3 content are 2.92,169.11 and 9.41g / L
- Ca mass ratio of lithium is 57.91: 1, wherein the Na +, K +, Mg 2+ and Cl - in The content is 4.13, 14.46, 9.27 and 361.31g/L
- the density of the brine is 1.39g/cm 3
- the pH value of the brine is adjusted to 1.7
- the ion concentration in the brine is prepared according to the composition of the brine from an oilfield in Nanyishan, Qaidam Basin, Qinghai.
- the brine is degreasing in advance with an oil-water separator.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge.
- the two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained.
- Transfer the loaded organic phase to another 100 mL conical flask, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 30 min. Then transfer the mixed liquid to a 100mL plastic test tube, and centrifuge at 4000r/min for 10min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
- the single-stage extraction rate of Li + is 36.20%
- the single-stage extraction rate of Ca 2+ is 4.44%
- the lithium-calcium separation coefficient is 12.22.
- the Li + single-stage stripping rate was 70.32%
- the Ca 2+ single-stage stripping rate was 84.57%
- the lithium-calcium separation coefficient after the stripping was 0.43
- the calcium-lithium mass ratio in the water phase dropped to 8.54.
- the single-stage extraction rate of B 2 O 3 is 47.42%
- the single-stage back extraction rate of B 2 O 3 is 68.80%.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge.
- the two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained.
- Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 25 min. Then transfer the mixed liquid to a 100mL plastic test tube, and centrifuge at 4000r/min for 10min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
- the single-stage extraction rate of Li + is 43.82%
- the single-stage extraction rate of Ca 2+ is 3.45%
- the lithium-calcium separation coefficient is 21.81.
- the Li + single-stage back-extraction rate was 88.04%
- the Ca 2+ single-stage back-extraction rate was 89.34%.
- the lithium-calcium separation coefficient was 0.92
- the calcium-lithium mass ratio in the water phase dropped to 4.63.
- the single-stage extraction rate of B 2 O 3 is 53.14%
- the single-stage back extraction rate of B 2 O 3 is 87.72%.
- the magnet in the Erlenmeyer flask insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained.
- the single-stage extraction rate of Li + is 36.16%
- the single-stage extraction rate of Ca 2+ is 4.78%
- the separation coefficient of lithium and calcium is 11.28.
- the Li + single-stage stripping rate was 70.61%
- the Ca 2+ single-stage stripping rate was 95.38%.
- the lithium-calcium separation coefficient was 0.12
- the calcium-lithium mass ratio dropped to 10.35.
- the single-stage extraction rate of B 2 O 3 is 41.32%
- the single-stage back extraction rate of B 2 O 3 is 93.23%.
- the magnet in the Erlenmeyer flask insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, centrifuged at 4000r/min for 15min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained.
- the single-stage extraction rate of Li + is 33.16%
- the single-stage extraction rate of Ca 2+ is 4.02%
- the lithium-calcium separation coefficient is 11.84.
- the Li + single-stage stripping rate was 95.25%
- the Ca 2+ single-stage stripping rate was 89.99%
- the lithium-calcium separation coefficient after the stripping was 2.23
- the calcium-lithium mass ratio in the water phase dropped to 6.63.
- the single-stage extraction rate of B 2 O 3 was 44.89%
- the single-stage back extraction rate of B 2 O 3 was 92.42%.
- the single-stage extraction rate of Li + is 39.60%
- the single-stage extraction rate of Ca 2+ is 5.37%
- the lithium-calcium separation coefficient is 11.56.
- the Li + single-stage stripping rate was 80.19%
- the Ca 2+ single-stage stripping rate was 94.99%
- the lithium-calcium separation coefficient after the stripping was 0.21
- the calcium-lithium mass ratio in the water phase dropped to 9.30.
- the single-stage extraction rate of B 2 O 3 is 50.29%
- the single-stage back extraction rate of B 2 O 3 is 92.05%.
- Example 1 Take 5mL of the calcium-containing brine in Example 1 into a 100mL conical flask, and then add 0.56g of 99% pure ferric trichloride hexahydrate, dissolve it, and then add 20mL N-pentylisonon Amide and 5mL 2-butyloctanol are used as extractants. Alkyl alcohol accounts for 20% of the volume of the organic phase. The volume ratio of the organic phase to the calcium-containing brine is 5:1.
- the magnet in the Erlenmeyer flask insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained.
- the single-stage extraction rate of Li + is 42.71%
- the single-stage extraction rate of Ca 2+ is 3.90%
- the separation coefficient of lithium and calcium is 18.35.
- the Li + single-stage stripping rate was 89.06%
- the Ca 2+ single-stage stripping rate was 92.31%.
- the lithium-calcium separation coefficient was 0.68
- the calcium-lithium mass ratio in the water phase dropped to 5.48.
- the single-stage extraction rate of B 2 O 3 is 37.60%, and the single-stage back extraction rate of B 2 O 3 is 92.75%.
- the contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 0.26, 210.54, 374.11 and 0.91g/L, respectively, the mass ratio of calcium to lithium is 825.65:1, and the brine density is 1.41g/cm 3 ,
- the pH of brine is 2.0. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir and extract at 25°C for 25 minutes. Then, the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4300r/min for 15min to obtain the extracted organic phase and the remaining brine phase.
- the single-stage extraction rate of Li + is 47.71%
- the single-stage extraction rate of Ca 2+ is 7.59%
- the lithium-calcium separation coefficient is 11.11.
- the Li + single-stage back extraction rate was 63.27%
- the Ca 2+ single-stage back extraction rate was 93.15%
- the lithium-calcium separation coefficient after the back-extraction was 0.13
- the calcium-lithium mass ratio in the water phase dropped to 193.43.
- the single-stage extraction rate of B 2 O 3 is 31.73%
- the single-stage back extraction rate of B 2 O 3 is 79.72%.
- the magnet in the Erlenmeyer flask insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, centrifuged in a LD5-10 benchtop centrifuge at 4000r/min for 5 minutes, the two-phase interface was clear, and the extracted organic phase and the remaining brine phase were obtained after phase separation.
- Table 8 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isooctylheptanamide and 2-propylheptanol
- the single-stage extraction rate of Li + is 6.50%
- the single-stage extraction rate of Ca 2+ is 1.91%
- the separation coefficient of lithium and calcium is 3.57.
- the Li + single-stage back extraction rate was 48.99%
- the Ca 2+ single-stage back extraction rate was 23.35%
- the lithium-calcium separation coefficient after the back-extraction was 3.15
- the calcium-lithium mass ratio in the water phase dropped to 8.11.
- the single-stage extraction rate of B 2 O 3 is 91.26%
- the single-stage back extraction rate of B 2 O 3 is 48.29%.
- Example 7 3 mL of the calcium-containing brine in Example 7 was added thereto, and the volume ratio of the organic phase to the calcium-containing brine was 10:1. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir and extract at 25°C for 25 minutes. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged at 4200 r/min in an LD5-10 benchtop centrifuge for 8 minutes to obtain the extracted organic phase and the remaining brine phase.
- the single-stage extraction rate of Li + is 30.75%
- the single-stage extraction rate of Ca 2+ is 2.37%
- the separation coefficient of lithium and calcium is 18.32.
- the Li + single-stage stripping rate was 94.15%
- the Ca 2+ single-stage stripping rate was 92.24%
- the lithium-calcium separation coefficient after the stripping was 1.35
- the calcium-lithium mass ratio in the water phase dropped to 62.27.
- the single-stage extraction rate of B 2 O 3 was 42.65%
- the single-stage back extraction rate of B 2 O 3 was 75.51%.
- the single-stage extraction rate of Li + is 32.88%
- the single-stage extraction rate of Ca 2+ is 1.75%
- the separation coefficient of lithium and calcium is 27.53.
- the Li + single-stage back extraction rate was 88.87%
- the Ca 2+ single-stage back extraction rate was 94.48%
- the lithium-calcium separation coefficient after the back-extraction was 0.47
- the calcium-lithium mass ratio in the water phase dropped to 46.69.
- the single-stage extraction rate of B 2 O 3 is 87.23%
- the single-stage back extraction rate of B 2 O 3 is 25.97%.
- the content of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 3.99, 274.10, 514.18 and 2.01g/L, respectively, the mass ratio of calcium to lithium is 68.70:1, and the brine density is 1.55g/cm 3 , The brine pH is 0.6. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20°C, and extract for 25min.
- the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase.
- Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 25 min.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
- the single-stage extraction rate of Li + is 36.90%
- the single-stage extraction rate of Ca 2+ is 7.51%
- the separation coefficient of lithium and calcium is 7.21.
- the Li + single-stage stripping rate was 95.64%
- the Ca 2+ single-stage stripping rate was 83.01%.
- the lithium-calcium separation coefficient was 4.49
- the calcium-lithium mass ratio in the water phase dropped to 12.14.
- the single-stage extraction rate of B 2 O 3 was 85.05%
- the single-stage back extraction rate of B 2 O 3 was 77.92%.
- the contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 23.87, 179.61, 439.81 and 0.50g/L, respectively, the mass ratio of calcium to lithium is 7.52:1, and the density of the brine is 1.40g/cm 3 , Its pH value is adjusted to 2.4 with concentrated hydrochloric acid. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes.
- the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase.
- Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 30 min.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
- the single-stage extraction rate of Li + is 40.83%
- the single-stage extraction rate of Ca 2+ is 6.16%
- the separation coefficient of lithium and calcium is 10.52.
- the Li + single-stage stripping rate was 70.83%
- the Ca 2+ single-stage stripping rate was 84.22%.
- the lithium-calcium separation coefficient was 0.46
- the calcium-lithium mass ratio in the water phase dropped to 1.36.
- the single-stage extraction rate of B 2 O 3 is 50.41%
- the single-stage back extraction rate of B 2 O 3 is 89.29%.
- the contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 2.51, 147.61, 274.31 and 2.48g/L, respectively, the mass ratio of calcium to lithium is 58.80:1, and the density of the brine is 1.30g/cm 3 ,
- the pH of brine is 2.0. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20°C, and extract for 25min.
- the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase.
- Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 25 min.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
- the single-stage extraction rate of Li + is 38.11%
- the single-stage extraction rate of Ca 2+ is 5.03%
- the separation coefficient of lithium and calcium is 11.62.
- the Li + single-stage stripping rate was 76.74%
- the Ca 2+ single-stage stripping rate was 87.96%
- the lithium-calcium separation coefficient after the stripping was 0.45
- the calcium-lithium mass ratio in the water phase dropped to 8.91.
- the single-stage extraction rate of B 2 O 3 is 35.06%
- the single-stage back extraction rate of B 2 O 3 is 79.20%.
- the content of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine is 0.21, 210.79, 374.33 and 1.35g/L, respectively, the mass ratio of calcium to lithium is 1003.76:1, and the density of brine is 1.41g/cm 3 , Its pH value is adjusted to 2.0 with concentrated hydrochloric acid. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20°C, and extract for 25min.
- the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase.
- Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:2 to the organic phase, and place it in a DF-101S heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 25 min.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
- Table 14 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
- the single-stage extraction rate of Li + is 29.39%
- the single-stage extraction rate of Ca 2+ is 8.68%
- the lithium-calcium separation coefficient is 4.38.
- the Li + single-stage stripping rate was 82.76%
- the Ca 2+ single-stage stripping rate was 81.09%.
- the lithium-calcium separation coefficient was 1.13
- the calcium-lithium mass ratio in the water phase dropped to 290.47.
- the single-stage extraction rate of B 2 O 3 was 23.14%
- the single-stage back extraction rate of B 2 O 3 was 94.61%.
- the contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 0.094, 178.60, 316.43 and 1.01g/L, respectively, the mass ratio of calcium to lithium is 1900.00:1, and the brine density is 1.36g/cm 3 , Its pH value is adjusted to 7.0 with concentrated ammonia water. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20°C, and extract for 25min.
- the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase.
- Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 25 min.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
- Table 15 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
- the single-stage extraction rate of Li + is 42.68%
- the single-stage extraction rate of Ca 2+ is 3.70%
- the lithium-calcium separation coefficient is 19.33.
- the Li + single-stage stripping rate was 92.13%
- the Ca 2+ single-stage stripping rate was 89.55%
- the lithium-calcium separation coefficient after the stripping was 1.37
- the calcium-lithium mass ratio in the water phase dropped to 160.10.
- the single-stage extraction rate of B 2 O 3 is 58.51%
- the single-stage back extraction rate of B 2 O 3 is 92.54%.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 15min to obtain the extracted organic phase and the remaining brine phase.
- Transfer the loaded organic phase to another 100 mL conical flask, add deionized water at a volume ratio of 1:1 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at °C and mix the two phases for 25 min.
- the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4200r/min for 15min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
- the single-stage extraction rate of Li + is 32.70%
- the single-stage extraction rate of Ca 2+ is 4.67%
- the lithium-calcium separation coefficient is 9.72.
- the Li + single-stage stripping rate was 72.14%
- the Ca 2+ single-stage stripping rate was 89.10%
- the lithium-calcium separation coefficient after the stripping was 0.32
- the calcium-lithium mass ratio in the water phase dropped to 145.64.
- the single-stage extraction rate of B 2 O 3 was 15.38%
- the single-stage back extraction rate of B 2 O 3 was 92.26%.
- Table 17 The three-stage countercurrent extraction and single-stage back extraction of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
- the more multi-stage counter-current extraction stages the higher the extraction rate of lithium and boron in the brine, and the greater the lithium-calcium separation coefficient.
- the more multi-stage counter-current extraction stages are more beneficial to the reaction.
- the concentration of Li + and B 2 O 3 in the aqueous phase increased after extraction. Further increase the countercurrent extraction and countercurrent stripping stages, the extraction rate and stripping rate of Li + and B 2 O 3 are further improved, while the extraction rate of Ca 2+ is basically unchanged, and the extraction rate of Mg 2+ is not large.
- the organic phase after the stripping is returned and remixed with the brine phase before the extraction to realize the recycling of the extractant.
- the water phase solution obtained after the back extraction is degreasing, and after two-effect evaporation is concentrated to a Li + concentration of 30g/L
- sodium sulfate and sodium carbonate solutions are respectively added to completely precipitate and remove Ca 2+
- chlorination is added separately
- the barium and sodium hydroxide solution are completely precipitated to remove the sulfate radical and Mg 2+ , and then the remaining solution is evaporated and concentrated, cooled and crystallized, filtered and dried to obtain anhydrous lithium chloride product.
- the lithium chloride concentrate obtained after purification and purification is placed in an ion-exchange membrane electrolyzer for electrolysis, a lithium hydroxide solution with a mass concentration of 12% is obtained at the cathode, and lithium hydroxide monohydrate is obtained after concentration and crystallization. After washing and drying, an anhydrous lithium hydroxide product is prepared. At the same time, hydrogen and chlorine are by-produced, and hydrogen and chlorine are further reacted to produce hydrochloric acid.
