WO2023173776A1 - 一种三元前驱体母液的回收方法及回收系统 - Google Patents
一种三元前驱体母液的回收方法及回收系统 Download PDFInfo
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- WO2023173776A1 WO2023173776A1 PCT/CN2022/131588 CN2022131588W WO2023173776A1 WO 2023173776 A1 WO2023173776 A1 WO 2023173776A1 CN 2022131588 W CN2022131588 W CN 2022131588W WO 2023173776 A1 WO2023173776 A1 WO 2023173776A1
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- mother liquor
- ternary precursor
- recovery method
- liquid phase
- recovery
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- 239000002243 precursor Substances 0.000 title claims abstract description 59
- 239000012452 mother liquor Substances 0.000 title claims abstract description 51
- 238000011084 recovery Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007791 liquid phase Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000000292 calcium oxide Substances 0.000 claims abstract description 23
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000005273 aeration Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- -1 sulfide ions Chemical class 0.000 claims abstract description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 230000009615 deamination Effects 0.000 claims description 32
- 238000006481 deamination reaction Methods 0.000 claims description 32
- 238000007664 blowing Methods 0.000 claims description 7
- 230000008901 benefit Effects 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 15
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 30
- 239000011572 manganese Substances 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 14
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 14
- 239000011575 calcium Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052602 gypsum Inorganic materials 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910018661 Ni(OH) Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/10—Separation of ammonia from ammonia liquors, e.g. gas liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/14—Preparation of sulfites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
- C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Definitions
- the invention belongs to the technical field of wastewater treatment, and specifically relates to a recovery method and recovery system of ternary precursor mother liquor.
- ternary cathode materials in industry are generally made of hydroxides of Ni, Co, and Mn (Ni a Co b Mn 1-ab (OH) 2 ) as precursors and calcined with lithium.
- the mainstream process for preparing ternary material precursors is the co-precipitation method, which is a metal salt solution (usually sulfate) containing Ni 2+ , Co 2+ , Mn 2+ , NaOH solution (precipitant) and ammonia water (complexing agent) , the main form NH 3 ⁇ H 2 O) in ammonia water is added in parallel flow, and a quasi-spherical ternary hydroxide precursor is produced by co-precipitation.
- This process can relatively easily control the particle size, specific surface area, morphology and tap density of the precursor, but at the same time it will produce a large amount of wastewater (ternary precursor mother liquor).
- ternary precursor mother liquor For every ton of precursor produced, the ternary precursor mother liquor The production volume is 9 to 20 cubic meters (industry experience). As the production capacity increases, the amount of ternary precursor mother liquor produced is huge, and methods need to be designed to recycle and utilize it.
- the ternary precursor mother liquor has the characteristics of high heavy metal content, high ammonia nitrogen concentration (the sum of ammonia water and ammonium ions), high salt content and high alkalinity.
- the heavy metals and ammonia and other components in it have high economic benefits. If Direct discharge will bring economic losses. In addition, complex components such as heavy metal ions and alkalis have a great impact on the surrounding environment. Direct discharge also poses environmental risks.
- the treatment of the ternary precursor mother liquor is usually to first send it to a stripping deamination tower for stripping and deamination treatment, recover the ammonia water in it, and then remove the heavy metals Ni, Co, and Mn through sedimentation, and then filter it.
- the heavy metals are recovered and finally sent to the MVR system (mechanical vapor recompression, mechanical vapor recompression technology) for evaporation and concentration to recover Na 2 SO 4 (usually containing crystal water) and produce pure water for reuse.
- MVR system mechanical vapor recompression, mechanical vapor recompression technology
- stripping deamination requires a large amount of steam, and the ammonia content of the effluent is about 10 mg/L, and the heavy metal ions are also about 3 mg/L.
- Direct emission still has certain environmental risks; at the same time, Na 2 is prepared through MVR evaporation and concentration.
- SO 4 SO 4 is used, the energy consumption is higher, and the economic value of the sodium sulfate produced in the market is low, with the market price being about 500 yuan/ton. The overall economy is poor, and most manufacturers choose to treat it externally and pay a certain water treatment fee.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for recovering the ternary precursor mother liquor, which can convert the solute in the ternary precursor mother liquor into products with high economic benefits. At the same time, the treated ternary precursor mother liquor has few impurities and has the advantages of Higher environmental benefits.
