CN117361587A - Method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone - Google Patents
Method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone Download PDFInfo
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 title claims abstract description 124
- 239000002253 acid Substances 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- 150000002596 lactones Chemical class 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 37
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000004821 distillation Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 239000012452 mother liquor Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000007363 ring formation reaction Methods 0.000 claims description 19
- 239000010413 mother solution Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- ZSYZSZTWBOHQQK-UHFFFAOYSA-L dilithium;dichloride Chemical compound [Li+].[Li+].[Cl-].[Cl-] ZSYZSZTWBOHQQK-UHFFFAOYSA-L 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 9
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 229960002685 biotin Drugs 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 235000020958 biotin Nutrition 0.000 description 4
- 239000011616 biotin Substances 0.000 description 4
- 229930003756 Vitamin B7 Natural products 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011735 vitamin B7 Substances 0.000 description 2
- 235000011912 vitamin B7 Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004136 fatty acid synthesis Effects 0.000 description 1
- 230000009229 glucose formation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for recycling lithium chloride from lithium-containing waste acid water of chiral lactone, and belongs to the technical field of waste water recycling. The process method of the invention comprises the following steps: taking lithium-containing waste acid water, slowly adding lithium carbonate into the waste acid water for neutralization while fully stirring, stopping adding the lithium carbonate when the pH value of a system is accurately controlled to be 3-4, and standing to obtain lithium chloride mother liquor; adding a decoloring agent for stirring decoloring, carrying out suction filtration and reduced pressure distillation, and finally, carrying out spray drying on a reduced pressure distillation product to obtain a high-purity lithium chloride product. The invention obviously improves the recovery rate of lithium ions in the lithium-containing waste acid water of chiral lactone, and the obtained lithium chloride can also be used for synthesizing lithium hydroxycarboxylic acid salt so as to be directly reused for synthesizing chiral lactone, thereby comprehensively reducing the production cost and reducing the waste water discharge.
Description
Technical Field
The invention belongs to the technical field of wastewater recycling, and particularly relates to a method for recycling lithium chloride from lithium-containing waste acid water of chiral lactone.
Background
Biotin (Biotin), also known as vitamin H or coenzyme R, is a water-soluble B-vitamin. Production of reversible carboxyl groups by biotin and CO as coenzymes for various carboxylase enzymes 2 Plays an important role in the transmission of many biochemical processes such as glucose synthesis, fatty acid synthesis, protein and nucleic acid metabolism. Chiral lactones are an intermediate indispensable for the synthesis of biotin:
at present, the synthesis method of chiral lactone is more, in the process of preparing chiral lactone by adopting lithium hydroxy carboxylate through cyclization reaction, after extracting agent is added into the cyclization reaction product to extract and separate chiral lactone of organic layer, a plurality of components such as inorganic acid, inorganic salt, impurities and the like are simultaneously present in the residual aqueous waste acid water, and lithium ions are dissolved in the aqueous waste acid water (figure 1). Nowadays, with the rapid development of new energy automobiles and energy storage technologies, lithium resources are taken as important battery materials, the consumption of the lithium resources is rapidly increased, and the price is also continuously increased; therefore, the method is necessary for recycling lithium resources in waste acid water remained after chiral lactone separation, however, the traditional recycling process has long period, and the recycled lithium product has the defects of low content, more impurities, low recycling rate, crystallization water and the like. Chinese patent 201210334501.4 discloses a method for producing anhydrous lithium chloride special for electrolysis by recovering lithium from lithium-containing pharmaceutical wastewater, which comprises the steps of proportioning, removing impurities, primarily removing organic matters, deeply removing the organic matters through micro-electrolysis, concentrating, precipitating sodium, evaporating, crystallizing, centrifugally separating, drying, cooling and packaging; chinese patent 201510526678.8 discloses a process method for recycling lithium from medical and synthetic plastic lithium-containing waste liquid, which comprises the steps of evaporating, concentrating and roasting to obtain powdery lithium carbonate crude product; slurrying with water and introducing CO 2 Acidifying and purifying the resin to obtain lithium bicarbonate purifying liquid; and (5) heating to decompose and dry to obtain a powdery lithium carbonate pure product. In a comprehensive view, the existing lithium recovery process is easy to introduce new impurities to cause repeated impurity removal, the whole process is still complicated, and the process cost is high. Therefore, in order to improve the recovery rate of lithium resources, improve the quality of recovered lithium products, reduce the emission of waste water, reduce the energy consumption and save the process cost, further intensive researches and improvements on the recovery process are still needed.