- Table 18 The three-stage countercurrent extraction and extraction of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isobutylisononylamide, N-isooctylisovaleramide and 2-octyldodecanol Secondary countercurrent extraction situation
- the extraction rate of B 2 O 3 was 56.41% after the brine was subjected to three-stage countercurrent, and the second- stage counter-current extraction rate of B 2 O 3 was 96.14%, indicating that the extraction system can extract Li + while also effectively extracting B 2 O 3 .
- Further increase the countercurrent extraction and countercurrent stripping stages the extraction rate and stripping rate of Li + and B 2 O 3 are further improved, while the extraction rate of Ca 2+ is basically unchanged, and the extraction rate of Mg 2+ is not large.
- the water phase solution obtained after the back extraction is degreasing, and after two-effect evaporation is concentrated to a Li + concentration of 20g/L
- sodium sulfate and sodium carbonate solutions are respectively added to completely precipitate and remove Ca 2+
- chlorination is added separately
- the barium and sodium hydroxide solutions are completely precipitated to remove sulfate radicals and Mg 2+ in them , and a refined solution of lithium chloride is obtained.
- a sodium carbonate solution with a concentration of 250 g/L was added to it at 1.1 times the theoretical amount to produce a lithium carbonate precipitate, which was filtered and dried to obtain a lithium carbonate product.
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Abstract
Disclosed are an extraction system and extraction method for extracting lithium and boron by separating calcium from a calcium-containing brine with a secondary amide/alkyl alcohol composite solvent and the use of the extraction method. In the extraction system, a secondary amide and an alkyl alcohol are contained and used as extractants for extracting lithium and boron, respectively, and composed of a single compound or a mixture of two or more compounds. The total number of carbon atoms in the molecules is 12-18 and 8-20, respectively. The freezing point of the extraction system is less than 0ºC. A single-stage or multi-stage countercurrent extraction is conducted under the conditions that the volume ratio of an organic phase to a brine phase is 1-10 : 1, the density of the brine is 1.30 to 1.56 g/cm3, the pH value of the brine is 0 to 7 and the temperature is 0 to 50℃, an aqueous phase with a low calcium-lithium ratio is obtained through back extraction, and lithium chloride, lithium carbonate, lithium hydroxide and boric acid are respectively obtained through concentration, impurity removal and preparation. The secondary amide of the present invention has a simple molecular structure, and the composite solvent improved by an alkyl alcohol can extract lithium and boron simultaneously. The multi-stage extraction rate is high, the back extraction is carried out with water, and the acid and alkali consumption is greatly reduced. The extraction separation flow is shortened, and the extraction system has little solution loss and is suitable for development of oilfield brine.
Description
本发明涉及一种从含钙卤水中提取锂和硼的方法,尤其涉及到用复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系、萃取方法和其应用。The invention relates to a method for extracting lithium and boron from calcium-containing brine, in particular to an extraction system, an extraction method and its application for separating calcium from calcium-containing brine using a composite solvent to extract lithium and boron.
在我国青海柴达木盆地西部南翼山地区拥有丰富的油田地下卤水,其资源储量可与柴达木盆地盐湖储量媲美,为世界罕见的多元素共存特大型矿床,具有极大的工业开发价值。其中钾硼锂碘等有用组分多、含量高,资源赋存状态与已开发盐湖资源种类有较大差别,属于苏林分类中的氯化钙型卤水,呈现高矿化度、高钙、低镁和低硫酸根特征,经盐田日晒浓缩后其中氯化钙含量高达30.8~43.0%。There are abundant oilfield underground brines in the Nanyishan area in the western part of Qaidam Basin, Qinghai, my country. Its resource reserves are comparable to those of salt lakes in the Qaidam Basin. It is a rare multi-element coexisting super large deposit in the world and has great industrial development value. . Among them, potassium, boron, lithium, iodine and other useful components are many and high in content, and the resource occurrence state is quite different from the types of developed salt lake resources. It belongs to the calcium chloride type brine in the Surin classification, showing high salinity, high calcium, Low-magnesium and low-sulfate characteristics, the calcium chloride content is as high as 30.8-43.0% after being concentrated by the salt field in the sun.
目前从高钙锂比卤水中同时提取有价元素锂和硼的研究还处于初始阶段,涉及到的主要工作有:(1)崔香梅等对南翼山高钙含硼盐卤体系进行蒸发,发现其中硼的行为与已往报道的高镁含硼盐卤体系有较大不同,硼的特殊结晶行为受体系pH值和离子组成制约[无机化学学报,2009,25(8),1434–1438]。(2)余晓平等首先通过酸法沉硼和采用萃取或吸附法深度回收硼,然后采用碳酸钠对钙和大部分镁进行沉淀,通过蒸发结晶和/或冷却结晶分离回收氯化钠和/或氯化钾,含锂浓缩液采用碳酸钠沉淀法回收碳酸锂(CN108264064A)。(3)彭时利等针对川西平落四井气田卤水采用萃取法脱硼、芒硝除钙、烧碱沉镁和纯碱沉淀法提锂的工艺流程进行综合利用[广东化工,2010,37(7),24–25]。(4)郑绵平等用石灰乳和芒硝除去提钾母液中的镁钙、加入盐酸或硫酸得到粗硼酸,含锂母液经螯合或吸附净化除杂,再在精制富锂母液中加碱沉淀、洗涤得到粗碳酸锂(CN108584995A)。从以上方法可以看出,从卤水中同时提取锂和硼的过程实为按不同技术特点分开进行、工艺流程长,采用传统的除钙镁方法,一直存在沉淀处理量大,原子经济利用率不高等缺点,影响到产品的生产成本和市场竞争力。At present, the research on the simultaneous extraction of the valuable elements lithium and boron from high calcium lithium ratio brine is still in the initial stage. The main work involved is: (1) Cui Xiangmei et al. evaporated the Nanyishan high calcium boron brine system and found that boron was among them. The behavior of boron is quite different from the previously reported high-magnesium boron-containing brine systems. The special crystallization behavior of boron is restricted by the pH value and ion composition of the system [Acta Inorganic Chemistry, 2009, 25(8), 1434–1438]. (2) Yu Xiaoping first adopts acid method to precipitate boron and adopts extraction or adsorption method to deeply recover boron, then uses sodium carbonate to precipitate calcium and most of magnesium, and separates and recovers sodium chloride and/ by evaporative crystallization and/or cooling crystallization. Or potassium chloride, lithium-containing concentrated solution adopts sodium carbonate precipitation method to recover lithium carbonate (CN108264064A). (3) Peng Shili et al. comprehensively utilize the process flow of extracting boron removal from the Sijing gas field in Pingluo, western Sichuan, removing calcium from Glauber's salt, precipitating magnesium with caustic soda, and extracting lithium with soda ash precipitation [Guangdong Chemical Industry, 2010, 37(7), 24 –25]. (4) Zheng Mianping used lime milk and Glauber's salt to remove the magnesium and calcium in the potassium extraction mother liquor, added hydrochloric acid or sulfuric acid to obtain crude boric acid. The lithium-containing mother liquor was purified by chelation or adsorption to remove impurities, and then added alkali precipitation in the refined lithium-rich mother liquor. , Wash to obtain crude lithium carbonate (CN108584995A). It can be seen from the above methods that the process of simultaneously extracting lithium and boron from brine is actually carried out separately according to different technical characteristics, and the process flow is long. The traditional method of removing calcium and magnesium has always had a large amount of precipitation treatment and poor atomic economic utilization. High-level shortcomings affect the production cost and market competitiveness of the product.
然而在诸多技术方法中,溶剂萃取法被认为是针对高镁锂比盐湖卤水最有前途的提锂方法[Song J.F.,Nghiem L.D.,Li X.M.,He T..Environ.Sci.:Water Res.Technol.,2017,3(4),593–597],该种方法也同样可能应用于高钙锂比油田卤水,从中同时提取锂和硼的新型萃取剂开发显得至关重要。烷基醇作为一类从卤水中萃取硼的有效中性溶剂,与其他有效成分组合可能构成新的高效萃取体系。将高钙锂比卤水实现锂钙分离转变为低钙锂比卤水后,能制得市场上特别需要的碳酸锂、氯化锂和氢氧化锂等基础化工产品,同时也能净化卤水、富集硼元素制备出硼酸产品。However, among many technical methods, the solvent extraction method is considered to be the most promising method for extracting lithium from salt lake brine with high magnesium-lithium ratio [Song JF, Nghiem LD, Li XM, He T..Environ.Sci.:Water Res.Technol .,2017,3(4),593–597], this method may also be applied to high calcium-to-lithium ratio oilfield brines. The development of new extractants that simultaneously extract lithium and boron from it is very important. Alkyl alcohol, as an effective neutral solvent for extracting boron from brine, may be combined with other effective ingredients to form a new high-efficiency extraction system. After the high-calcium-lithium ratio brine is converted into low-calcium-lithium ratio brine, the basic chemical products such as lithium carbonate, lithium chloride and lithium hydroxide can be produced, and the brine can also be purified and enriched. Boron elements produce boric acid products.
发明内容Summary of the invention
本发明的目的是针对现有技术方法中存在的不足,提供一种经济有效的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系、萃取方法和其应用。The purpose of the present invention is to provide an economical and effective extraction system, extraction method and application for extracting lithium and boron from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent to solve the deficiencies in the prior art methods. .
本发明提供的技术方案和工艺过程如下:The technical scheme and technological process provided by the present invention are as follows:
1.用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系,该萃取体系中含有A和B两类物质;其中A类物质为仲酰胺由单一化合物或两种以上的混合物组成;其中,单一化合物具有如式(I)所示的结构:1. An extraction system for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron. The extraction system contains two types of substances A and B; the type A substance is a single compound or two secondary amides. It is composed of a mixture of more than one species; wherein, a single compound has a structure as shown in formula (I):
其中,R
1选自C1~C12的烷基或含有单环结构的C3~C12的环烷基,R
2选自C1~C11的烷基或含有单环结构的C3~C11的环烷基,并且R
1和R
2两基团中所含碳原子数目之和为11~17,其中烷基或环烷基包括各种同分异构体(因R
1、R
2是能够变化的,当R
1、R
2唯一确定时,A类物质为单一化合物,混合物是指随着R
1、R
2的变化而产生的两种以上的化合物混合而成的物质);
Wherein, R 1 is selected from a C1-C12 alkyl group or a C3-C12 cycloalkyl group containing a monocyclic structure, and R 2 is selected from a C1-C11 alkyl group or a C3-C11 cycloalkyl group containing a monocyclic structure, And the sum of the number of carbon atoms contained in the two groups R 1 and R 2 is 11-17, where alkyl or cycloalkyl includes various isomers (because R 1 and R 2 can be changed, when When R 1 and R 2 are uniquely determined, the Type A substance is a single compound, and the mixture refers to a substance formed by mixing two or more compounds produced with the change of R 1 and R 2 );
其中B类物质为烷基醇由单一化合物或两种以上的混合物组成;其中,单一化合物具有如式(Ⅱ)所示的结构:Among them, type B substances are alkyl alcohols consisting of a single compound or a mixture of two or more; among them, a single compound has a structure as shown in formula (II):
R
3-OH (Ⅱ);
R 3 -OH (Ⅱ);
其中,R
3选自C8~C20的烷基,其中烷基包含直链的或带有支链的各种同分异构体(因R
3是能够变化的,当R
3唯一确定时,B类物质为单一化合物,混合物是指随着R
3的变化而产生的两种以上的化合物混合而成的物质);
Among them, R 3 is selected from C8 to C20 alkyl groups, where the alkyl groups include linear or branched various isomers (because R 3 can be changed, when R 3 is uniquely determined, B The class substance is a single compound, and the mixture refers to a substance formed by mixing two or more compounds produced with the change of R 3);
含有A和B两类物质的萃取体系的凝固点小于0℃(构成萃取体系的单一组分的凝固点可能小于、等于或者大于0℃,当单一组分的凝固点小于0℃时即能够满足作为本发明萃取体系的条件;当单一组分的凝固点大于等于0℃时有可能与凝固点小于0℃的其他组分混合、发生溶解而最终形成凝固点小于0℃的混合物)。The freezing point of an extraction system containing two types of substances A and B is less than 0°C (the freezing point of a single component constituting the extraction system may be less than, equal to, or greater than 0°C. When the freezing point of a single component is less than 0°C, it can meet the requirements of the present invention The conditions of the extraction system; when the freezing point of a single component is greater than or equal to 0°C, it may be mixed with other components with a freezing point less than 0°C, dissolve and finally form a mixture with a freezing point less than 0°C).
在萃取体系中,所述A类物质主要起萃取锂的作用在整个有机相中所占的体积百分数为0~100%,不包括两个端点值(当A类物质所占体积百分数高时有利于从含钙卤水中提取锂);在萃取体系中所述B类物质主要起萃取硼的作用在整个有机相中所占的体积百分数为0~100%,不包括两个端点值(当B类物质所占体积百分数高时有利于从含钙卤水中提取硼)。In the extraction system, the type A substance mainly plays the role of extracting lithium. The volume percentage in the entire organic phase is 0-100%, excluding the two endpoints (when the volume percentage of the type A substance is high, there is Facilitate the extraction of lithium from calcium-containing brine); in the extraction system, the B-type substances mainly play the role of extracting boron. The volume percentage in the entire organic phase is 0-100%, excluding the two endpoints (when B When the volume percentage of such substances is high, it is beneficial to extract boron from calcium-containing brine).
在萃取体系中,萃取体系有利于同时萃取锂和硼时,所述A类物质在整个有机相中所占的体积百分数为50~90%,所述B类物质在整个有机相中所占的体积百分数为10~50%(当A和B两类物质体积百分数都比较大时,有利于从含钙卤水中同时提取锂和硼)。In the extraction system, when the extraction system is conducive to the simultaneous extraction of lithium and boron, the volume percentage of the A substance in the entire organic phase is 50-90%, and the B substance in the entire organic phase The volume percentage is 10-50% (when the volume percentages of the two types of substances A and B are relatively large, it is beneficial to extract lithium and boron from the calcium-containing brine at the same time).
在所述萃取体系中,还包含有起稀释作用的稀释剂260#溶剂油、300#溶剂油或磺化煤油。In the extraction system, the diluent 260# solvent oil, 300# solvent oil or sulfonated kerosene is also included.