- the present invention also proposes a recycling system that implements the above recycling method.
- a recovery method of ternary precursor mother liquor which includes the following steps:
- step S2 Make the oxidant react with the liquid phase component obtained in step S1 and then separate the solid and liquid;
- step S3 Treat the liquid phase component obtained in step S2 with quicklime (CaO) and collect the resulting gas;
- step S5. Perform crystallization treatment on the liquid phase component obtained in step S4.
- Step S1 The ternary precursor mother liquor contains a certain amount of Ni 2+ , Co 2+ , Mn 2+ , NaOH and solid matter (precursors with small particle sizes that have not been separated can be regarded as colloidal particles), and also contains With a larger amount of NH 3 ⁇ H 2 O and Na 2 SO 4 , due to the complexation of a large amount of NH 3 , even under higher pH conditions, Ni 2+ and Co 2+ will not precipitate, but will form It exists in the form of complex metal ions, and there are also some suspended Ni(OH) 2 and Co(OH) 2 with small particle sizes;
- NiS and CoS Compared with Ni(OH) 2 and Co(OH) 2 , NiS and CoS have smaller solubility products and are easier to precipitate. Therefore, the present invention reacts sulfide ions (S 2- ) with the ternary precursor mother liquor to form NiS and CoS precipitate, and the liquid phase system is separated during the solid-liquid separation process of the above precipitation; the specific reactions that occur include:
- Ni 2+ +S 2- NiS ⁇
- Step S2 Since the precipitation equilibrium constant of MnS is greater than Mn(OH) 2 , in step S1, manganese will not precipitate in the form of MnS. Therefore, the liquid phase component obtained in step S1 contains Mn 2+ and small particle size Mn ( OH) 2 , S 2- , NH 3 ⁇ H 2 O and Na 2 SO 4 that were not completely reacted in step S1; after treatment with oxidant, the manganese in Mn 2+ and small particle size Mn(OH) 2 will be + The 2 valence is converted into +4 valence, forming a MnO 2 precipitate. After solid-liquid separation, the liquid phase system is separated in the form of a solid phase; the remaining S 2- will also be oxidized to SO 4 2- under the action of the oxidant.
- Step S3 The liquid phase component obtained in step S2 contains a large amount of Na 2 SO 4 and NH 3. Ammonia gas is easily soluble in water to form NH 3 ⁇ H 2 O. Therefore, the commonly used stripping deamination treatment has high energy consumption and The treatment effect is limited; in the present invention, CaO is used to treat the liquid phase component obtained in step S2. CaO reacts with H 2 O to release a large amount of heat, and at the same time generates an alkaline substance Ca(OH) 2 , in which heat can promote the decomposition of NH 3 ⁇ H 2 O NH 3 is generated and escapes from the liquid phase system. Ca(OH) 2 can inhibit the combination of NH 3 and water to form NH 3 ⁇ H 2 O (inhibiting the reverse reaction). In this step, NH 3 is separated in the form of gas (may contain a certain amount of water vapor) After exiting the liquid phase system, the reactions that occur include:
- Step S4 The mixture obtained in step S3 includes a large amount of Na 2 SO 4 and Ca(OH) 2 generated by the reaction in step S3, and also includes calcium sulfate precipitate formed by the combination of calcium ions and sulfate ions. It is difficult to separate each substance.
- treating the mixture obtained in step S3 with SO 2 can convert the Ca(OH) 2 into CaSO 4 ⁇ 2H 2 O (gypsum precipitation) and generate Na 2 SO 3 at the same time, which also makes the reaction more complete.
- Responses include:
- Step S5 The liquid phase component obtained in step S4 contains a large amount of Na 2 SO 3 . After crystallization treatment, solid Na 2 SO 3 (which may contain a certain amount of crystal water depending on the crystallization conditions) and the processed ternary precursor mother liquor are obtained. .
- the additional products obtained from the ternary precursor mother liquor mainly include NH 3 and Na 2 SO 4 ; the price of Na 2 SO 4 is about 500 yuan/ton;
- the products obtained by the present invention also include CaSO 4 ⁇ 2H 2 O and Na 2 SO 3.
- the market price of Na 2 SO 3 is higher than 4,000 yuan/ton, which is different from the Na 2 SO 4 produced by traditional technology. It has higher economic benefits compared with others.
