CN116425353A - Ternary precursor wastewater treatment method - Google Patents
Ternary precursor wastewater treatment method Download PDFInfo
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- CN116425353A CN116425353A CN202310442058.0A CN202310442058A CN116425353A CN 116425353 A CN116425353 A CN 116425353A CN 202310442058 A CN202310442058 A CN 202310442058A CN 116425353 A CN116425353 A CN 116425353A
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- 239000002243 precursor Substances 0.000 title claims abstract description 35
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- 239000012452 mother liquor Substances 0.000 claims abstract description 51
- 238000000926 separation method Methods 0.000 claims abstract description 49
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 44
- 238000001704 evaporation Methods 0.000 claims abstract description 43
- 230000008020 evaporation Effects 0.000 claims abstract description 42
- 230000009615 deamination Effects 0.000 claims abstract description 32
- 238000006481 deamination reaction Methods 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004064 recycling Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 23
- 230000000694 effects Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 239000010413 mother solution Substances 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- 239000013505 freshwater Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000009388 chemical precipitation Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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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
- 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
- C02F1/02—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a ternary precursor wastewater treatment method, which comprises the following steps: step one: the ternary washing water is coarsely filtered by a security filtering device before the membrane and then enters a membrane treatment device; step two: heavy metals are removed from the wastewater in the ternary mother liquor pool, and the wastewater after heavy metal removal enters a deamination device for deamination treatment; step three: the deaminated material enters an evaporator device for evaporation, the evaporated condensed water enters a condensed water film treatment device, the produced water after film separation enters a recycling water tank, and the concentrated water after film separation enters a ternary mother liquor tank for mixing with ternary mother liquor; step four: after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, whether centrifugal mother liquor is required to be pumped back to a ternary mother liquor pool or not is judged according to the enrichment degree of impurities in the mother liquor, and heavy ammonia removal treatment is carried out again; can realize heavy metal recycling, ammonia water recycling, water quality up to standard discharge and salt as a byproduct production.
Description
Technical Field
The invention relates to the technical field of ternary precursor wastewater treatment, in particular to a ternary precursor wastewater treatment method.
Background
The ternary precursor (nickel cobalt manganese ternary oxide) is a novel positive electrode material of a power battery, and the production process is as follows: 1. adding proper amounts of manganese sulfate and pure water into a nickel sulfate solution and a cobalt sulfate solution, wherein the ratio of Ni to Co to Mn is 5:2:3, preparing a nickel-cobalt-manganese ternary solution; 2. adding ammonia water and sodium hydroxide into the ternary solution of nickel, cobalt and manganese, and reacting and precipitating the ternary solution with the sodium hydroxide under the condition that the ammonia water is used as a complexing agent. The precipitate is nickel-cobalt-manganese ternary precursor after centrifugal separation, and the liquid is ternary mother liquor. Washing the precipitate of the centrifuge (washing water is called ternary washing water), drying and screening to remove iron, and obtaining a ternary precursor product.
The ternary mother liquor and ternary washing water are main waste water sources in the production process of ternary precursors, and the main components are sodium sulfate, and contain a small amount of ammonium sulfate and trace amounts of heavy metals such as nickel, cobalt and manganese ions. Aiming at the wastewater to carry out resource recovery treatment and wastewater standard discharge treatment, we propose a ternary precursor wastewater treatment method to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a ternary precursor wastewater treatment method for solving the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the ternary precursor wastewater treatment method comprises the following steps of:
step one: the ternary washing water is subjected to coarse filtration by a pre-membrane security filtering device and then enters a membrane treatment device, fresh water after membrane separation enters a recycling water tank, and concentrated water after membrane separation enters a ternary mother liquor tank and is mixed with ternary mother liquor;
step two: pumping the wastewater of the ternary mother solution pool into a heavy metal removing device under the action of a pump to remove heavy metals, and enabling the wastewater after heavy metal removal to enter a deamination device for deamination;
step three: the deaminated material enters an evaporator device for evaporation, the evaporated condensed water enters a condensed water film treatment device, the produced water after film separation enters a recycling water tank, and the concentrated water after film separation enters a ternary mother liquor tank for mixing with ternary mother liquor;
step four: after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, and as the heavy metal and ammonia cannot be removed from the wastewater by 100% by the heavy metal removal device and the ammonia removal device, in the evaporation concentration process, the impurities are continuously enriched in the centrifugal mother liquor, whether the centrifugal mother liquor needs to be pumped back to a ternary mother liquor pool again is judged according to the enrichment degree of the impurities in the mother liquor, the heavy metal removal and ammonia removal treatment is carried out again, and the quality of the ternary precursor wastewater treatment is improved.