2.用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,包括以下步骤:2. The extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron includes the following steps:
S1、以含钙卤水作为萃取前卤水相;其中,在所述含钙卤水中,锂离子的浓度为0.09~24g/L,钙离子的浓度为145~277g/L,氯离子的浓度为271~517g/L,钙锂质量比为7.5~1900:1,硼酸及其硼氧酸根离子的浓度以B
2O
3合计为0.5~17g/L,卤水密度20℃时为1.30~1.56g/cm
3,用盐酸或硫酸调节卤水pH值在0~7之间;
S1. The calcium-containing brine is used as the pre-extraction brine phase; wherein, in the calcium-containing brine, the concentration of lithium ions is 0.09-24g/L, the concentration of calcium ions is 145-277g/L, and the concentration of chloride ions is 271 ~517g/L, the mass ratio of calcium to lithium is 7.5~1900:1, the total concentration of boric acid and its borate ion is 0.5~17g/L based on B 2 O 3 , and the brine density is 1.30~1.56g/cm at 20℃ 3. Use hydrochloric acid or sulfuric acid to adjust the pH value of brine between 0-7;
S2、以上述1中所述的萃取体系作为萃取前有机相;S2, using the extraction system described in 1 above as the organic phase before extraction;
S3、将所述萃取前有机相和所述萃取前卤水相按照体积比为1~10:1混合,进行单级萃取或多级逆流萃取,两相分离后得到负载有机相和萃取后卤水相。S3. Mix the pre-extraction organic phase and the pre-extraction brine phase in a volume ratio of 1-10:1, perform single-stage extraction or multi-stage countercurrent extraction, and obtain a loaded organic phase and a post-extraction brine phase after the two phases are separated .
在所述含钙卤水中,还含有钠离子、钾离子、镁离子、铁离子或亚铁离子中的一种或两种以上。The calcium-containing brine also contains one or more of sodium ion, potassium ion, magnesium ion, iron ion or ferrous ion.
所述的含钙卤水包括含锂和硼的油田卤水或地下卤水,但不仅限于该种卤水。The calcium-containing brine includes oilfield brine or underground brine containing lithium and boron, but is not limited to this kind of brine.
进一步地,在所述步骤S3中,萃取温度为0~50℃;两相混合通过搅拌方式进行,萃取后两相分离采取离心分离方式或澄清沉降方式进行。Further, in the step S3, the extraction temperature is 0-50°C; the two-phase mixing is performed by stirring, and the two-phase separation after extraction is performed by centrifugal separation or clarification and sedimentation.
进一步地,在所述步骤S3后,还包括步骤:Further, after the step S3, the method further includes the following steps:
S4、以水作为反萃取剂,对所述负载有机相进行单级反萃取或多级逆流反萃取,反萃相比即反萃取剂对负载有机相体积之比为1:1~20,两相分离后得到反萃取后有机相和反萃取后水相;S4. Using water as the stripping agent, single-stage stripping or multi-stage countercurrent stripping is performed on the loaded organic phase. The stripping ratio, that is, the ratio of the stripping agent to the volume of the loaded organic phase is 1:1-20. After phase separation, a back-extracted organic phase and a back-extracted aqueous phase are obtained;
S5、使所述反萃取后有机相返回步骤S2,实现萃取体系的循环使用。S5. Return the organic phase after the stripping to step S2 to realize the recycling use of the extraction system.
进一步地,在所述步骤S4中,反萃取温度为0~50℃;两相混合通过搅拌方式进行,反萃取后两相分离采取离心分离方式或澄清沉降方式进行。Further, in the step S4, the stripping temperature is 0-50°C; the two-phase mixing is carried out by stirring, and the two-phase separation after stripping is carried out by centrifugal separation or clarification and sedimentation.
3.用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得硼产品硼酸中的应用,在所述步骤S4后,还包括步骤:3. The application of the extraction method for separating calcium and extracting lithium and boron from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent in obtaining boron product boric acid, after the step S4, further includes the following steps:
S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品。S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying.
4.用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得锂产品氯化锂中的应用,在所述步骤S4后,还包括步骤:4. The application of the extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol compound solvent to extract lithium and boron in obtaining the lithium product lithium chloride, after the step S4, further includes the following steps:
S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品;S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying;
S7、在所述析出硼酸后的含锂溶液中,加入除杂剂对其中剩余钙离子和少量镁离子进行去除,得到含锂溶液精制后的氯化锂溶液;所用除杂剂为硫酸钠、碳酸钠、草酸钠、氯化钡或氢氧化钠中的一种或两种以上的化合物;S7. In the lithium-containing solution after the boric acid is precipitated, an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution; the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;
S8、对所述精制后的氯化锂溶液进行浓缩、结晶、分离和干燥过程,制得氯化锂产品。S8. The refined lithium chloride solution is concentrated, crystallized, separated and dried to obtain a lithium chloride product.
5.用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得锂产品碳酸锂中的应用,在所述步骤S4后,还包括步骤:5. The application of the extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron in obtaining the lithium product lithium carbonate, after the step S4, further includes the following steps:
S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品;S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying;
S7、在所述析出硼酸后的含锂溶液中,加入除杂剂对其中剩余钙离子和少量镁离子进行去除,得到含锂溶液精制后的氯化锂溶液;所用除杂剂为硫酸钠、碳酸钠、草酸钠、氯化钡或氢氧化钠中的一种或两种以上的化合物;S7. In the lithium-containing solution after the boric acid is precipitated, an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution; the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;
S9、在精制后的氯化锂溶液中加入碳酸钠得到碳酸锂沉淀,对碳酸锂沉淀进行分离、干燥过程,制得碳酸锂产品。S9, adding sodium carbonate to the refined lithium chloride solution to obtain a lithium carbonate precipitate, and performing separation and drying processes on the lithium carbonate precipitate to obtain a lithium carbonate product.
6.用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得锂产品氢氧化锂中的应用,在所述步骤S4后,还包括步骤:6. The application of the extraction method for separating calcium from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent to extract lithium and boron in obtaining the lithium product lithium hydroxide, after the step S4, the method further includes the following steps:
S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品;S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying;
S7、在所述析出硼酸后的含锂溶液中,加入除杂剂对其中剩余钙离子和少量镁离子进行去除,得到含锂溶液精制后的氯化锂溶液;所用除杂剂为硫酸钠、碳酸钠、草酸钠、氯化钡或氢氧化钠中的一种或两种以上的化合物;S7. In the lithium-containing solution after the boric acid is precipitated, an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution; the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;
S10、对所述精制后的氯化锂溶液进行电解,制得氢氧化锂产品,同时副产氢气和氯气、可用于生产盐酸;S10, electrolyzing the refined lithium chloride solution to obtain a lithium hydroxide product, and at the same time by-produce hydrogen and chlorine, which can be used to produce hydrochloric acid;
或在所述步骤S7后,还包括步骤:Or after the step S7, the method further includes the following steps:
S9、在精制后的氯化锂溶液中加入碳酸钠得到碳酸锂沉淀,对碳酸锂沉淀进行分离、干燥过程,制得碳酸锂产品;S9, adding sodium carbonate to the refined lithium chloride solution to obtain a lithium carbonate precipitate, and performing separation and drying processes on the lithium carbonate precipitate to obtain a lithium carbonate product;
S11、在制得的碳酸锂中加入氢氧化钙乳液,进行固-液反应,分离后得到氢氧化锂溶液,对其进行浓缩、结晶和干燥过程,制得氢氧化锂产品。S11. Adding a calcium hydroxide emulsion to the prepared lithium carbonate, performing a solid-liquid reaction, and obtaining a lithium hydroxide solution after separation, which is subjected to the processes of concentration, crystallization and drying to obtain a lithium hydroxide product.
在本发明中实施例所用仲酰胺型化合物的来源是由有机酰氯或酸酐与伯胺按化学计量比反 应合成,再用水洗涤和减压蒸馏方式纯化,用美国安捷伦7890A/5975C型气质联用仪检测评价获得。在本发明中实施例所用烷基醇型化合物的来源是从市场上化工产品公司购买获得。The source of the secondary amide compound used in the examples of the present invention is synthesized by reacting organic acid chlorides or acid anhydrides with primary amines in a stoichiometric ratio, and then washed with water and purified by vacuum distillation, using the Agilent 7890A/5975C GC/MS instrument. Test evaluation is obtained. The source of the alkyl alcohol compound used in the examples of the present invention is purchased from a chemical product company on the market.
本发明与现有技术相比,我们已发现以式(I)和式(Ⅱ)所示的化合物组成的仲酰胺/烷基醇复合溶剂作为新的萃取体系,从而获得新的用于从含钙卤水中分离钙提取锂和硼的萃取方法和其应用,取得了意想不到的效果,未见用仲酰胺与烷基醇混合组成的溶剂作为卤水提锂萃取体系的文献报道,为当前高钙锂比油田卤水锂资源开发提供了新技术。本发明具有以下优点:Compared with the prior art, the present invention has found that a secondary amide/alkyl alcohol composite solvent composed of compounds represented by formula (I) and formula (II) is used as a new extraction system, thereby obtaining a new extraction system for The extraction method of separating calcium from calcium brine to extract lithium and boron and its application have achieved unexpected results. There is no literature report on the use of a mixture of secondary amide and alkyl alcohol as a brine extraction system for lithium extraction, which is the current high calcium The development of brine lithium resources in Libi oilfield provides new technologies. The invention has the following advantages:
1)仲酰胺作为萃取体系中的A物质分子结构简单,来源易得,容易生产,用作锂的萃取剂,是一类从含钙卤水中分离钙提取锂的新型特效成分,其中仲酰胺官能团是锂钙分离萃取锂的关键部位,N–H上的氢原子在萃取前后
1H NMR谱向低场发生位移,对Li
+的萃取起着关键作用。烷基醇作为萃取体系中的B物质用作卤水中硼的萃取剂,能有效改进复合溶剂的粘度和凝固点等物理性质,增大体系的混合熵、产生协同共萃效果。
1) The secondary amide as the A substance in the extraction system has a simple molecular structure, easy to obtain and easy to produce. It is used as an extractant for lithium. It is a new type of special component for separating calcium and extracting lithium from calcium-containing brine. The secondary amide functional group It is the key part of lithium-calcium separation and extraction of lithium. The hydrogen atom on N–H shifts to a low field in the 1 H NMR spectrum before and after extraction, which plays a key role in the extraction of Li +. Alkyl alcohol as the B substance in the extraction system is used as an extractant for boron in brine, which can effectively improve the physical properties of the composite solvent such as the viscosity and freezing point, increase the mixing entropy of the system, and produce a synergistic co-extraction effect.
2)在保证Li
+一定大小的单级萃取能力的前提下,负载有机相容易用水直接反萃取,不需要使用酸强化Li
+的反萃取,同时也不需要使用碱中和前面的酸恢复有机相的萃取能力和水相酸碱性,酸碱消耗量小,实现了萃取和反萃取过程的双向平衡,在萃取锂和硼的同时也容易进行锂和硼的反萃取。含钙卤水经过多级逆流萃取后锂钙分离系数大,反萃取后水相中的钙锂质量比显著降低。
2) Under the premise of ensuring a certain level of single-stage extraction capacity of Li + , the loaded organic phase is easy to back-extract with water directly, without the need to use acid to strengthen the back-extraction of Li + , and there is no need to use alkali to neutralize the previous acid to restore organic The extraction capacity of the phase and the acidity and alkalinity of the water phase, the consumption of acid and alkali is small, and the two-way balance of the extraction and stripping process is realized. It is easy to carry out the stripping of lithium and boron while extracting lithium and boron. After the calcium-containing brine is subjected to multi-stage countercurrent extraction, the lithium-calcium separation coefficient is large, and the calcium-lithium mass ratio in the water phase after the stripping is significantly reduced.
3)整个萃取分离过程简单,有机相直接循环使用,设备腐蚀程度小,生产过程易于控制。有机相密度小适合于用水反萃取负载有机相时的两相分离。通过调整萃取体系的分子结构和组成,优选的萃取体系在水中的溶解度与TBP的溶解度比较显著减少。3) The entire extraction and separation process is simple, the organic phase is directly recycled, the degree of equipment corrosion is small, and the production process is easy to control. The low density of the organic phase is suitable for the separation of the two phases when the organic phase is loaded by back extraction with water. By adjusting the molecular structure and composition of the extraction system, the solubility of the preferred extraction system in water is significantly reduced compared to the solubility of TBP.
附图表说明Attached table description
图1是本发明用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系、萃取方法和其应用的工艺流程框图。Fig. 1 is an extraction system, an extraction method and a process flow diagram of its application for separating calcium from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent to extract lithium and boron according to the present invention.
表19是本发明实施例中涉及到的A物质仲酰胺的常用名称、对应规范名称和代号。Table 19 shows the common names, corresponding standardized names and codes of the secondary amides of substance A involved in the examples of the present invention.
表20是本发明实施例中涉及到的B物质烷基醇的常用名称、对应规范名称和CAS号。Table 20 shows the common names, corresponding normative names and CAS numbers of substance B alkyl alcohols involved in the examples of the present invention.
下面结合实施例对本发明做进一步说明:In the following, the present invention will be further described in conjunction with the embodiments:
实施例1Example 1
某含钙卤水中Li
+、Ca
2+和B
2O
3含量分别为2.92、169.11和9.41g/L,钙锂质量比为57.91:1,其中Na
+、K
+、Mg
2+和Cl
-含量分别为4.13、14.46、9.27和361.31g/L,卤水密度为1.39g/cm
3,卤水pH值调整为1.7,卤水中离子浓度按照青海柴达木盆地南翼山某油田卤水组成配制,油田卤水预先用油水分离器除油。取5mL该种卤水于100mL磨口锥形瓶中,然后在其中加入20mL N-异辛基异己酰胺和5mL 3,5,5-三甲基己醇作为萃取剂,烷基醇占有机相体积的20%,有机相与卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,得到反萃取后的有机相和水相。
A calcium brines Li +, Ca 2+ B 2 O 3 content are 2.92,169.11 and 9.41g / L, Ca mass ratio of lithium is 57.91: 1, wherein the Na +, K +, Mg 2+ and Cl - in The content is 4.13, 14.46, 9.27 and 361.31g/L, the density of the brine is 1.39g/cm 3 , the pH value of the brine is adjusted to 1.7, and the ion concentration in the brine is prepared according to the composition of the brine from an oilfield in Nanyishan, Qaidam Basin, Qinghai. The brine is degreasing in advance with an oil-water separator. Take 5mL of this kind of brine in a 100mL conical flask, and then add 20mL of N-isooctylisohexanamide and 5mL of 3,5,5-trimethylhexanol as the extractant, and the alkyl alcohol accounts for the volume of the organic phase. The volume ratio of organic phase to brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained. Transfer the loaded organic phase to another 100 mL conical flask, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 30 min. Then transfer the mixed liquid to a 100mL plastic test tube, and centrifuge at 4000r/min for 10min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出萃取率E、反萃取率S、分配比D和锂钙分离系数β,结果如表1所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 content, the extraction rate E, the stripping rate S, the distribution ratio D and the lithium-calcium separation coefficient β are calculated, and the results are shown in Table 1.