- the present invention obtains NH 3 from the liquid phase component obtained in CaO treatment step S2. Compared with the traditional stripping deamination method, the application of steam is omitted, the operation is simpler, and the energy consumption is lower.
- the content of ammonia nitrogen in the treated ternary precursor mother liquor is ⁇ 8 mg/L, and the content of heavy metal ions (Ni 2+ , Co 2+ , Mn 2+ ) is The sum of the contents is ⁇ 2.5mg/L.
- the impurities in the resulting water are significantly reduced, which has significant environmental benefits;
- NiS, CoS and MnO 2 can be used in the preparation of lithium battery cathode materials, catalysts and other materials (or need to be converted before use); NH 3 can be reused in the preparation of ternary precursors; Na 2 SO 3 can be widely used in textile, printing and dyeing, tanning and papermaking industries.
- the prepared CaSO 4 ⁇ 2H 2 O can be widely used in building materials, cement raw materials, rubber, plastics, fertilizers, pesticides, paints, textiles, etc. Food, medicine, papermaking, daily chemicals, arts and crafts, culture and education and other industries. That is, the by-products recovered from the recovery have high practical value, and the recovery method provided by the present invention has high economy and practicality.
- the composition of the ternary precursor mother liquor is: pH>12, ammonia nitrogen 6 ⁇ 8g/L, total amount of Ni, Co, Mn ⁇ 500mg/L, Na 2 SO 4 : 100 ⁇ 120g/L.
- step S1 the ratio of the amount of the sulfide ions to the volume of the ternary precursor mother liquid is 0.035 to 0.11 mol/m 3 .
- the source of S 2- includes at least one of sodium sulfide (Na 2 S) and potassium sulfide.
- the source of S 2- includes sodium sulfide (Na 2 S).
- the source of S 2- is the sodium sulfide (Na 2 S)
- the purity of the sodium sulfite obtained in step S5 is higher, and impurities introduced by other sources of S 2- can be avoided.
- the ratio of the mass of Na 2 S to the volume of the ternary precursor mother liquid is 5 to 15 g/m 3 .
- the solid-liquid separation method includes at least one of sedimentation and filtration.
- step S2 the ratio of the amount of the oxidizing agent to the volume of the liquid phase component obtained in step S1 is 2 to 3 mol/m 3 .
- the oxidizing agent includes at least one of hydrogen peroxide (H 2 O 2 ) and sodium peroxide.
- the oxidizing agent includes hydrogen peroxide (H 2 O 2 ).
- the reaction in step S2 includes:
- the solid-liquid separation method includes at least one of sedimentation and filtration.
- step S2 when the solid-liquid separation method includes settling, the required settling time is 30 to 60 minutes.
- step S3 the ratio of the mass of CaO to the volume of the liquid phase component obtained in step S2 is 40 to 55 g/L.
- step S3 collecting the resulting gas includes blowing air into the CaO-treated mixed system, and condensing and collecting the blown gas.
- the gas blown into the blast includes air.
- the flow rate of the air is 60-120L/min.
- the duration of blowing air into the CaO-treated mixed system is 3 to 6 hours.
- the generated NH 3 can be blown out of the system in time, suppressing the reaction between NH 3 and water as much as possible, and improving the recovery rate of NH 3 .
- the sodium sulfate contained in the liquid phase component obtained in step S2 will also inhibit the production of NH to a certain extent (sodium sulfate and calcium react to form slightly soluble calcium sulfate, which hinders the progress of the reaction), and the air blast can promote the The contact between quicklime and liquid phase components weakens the influence of Na 2 SO 4 to a certain extent.
- Blowing air into the CaO-treated mixed system can also increase the contact between the CaO and the liquid phase components obtained in step S2, thereby promoting the generation of NH 3 .
- the condensation collection is performed in a condenser.
- step S3 the gas collected by condensation is mainly NH 3 , which can be recycled and used to prepare a new ternary precursor.
- the gas that cannot be condensed is mainly the air introduced by the blast, which can be directly discharged from the system or recycled. Continue Air is blown into the CaO-treated mixed system to achieve cost savings.
- step S4 the air flow rate of the aeration process is 60-120L/min.
- the pH of the mixture obtained by the aeration treatment is between 6 and 7.