As a further scheme of the invention: the weight removing device comprises two methods of physical and chemical precipitation and resin adsorption.
As a further scheme of the invention: heavy metal separated by the heavy metal removing device is recycled through the heavy metal recycling device.
As a further scheme of the invention: the deamination device is a multiphase critical membrane deamination unit, deamination treatment is carried out by the deamination device, and produced ammonia water enters an ammonia water collecting tank for recycling.
As a further scheme of the invention: the evaporator device comprises MVR, TVR, single effect and multiple effect evaporation modes.
As a further scheme of the invention: and after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, the separated solid phase is a sodium sulfate product, and the mother solution after centrifugation is a saturated sodium sulfate solution.
As a further scheme of the invention: the sodium sulfate product is anhydrous sodium sulfate or sodium sulfate decahydrate.
As a further scheme of the invention: the saturated sodium sulfate solution after centrifugation is recovered through a mother solution collecting tank, and then returned to an evaporator device for evaporation concentration under the action of a pump.
As a further scheme of the invention: the evaporator device is at a temperature of 98-110 ℃ when evaporating.
As still further aspects of the invention: the weight removing ratio of the weight removing step is more than 88%.
Compared with the prior art, the invention has the beneficial effects that: according to the ternary precursor wastewater treatment method, ternary washing water is concentrated through a membrane device, concentrated water is mixed with ternary mother liquor, heavy metal is removed for deamination, the ternary washing water enters an evaporation device for evaporation crystallization, then enters a solid-liquid separation device for solid-liquid separation, and the produced crystallized salt is sodium sulfate product, so that heavy metal recycling, ammonia water recycling, water quality standard reaching emission and salt production can be achieved as byproducts.
Drawings
FIG. 1 is a schematic diagram of a ternary precursor wastewater treatment process according to the present invention.
FIG. 2 is a schematic flow chart of a ternary precursor wastewater treatment method in the invention.
Detailed Description
Example 1
In one embodiment, as shown in fig. 1-2, a method for treating ternary precursor wastewater, the ternary precursor wastewater comprising ternary wash water and ternary mother liquor, is characterized by comprising the steps of:
step one: the ternary washing water is subjected to coarse filtration by a pre-membrane security filtering device and then enters a membrane treatment device, fresh water after membrane separation enters a recycling water tank, and concentrated water after membrane separation enters a ternary mother liquor tank and is mixed with ternary mother liquor;
step two: pumping the wastewater of the ternary mother solution pool into a heavy metal removing device under the action of a pump to remove heavy metals, and enabling the wastewater after heavy metal removal to enter a deamination device for deamination;
step three: the deaminated material enters an evaporator device for evaporation, the temperature of the evaporated material is 98 ℃, condensed water after evaporation enters a condensed water film treatment device, produced water after film separation enters a recycling water pool, and concentrated water after film separation enters a ternary mother liquor pool for mixing with ternary mother liquor;
step four: after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, and as the heavy metal and ammonia cannot be removed from the wastewater by 100% by the heavy metal removal device and the ammonia removal device, in the evaporation concentration process, the impurities are continuously enriched in the centrifugal mother liquor, whether the centrifugal mother liquor needs to be pumped back to a ternary mother liquor pool again is judged according to the enrichment degree of the impurities in the mother liquor, the heavy metal removal and ammonia removal treatment is carried out again, and the quality of the ternary precursor wastewater treatment is improved.