表1 N-异辛基异己酰胺和3,5,5-三甲基己醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
*
Table 1 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isooctylisohexanamide and 3,5,5-trimethylhexanol *
*其中符号含义分别指定为
a:有机相对水相体积比,
b:Li
+萃取率,
c:Ca
2+萃取率,
d:Li
+分配比,
e:Ca
2+分配比,
f:锂钙分离系数,
g:萃取后有机相中钙锂质量比,
h:萃取后卤水中钙锂质量比,
i:B
2O
3萃取率;
j:水相对有机相体积比,
k:Li
+反萃率,
l:Ca
2+反萃率,
m:Li
+反萃分配比,
n:Ca
2+反萃分配比,
o:锂钙反萃分离系数,
p:反萃取后有机相中钙锂质量比,
q:反萃取后水相中钙锂质量比,
r:B
2O
3反萃取率;在下列表2至表18中符号含义亦与此相同。
* The meanings of the symbols are respectively designated as a : organic relative water phase volume ratio, b : Li + extraction rate, c : Ca 2+ extraction rate, d : Li + distribution ratio, e : Ca 2+ distribution ratio, f : lithium calcium Separation coefficient, g : mass ratio of calcium to lithium in the organic phase after extraction, h : mass ratio of calcium to lithium in the brine after extraction, i : extraction rate of B 2 O 3 ; j : volume ratio of water to organic phase, k : Li + back extraction Rate, l : Ca 2+ back-extraction rate, m : Li + back-extraction distribution ratio, n : Ca 2+ back-extraction distribution ratio, o : lithium-calcium back-extraction separation coefficient, p : quality of calcium and lithium in the organic phase after back-extraction Ratio, q : mass ratio of calcium to lithium in the aqueous phase after stripping, r : stripping rate of B 2 O 3 ; the meanings of the symbols in Table 2 to Table 18 below are also the same.
从表1可以看出,Li
+单级萃取率为36.20%,Ca
2+单级萃取率为4.44%,锂钙分离系数为12.22。Li
+单级反萃取率为70.32%,Ca
2+单级反萃取率为84.57%,反萃取后锂钙分离系数为0.43,水相中钙锂质量比下降至8.54。B
2O
3单级萃取率为47.42%,B
2O
3单级反萃取率为68.80%。
It can be seen from Table 1 that the single-stage extraction rate of Li + is 36.20%, the single-stage extraction rate of Ca 2+ is 4.44%, and the lithium-calcium separation coefficient is 12.22. The Li + single-stage stripping rate was 70.32%, the Ca 2+ single-stage stripping rate was 84.57%, the lithium-calcium separation coefficient after the stripping was 0.43, and the calcium-lithium mass ratio in the water phase dropped to 8.54. The single-stage extraction rate of B 2 O 3 is 47.42%, and the single-stage back extraction rate of B 2 O 3 is 68.80%.
实施例2Example 2
取24mL N-戊基异壬酰胺和6mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入3mL实施例1中的含钙卤水,有机相与含钙卤水体积比为10:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:10的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,得到反萃取后的有机相和水相。Take 24mL of N-pentylisononylamide and 6mL of 2-propylheptanol as extractants in a 100mL conical flask. Alkyl alcohol accounts for 20% of the volume of the organic phase, and then add 3mL of Example 1 For calcium-containing brine, the volume ratio of organic phase to calcium-containing brine is 10:1. Put the magnet in the conical flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 25min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained. Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then transfer the mixed liquid to a 100mL plastic test tube, and centrifuge at 4000r/min for 10min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表2所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 content, the calculated experimental results are shown in Table 2.
表2 N-戊基异壬酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 2 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
从表2可以看出,Li
+单级萃取率为43.82%,Ca
2+单级萃取率为3.45%,锂钙分离系数为21.81。Li
+单级反萃取率为88.04%,Ca
2+单级反萃取率为89.34%,反萃取后锂钙分离系数为0.92,水相中钙锂质量比下降至4.63。B
2O
3单级萃取率为53.14%,B
2O
3单级反萃取率为87.72%。
It can be seen from Table 2 that the single-stage extraction rate of Li + is 43.82%, the single-stage extraction rate of Ca 2+ is 3.45%, and the lithium-calcium separation coefficient is 21.81. The Li + single-stage back-extraction rate was 88.04%, and the Ca 2+ single-stage back-extraction rate was 89.34%. After the back-extraction, the lithium-calcium separation coefficient was 0.92, and the calcium-lithium mass ratio in the water phase dropped to 4.63. The single-stage extraction rate of B 2 O 3 is 53.14%, and the single-stage back extraction rate of B 2 O 3 is 87.72%.
实施例3Example 3
取10mL N-异丁基异壬酰胺(受热后液体)、10mL N-异辛基戊酰胺和5mL 2-己基癸醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入5mL实施例1中的含钙卤水,有机相与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,得到反萃取后的有机相和水相。Take 10mL N-isobutylisononylamide (liquid after heating), 10mL N-isooctylpentanoamide and 5mL 2-hexyldecanol as the extractant in a 100mL conical flask. Alkyl alcohol accounts for 20% of the volume of the organic phase. %, and then add 5 mL of the calcium-containing brine in Example 1 to it, and the volume ratio of the organic phase to the calcium-containing brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained. Transfer the loaded organic phase to another 100 mL conical flask, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 30 min. Then transfer the mixed liquid to a 100mL plastic test tube, and centrifuge at 4000r/min for 10min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表3所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 3.
表3 N-异丁基异壬酰胺、N-异辛基戊酰胺和2-己基癸醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 3 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isobutylisononylamide, N-isooctylpentanamide and 2-hexyldecanol
从表3可以看出,Li
+单级萃取率为36.16%,Ca
2+单级萃取率为4.78%,锂钙分离系数为11.28。Li
+单级反萃取率为70.61%,Ca
2+单级反萃取率为95.38%,反萃取后锂钙分离系数为0.12,钙锂质量比下降至10.35。B
2O
3单级萃取率为41.32%,B
2O
3单级反萃取率为93.23%。
It can be seen from Table 3 that the single-stage extraction rate of Li + is 36.16%, the single-stage extraction rate of Ca 2+ is 4.78%, and the separation coefficient of lithium and calcium is 11.28. The Li + single-stage stripping rate was 70.61%, and the Ca 2+ single-stage stripping rate was 95.38%. After the stripping, the lithium-calcium separation coefficient was 0.12, and the calcium-lithium mass ratio dropped to 10.35. The single-stage extraction rate of B 2 O 3 is 41.32%, and the single-stage back extraction rate of B 2 O 3 is 93.23%.
实施例4Example 4
取10mL N-异丁基异壬酰胺(受热后液体)、10mL N-戊基异壬酰胺和5mL 2-丁基辛醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入5mL实施例1中的含钙卤水,有机相与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心15min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心15min,得到反萃取后的有机相和水相。Take 10mL of N-isobutylisononylamide (liquid after heating), 10mL of N-pentylisononylamide and 5mL of 2-butyloctanol as the extractant in a 100mL conical flask. Alkyl alcohol accounts for a fraction of the volume of the organic phase. 20%, and then add 5 mL of the calcium-containing brine in Example 1 into it, and the volume ratio of the organic phase to the calcium-containing brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, centrifuged at 4000r/min for 15min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained. Transfer the loaded organic phase to another 100 mL conical flask, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 30 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4000r/min for 15min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量, 计算出实验结果如表4所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 4.
表4 N-异丁基异壬酰胺、N-戊基异壬酰胺和2-丁基辛醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 4 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isobutylisononylamide, N-pentylisononylamide and 2-butyloctanol
从表4可以看出,Li
+单级萃取率为33.16%,Ca
2+单级萃取率为4.02%,锂钙分离系数为11.84。Li
+单级反萃取率为95.25%,Ca
2+单级反萃取率为89.99%,反萃取后锂钙分离系数为2.23,水相中钙锂质量比下降至6.63。B
2O
3单级萃取率为44.89%,B
2O
3单级反萃取率为92.42%。
It can be seen from Table 4 that the single-stage extraction rate of Li + is 33.16%, the single-stage extraction rate of Ca 2+ is 4.02%, and the lithium-calcium separation coefficient is 11.84. The Li + single-stage stripping rate was 95.25%, the Ca 2+ single-stage stripping rate was 89.99%, the lithium-calcium separation coefficient after the stripping was 2.23, and the calcium-lithium mass ratio in the water phase dropped to 6.63. The single-stage extraction rate of B 2 O 3 was 44.89%, and the single-stage back extraction rate of B 2 O 3 was 92.42%.
实施例5Example 5
取20mL N-戊基异壬酰胺和2.5mL 2-丙基庚醇、2.5mL 3,5,5-三甲基己醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入5mL实施例1中的含钙卤水,有机相与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于0℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心8min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入水,置于DF-101S型集热式恒温加热磁力搅拌器中,在0℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心8min,得到反萃取后的有机相和水相。Take 20mL of N-pentylisononylamide, 2.5mL of 2-propylheptanol, 2.5mL of 3,5,5-trimethylhexanol as the extractant in a 100mL conical flask. Alkyl alcohol occupies the organic phase. 20% of the volume, and then add 5 mL of the calcium-containing brine in Example 1 into it, and the volume ratio of the organic phase to the calcium-containing brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 0°C for 30 minutes. Then transfer the mixed liquid to a 100mL plastic test tube, centrifuge at 4000r/min for 8min in an LD5-10 benchtop centrifuge. The two-phase interface is clear. After phase separation, the extracted organic phase and the remaining brine phase are obtained. Transfer the loaded organic phase to another 100mL conical flask with a ground mouth, add water according to the volume ratio of 1:5 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer at 0℃ Perform back extraction and mix the two phases for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4000r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表5所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 5.
表5 N-戊基异壬酰胺和2-丙基庚醇、3,5,5-三甲基己醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 5 N-pentylisononylamide and 2-propylheptanol, 3,5,5-trimethylhexanol composite solvent for the two phases of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine Separation situation
从表5可以看出,Li
+单级萃取率为39.60%,Ca
2+单级萃取率为5.37%,锂钙分离系数为11.56。Li
+单级反萃取率为80.19%,Ca
2+单级反萃取率为94.99%,反萃取后锂钙分离系数为0.21,水相中钙锂质量比下降至9.30。B
2O
3单级萃取率为50.29%,B
2O
3单级反萃取率为92.05%。
It can be seen from Table 5 that the single-stage extraction rate of Li + is 39.60%, the single-stage extraction rate of Ca 2+ is 5.37%, and the lithium-calcium separation coefficient is 11.56. The Li + single-stage stripping rate was 80.19%, the Ca 2+ single-stage stripping rate was 94.99%, the lithium-calcium separation coefficient after the stripping was 0.21, and the calcium-lithium mass ratio in the water phase dropped to 9.30. The single-stage extraction rate of B 2 O 3 is 50.29%, and the single-stage back extraction rate of B 2 O 3 is 92.05%.
实施例6Example 6
取5mL实施例1中的含钙卤水于100mL磨口锥形瓶中,然后在其中加入纯度为99%的六水合三氯化铁0.56g,使其溶解后再加入20mL N-戊基异壬酰胺和5mL 2-丁基辛醇作为萃取剂,烷基醇占有机相体积的20%,有机相与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入 配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心10min,得到反萃取后的有机相和水相。Take 5mL of the calcium-containing brine in Example 1 into a 100mL conical flask, and then add 0.56g of 99% pure ferric trichloride hexahydrate, dissolve it, and then add 20mL N-pentylisonon Amide and 5mL 2-butyloctanol are used as extractants. Alkyl alcohol accounts for 20% of the volume of the organic phase. The volume ratio of the organic phase to the calcium-containing brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4000r/min for 10min in an LD5-10 benchtop centrifuge. The two-phase interface was clear. After phase separation, the extracted organic phase and the remaining brine phase were obtained. Transfer the loaded organic phase to another 100 mL conical flask with a ground mouth, add water according to the volume ratio of 1:5 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer at 20°C Perform back extraction and mix the two phases for 30 minutes. Then transfer the mixed liquid to a 100mL plastic test tube, and centrifuge at 4000r/min for 10min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表6所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 6.
表6 N-戊基异壬酰胺和2-丁基辛醇复合溶剂对某含Fe
3+卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 6 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a Fe 3+ brine containing N-pentylisononylamide and 2-butyloctanol composite solvent
从表6可以看出,Li
+单级萃取率为42.71%,Ca
2+单级萃取率为3.90%,锂钙分离系数为18.35。Li
+单级反萃取率为89.06%,Ca
2+单级反萃取率为92.31%,反萃取后锂钙分离系数为0.68,水相中钙锂质量比下降至5.48。B
2O
3单级萃取率为37.60%,B
2O
3单级反萃取率为92.75%。
It can be seen from Table 6 that the single-stage extraction rate of Li + is 42.71%, the single-stage extraction rate of Ca 2+ is 3.90%, and the separation coefficient of lithium and calcium is 18.35. The Li + single-stage stripping rate was 89.06%, and the Ca 2+ single-stage stripping rate was 92.31%. After the stripping, the lithium-calcium separation coefficient was 0.68, and the calcium-lithium mass ratio in the water phase dropped to 5.48. The single-stage extraction rate of B 2 O 3 is 37.60%, and the single-stage back extraction rate of B 2 O 3 is 92.75%.
实施例7Example 7
取24.55mL N-戊基异壬酰胺、0.20mL N-己基-3-环戊基丙酰胺和0.25mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,其中仲酰胺占有机相体积的99%、烷基醇占有机相体积的1%。然后在其中加入5mL含钙卤水,有机相与卤水体积比为5:1。该含钙卤水中Li
+、Ca
2+、Cl
-和B
2O
3含量分别为0.26、210.54、374.11和0.91g/L,钙锂质量比为825.65:1,卤水密度为1.41g/cm
3,卤水pH值为2.0。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于25℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4300r/min转速离心15min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在25℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4300r/min转速离心15min,得到反萃取后的有机相和水相。
Take 24.55mL N-pentylisononylamide, 0.20mL N-hexyl-3-cyclopentylpropionamide and 0.25mL 2-propylheptanol as the extractant in a 100mL conical flask, where the secondary amide accounts for the organic 99% of the volume of the phase and 1% of the volume of the organic phase. Then add 5 mL of calcium-containing brine, and the volume ratio of organic phase to brine is 5:1. The contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 0.26, 210.54, 374.11 and 0.91g/L, respectively, the mass ratio of calcium to lithium is 825.65:1, and the brine density is 1.41g/cm 3 , The pH of brine is 2.0. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir and extract at 25°C for 25 minutes. Then, the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4300r/min for 15min to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with a ground mouth, add deionized water at a volume ratio of 1:5 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4300r/min for 15min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表7所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 7.