- step S4 after unreacted SO 2 escapes from the reaction system, it can be recollected for the aeration treatment to achieve cost savings.
- the solid-liquid separation method includes filtration; preferably, the filtration includes at least one of normal pressure filtration and pressure filtration.
- step S3 Before solid-liquid separation in step S3, the system contains milk of lime (the main components are slightly soluble Ca(OH) 2 ) and Na 2 SO 4 .
- the mixture of the two is difficult to handle directly, so step S4 is added to convert it into water-soluble Na 2 SO 3 and CaSO 4 ⁇ 2H 2 O, which are not water-soluble, on the one hand facilitate the solid-liquid separation of each component, on the other hand the products obtained have higher economic value, improving the economics of the recovery method .
- the crystallization treatment includes sequential evaporation concentration, cooling and fine crystallization, solid-liquid separation and solid phase drying.
- step S5 the water evaporated by evaporation, concentration, and solid-phase drying, as well as the clear liquid produced by solid-liquid separation, are the ternary precursor mother liquor processed by the recovery method.
- a recovery system for ternary precursor mother liquor is proposed for implementing the recovery method
- the recovery system includes a mother liquor pool, a No. 1 filter, a settling tank, a No. 2 filter, a deamination tower, a filter press and a crystallization system connected in sequence via pipelines.
- the present invention can make full use of various raw materials and recover various by-products, and has good economic and environmental benefits.
- a blower is connected to the deamination tower.
- a condenser is connected to the deamination tower.
- the condenser is provided with an exhaust port and a liquid drain port.
- the condenser and the blower are connected via the duct.
- the steps of the recycling method include:
- step S2 The liquid phase component obtained in step S1 is transferred to the settling tank through the pipeline, the oxidant is added to the settling tank, and the mixture is settled after the reaction, and the mixture obtained in this step is transferred to the settling tank through the pipeline.
- step S3 Send the liquid phase component obtained in step S2 into the deamination tower through the pipeline, and add the CaO to the deamination tower to generate NH 3 ;
- the generated NH 3 escapes from the deamination tower together with the air and is transferred to the condenser.
- the condenser works and the NH 3 in it is condensed into a liquid. (ammonia NH 3 ⁇ H 2 O) is recovered through the drain port.
- the air continues to pass through the blower along the pipeline and then blows the deamination tower until the blowing is completed.
- the air passes through the exhaust port discharge system;
- step S4 Aerate the liquid phase component obtained in step S3 with the SO 2 through the blower.
- the circulation path of the SO 4 is the cycle of the blower, deamination tower, condenser, and deamination tower, during which condensation The device does not work; when the pH value in the deamination tower is 6 to 7, the aeration process ends, and the remaining SO 4 is recovered through the exhaust port.
- the mixture in the deamination tower is then transferred to the filter press for solid-liquid separation via a pipeline to obtain a filter cake (gypsum) and the liquid phase component obtained in step S4;
- step S5 Transfer the liquid phase components obtained in step S4 to the crystallization system through a pipeline, and crystallize to obtain Na 2 SO 3 and the treated ternary precursor mother liquor.
- Figure 1 is a schematic structural diagram of the recovery system used in Embodiment 1 of the present invention.
- the parameters of the ternary precursor mother liquor used in the present invention are as follows: pH is 12.3, ammonia nitrogen is 8g/L, the total amount of Ni, Co, and Mn is about 38mg/L, Na 2 SO 4 : about 120g/L L.
- a ternary precursor mother liquor is recovered.
- the recovery system used is shown in Figure 1. The specific process is:
- the mixture in the mother liquor tank 100 is transferred to the No. 1 filter 200 via the pipeline 800 for filtration processing to obtain a filter cake whose main components are NiS and CoS, and a filtrate; the filter cake is discharged from the No. 1 filter 200 (Fig. 1 No. 1 filter 200 (shown by the downward arrow);
- the composition of the filtrate obtained in this step is as follows: pH is 12.4, ammonia nitrogen is about 8g/L, the total amount of Ni, Co, and Mn is about 10mg/L, and Na 2 SO 4 is about 120g/L.