The mother liquor in the ternary precursor wastewater is different from the quality of the washing water, ammonia nitrogen and total salt in the washing water are low, if the washing water and the mother liquor are directly mixed and then subjected to stripping deamination, the deamination wastewater is high in treatment capacity, high in investment cost and high in operation energy consumption, the burden of a subsequent evaporator device can be increased, the pre-membrane security filtering device is adopted to coarsely filter and then enter the membrane treatment device, the treatment capacity of the stripping ammonia distillation wastewater is reduced by 2/3, fresh water after membrane separation enters a recycling pool, and concentrated water after membrane separation enters the ternary mother pool and is mixed with the ternary mother liquor, so that the production operation cost can be greatly reduced.
The weight removing device comprises two methods of physical and chemical precipitation and resin adsorption; the heavy metal separated by the heavy metal removing device is recycled by a heavy metal recycling device;
physical precipitation is classified into four types according to the level of suspended matters in water and the sinkability of suspended particles: free precipitation: discrete particles, the sinking speed is unchanged; flocculation precipitation: flocculation particles, the sedimentation rate is increased; crowded precipitation: also called layering or regional precipitation, the concentration of particles is higher, mutual interference occurs in precipitation, the particles are extruded into a group, and layering occurs; compression precipitation: the particles have high concentration, contact each other, support each other and squeeze into a block structure.
The adsorption resin refers to a high molecular polymer which can be used for removing organic matters in wastewater, decoloring sugar liquor, separating and refining natural products and biochemical products, and the like, has a plurality of adsorption resin varieties, can endow various special performances to the resin by monomer change and monomer upper functional group change, and is commonly used high molecular polymers such as polystyrene resin, polyacrylate resin and the like, and the adsorption resin is a resin adsorbent with a porous three-dimensional structure and is characterized by adsorption; the adsorption resin is widely used for wastewater treatment, medicament separation and purification, is used as a carrier of a chemical reaction catalyst, and is used as a filler of a molecular weight grading column of gas chromatography and gel permeation chromatography, and is characterized by easy regeneration, repeated use, such as matching with anion and cation exchange resins, and extremely high separation and purification level.
The deamination device is a multiphase critical membrane deamination unit, deamination treatment is carried out by the deamination device, and the produced ammonia water enters an ammonia water collecting tank for recycling;
the evaporator device comprises MVR, TVR, single effect and multiple effect evaporation modes; after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, the separated solid phase is sodium sulfate product, and the mother solution after centrifugation is saturated sodium sulfate solution; the sodium sulfate product is anhydrous sodium sulfate or sodium sulfate decahydrate;
the MVR evaporator is short for mechanical vapor recompression technology, and utilizes secondary vapor and energy thereof generated by an evaporation system, compression work is performed by a vapor compressor, enthalpy of the secondary vapor is improved, the secondary vapor is led into a cooling tower, and cooling water of the cooling tower circularly preheats materials; TVR evaporators are improved over systems that directly discharge secondary vapors by utilizing a spray heat pump to recover a portion of the secondary vapor; single effect evaporation is one of the evaporation operations, and is characterized in that the generated secondary steam is not used for further evaporation of materials, but is only the evaporation of a single device, and for single effect evaporation, after given production tasks and determined operation conditions, the water evaporation amount, the heating steam consumption amount and the heat transfer area of the evaporator are generally required to be calculated; the multi-effect evaporation is a series evaporation operation of taking the secondary steam of the previous effect as the heating steam of the next effect, and in the multi-effect evaporation, the operation pressure of each effect, the temperature of the corresponding heating steam and the boiling point of the solution are sequentially reduced.
The centrifuged saturated sodium sulfate solution is recovered by a mother solution collecting tank and then returned to an evaporator device for evaporation concentration under the action of a pump; the weight removing ratio in the weight removing step is more than 88%.