表7 N-戊基异壬酰胺、N-己基-3-环戊基丙酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 7 N-pentylisononylamide, N-hexyl-3-cyclopentylpropionamide and 2-propylheptanol composite solvent for the two phases of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine Separation situation
从表7可以看出,Li
+单级萃取率为47.71%,Ca
2+单级萃取率为7.59%,锂钙分离系数为11.11。Li
+单级反萃取率为63.27%,Ca
2+单级反萃取率为93.15%,反萃取后锂钙分离系数为0.13,水相中钙锂质量比下降至193.43。B
2O
3单级萃取率为31.73%,B
2O
3单级反萃取率为79.72%。仲酰胺萃取剂在有机相中的体积占比高时,更有利于卤水中Li
+的萃取。
It can be seen from Table 7 that the single-stage extraction rate of Li + is 47.71%, the single-stage extraction rate of Ca 2+ is 7.59%, and the lithium-calcium separation coefficient is 11.11. The Li + single-stage back extraction rate was 63.27%, the Ca 2+ single-stage back extraction rate was 93.15%, the lithium-calcium separation coefficient after the back-extraction was 0.13, and the calcium-lithium mass ratio in the water phase dropped to 193.43. The single-stage extraction rate of B 2 O 3 is 31.73%, and the single-stage back extraction rate of B 2 O 3 is 79.72%. When the volume ratio of the secondary amide extractant in the organic phase is high, it is more conducive to the extraction of Li + from the brine.
实施例8Example 8
取0.25mL N-异辛基庚酰胺和24.75mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,其中仲酰胺占有机相体积的1%、烷基醇占有机相体积的99%。然后在其中加入5mL实施例1中的含钙卤水,萃取剂与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心5min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心5min,得到反萃取后的有机相和水相。Take 0.25mL N-isooctylheptanamide and 24.75mL 2-propylheptanol as extractants in a 100mL conical flask with a ground mouth. The secondary amide accounts for 1% of the volume of the organic phase and the alkyl alcohol accounts for 99% of the volume of the organic phase. . Then, 5 mL of the calcium-containing brine in Example 1 was added thereto, and the volume ratio of the extractant to the calcium-containing brine was 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, centrifuged in a LD5-10 benchtop centrifuge at 4000r/min for 5 minutes, the two-phase interface was clear, and the extracted organic phase and the remaining brine phase were obtained after phase separation. Transfer the loaded organic phase to another 100 mL conical flask, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 30 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4000r/min for 5min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表8所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 8.
表8 N-异辛基庚酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 8 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isooctylheptanamide and 2-propylheptanol
从表8可以看出,Li
+单级萃取率为6.50%,Ca
2+单级萃取率为1.91%,锂钙分离系数为3.57。Li
+单级反萃取率为48.99%,Ca
2+单级反萃取率为23.35%,反萃取后锂钙分离系数为3.15,水相中钙锂质量比下降至8.11。B
2O
3单级萃取率为91.26%,B
2O
3单级反萃取率为48.29%。烷基醇萃取剂在有机相中的体积占比高时,更有利于卤水中B
2O
3的萃取。
It can be seen from Table 8 that the single-stage extraction rate of Li + is 6.50%, the single-stage extraction rate of Ca 2+ is 1.91%, and the separation coefficient of lithium and calcium is 3.57. The Li + single-stage back extraction rate was 48.99%, the Ca 2+ single-stage back extraction rate was 23.35%, the lithium-calcium separation coefficient after the back-extraction was 3.15, and the calcium-lithium mass ratio in the water phase dropped to 8.11. The single-stage extraction rate of B 2 O 3 is 91.26%, and the single-stage back extraction rate of B 2 O 3 is 48.29%. When the volume ratio of the alkyl alcohol extractant in the organic phase is high, it is more conducive to the extraction of B 2 O 3 from the brine.
实施例9Example 9
取14.7mL N-戊基异壬酰胺、0.2mL N-环丙基癸酰胺(受热后液体)、0.1mL N-(4-叔丁基环己基)辛酰胺、3mL 2-辛基十二醇和12mL 260#溶剂油(上海优塔化工科技有限公司提供,下同)作为萃取剂和稀释剂于100mL磨口锥形瓶中,烷基醇和稀释剂分别占有机相体积的10%和40%。然后在其中加入3mL实施例7中的含钙卤水,有机相与含钙卤水体积比为10:1。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于25℃下混合搅拌、萃取25min。接着 将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:20的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在25℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到反萃取后的有机相和水相。Take 14.7mL N-pentylisononylamide, 0.2mL N-cyclopropyldecamide (liquid after heating), 0.1mL N-(4-tert-butylcyclohexyl)octamide, 3mL 2-octyldodecanol and 12mL 260 #Solvent oil (provided by Shanghai Youta Chemical Technology Co., Ltd., the same below) is used as the extractant and diluent in a 100mL conical flask with a grinding mouth. Alkyl alcohol and diluent account for 10% and 40% of the volume of the organic phase, respectively. Then, 3 mL of the calcium-containing brine in Example 7 was added thereto, and the volume ratio of the organic phase to the calcium-containing brine was 10:1. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir and extract at 25°C for 25 minutes. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged at 4200 r/min in an LD5-10 benchtop centrifuge for 8 minutes to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with a ground mouth, add deionized water at a volume ratio of 1:20 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表9所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 9.
表9 N-戊基异壬酰胺、N-环丙基癸酰胺、N-(4-叔丁基环己基)辛酰胺、2-辛基十二醇和260#溶剂油复合体系对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 9 The effect of N-pentylisononylamide, N-cyclopropyl decanamide, N-(4-tert-butylcyclohexyl) octylamide, 2-octyldodecanol and 260# solvent oil composite system on Li in a calcium-containing brine + , Ca 2+ and B 2 O 3 phase separation
从表9可以看出,Li
+单级萃取率为30.75%,Ca
2+单级萃取率为2.37%,锂钙分离系数为18.32。Li
+单级反萃取率为94.15%,Ca
2+单级反萃取率为92.24%,反萃取后锂钙分离系数为1.35,水相中钙锂质量比下降至62.27。B
2O
3单级萃取率为42.65%,B
2O
3单级反萃取率为75.51%。
It can be seen from Table 9 that the single-stage extraction rate of Li + is 30.75%, the single-stage extraction rate of Ca 2+ is 2.37%, and the separation coefficient of lithium and calcium is 18.32. The Li + single-stage stripping rate was 94.15%, the Ca 2+ single-stage stripping rate was 92.24%, the lithium-calcium separation coefficient after the stripping was 1.35, and the calcium-lithium mass ratio in the water phase dropped to 62.27. The single-stage extraction rate of B 2 O 3 was 42.65%, and the single-stage back extraction rate of B 2 O 3 was 75.51%.
实施例10Example 10
取14.4mL N-戊基异壬酰胺、0.5mL N-异辛基-1-环丙基甲酰胺、0.1g N-环十二基乙酰胺、14.85mL 2-丙基庚醇和0.15mL 260#溶剂油作为萃取剂和稀释剂于100mL磨口锥形瓶中,烷基醇和稀释剂分别占有机相体积的49.5%和0.5%。然后在其中加入3mL实施例7中的含钙卤水,其中B
2O
3含量调整为14.30g/L,卤水pH值在硼酸加入后为0.0,有机相与含钙卤水体积比为10:1。在锥形瓶中插入聚四氟乙烯搅拌杆,用DW-1-60型直流恒速搅拌器于50℃下混合搅拌、萃取25min。接着使混合液体自然澄清沉降60min,两相分离后得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:20的体积比加入去离子水,插入聚四氟乙烯搅拌杆,用DW-1-60型直流恒速搅拌器在50℃下进行反萃取、两相混合25min。然后让混合液体自然澄清沉降60min,两相分离后得到反萃取后的有机相和水相。
Take 14.4mL N-pentylisononylamide, 0.5mL N-isooctyl-1-cyclopropylformamide, 0.1g N-cyclododecylacetamide, 14.85mL 2-propylheptanol and 0.15mL 260# Solvent oil is used as an extractant and a diluent in a 100 mL conical flask with a ground mouth. Alkyl alcohol and diluent account for 49.5% and 0.5% of the volume of the organic phase, respectively. Then, 3 mL of the calcium-containing brine of Example 7 was added to it, wherein the content of B 2 O 3 was adjusted to 14.30 g/L, the pH of the brine was 0.0 after the addition of boric acid, and the volume ratio of the organic phase to the calcium-containing brine was 10:1. Insert a polytetrafluoroethylene stirring rod into the conical flask, mix, stir, and extract with a DW-1-60 DC constant speed stirrer at 50°C for 25 minutes. Then, the mixed liquid is naturally clarified and settled for 60 minutes, and the two phases are separated to obtain the loaded organic phase and the remaining brine phase after extraction. Transfer the loaded organic phase to another 100 mL conical flask with a ground mouth, add deionized water at a volume ratio of 1:20 to the organic phase, insert a PTFE stirring rod, and use DW-1-60 DC constant speed The stirrer performs back extraction at 50°C, and the two phases are mixed for 25 minutes. Then, the mixed liquid is allowed to naturally clarify and settle for 60 minutes, and the organic phase and the water phase after the back extraction are obtained after the two phases are separated.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表10所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 10.
表10 N-戊基异壬酰胺、N-异辛基-1-环丙基甲酰胺、N-环十二基乙酰胺、2-丙基庚醇和260#溶剂油复合体系对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 10 The effect of N-pentylisononylamide, N-isooctyl-1-cyclopropylformamide, N-cyclododecylacetamide, 2-propylheptanol and 260# solvent oil composite system on a calcium-containing brine The two-phase separation of Li + , Ca 2+ and B 2 O 3
从表10可以看出,Li
+单级萃取率为32.88%,Ca
2+单级萃取率为1.75%,锂钙分离系数为27.53。Li
+单级反萃取率为88.87%,Ca
2+单级反萃取率为94.48%,反萃取后锂钙分离系数为0.47,水相中钙锂质量比下降至46.69。B
2O
3单级萃取率为87.23%,B
2O
3单级反萃取率为25.97%。
It can be seen from Table 10 that the single-stage extraction rate of Li + is 32.88%, the single-stage extraction rate of Ca 2+ is 1.75%, and the separation coefficient of lithium and calcium is 27.53. The Li + single-stage back extraction rate was 88.87%, the Ca 2+ single-stage back extraction rate was 94.48%, the lithium-calcium separation coefficient after the back-extraction was 0.47, and the calcium-lithium mass ratio in the water phase dropped to 46.69. The single-stage extraction rate of B 2 O 3 is 87.23%, and the single-stage back extraction rate of B 2 O 3 is 25.97%.
实施例11Example 11
取13.5mL N-戊基异壬酰胺、1mL N-异辛基新癸酰胺、0.5mL N-十二基乙酰胺(受热后液体)和15mL 3-辛醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的50%,然后在其中加入3mL含钙卤水,有机相与卤水体积比为10:1。该含钙卤水中Li
+、Ca
2+、Cl
-和B
2O
3含量分别为3.99、274.10、514.18和2.01g/L,钙锂质量比为68.70:1,卤水密度为1.55g/cm
3,卤水pH值为0.6。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:10的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到反萃取后的有机相和水相。
Take 13.5mL N-pentylisononylamide, 1mL N-isooctylneodecylamide, 0.5mL N-dodecylacetamide (liquid after heating) and 15mL 3-octanol as extractant in a 100mL grinding cone In the bottle, the alkyl alcohol accounts for 50% of the volume of the organic phase, and then 3 mL of calcium-containing brine is added to the bottle, and the volume ratio of the organic phase to the brine is 10:1. The content of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 3.99, 274.10, 514.18 and 2.01g/L, respectively, the mass ratio of calcium to lithium is 68.70:1, and the brine density is 1.55g/cm 3 , The brine pH is 0.6. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20℃, and extract for 25min. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表11所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 11.
表11 N-戊基异壬酰胺、N-异辛基新癸酰胺、N-十二基乙酰胺和3-辛醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 11 The effects of N-pentylisononylamide, N-isooctylneodecylamide, N-dodecylacetamide and 3-octanol composite solvent on Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine The two-phase separation
从表11可以看出,Li
+单级萃取率为36.90%,Ca
2+单级萃取率为7.51%,锂钙分离系数为7.21。Li
+单级反萃取率为95.64%,Ca
2+单级反萃取率为83.01%,反萃取后锂钙分离系数为4.49,水相中钙锂质量比下降至12.14。B
2O
3单级萃取率为85.05%,B
2O
3单级反萃取率为77.92%。
It can be seen from Table 11 that the single-stage extraction rate of Li + is 36.90%, the single-stage extraction rate of Ca 2+ is 7.51%, and the separation coefficient of lithium and calcium is 7.21. The Li + single-stage stripping rate was 95.64%, and the Ca 2+ single-stage stripping rate was 83.01%. After the stripping, the lithium-calcium separation coefficient was 4.49, and the calcium-lithium mass ratio in the water phase dropped to 12.14. The single-stage extraction rate of B 2 O 3 was 85.05%, and the single-stage back extraction rate of B 2 O 3 was 77.92%.
实施例12Example 12
取23.5mL N-戊基异壬酰胺、0.5mL N-乙基-1-(4-戊基环己基)甲酰胺和6mL 2-丁基辛醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入3mL含钙卤水,有机相与卤水体积比为10:1。该含钙卤水中Li
+、Ca
2+、Cl
-和B
2O
3含量分别为23.87、179.61、439.81和0.50g/L,钙锂质量比为7.52:1,卤水密度为1.40g/cm
3,其pH值用浓盐酸调整至2.4。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:10的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到反萃取后的有机相和水相。
Take 23.5mL N-pentylisononylamide, 0.5mL N-ethyl-1-(4-pentylcyclohexyl)formamide and 6mL 2-butyloctanol as the extractant in a 100mL conical flask with a ground mouth. Alkyl alcohol accounts for 20% of the volume of the organic phase, and then 3 mL of calcium-containing brine is added to it, and the volume ratio of the organic phase to the brine is 10:1. The contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 23.87, 179.61, 439.81 and 0.50g/L, respectively, the mass ratio of calcium to lithium is 7.52:1, and the density of the brine is 1.40g/cm 3 , Its pH value is adjusted to 2.4 with concentrated hydrochloric acid. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 30 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对 萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表12所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 12.