- step S2 Transfer the filtrate obtained in step S1 to the settling tank 300 through the pipeline 800, and add H 2 O 2 to the settling tank 300 according to the ratio of 2 mol/m 3 filtrate, and settle in the settling tank 300 for 30 minutes after the addition is completed;
- the mixture in the sedimentation tank 300 enters the No. 2 filter 400 through the pipeline 800. After solid-liquid separation, the filter residue and filtrate whose main components are MnO 2 are obtained; the filter residue is discharged from the No. 2 filter 400 (the No. 2 filter 400 in Figure 1 goes to (shown by the downward arrow);
- the components of the filtrate obtained in this step are: pH is 12.4, ammonia nitrogen is about 8g/L, Ni is about 0.3mg/L, Co is about 0.3mg/L, Mn is about 0.1mg/L, Na 2 SO 4 is about 122g/L.
- step S3 Send the filtrate obtained in step S2 into the deamination tower 500, and add CaO to the deamination tower 500.
- the ratio of the mass of CaO to the volume of the filtrate is 40g/L;
- the blower 510 to blow air into the deamination tower 500 with an air flow rate of 60L/min and a time of 6 hours.
- the NH 3 and air mixture generated during this period enters the condenser 520 from the top of the deamination tower 500 (set as The ammonia water condensed by the condenser 520 (at a constant temperature -15°C) (as the blast proceeds, a part of the water vapor will be brought out when the ammonia is discharged, and the ammonia itself will also combine with a certain amount of water, so the ammonia generated after condensation Ammonia water, not liquid ammonia gas) is discharged from the condenser 520 through the liquid drain port 521, and the generated non-condensable gas (air) continues to be blown into the deamination tower 500 by the blower 510 along the pipeline 800, and the cycle continues; the non-condensable gas (air) after the cycle is completed
- the gas is discharged from the condenser 520 through the exhaust
- the mass concentration of ammonia is 18.2%;
- ammonia nitrogen is 8 mg/L, and the ammonia recovery rate is greater than 99% (1-ammonia nitrogen content in the liquid phase component obtained in this step/ammonia nitrogen content in the ternary precursor mother liquor).
- the mixture in the deamination tower 500 is transferred to the filter press 600 via the pipeline 800 for press filtering to obtain the filter cake raw gypsum (discharged from the filter press 600, the filter press 600 is cut downward in Figure 1 (shown in the header) and filtrate;
- the components (mass percentage) of medium-grade gypsum are: Ca content is 18.8%, SO 4 2- content is 49.3%, Na content is 1.3%, SO 3 2- content is 1.9%, water and other impurity content is 28.7% (not dried).
- step S5 Transfer the filtrate obtained in step S4 to the crystallization system 700 through the pipeline 800. After evaporation, concentration, cooling, crystallization and drying, the Na 2 SO 3 product is obtained (the discharge path is indicated by the right arrow of the crystallization system 700 in Figure 1 Show);
- the components of the sodium sulfite product obtained in this step are (mass percentage content): Na 2 SO 3 content is 95.7%, Ca content is 0.7%, and SO 4 2- content is 3.3%.
- Example 1 a ternary precursor mother liquor is recovered.
- the specific differences from Example 1 are:
- step S1 the volume ratio of the mass of Na 2 S to the ternary precursor mother liquid is 10g/m 3 ;
- step S2 the ratio of the amount of H 2 O 2 to the volume of the filtrate is 2.5 mol/m 3 ;
- step S3 the mass ratio of CaO to the volume of the filtrate is 50g/L;
- step S3 the flow rate of the blown air is 90L/min and the time is 5h;
- step S4 the blast volume of SO 2 is 90L/min;
- Example 1 a ternary precursor mother liquor is recovered.
- the specific differences from Example 1 are:
- step S1 the volume ratio of the mass of Na 2 S to the ternary precursor mother liquid is 15g/m 3 ;
- step S2 the ratio of the amount of H 2 O 2 to the volume of the filtrate is 3 mol/m 3 ;
- step S3 the mass ratio of CaO to the volume of the filtrate is 55g/L;
- step S3 the flow rate of the blown air is 120L/min, and the time is 3h;
- step S4 the blast volume of SO 2 is 120L/min;
- Table 1 The mass concentration and recovery rate of ammonia recovered in Examples 1 to 3
- the mass percentage of ammonia in commercially available concentrated ammonia water is ⁇ 15wt% (approximately 7.4mol/L).
- the concentration of ammonia recovered in the present invention is between 18.2 and 20.3% (9 and 10.01mol/L), which is used to prepare ternary components.