Example 2
In one embodiment, as shown in fig. 1-2, a method for treating ternary precursor wastewater, the ternary precursor wastewater comprising ternary wash water and ternary mother liquor, is characterized by comprising the steps of:
step one: the ternary washing water is subjected to coarse filtration by a pre-membrane security filtering device and then enters a membrane treatment device, fresh water after membrane separation enters a recycling water tank, and concentrated water after membrane separation enters a ternary mother liquor tank and is mixed with ternary mother liquor;
step two: pumping the wastewater of the ternary mother solution pool into a heavy metal removing device under the action of a pump to remove heavy metals, and enabling the wastewater after heavy metal removal to enter a deamination device for deamination;
step three: the deaminated materials enter an evaporator device for evaporation, the temperature of the evaporator device is 110 ℃, the evaporated condensed water enters a condensed water film treatment device, the produced water after film separation enters a recycling water pool, and the concentrated water after film separation enters a ternary mother liquor pool for mixing with the ternary mother liquor;
step four: after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, and as the heavy metal and ammonia cannot be removed from the wastewater by 100% by the heavy metal removal device and the ammonia removal device, in the evaporation concentration process, the impurities are continuously enriched in the centrifugal mother liquor, whether the centrifugal mother liquor needs to be pumped back to a ternary mother liquor pool again is judged according to the enrichment degree of the impurities in the mother liquor, the heavy metal removal and ammonia removal treatment is carried out again, and the quality of the ternary precursor wastewater treatment is improved.
The mother liquor in the ternary precursor wastewater is different from the quality of the washing water, ammonia nitrogen and total salt in the washing water are low, if the washing water and the mother liquor are directly mixed and then subjected to stripping deamination, the deamination wastewater is high in treatment capacity, high in investment cost and high in operation energy consumption, the burden of a subsequent evaporator device can be increased, the pre-membrane security filtering device is adopted to coarsely filter and then enter the membrane treatment device, the treatment capacity of the stripping ammonia distillation wastewater is reduced by 2/3, fresh water after membrane separation enters a recycling pool, and concentrated water after membrane separation enters the ternary mother pool and is mixed with the ternary mother liquor, so that the production operation cost can be greatly reduced.
The weight removing device comprises two methods of physical and chemical precipitation and resin adsorption; the heavy metal separated by the heavy metal removing device is recycled by a heavy metal recycling device;
physical precipitation is classified into four types according to the level of suspended matters in water and the sinkability of suspended particles: free precipitation: discrete particles, the sinking speed is unchanged; flocculation precipitation: flocculation particles, the sedimentation rate is increased; crowded precipitation: also called layering or regional precipitation, the concentration of particles is higher, mutual interference occurs in precipitation, the particles are extruded into a group, and layering occurs; compression precipitation: the particles have high concentration, contact each other, support each other and squeeze into a block structure.
The adsorption resin refers to a high molecular polymer which can be used for removing organic matters in wastewater, decoloring sugar liquor, separating and refining natural products and biochemical products, and the like, has a plurality of adsorption resin varieties, can endow various special performances to the resin by monomer change and monomer upper functional group change, and is commonly used high molecular polymers such as polystyrene resin, polyacrylate resin and the like, and the adsorption resin is a resin adsorbent with a porous three-dimensional structure and is characterized by adsorption; the adsorption resin is widely used for wastewater treatment, medicament separation and purification, is used as a carrier of a chemical reaction catalyst, and is used as a filler of a molecular weight grading column of gas chromatography and gel permeation chromatography, and is characterized by easy regeneration, repeated use, such as matching with anion and cation exchange resins, and extremely high separation and purification level.
The deamination device is a multiphase critical membrane deamination unit, deamination treatment is carried out by the deamination device, and the produced ammonia water enters an ammonia water collecting tank for recycling;
the evaporator device comprises MVR, TVR, single effect and multiple effect evaporation modes; after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, the separated solid phase is sodium sulfate product, and the mother solution after centrifugation is saturated sodium sulfate solution; the sodium sulfate product is anhydrous sodium sulfate or sodium sulfate decahydrate;
the MVR evaporator is short for mechanical vapor recompression technology, and utilizes secondary vapor and energy thereof generated by an evaporation system, compression work is performed by a vapor compressor, enthalpy of the secondary vapor is improved, the secondary vapor is led into a cooling tower, and cooling water of the cooling tower circularly preheats materials; TVR evaporators are improved over systems that directly discharge secondary vapors by utilizing a spray heat pump to recover a portion of the secondary vapor; single effect evaporation is one of the evaporation operations, and is characterized in that the generated secondary steam is not used for further evaporation of materials, but is only the evaporation of a single device, and for single effect evaporation, after given production tasks and determined operation conditions, the water evaporation amount, the heating steam consumption amount and the heat transfer area of the evaporator are generally required to be calculated; the multi-effect evaporation is a series evaporation operation of taking the secondary steam of the previous effect as the heating steam of the next effect, and in the multi-effect evaporation, the operation pressure of each effect, the temperature of the corresponding heating steam and the boiling point of the solution are sequentially reduced.