表12 N-戊基异壬酰胺、N-乙基-1-(4-戊基环己基)甲酰胺和2-丁基辛醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 12 The effects of N-pentylisononylamide, N-ethyl-1-(4-pentylcyclohexyl)formamide and 2-butyloctanol composite solvent on Li + , Ca 2+ and B in a calcium-containing brine Two-phase separation of 2 O 3
从表12可以看出,Li
+单级萃取率为40.83%,Ca
2+单级萃取率为6.16%,锂钙分离系数为10.52。Li
+单级反萃取率为70.83%,Ca
2+单级反萃取率为84.22%,反萃取后锂钙分离系数为0.46,水相中钙锂质量比下降至1.36。B
2O
3单级萃取率为50.41%,B
2O
3单级反萃取率为89.29%。
It can be seen from Table 12 that the single-stage extraction rate of Li + is 40.83%, the single-stage extraction rate of Ca 2+ is 6.16%, and the separation coefficient of lithium and calcium is 10.52. The Li + single-stage stripping rate was 70.83%, and the Ca 2+ single-stage stripping rate was 84.22%. After the stripping, the lithium-calcium separation coefficient was 0.46, and the calcium-lithium mass ratio in the water phase dropped to 1.36. The single-stage extraction rate of B 2 O 3 is 50.41%, and the single-stage back extraction rate of B 2 O 3 is 89.29%.
实施例13Example 13
取25.5mL N-戊基异壬酰胺、1mL N-异辛基丁酰胺、0.45g N-乙基月桂酰胺、2.85mL 2-己基癸醇和0.15mL 260#溶剂油作为萃取剂和稀释剂于100mL磨口锥形瓶中,烷基醇和稀释剂分别占有机相体积的9.5%和0.5%,然后在其中加入3mL含钙卤水,有机相与卤水体积比为10:1。该含钙卤水中Li
+、Ca
2+、Cl
-和B
2O
3含量分别为2.51、147.61、274.31和2.48g/L,钙锂质量比为58.80:1,卤水密度为1.30g/cm
3,卤水pH值为2.0。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:10的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到反萃取后的有机相和水相。
Take 25.5mL N-pentylisononylamide, 1mL N-isooctylbutanamide, 0.45g N-ethyl lauramide, 2.85mL 2-hexyldecanol and 0.15mL 260# solvent oil as extractant and diluent in 100mL In the ground conical flask, the alkyl alcohol and the diluent accounted for 9.5% and 0.5% of the volume of the organic phase respectively, and then 3 mL of calcium-containing brine was added into it, and the volume ratio of the organic phase to the brine was 10:1. The contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 2.51, 147.61, 274.31 and 2.48g/L, respectively, the mass ratio of calcium to lithium is 58.80:1, and the density of the brine is 1.30g/cm 3 , The pH of brine is 2.0. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20℃, and extract for 25min. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表13所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 13.
表13 N-异辛基丁酰胺、N-乙基月桂酰胺、N-戊基异壬酰胺、2-己基癸醇和260#溶剂油复合体系对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 13 The effects of N-isooctylbutanamide, N-ethyl lauramide, N-pentylisononylamide, 2-hexyldecanol and 260# solvent oil composite system on Li + , Ca 2+ and B in a calcium-containing brine Two-phase separation of 2 O 3
从表13可以看出,Li
+单级萃取率为38.11%,Ca
2+单级萃取率为5.03%,锂钙分离系数为11.62。Li
+单级反萃取率为76.74%,Ca
2+单级反萃取率为87.96%,反萃取后锂钙分离系数为0.45,水相中钙锂质量比下降至8.91。B
2O
3单级萃取率为35.06%,B
2O
3单级反萃取率为79.20%。
It can be seen from Table 13 that the single-stage extraction rate of Li + is 38.11%, the single-stage extraction rate of Ca 2+ is 5.03%, and the separation coefficient of lithium and calcium is 11.62. The Li + single-stage stripping rate was 76.74%, the Ca 2+ single-stage stripping rate was 87.96%, the lithium-calcium separation coefficient after the stripping was 0.45, and the calcium-lithium mass ratio in the water phase dropped to 8.91. The single-stage extraction rate of B 2 O 3 is 35.06%, and the single-stage back extraction rate of B 2 O 3 is 79.20%.
实施例14Example 14
取18mL N-戊基异壬酰胺和2mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,其中仲酰胺占有机相体积的90%、烷基醇占有机相体积的10%。然后在其中加入10mL含钙卤水,有机相与卤水体积比为2:1。该含钙卤水中Li
+、Ca
2+、Cl
-和B
2O
3含量分别为0.21、210.79、374.33和1.35g/L,钙锂质量比为1003.76:1,卤水密度为1.41g/cm
3,其pH值用浓盐酸调整至2.0。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:2的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到反萃取后的有机相和水相。
Take 18mL of N-pentylisononylamide and 2mL of 2-propylheptanol as extractants in a 100mL conical flask with a ground mouth. The secondary amide accounts for 90% of the volume of the organic phase and the alkyl alcohol accounts for 10% of the volume of the organic phase. . Then add 10 mL of calcium-containing brine, and the volume ratio of organic phase to brine is 2:1. The content of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine is 0.21, 210.79, 374.33 and 1.35g/L, respectively, the mass ratio of calcium to lithium is 1003.76:1, and the density of brine is 1.41g/cm 3 , Its pH value is adjusted to 2.0 with concentrated hydrochloric acid. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20℃, and extract for 25min. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:2 to the organic phase, and place it in a DF-101S heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表14所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 14.
表14 N-戊基异壬酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 14 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
从表14可以看出,Li
+单级萃取率为29.39%,Ca
2+单级萃取率为8.68%,锂钙分离系数为4.38。Li
+单级反萃取率为82.76%,Ca
2+单级反萃取率为81.09%,反萃取后锂钙分离系数为1.13,水相中钙锂质量比下降至290.47。B
2O
3单级萃取率为23.14%,B
2O
3单级反萃取率为94.61%。
It can be seen from Table 14 that the single-stage extraction rate of Li + is 29.39%, the single-stage extraction rate of Ca 2+ is 8.68%, and the lithium-calcium separation coefficient is 4.38. The Li + single-stage stripping rate was 82.76%, and the Ca 2+ single-stage stripping rate was 81.09%. After the stripping, the lithium-calcium separation coefficient was 1.13, and the calcium-lithium mass ratio in the water phase dropped to 290.47. The single-stage extraction rate of B 2 O 3 was 23.14%, and the single-stage back extraction rate of B 2 O 3 was 94.61%.
实施例15Example 15
取21mL N-戊基异壬酰胺和9mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,其中仲酰胺占有机相体积的70%、烷基醇占有机相体积的30%,然后在其中加入3mL含钙卤水,有机相与卤水体积比为10:1。该含钙卤水中Li
+、Ca
2+、Cl
-和B
2O
3含量分别为0.094、178.60、316.43和1.01g/L,钙锂质量比为1900.00:1,卤水密度为1.36g/cm
3,其pH值用浓氨水调整至7.0。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:10的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心8min,得到反萃取后的有机相和水相。
Take 21mL of N-pentylisononylamide and 9mL of 2-propylheptanol as extractants in a 100mL conical flask, where the secondary amide accounts for 70% of the volume of the organic phase, and the alkyl alcohol accounts for 30% of the volume of the organic phase. , And then add 3mL calcium-containing brine, the volume ratio of organic phase to brine is 10:1. The contents of Li + , Ca 2+ , Cl - and B 2 O 3 in the calcium-containing brine are 0.094, 178.60, 316.43 and 1.01g/L, respectively, the mass ratio of calcium to lithium is 1900.00:1, and the brine density is 1.36g/cm 3 , Its pH value is adjusted to 7.0 with concentrated ammonia water. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20℃, and extract for 25min. Then, the mixed liquid was transferred to a 100 mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4200 r/min for 8 minutes to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask with ground mouth, add deionized water at a volume ratio of 1:10 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表15所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 15.
表15 N-戊基异壬酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 15 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
从表15可以看出,Li
+单级萃取率为42.68%,Ca
2+单级萃取率为3.70%,锂钙分离系数为19.33。Li
+单级反萃取率为92.13%,Ca
2+单级反萃取率为89.55%,反萃取后锂钙分离系数为1.37,水相中钙锂质量比下降至160.10。B
2O
3单级萃取率为58.51%,B
2O
3单级反萃取率为92.54%。
It can be seen from Table 15 that the single-stage extraction rate of Li + is 42.68%, the single-stage extraction rate of Ca 2+ is 3.70%, and the lithium-calcium separation coefficient is 19.33. The Li + single-stage stripping rate was 92.13%, the Ca 2+ single-stage stripping rate was 89.55%, the lithium-calcium separation coefficient after the stripping was 1.37, and the calcium-lithium mass ratio in the water phase dropped to 160.10. The single-stage extraction rate of B 2 O 3 is 58.51%, and the single-stage back extraction rate of B 2 O 3 is 92.54%.
实施例16Example 16
取9.5mL N-戊基异壬酰胺和0.5mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,其中仲酰胺占有机相体积的95%、烷基醇占有机相体积的5%。然后在其中加入10mL实施例7中的含钙卤水,有机相与含钙卤水体积比为1:1。在锥形瓶中放入磁子,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取25min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心15min,得到萃取后负载有机相和剩余卤水相。把负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:1的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行反萃取、两相混合25min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4200r/min转速离心15min,得到反萃取后的有机相和水相。Take 9.5 mL of N-pentylisononylamide and 0.5 mL of 2-propylheptanol as extractants in a 100 mL conical flask. The secondary amide accounts for 95% of the volume of the organic phase, and the alkyl alcohol accounts for 95% of the volume of the organic phase. 5%. Then, 10 mL of the calcium-containing brine in Example 7 was added thereto, and the volume ratio of the organic phase to the calcium-containing brine was 1:1. Put the magnet in the Erlenmeyer flask, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix and stir at 20℃, and extract for 25min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 benchtop centrifuge at 4200r/min for 15min to obtain the extracted organic phase and the remaining brine phase. Transfer the loaded organic phase to another 100 mL conical flask, add deionized water at a volume ratio of 1:1 to the organic phase, and place it in a DF-101S type heat-collecting thermostatic heating magnetic stirrer. Perform back extraction at ℃ and mix the two phases for 25 min. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged at 4200r/min for 15min in an LD5-10 benchtop centrifuge to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表16所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 16.
表16 N-戊基异壬酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的两相分离情况
Table 16 The two-phase separation of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
从表16可以看出,Li
+单级萃取率为32.70%,Ca
2+单级萃取率为4.67%,锂钙分离系数为9.72。Li
+单级反萃取率为72.14%,Ca
2+单级反萃取率为89.10%,反萃取后锂钙分离系数为0.32,水相中钙锂质量比下降至145.64。B
2O
3单级萃取率为15.38%,B
2O
3单级反萃取率为92.26%。
It can be seen from Table 16 that the single-stage extraction rate of Li + is 32.70%, the single-stage extraction rate of Ca 2+ is 4.67%, and the lithium-calcium separation coefficient is 9.72. The Li + single-stage stripping rate was 72.14%, the Ca 2+ single-stage stripping rate was 89.10%, the lithium-calcium separation coefficient after the stripping was 0.32, and the calcium-lithium mass ratio in the water phase dropped to 145.64. The single-stage extraction rate of B 2 O 3 was 15.38%, and the single-stage back extraction rate of B 2 O 3 was 92.26%.
实施例17Example 17
取20mL N-戊基异壬酰胺和5mL 2-丙基庚醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入5mL实施例1中的含钙卤水,有机相与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取20min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心8min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。接着按照萃取串级交叉操作步骤进行三级逆流萃取,得到三级 逆流萃取后的负载有机相和剩余卤水相。Take 20mL of N-pentylisononylamide and 5mL of 2-propylheptanol as extractants in a 100mL conical flask with a ground mouth. Alkyl alcohol accounts for 20% of the volume of the organic phase, and then add 5mL of Example 1 For calcium-containing brine, the volume ratio of organic phase to calcium-containing brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, place it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 20 minutes. Then transfer the mixed liquid to a 100mL plastic test tube, centrifuge at 4000r/min for 8min in an LD5-10 benchtop centrifuge. The two-phase interface is clear. After phase separation, the extracted organic phase and the remaining brine phase are obtained. Then, perform three-stage countercurrent extraction according to the extraction cascade crossover operation steps to obtain the loaded organic phase and the remaining brine phase after the three-stage countercurrent extraction.
把三级逆流萃取后的负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行单级反萃取、两相混合20min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心8min,得到反萃取后的有机相和水相。Transfer the loaded organic phase after the three-stage countercurrent extraction to another 100mL conical flask with ground mouth, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic force In the stirrer, single-stage back extraction and two-phase mixing were carried out at 20°C for 20 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4000r/min for 8min to obtain the organic phase and the water phase after the stripping.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表17所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 17.
表17 N-戊基异壬酰胺和2-丙基庚醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的三级逆流萃取和单级反萃取情况
Table 17 The three-stage countercurrent extraction and single-stage back extraction of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-pentylisononylamide and 2-propylheptanol
从表17可以看出,卤水经过三级逆流萃取后Li
+萃取率为54.62%,Ca
2+萃取率为6.14%,锂钙分离系数达到18.40。Li
+单级反萃取率为72.28%,Ca
2+单级反萃取率为58.12%,反萃取后锂钙分离系数为1.88,水相中钙锂质量比下降至5.23,卤水中的Li
+与Ca
2+实现有效分离。其中卤水经过三级逆流后B
2O
3的萃取率为79.48%,B
2O
3的单级反萃取率为92.50%,表明该萃取体系能提取Li
+的同时也能有效提取B
2O
3。多级逆流萃取级数越多,卤水中的锂和硼的萃取率越高、锂钙分离系数越大,在减少水相用量的情况下,多级逆流反萃取级数越多越有利于反萃取后水相中Li
+和B
2O
3浓度的提高。进一步提高逆流萃取和逆流反萃取级数,Li
+和B
2O
3的萃取率和反萃取率进一步提高,而Ca
2+的萃取率基本不变、Mg
2+的萃取率不大。
It can be seen from Table 17 that after the three-stage countercurrent extraction of brine, the extraction rate of Li + is 54.62%, the extraction rate of Ca 2+ is 6.14%, and the separation coefficient of lithium and calcium reaches 18.40. Li + single stage inverse extraction rate 72.28%, Ca 2+ single stage inverse extraction rate 58.12%, lithium, calcium separation factor 1.88 back extracted the aqueous phase mass ratio of lithium, calcium decreased to 5.23, and Li + in the brine Ca 2+ achieves effective separation. Among them, the extraction rate of B 2 O 3 was 79.48% after three-stage countercurrent of brine , and the single-stage back-extraction rate of B 2 O 3 was 92.50%, indicating that the extraction system can extract Li + and also effectively extract B 2 O 3 . The more multi-stage counter-current extraction stages, the higher the extraction rate of lithium and boron in the brine, and the greater the lithium-calcium separation coefficient. In the case of reducing the amount of water phase, the more multi-stage counter-current extraction stages are more beneficial to the reaction. The concentration of Li + and B 2 O 3 in the aqueous phase increased after extraction. Further increase the countercurrent extraction and countercurrent stripping stages, the extraction rate and stripping rate of Li + and B 2 O 3 are further improved, while the extraction rate of Ca 2+ is basically unchanged, and the extraction rate of Mg 2+ is not large.