- the concentration of ammonia water in the precursor is generally 2 to 10 mol/L; that is to say, the concentrated ammonia water recovered in the present invention can be used to prepare the ternary precursor directly or after dilution, realizing the reuse of ammonia water and having high economic benefits. .
- the present invention also summarizes the components of the raw gypsum obtained in Examples 1 to 3, as shown in Table 2.
- Example 1 Example 2 Example 3 calcium% 18.8 19.3 19.6 SO 4 2- % 49.3 49.8 50.1 Na% 1.3 0.8 0.7 SO 3 2- % 1.9 1.5 1.7 Water and other impurities% 28.7 28.6 27.9
- Table 2 show that the sulfite content in the raw gypsum recovered by the present invention is low, so the quality of the obtained raw gypsum is relatively stable, and can meet the needs of building materials, cement raw materials, rubber, plastics, fertilizers, pesticides, paints, textiles, food, Applications in medicine, papermaking, daily chemicals, arts and crafts, culture and education and other industries can obtain better economic benefits.
- the present invention also summarizes the components of sodium sulfite obtained in Examples 1 to 3, as shown in Table 3.
- Example 1 Example 2 Example 3 Na 2 SO 3 % 95.7 96.1 96.3 Ca% 0.7 0.8 0.8 SO 4 2- % 3.3 2.7 2.6
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Abstract
Description
实施例1 | 实施例2 | 实施例3 |
回收氨的质量浓度% | 18.2 | 19.6 | 20.3 |
氨的回收率% | 99.0 | 99.1 | 99.2 |
实施例1 | 实施例2 | 实施例3 | |
钙% | 18.8 | 19.3 | 19.6 |
SO 4 2-% | 49.3 | 49.8 | 50.1 |
Na% | 1.3 | 0.8 | 0.7 |
SO 3 2-% | 1.9 | 1.5 | 1.7 |
水及其他杂质% | 28.7 | 28.6 | 27.9 |
实施例1 | 实施例2 | 实施例3 | |
Na 2SO 3% | 95.7 | 96.1 | 96.3 |
Ca% | 0.7 | 0.8 | 0.8 |
SO 4 2-% | 3.3 | 2.7 | 2.6 |
Claims (10)
- 一种三元前驱体母液的回收方法,其特征在于,包括以下步骤:S1.使硫离子和所述三元前驱体母液反应后固液分离;S2.使氧化剂和步骤S1所得液相组分反应后固液分离;S3.以生石灰处理步骤S2所得液相组分,收集所得气体;S4.以二氧化硫对步骤S3残留的混合物进行曝气处理后固液分离;S5.对步骤S4所得液相组分进行结晶处理。
- 根据权利要求1所述的回收方法,其特征在于,步骤S1中,所述硫离子的物质的量与所述三元前驱体母液的体积之比为0.035~0.11mol/m 3。
- 根据权利要求1所述的回收方法,其特征在于,步骤S2中,所述氧化剂的物质的量与步骤S1所得液相组分的体积之比为2~3mol/m 3。
- 根据权利要求1所述的回收方法,其特征在于,步骤S3中,所述生石灰的质量与步骤S2所得液相组分的体积之比为40~55g/L。
- 根据权利要求1~4中任一项所述的回收方法,其特征在于,步骤S3中,所述收集所得气体,包括向所述生石灰处理后的混合体系鼓风,并冷凝收集鼓出气体。
- 根据权利要求1所述的回收方法,其特征在于,步骤S4中,所述曝气处理中二氧化硫的流量为60~120L/min。
- 根据权利要求1所述的回收方法,其特征在于,步骤S4中,所述曝气处理所得混合物的pH在6~7之间。
- 一种三元前驱体母液的回收系统,其特征在于,用于实施权利要求1~7中任一项所述的回收方法;所述回收系统包括经由管道(800)依次连接的母液池(100)、1号过滤器(200)、沉降池(300)、2号过滤器(400)、脱氨塔(500)、压滤机(600)和结晶系统(700)。
- 根据权利要求8所述的回收系统,其特征在于,所述脱氨塔(500)上连有鼓风机(510)。
- 根据权利要求8所述的回收系统,其特征在于,所述脱氨塔(500)上连有冷凝器(520)。
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