The centrifuged saturated sodium sulfate solution is recovered by a mother solution collecting tank and then returned to an evaporator device for evaporation concentration under the action of a pump; the weight removing ratio in the weight removing step is more than 88%.
In summary, according to the ternary precursor wastewater treatment method, ternary washing water is concentrated through the membrane device, concentrated water is mixed with ternary mother liquor, heavy metal is removed for deamination, then the ternary washing water enters the evaporation device for evaporation crystallization, then enters the solid-liquid separation device for solid-liquid separation, and the produced crystallized salt is sodium sulfate product, so that heavy metal recovery and use, ammonia water recovery and use, water quality up to standard emission and salt as byproduct production can be achieved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The ternary precursor wastewater treatment method is characterized by comprising the following steps of:
step one: the ternary washing water is subjected to coarse filtration by a pre-membrane security filtering device and then enters a membrane treatment device, fresh water after membrane separation enters a recycling water tank, and concentrated water after membrane separation enters a ternary mother liquor tank and is mixed with ternary mother liquor;
step two: pumping the wastewater of the ternary mother solution pool into a heavy metal removing device under the action of a pump to remove heavy metals, and enabling the wastewater after heavy metal removal to enter a deamination device for deamination;
step three: the deaminated material enters an evaporator device for evaporation, the evaporated condensed water enters a condensed water film treatment device, the produced water after film separation enters a recycling water tank, and the concentrated water after film separation enters a ternary mother liquor tank for mixing with ternary mother liquor;
step four: after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, and as the heavy metal and ammonia cannot be removed from the wastewater by 100% by the heavy metal removal device and the ammonia removal device, in the evaporation concentration process, the impurities are continuously enriched in the centrifugal mother liquor, whether the centrifugal mother liquor needs to be pumped back to a ternary mother liquor pool again is judged according to the enrichment degree of the impurities in the mother liquor, the heavy metal removal and ammonia removal treatment is carried out again, and the quality of the ternary precursor wastewater treatment is improved.
2. The method for treating ternary precursor wastewater according to claim 1, wherein the weight removing device comprises two methods of physical and chemical precipitation and resin adsorption.
3. The ternary precursor wastewater treatment method according to claim 1, wherein the heavy metals separated by the heavy metal removing device are recycled by a heavy metal recycling device.
4. The ternary precursor wastewater treatment method according to claim 1, wherein the deamination device is a multiphase critical film deamination unit, deamination treatment is carried out by the deamination device, and produced ammonia water enters an ammonia water collecting tank for recycling.
5. The method of claim 1, wherein the evaporator device comprises MVR, TVR, single effect, multiple effect multiple evaporation modes.
6. The method for treating ternary precursor wastewater according to claim 1, wherein after the evaporated wastewater reaches a proper concentration, the wastewater enters a centrifugal separation device for solid-liquid separation, the separated solid phase is sodium sulfate product, and the mother solution after centrifugation is saturated sodium sulfate solution.
7. The method for treating ternary precursor wastewater according to claim 6, wherein the sodium sulfate product is anhydrous sodium sulfate or sodium sulfate decahydrate.
8. The method for treating ternary precursor wastewater according to claim 6, wherein the centrifuged saturated sodium sulfate solution is recovered by a mother liquor collecting tank and then returned to the evaporator device for evaporation concentration by the action of a pump.
9. A method of ternary precursor wastewater treatment according to claim 1 wherein the evaporator means is at a temperature of 98-110 ℃.
10. The method for treating ternary precursor wastewater according to claim 1, wherein the weight removal ratio of the weight removal step is more than 88%.
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