把反萃取后有机相返回与萃取前卤水相重新混合,实现萃取剂的循环使用。The organic phase after the stripping is returned and remixed with the brine phase before the extraction to realize the recycling of the extractant.
接着把反萃取后得到的水相溶液进行除油、经过二效蒸发浓缩至Li
+浓度为30g/L后,分别加入硫酸钠、碳酸钠溶液彻底沉淀除去其中的Ca
2+,分别加入氯化钡、氢氧化钠溶液彻底沉淀除去其中的硫酸根、Mg
2+,然后对剩余溶液进行蒸发浓缩、冷却结晶、过滤干燥后制得无水氯化锂产品。
Then the water phase solution obtained after the back extraction is degreasing, and after two-effect evaporation is concentrated to a Li + concentration of 30g/L, sodium sulfate and sodium carbonate solutions are respectively added to completely precipitate and remove Ca 2+ , and chlorination is added separately The barium and sodium hydroxide solution are completely precipitated to remove the sulfate radical and Mg 2+ , and then the remaining solution is evaporated and concentrated, cooled and crystallized, filtered and dried to obtain anhydrous lithium chloride product.
把经过除杂精制后得到的氯化锂浓缩液置于离子膜电解槽中进行电解,在阴极得到质量浓度为12%的氢氧化锂溶液,经浓缩、结晶后得到单水氢氧化锂,再经水洗、干燥后制得无水氢氧化锂产品。同时副产氢气和氯气,使氢气和氯气进一步反应制得盐酸。The lithium chloride concentrate obtained after purification and purification is placed in an ion-exchange membrane electrolyzer for electrolysis, a lithium hydroxide solution with a mass concentration of 12% is obtained at the cathode, and lithium hydroxide monohydrate is obtained after concentration and crystallization. After washing and drying, an anhydrous lithium hydroxide product is prepared. At the same time, hydrogen and chlorine are by-produced, and hydrogen and chlorine are further reacted to produce hydrochloric acid.
实施例18Example 18
取10mL N-异丁基异壬酰胺(受热后液体)、10mL N-异辛基异戊酰胺和5mL 2-辛基十二醇作为萃取剂于100mL磨口锥形瓶中,烷基醇占有机相体积的20%,然后在其中加入5mL实施例1中的含钙卤水,其pH值通过加浓盐酸调至0.9,有机相与含钙卤水体积比为5:1。在锥形瓶中放入磁子,其瓶口插入配套的空气冷凝管防止液体溅出,置于DF-101S型集热式恒温加热磁力搅拌器中,于20℃下混合搅拌、萃取30min。接着将混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心8min,两相界面清晰,分相后得到萃取后负载有机相和剩余卤水相。接着按照萃取串级交叉操作步骤进行三级逆流萃取,得到三级逆流萃取后的负载有机相和剩余卤水相。Take 10mL N-isobutylisononylamide (liquid after heating), 10mL N-isooctylisovaleramide and 5mL 2-octyldodecanol as extractants in a 100mL ground-mouth Erlenmeyer flask. Alkyl alcohol accounts for the organic phase. 20% of the volume, and then add 5 mL of the calcium-containing brine in Example 1 into it, the pH value of which is adjusted to 0.9 by adding concentrated hydrochloric acid, and the volume ratio of the organic phase to the calcium-containing brine is 5:1. Put the magnet in the Erlenmeyer flask, insert the matching air condenser at the mouth of the flask to prevent the liquid from splashing out, put it in the DF-101S type heat-collecting thermostatic heating magnetic stirrer, mix, stir, and extract at 20°C for 30 minutes. Then transfer the mixed liquid to a 100mL plastic test tube, centrifuge at 4000r/min for 8min in an LD5-10 benchtop centrifuge. The two-phase interface is clear. After phase separation, the extracted organic phase and the remaining brine phase are obtained. Then, three-stage countercurrent extraction is performed according to the extraction cascade crossover operation steps to obtain the loaded organic phase and the remaining brine phase after the three-stage countercurrent extraction.
把三级逆流萃取后的负载有机相转移至另一个100mL的磨口锥形瓶中,按与有机相1:5的体积比加入去离子水,置于DF-101S型集热式恒温加热磁力搅拌器中,在20℃下进行单级反萃取、两相混合30min。然后把混合液体转移至100mL塑料试筒中,在LD5-10型台式离心机中以4000r/min转速离心8min,得到反萃取后的有机相和水相。接着按照串级交叉操作步骤进行二级逆流反萃取,得到二级逆流反萃取后的有机相和水相。Transfer the loaded organic phase after the three-stage countercurrent extraction to another 100mL conical flask with ground mouth, add deionized water according to the volume ratio of 1:5 to the organic phase, and place it in the DF-101S type heat-collecting thermostatic heating magnetic force In the stirrer, single-stage back extraction and two-phase mixing were carried out at 20°C for 30 minutes. Then the mixed liquid was transferred to a 100mL plastic test tube, and centrifuged in an LD5-10 tabletop centrifuge at 4000r/min for 8min to obtain the organic phase and the water phase after the stripping. Then, the secondary countercurrent back extraction is performed according to the cascade crossover operation steps to obtain the organic phase and the water phase after the second countercurrent back extraction.
分别采用日本岛津AA-7000型原子吸收分光光度计标准加入法、EDTA滴定法和甘露醇法对萃取和反萃取过程中的卤水相和水相进行定容、配成分析溶液,取样分析Li
+、Ca
2+和B
2O
3含量,计算出实验结果如表18所示。
The standard addition method of Japan Shimadzu AA-7000 atomic absorption spectrophotometer, EDTA titration method and mannitol method were used to determine the volume of the brine phase and the water phase in the extraction and stripping process, prepare the analysis solution, and sample and analyze the Li + , Ca 2+ and B 2 O 3 contents, calculated experimental results are shown in Table 18.
表18 N-异丁基异壬酰胺、N-异辛基异戊酰胺和2-辛基十二醇复合溶剂对某含钙卤水中Li
+、Ca
2+和B
2O
3的三级逆流萃取和二级逆流反萃取情况
Table 18 The three-stage countercurrent extraction and extraction of Li + , Ca 2+ and B 2 O 3 in a calcium-containing brine by the composite solvent of N-isobutylisononylamide, N-isooctylisovaleramide and 2-octyldodecanol Secondary countercurrent extraction situation
从表18可以看出,卤水经过三级逆流萃取后Li
+萃取率为45.37%,Ca
2+萃取率为3.98%,锂钙分离系数达到20.04。负载有机相经过二级逆流反萃取后Li
+反萃取率为86.81%,Ca
2+反萃取率为89.47%,反萃取后锂钙分离系数为0.77,水相中钙锂质量比下降至5.24,卤水中的Li
+与Ca
2+实现有效分离。其中卤水经过三级逆流后B
2O
3的萃取率为56.41%,B
2O
3的二级逆流反萃取率为96.14%,表明该萃取体系能提取Li
+的同时也能有效提取B
2O
3。进一步提高逆流萃取和逆流反萃取级数,Li
+和B
2O
3的萃取率和反萃取率进一步提高,而Ca
2+的萃取率基本不变、Mg
2+的萃取率不大。
It can be seen from Table 18 that after the three-stage countercurrent extraction of brine, the extraction rate of Li + is 45.37%, the extraction rate of Ca 2+ is 3.98%, and the separation coefficient of lithium and calcium reaches 20.04. After the loaded organic phase is subjected to secondary countercurrent stripping, the Li + stripping rate is 86.81%, the Ca 2+ stripping rate is 89.47%, the lithium-calcium separation coefficient after stripping is 0.77, and the calcium-lithium mass ratio in the water phase drops to 5.24. Li + and Ca 2+ in brine are effectively separated. Among them, the extraction rate of B 2 O 3 was 56.41% after the brine was subjected to three-stage countercurrent, and the second- stage counter-current extraction rate of B 2 O 3 was 96.14%, indicating that the extraction system can extract Li + while also effectively extracting B 2 O 3 . Further increase the countercurrent extraction and countercurrent stripping stages, the extraction rate and stripping rate of Li + and B 2 O 3 are further improved, while the extraction rate of Ca 2+ is basically unchanged, and the extraction rate of Mg 2+ is not large.
接着把反萃取后得到的水相溶液进行除油、经过二效蒸发浓缩至Li
+浓度为20g/L后,分别加入硫酸钠、碳酸钠溶液彻底沉淀除去其中的Ca
2+,分别加入氯化钡、氢氧化钠溶液彻底沉淀除去其中的硫酸根、Mg
2+,得到氯化锂精制溶液。然后在其中按其理论用量的1.1倍加入浓度为250g/L的碳酸钠溶液,产生碳酸锂沉淀,经过过滤、干燥后制得碳酸锂产品。
Then the water phase solution obtained after the back extraction is degreasing, and after two-effect evaporation is concentrated to a Li + concentration of 20g/L, sodium sulfate and sodium carbonate solutions are respectively added to completely precipitate and remove Ca 2+ , and chlorination is added separately The barium and sodium hydroxide solutions are completely precipitated to remove sulfate radicals and Mg 2+ in them , and a refined solution of lithium chloride is obtained. Then, a sodium carbonate solution with a concentration of 250 g/L was added to it at 1.1 times the theoretical amount to produce a lithium carbonate precipitate, which was filtered and dried to obtain a lithium carbonate product.
在获得的碳酸锂中加入氢氧化钙乳液,加热并强力搅拌进行固-液反应生成氢氧化锂溶液和碳酸钙沉淀,两相分离后得到氢氧化锂溶液,对其进行减压浓缩、结晶和在130~140℃下干燥后制得单水氢氧化锂,再在150~180℃下减压加热制得无水氢氧化锂产品。Add calcium hydroxide emulsion to the obtained lithium carbonate, heat and vigorously stir for solid-liquid reaction to produce lithium hydroxide solution and calcium carbonate precipitate, after the two phases are separated, the lithium hydroxide solution is obtained, which is concentrated under reduced pressure, crystallized and After drying at 130-140°C, monohydrate lithium hydroxide is prepared, and then heated under reduced pressure at 150-180°C to prepare anhydrous lithium hydroxide product.
以上仅为本发明选择提供的部分实施案例而已,本发明的实施方式不受上述实施例的限制。对于本领域技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、组合和改进等以及依此进行形式和细节上的各种变化,都归属于本项技术发明的保护范围。The above are only part of the implementation cases selected and provided by the present invention, and the implementation of the present invention is not limited by the foregoing embodiments. For those skilled in the art, the present invention can have various modifications and changes. Any modifications, equivalent substitutions, combinations and improvements made within the spirit and principle of the present invention, as well as various changes in form and details made accordingly, fall within the protection scope of this technical invention.
表19实施例中涉及到的A物质仲酰胺的常用名称、对应规范名称和代号Table 19: Common names, corresponding standard names and codes of the secondary amides of substance A involved in the Examples
序号Serial number | 部分A物质仲酰胺常用名称Common names of secondary amides of part A substances | 部分A物质仲酰胺对应规范名称Part A substance secondary amide corresponding to the standard name | 代号Codename |
11 | N-异辛基丁酰胺N-Isooctyl Butanamide | N-(2-乙基己基)正丁酰胺N-(2-ethylhexyl) n-butanamide | Z842Z842 |
22 | N-异丁基异壬酰胺N-isobutylisononylamide | N-(2-甲基丙基)-3,5,5-三甲基己酰胺N-(2-methylpropyl)-3,5,5-trimethylhexanamide | Z494Z494 |
33 | N-异辛基戊酰胺N-isooctyl valeramide | N-(2-乙基己基)正戊酰胺N-(2-ethylhexyl) n-pentanoamide | Z852Z852 |
44 | N-异辛基异戊酰胺N-Isooctyl Isovaleramide | N-(2-乙基己基)-3-甲基丁酰胺N-(2-ethylhexyl)-3-methylbutanamide | Z854Z854 |
55 | N-乙基月桂酰胺N-ethyl lauramide | N-乙基正十二酰胺N-ethyl n-dodecamide | Z2121Z2121 |
66 | N-戊基异壬酰胺N-Pentylisononamide | N-戊基-3,5,5-三甲基己酰胺N-pentyl-3,5,5-trimethylhexanamide | Z593Z593 |
77 | N-十二基乙酰胺N-Dodecylacetamide | N-正十二基乙酰胺N-Dodecylacetamide | Z1221Z1221 |
88 | N-异辛基异己酰胺N-isooctylisohexanamide | N-(2-乙基己基)-4-甲基戊酰胺N-(2-ethylhexyl)-4-methylpentanamide | Z864Z864 |
99 | N-异辛基庚酰胺N-Isooctylheptanamide | N-(2-乙基己基)正庚酰胺N-(2-Ethylhexyl) n-heptanamide | Z872Z872 |
1010 | N-异辛基新癸酰胺N-Isooctyl Neodecylamide | N-(2-乙基己基)-7,7-二甲基辛酰胺N-(2-Ethylhexyl)-7,7-Dimethyloctylamide | Z8104Z8104 |
1111 | N-异辛基-1-环丙基甲酰胺N-isooctyl-1-cyclopropylformamide | N-(2-乙基己基)-1-环丙基甲酰胺N-(2-ethylhexyl)-1-cyclopropylformamide | Z84h2Z84h2 |
1212 | N-环丙基癸酰胺N-cyclopropyl decanamide | N-环丙基正癸酰胺N-Cyclopropyl-n-decylamide | Z3h101Z3h101 |
1313 | N-乙基-1-(4-戊基环己基)甲酰胺N-ethyl-1-(4-pentylcyclohexyl)formamide | N-乙基-1-(4-正戊基环己基)甲酰胺N-ethyl-1-(4-n-pentylcyclohexyl)formamide | Z212h1Z212h1 |
1414 | N-环十二基乙酰胺N-Cyclododecylacetamide | N-环十二基乙酰胺N-Cyclododecylacetamide | Z12h21Z12h21 |
1515 | N-己基-3-环戊基丙酰胺N-hexyl-3-cyclopentyl propionamide | N-正己基-3-环戊基丙酰胺N-hexyl-3-cyclopentyl propionamide | Z68h1Z68h1 |
1616 | N-(4-叔丁基环己基)辛酰胺N-(4-tert-butylcyclohexyl)octylamide | N-(4-叔丁基环己基)正辛酰胺N-(4-tert-butylcyclohexyl) n-octylamide | Z10h82Z10h82 |
表20实施例中涉及到的B物质烷基醇的常用名称、对应规范名称和CAS号
*
Table 20: Common names, corresponding normative names and CAS numbers of substance B alkyl alcohols involved in the examples *
序号Serial number | 部分B物质烷基醇常用名称Common Names of Part B Alkyl Alcohols | 部分B物质烷基醇对应规范名称Part B Alkyl Alcohol Corresponding Specification Name | CAS号CAS number |
11 | 3-辛醇3-octanol | 3-辛醇3-octanol | 589-98-0589-98-0 |
22 | 3,5,5-三甲基己醇3,5,5-Trimethylhexanol | 3,5,5-三甲基-1-己醇3,5,5-Trimethyl-1-hexanol | 3452-97-93452-97-9 |
33 | 2-丙基庚醇2-propylheptanol | 2-正丙基-1-庚醇2-n-propyl-1-heptanol | 10042-59-810042-59-8 |
44 | 2-丁基辛醇2-Butyloctanol | 2-正丁基-1-辛醇2-n-Butyl-1-octanol | 3913-02-83913-02-8 |
55 | 2-己基癸醇2-hexyldecanol | 2-正己基-1-癸醇2-n-hexyl-1-decanol | 2425-77-62425-77-6 |
66 | 2-辛基十二醇2-octyldodecanol | 2-正辛基-1-十二醇2-n-octyl-1-dodecanol | 5333-42-65333-42-6 |
*CAS号为美国化学文摘社登记号。
* CAS number is the American Chemical Abstract Service registration number.