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides a method for recycling lithium chloride from lithium-containing waste acid water of chiral lactone. The lithium-containing waste acid water after chiral lactone is extracted and separated is sequentially neutralized, purified and dried, so that the obtained solid lithium chloride has high purity and small dry loss; the invention obviously improves the recovery rate of lithium ions in the waste acid water, and the obtained lithium chloride can be further used for synthesizing lithium hydroxycarboxylic acid salt and further directly reusing for synthesizing chiral lactone, thereby comprehensively reducing the production cost and reducing the waste water discharge.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone, which comprises the following steps:
step one, taking lithium-containing waste acid water, slowly adding lithium carbonate into the waste acid water for neutralization while fully stirring, stopping adding the lithium carbonate when the pH value of a system is accurately controlled to be 3-4, and standing to obtain lithium chloride mother liquor;
adding a decolorizing agent into the lithium chloride mother solution obtained in the step one for stirring and decolorizing, and then carrying out suction filtration and reduced pressure distillation;
and thirdly, carrying out spray drying on the reduced pressure distillation product obtained in the step two to obtain lithium chloride powder.
A process for synthesizing chiral lactone includes such steps as adding excessive inorganic acid to lithium hydroxy carboxylate for cyclic reaction to obtain acidic lithium-contained solution containing chiral lactone, extracting with extractant to obtain chiral lactone, and residual acid water. The method comprises the following steps: in order to avoid residual lithium hydroxycarboxylic acid salt and influence the recovery rate of lithium chloride, the inorganic acid is added in excess, and the inorganic acid dosage is at least twice of the molar quantity of the lithium hydroxycarboxylic acid salt; and then, when the chiral lactone is extracted and separated from the acidic lithium-containing solution, the using amount of the extracting agent is required to be slightly excessive so as to ensure that the chiral lactone is fully extracted. Based on this, a large amount of inorganic acid, inorganic salt, organic matter, impurities, etc. are present in the lithium-containing waste acid water remaining after extraction of chiral lactone, so that the recycling of the waste acid water is very difficult and the process cost is expensive. In order to solve the problems, the method firstly slowly adds lithium carbonate into the lithium-containing waste acid water for preliminary neutralization, blends excessive inorganic acid in the waste water, and simultaneously further reacts to generate lithium ions to be supplemented into the original waste acid water; and then adding a decoloring agent into the neutralized wastewater to decolor and remove impurities, concentrating to a saturated state, and finally, carrying out spray drying on the product to obtain the high-purity lithium chloride powder.
Preferably, in the step one, the lithium-containing waste acid water is lithium salt of hydroxycarboxylic acid, and the chiral lactone is prepared by acid addition cyclization reaction, and the water layer remained after the separation of the organic layer.
Preferably, the acid is added as hydrochloric acid, and the addition amount of the hydrochloric acid is 1 (2-3) according to the molar ratio of the lithium salt of hydroxycarboxylic acid to HCl; the cyclization reaction temperature is controlled to be 60-100 ℃.
Preferably, the extractant used for separating the organic layer is selected from one or more of toluene, ethylbenzene, o-xylene, m-xylene, methylene dichloride and chloroform.
Preferably, the addition amount of the extractant is 4-5 times of the mass of the lithium hydroxy carboxylate, and the extraction temperature is controlled to be 80-90 ℃.
Preferably, the decoloring agent in the second step is one or more selected from activated carbon, diatomite and an adsorption resin.
Preferably, the adding amount of the decoloring agent in the second step is 0.5-0.8% of the mass of the lithium chloride mother solution.
Preferably, the lithium dichloride mother liquor is stirred and decolorized and then distilled under reduced pressure to a saturated state.
Preferably, the temperature of the spray drying feed inlet in the third step is set to 150-300 ℃.
In the prior art, sodium carbonate is generally adopted for neutralization and recovery of wastewater containing lithium. However, sodium carbonate is added into lithium-containing waste acid water of the chiral lactone for neutralization, firstly, the sodium carbonate reacts with residual excessive hydrochloric acid to generate sodium chloride, and then, the sodium carbonate is continuously added, and the sodium carbonate reacts with lithium chloride in the solution to generate lithium carbonate and sodium chloride. Although lithium carbonate is insoluble in water, the process generates a large amount of sodium chloride, and lithium carbonate is highly soluble in sodium chloride solution, which results in re-dissolution of precipitated lithium carbonate in brine, resulting in low yield. Based on the method, lithium carbonate is directly added into the redirected lithium-containing waste acid water, the pH value of the redirected lithium-containing waste acid water is slowly added and accurately controlled to be 3-4, lithium chloride is generated by the reaction of the lithium carbonate and hydrochloric acid, so that the lithium chloride is all in the solution after the reaction, and finally, the lithium chloride in the solution is recovered through spray drying; the lithium chloride obtained by the method can also be directly used for synthesizing an intermediate lithium hydroxycarboxylic acid salt, and the lithium hydroxycarboxylic acid salt can be recycled after chiral lactone is synthesized.
Compared with the prior art, the invention has the beneficial effects that:
the invention aims at the problems that the lithium-containing waste acid water for chiral lactone has complex components, the conventional recovery and separation process is complex in steps, new impurities are easy to introduce to cause repeated impurity removal, the process cost is high and the product quality is low, lithium carbonate is directly adopted, the lithium-containing waste acid water after chiral lactone is extracted and separated is sequentially neutralized, purified and dried, no new impurities are introduced, the purity of the recovered lithium chloride product is high, the dry loss is small, and the method can be directly applied to synthesizing an intermediate lithium hydroxycarboxylic acid salt, so that the chiral lactone can be circularly prepared, and the process cost is remarkably reduced.
Drawings
FIG. 1 is a process flow diagram for preparing chiral lactones by hydroxycarboxylate cyclization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
1. Adding 250mL of water into 50g of lithium hydroxy carboxylate, starting stirring, slowly heating to 90 ℃ and continuously stirring for dissolution, adding 46mL of 30% hydrochloric acid after the system is dissolved, and maintaining the constant temperature of 90 ℃ for cyclization reaction for 2 hours after the addition is finished; 250g of toluene is added into the obtained cyclization reaction liquid at the temperature of 85 ℃, the mixture is stirred and extracted for 1h, and the mixture is kept stand for 0.5h for layering after the extraction is finished: concentrating toluene phase to obtain chiral lactone, and obtaining water phase as lithium-containing waste acid water.
2. Cooling lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 3.5 to obtain lithium chloride mother solution; a total of 16.9g of lithium carbonate was charged.
3. Adding active carbon with the mass of 0.6% into the obtained lithium chloride mother solution, stirring and decoloring for 1h, performing suction filtration, and performing reduced pressure distillation on the filtrate to reach a nearly saturated state, and ending distillation.
4. The inlet temperature of the spray dryer was set to 250 ℃, and after the temperature was stabilized, the reduced pressure distillation product was slowly fed and dried at a constant speed to obtain 15.6g of lithium chloride powder, the purity of the product was measured and the recovery rate was calculated.
Example 2
1. Adding 250mL of water into 50g of lithium hydroxy carboxylate, starting stirring, slowly heating to 90 ℃ and continuously stirring for dissolution, adding 38mL of 30% hydrochloric acid after the system is dissolved, and maintaining the constant temperature of 90 ℃ for cyclization reaction for 2 hours after the addition is finished; 200g of toluene is added into the obtained cyclization reaction liquid at the temperature of 85 ℃, the mixture is stirred and extracted for 1h, and the mixture is kept stand for 0.5h for layering after the extraction is finished: concentrating toluene phase to obtain chiral lactone, and obtaining water phase as lithium-containing waste acid water.
2. Cooling lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 3.5 to obtain lithium chloride mother solution; a total of 14.1g of lithium carbonate was charged.
3. Adding active carbon with the mass of 0.6% into the obtained lithium chloride mother solution, stirring and decoloring for 1h, performing suction filtration, and performing reduced pressure distillation on the filtrate to reach a nearly saturated state, and ending distillation.