Claims (14)
- 用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系,其特征在于,萃取体系中含有A和B两类物质;其中A类物质为仲酰胺由单一化合物或两种以上的混合物组成;其中,单一化合物具有如式(I)所示的结构:A secondary amide/alkyl alcohol composite solvent is used to separate calcium from calcium-containing brine to extract lithium and boron. The extraction system is characterized in that the extraction system contains two types of substances A and B; wherein the type A substance is a secondary amide compound or It is composed of a mixture of two or more; wherein, a single compound has a structure as shown in formula (I):其中,R 1选自C1~C12的烷基或含有单环结构的C3~C12的环烷基,R 2选自C1~C11的烷基或含有单环结构的C3~C11的环烷基,并且R 1和R 2两基团中所含碳原子数目之和为11~17,其中烷基或环烷基包括各种同分异构体; Wherein, R 1 is selected from a C1-C12 alkyl group or a C3-C12 cycloalkyl group containing a monocyclic structure, and R 2 is selected from a C1-C11 alkyl group or a C3-C11 cycloalkyl group containing a monocyclic structure, And the sum of the number of carbon atoms contained in the two groups R 1 and R 2 is 11-17, wherein alkyl or cycloalkyl includes various isomers;其中B类物质为烷基醇由单一化合物或两种以上的混合物组成;其中,单一化合物具有如式(Ⅱ)所示的结构:Among them, type B substances are alkyl alcohols consisting of a single compound or a mixture of two or more; among them, a single compound has a structure as shown in formula (II):R 3——OH (Ⅱ); R 3 ——OH (Ⅱ);其中,R 3选自C8~C20的烷基,其中烷基包含直链的或带有支链的各种同分异构体; Wherein, R 3 is selected from C8 to C20 alkyl groups, where the alkyl groups include linear or branched isomers;含有A和B两类物质的萃取体系的凝固点小于0℃。The freezing point of the extraction system containing two types of substances A and B is less than 0°C.
- 根据权利要求1所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系,其特征在于,所述A类物质主要起萃取锂的作用在整个有机相中所占的体积百分数为0~100%,不包括两个端点值;所述B类物质主要起萃取硼的作用在整个有机相中所占的体积百分数为0~100%,不包括两个端点值。The extraction system for separating calcium and extracting lithium and boron from calcium-containing brine using a secondary amide/alkyl alcohol composite solvent according to claim 1, wherein the type A substance mainly functions to extract lithium in the entire organic phase. The volume percentage in the organic phase is 0-100%, excluding the two endpoints; the B-type substance mainly functions to extract boron, and the volume percentage in the entire organic phase is 0-100%, excluding the two Endpoint value.
- 根据权利要求1所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系,其特征在于,萃取体系有利于同时萃取锂和硼时,所述A类物质在整个有机相中所占的体积百分数为50~90%,所述B类物质在整个有机相中所占的体积百分数为10~50%。The extraction system for extracting lithium and boron from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent according to claim 1, wherein the extraction system facilitates simultaneous extraction of lithium and boron. The volume percentage of the substance in the entire organic phase is 50-90%, and the volume percentage of the B-type substance in the entire organic phase is 10-50%.
- 根据权利要求1所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取体系,其特征在于,还包含有起稀释作用的稀释剂260#溶剂油、300#溶剂油或磺化煤油。The extraction system for separating calcium and extracting lithium and boron from calcium-containing brine using a secondary amide/alkyl alcohol composite solvent according to claim 1, characterized in that it also contains a diluent 260# solvent oil, 300 #Solvent oil or sulfonated kerosene.
- 用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,其特征在于,包括下列步骤:The extraction method for separating calcium from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent to extract lithium and boron is characterized in that it comprises the following steps:S1、以含钙卤水作为萃取前卤水相;其中,在所述含钙卤水中,锂离子的浓度为0.09~24g/L,钙离子的浓度为145~277g/L,氯离子的浓度为271~517g/L,钙锂质量比为7.5~1900:1,硼酸及其硼氧酸根离子的浓度以B 2O 3合计为0.5~17g/L,卤水密度20℃时为1.30~1.56g/cm 3,用盐酸或硫酸调节卤水pH值在0~7之间; S1. The calcium-containing brine is used as the pre-extraction brine phase; wherein, in the calcium-containing brine, the concentration of lithium ions is 0.09-24g/L, the concentration of calcium ions is 145-277g/L, and the concentration of chloride ions is 271 ~517g/L, the mass ratio of calcium to lithium is 7.5~1900:1, the concentration of boric acid and its borate ions is 0.5~17g/L based on B 2 O 3 , and the brine density is 1.30~1.56g/cm at 20℃ 3. Use hydrochloric acid or sulfuric acid to adjust the pH value of brine between 0-7;S2、以权利要求1至4中任一项所述的萃取体系作为萃取前有机相;S2, using the extraction system of any one of claims 1 to 4 as the organic phase before extraction;S3、将所述萃取前有机相和所述萃取前卤水相按照体积比为1~10:1混合,进行单级萃取或多级逆流萃取,两相分离后得到负载有机相和萃取后卤水相。S3. Mix the pre-extraction organic phase and the pre-extraction brine phase in a volume ratio of 1-10:1, perform single-stage extraction or multi-stage countercurrent extraction, and obtain a loaded organic phase and a post-extraction brine phase after the two phases are separated .
- 根据权利要求5所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,其特征在于,在所述含钙卤水中,还含有钠离子、钾离子、镁离子、铁离子或亚铁离子中的一种或两种以上。The extraction method for separating calcium and extracting lithium and boron from calcium-containing brine using a secondary amide/alkyl alcohol composite solvent according to claim 5, wherein the calcium-containing brine also contains sodium ions and potassium ions. , Magnesium ion, iron ion or ferrous ion one or more than two kinds.
- 根据权利要求5所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,其特征在于,所述的含钙卤水包括含锂和硼的油田卤水或地下卤水,但不仅限于该种卤水。The extraction method for separating calcium and extracting lithium and boron from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent according to claim 5, wherein the calcium-containing brine comprises lithium and boron-containing oilfield brine or Underground brine, but not limited to this kind of brine.
- 根据权利要求5所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,其特征在于,在所述步骤S3中,萃取温度为0~50℃;两相混合通过搅拌方式进行,萃取 后两相分离采取离心分离方式或澄清沉降方式进行。The extraction method for separating calcium and extracting lithium and boron from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent according to claim 5, wherein, in the step S3, the extraction temperature is 0-50°C; The two-phase mixing is carried out by stirring, and the two-phase separation after extraction is carried out by centrifugal separation or clarification and sedimentation.
- 根据权利要求5所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,其特征在于,在所述步骤S3后,还包括步骤:The extraction method for separating calcium and extracting lithium and boron from calcium-containing brine by using a secondary amide/alkyl alcohol composite solvent according to claim 5, characterized in that, after the step S3, the method further comprises:S4、以水作为反萃取剂,对所述负载有机相进行单级反萃取或多级逆流反萃取,反萃相比即反萃取剂对负载有机相体积之比为1:1~20,两相分离后得到反萃取后有机相和反萃取后水相;S4. Using water as the stripping agent, single-stage stripping or multi-stage countercurrent stripping is performed on the loaded organic phase. The stripping ratio, that is, the ratio of the stripping agent to the volume of the loaded organic phase is 1:1-20. After phase separation, a back-extracted organic phase and a back-extracted aqueous phase are obtained;S5、使所述反萃取后有机相返回步骤S2,实现萃取体系的循环使用。S5. Return the organic phase after the stripping to step S2 to realize the recycling use of the extraction system.
- 根据权利要求9所述的用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法,其特征在于,在所述步骤S4中,反萃取温度为0~50℃;The extraction method for separating calcium and extracting lithium and boron from calcium-containing brine using a secondary amide/alkyl alcohol composite solvent according to claim 9, characterized in that, in the step S4, the stripping temperature is 0-50°C ;两相混合通过搅拌方式进行,反萃取后两相分离采取离心分离方式或澄清沉降方式进行。The two-phase mixing is carried out by stirring, and the two-phase separation after back extraction is carried out by centrifugal separation or clarification sedimentation.
- 用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得硼产品硼酸中的应用,其特征在于,在所述步骤S4后,还包括步骤:The application of the extraction method for extracting lithium and boron from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent in obtaining boron product boric acid is characterized in that, after the step S4, the method further includes the following steps:S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品。S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying.
- 用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得锂产品氯化锂中的应用,其特征在于,在所述步骤S4后,还包括步骤:The application of the extraction method for extracting lithium and boron from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent in obtaining the lithium product lithium chloride is characterized in that, after the step S4, the method further includes the following steps:S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品;S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying;S7、在所述析出硼酸后的含锂溶液中,加入除杂剂对其中剩余钙离子和少量镁离子进行去除,得到含锂溶液精制后的氯化锂溶液;所用除杂剂为硫酸钠、碳酸钠、草酸钠、氯化钡或氢氧化钠中的一种或两种以上的化合物;S7. In the lithium-containing solution after the boric acid is precipitated, an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution; the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;S8、对所述精制后的氯化锂溶液进行浓缩、结晶、分离和干燥过程,制得氯化锂产品。S8. The refined lithium chloride solution is concentrated, crystallized, separated and dried to obtain a lithium chloride product.
- 用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得锂产品碳酸锂中的应用,其特征在于,在所述步骤S4后,还包括步骤:The application of the extraction method for extracting lithium and boron from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent in obtaining the lithium product lithium carbonate is characterized in that, after the step S4, the method further comprises the following steps:S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品;S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying;S7、在所述析出硼酸后的含锂溶液中,加入除杂剂对其中剩余钙离子和少量镁离子进行去除,得到含锂溶液精制后的氯化锂溶液;所用除杂剂为硫酸钠、碳酸钠、草酸钠、氯化钡或氢氧化钠中的一种或两种以上的化合物;S7. In the lithium-containing solution after the boric acid is precipitated, an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution; the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;S9、在精制后的氯化锂溶液中加入碳酸钠得到碳酸锂沉淀,对碳酸锂沉淀进行分离、干燥过程,制得碳酸锂产品。S9, adding sodium carbonate to the refined lithium chloride solution to obtain a lithium carbonate precipitate, and performing separation and drying processes on the lithium carbonate precipitate to obtain a lithium carbonate product.
- 用仲酰胺/烷基醇复合溶剂从含钙卤水中分离钙提取锂和硼的萃取方法在获得锂产品氢氧化锂中的应用,其特征在于,在所述步骤S4后,还包括步骤:The application of the extraction method for extracting lithium and boron from calcium-containing brine with a secondary amide/alkyl alcohol composite solvent in obtaining the lithium product lithium hydroxide is characterized in that, after the step S4, the method further includes the following steps:S6、对所述反萃取后水相进一步除油净化,浓缩,用盐酸或硫酸调节水相pH值、从溶液中析出硼酸,经洗涤、干燥后制得硼酸产品;S6. The water phase after the stripping is further deoiled and purified, concentrated, the pH value of the water phase is adjusted with hydrochloric acid or sulfuric acid, boric acid is precipitated from the solution, and the boric acid product is obtained after washing and drying;S7、在所述析出硼酸后的含锂溶液中,加入除杂剂对其中剩余钙离子和少量镁离子进行去除,得到含锂溶液精制后的氯化锂溶液;所用除杂剂为硫酸钠、碳酸钠、草酸钠、氯化钡或氢氧化钠中的一种或两种以上的化合物;S7. In the lithium-containing solution after the boric acid is precipitated, an impurity removing agent is added to remove the remaining calcium ions and a small amount of magnesium ions, to obtain a lithium chloride solution refined from the lithium-containing solution; the impurity removing agent used is sodium sulfate, One or more than two compounds of sodium carbonate, sodium oxalate, barium chloride or sodium hydroxide;S10、对所述精制后的氯化锂溶液进行电解,制得氢氧化锂产品,同时副产氢气和氯气、可用于生产盐酸;S10, electrolyzing the refined lithium chloride solution to obtain a lithium hydroxide product, and at the same time by-produce hydrogen and chlorine, which can be used to produce hydrochloric acid;或在所述步骤S7后,还包括步骤:Or after the step S7, the method further includes the following steps:S9、在精制后的氯化锂溶液中加入碳酸钠得到碳酸锂沉淀,对碳酸锂沉淀进行分离、干燥过 程,制得碳酸锂产品;S9, adding sodium carbonate to the refined lithium chloride solution to obtain a lithium carbonate precipitate, and performing a separation and drying process on the lithium carbonate precipitate to obtain a lithium carbonate product;S11、在制得的碳酸锂中加入氢氧化钙乳液,进行固-液反应,分离后得到氢氧化锂溶液,对其进行浓缩、结晶和干燥过程,制得氢氧化锂产品。S11. Adding a calcium hydroxide emulsion to the prepared lithium carbonate, performing a solid-liquid reaction, and obtaining a lithium hydroxide solution after separation, which is subjected to the processes of concentration, crystallization and drying to obtain a lithium hydroxide product.
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