4. The inlet temperature of the spray dryer was set to 250 ℃, and after the temperature was stabilized, the reduced pressure distillation product was slowly fed and dried at a constant speed to obtain 13.9g of lithium chloride powder, the purity of the product was measured and the recovery rate was calculated.
Example 3
1. Adding 250mL of water into 50g of lithium hydroxy carboxylate, starting stirring, slowly heating to 80 ℃ for continuous stirring and dissolution, adding 46mL of 30% hydrochloric acid after the system is dissolved, and maintaining the constant temperature of 80 ℃ for cyclization reaction for 2 hours after the addition is completed; 250g of toluene is added into the obtained cyclization reaction liquid at the temperature of 80 ℃, the mixture is stirred and extracted for 1h, and the mixture is kept stand for 0.5h for layering after the extraction is finished: concentrating toluene phase to obtain chiral lactone, and obtaining water phase as lithium-containing waste acid water.
2. Cooling lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 3.5 to obtain lithium chloride mother solution; a total of 17.5g of lithium carbonate was charged.
3. Adding active carbon with the mass of 0.6% into the obtained lithium chloride mother solution, stirring and decoloring for 1h, performing suction filtration, and performing reduced pressure distillation on the filtrate to reach a nearly saturated state, and ending distillation.
4. The inlet temperature of the spray dryer was set to 250 ℃, and after the temperature was stabilized, the reduced pressure distillation product was slowly fed and dried at a constant speed to obtain 16.0g of lithium chloride powder, the purity of the product was measured and the recovery rate was calculated.
Example 4
1. Adding 250mL of water into 50g of lithium hydroxy carboxylate, starting stirring, slowly heating to 90 ℃ and continuously stirring for dissolution, adding 46mL of 30% hydrochloric acid after the system is dissolved, and maintaining the constant temperature of 90 ℃ for cyclization reaction for 2 hours after the addition is finished; 200g of methylene dichloride is added into the obtained cyclization reaction liquid at the temperature of 85 ℃, the mixture is stirred and extracted for 1h, and the mixture is kept stand for 0.5h after the extraction is finished for layering: concentrating toluene phase to obtain chiral lactone, and obtaining water phase as lithium-containing waste acid water.
2. Cooling lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 3 to obtain lithium chloride mother solution; a total of 15.2g of lithium carbonate was charged.
3. Adding active carbon with the mass of 0.8% into the obtained lithium chloride mother solution, stirring and decoloring for 1h, performing suction filtration, and performing reduced pressure distillation on the filtrate to reach a nearly saturated state, and ending distillation.
4. The inlet temperature of the spray dryer was set to 250 ℃, and after the temperature was stabilized, the reduced pressure distillation product was slowly fed and dried at a constant speed to obtain 14.6g of lithium chloride powder, the purity of the product was measured and the recovery rate was calculated.
Example 5
1. Adding 250mL of water into 50g of lithium hydroxy carboxylate, starting stirring, slowly heating to 90 ℃ and continuously stirring for dissolution, adding 46mL of 30% hydrochloric acid after the system is dissolved, and maintaining the constant temperature of 90 ℃ for cyclization reaction for 2 hours after the addition is finished; 250g of toluene is added into the obtained cyclization reaction liquid at the temperature of 85 ℃, the mixture is stirred and extracted for 1h, and the mixture is kept stand for 0.5h for layering after the extraction is finished: concentrating toluene phase to obtain chiral lactone, and obtaining water phase as lithium-containing waste acid water.
2. Cooling lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 4 to obtain lithium chloride mother solution; a total of 17.9g of lithium carbonate was charged.
3. Adding active carbon with the mass of 0.5% into the obtained lithium chloride mother solution, stirring and decoloring for 1h, performing suction filtration, and performing reduced pressure distillation on the filtrate to reach a nearly saturated state, and ending distillation.
4. The inlet temperature of the spray dryer was set to 200 ℃, and after the temperature was stabilized, the reduced pressure distillation product was slowly fed and dried at a constant speed to obtain 16.2g of lithium chloride powder, the purity of the product was measured and the recovery rate was calculated.
Comparative example 1
The comparative example step parameters refer to example 1, except that the amount of hydrochloric acid used in the cyclization reaction was halved, namely:
1. 250mL of water is added into 50g of lithium hydroxy carboxylate, stirring is started, the temperature is slowly raised to 90 ℃ for continuous stirring and dissolution, 23mL of 30% hydrochloric acid is added after the system is dissolved, and the constant temperature cyclization reaction is kept at 90 ℃ for 2h after the addition is completed.
Adding 4.3g of lithium carbonate in total; finally, 21.7g of lithium chloride powder was obtained.
Comparative example 2
The comparative example step parameters refer to example 1 except that activated carbon was not added for decolorization.
Adding 17.2g of lithium carbonate in total; 16.2g of lithium chloride powder was finally obtained.
Comparative example 3
Comparative example step parameters reference example 1 except that the neutralization was performed with the same amount of sodium carbonate instead of lithium carbonate.
Adding 16.9g of sodium carbonate in total; 26.6g of lithium chloride powder was finally obtained.
Comparative example 4
The comparative example step parameters refer to example 1, except that the neutralization pH was controlled to 2, namely:
and cooling the lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 2 to obtain lithium chloride mother solution.
Adding 13.3g of lithium carbonate in total; 13.2g of lithium chloride powder was finally obtained.
Comparative example 5
The comparative example step parameters refer to example 1, except that the neutralization pH is controlled to 7, namely:
and cooling the lithium-containing waste acid to room temperature, slowly adding lithium carbonate into the waste acid, continuously stirring, and stopping adding when the pH value is 7 to obtain lithium chloride mother solution.
Adding 20.8g of lithium carbonate in total; 17.7g of lithium chloride powder was finally obtained.
The purity of the lithium chloride samples recovered in the above examples and comparative examples was measured, and the recovery rate was calculated based on the amount used, and the results are shown in Table 1.
TABLE 1
As can be seen from the detection results in Table 1, the lithium carbonate is selected to neutralize lithium-containing waste acid water of chiral lactone, meanwhile, the process parameters are optimized, and finally, the reaction solution is lithium chloride, most of lithium in the reaction solution can be recovered through spray drying, if the reaction solution is neutralized by sodium carbonate and the like, and finally, a large amount of sodium chloride or other salts exist in the solution, so that the lithium chloride product obtained after drying and recovery has more impurities and lower comprehensive yield.
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in more detail and are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art, and any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (9)
1. A method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone, comprising the steps of:
step one, taking lithium-containing waste acid water, slowly adding lithium carbonate into the waste acid water for neutralization while fully stirring, stopping adding the lithium carbonate when the pH value of a system is accurately controlled to be 3-4, and standing to obtain lithium chloride mother liquor;
adding a decolorizing agent into the lithium chloride mother solution obtained in the step one for stirring and decolorizing, and then carrying out suction filtration and reduced pressure distillation;
and thirdly, carrying out spray drying on the reduced pressure distillation product obtained in the step two to obtain lithium chloride powder.
2. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 1, wherein in the step one, the lithium-containing waste acid water is a water layer which remains after the separation of an organic layer after the preparation of chiral lactone by acid addition cyclization reaction of lithium salt of hydroxycarboxylic acid.
3. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 2, wherein the acid is added as hydrochloric acid, and the addition amount of the hydrochloric acid is 1 (2-3) in terms of molar ratio of lithium salt of hydroxycarboxylic acid to HCl; the cyclization reaction temperature is controlled to be 60-100 ℃.
4. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 2, wherein the extractant used for separating the organic layer is selected from one or more of toluene, ethylbenzene, o-xylene, m-xylene, methylene chloride and chloroform.
5. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 4, wherein the addition amount of the extractant is 4-5 times the mass of the lithium salt of hydroxycarboxylic acid, and the extraction temperature is controlled to 80-90 ℃.
6. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 1, wherein in the second step, the decoloring agent is one or more selected from activated carbon, diatomaceous earth and adsorption resin.
7. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 1, wherein the decoloring agent is added in an amount of 0.5% -0.8% of the mass of the lithium chloride mother liquor in the second step.
8. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 1, wherein the step of decoloring the lithium dichloride mother liquor by stirring and then distilling under reduced pressure to a saturated state.
9. The method for recovering lithium chloride from lithium-containing waste acid water of chiral lactone according to claim 1, wherein the spray-drying feed inlet temperature is set to 150-300 ℃.
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