CN106957124A - A kind of tertiary cathode material produces the processing method and processing system of waste water - Google Patents
A kind of tertiary cathode material produces the processing method and processing system of waste water Download PDFInfo
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- CN106957124A CN106957124A CN201710229153.7A CN201710229153A CN106957124A CN 106957124 A CN106957124 A CN 106957124A CN 201710229153 A CN201710229153 A CN 201710229153A CN 106957124 A CN106957124 A CN 106957124A
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- waste water
- liquid
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- tertiary cathode
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- 239000002351 wastewater Substances 0.000 title claims abstract description 82
- 239000010406 cathode material Substances 0.000 title claims abstract description 51
- 238000003672 processing method Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 239000012528 membrane Substances 0.000 claims abstract description 58
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000009615 deamination Effects 0.000 claims abstract description 32
- 238000006481 deamination reaction Methods 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 28
- 230000008025 crystallization Effects 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 23
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 21
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 20
- 239000006228 supernatant Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000002250 absorbent Substances 0.000 claims abstract description 5
- 230000002745 absorbent Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 38
- 238000009834 vaporization Methods 0.000 claims description 22
- 230000008016 vaporization Effects 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 230000006835 compression Effects 0.000 claims description 18
- 238000007906 compression Methods 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 7
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 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
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 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
- 239000000835 fiber Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000036186 satiety Effects 0.000 description 1
- 235000019627 satiety Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- 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
- C01D5/16—Purification
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to the processing method and processing system that a kind of tertiary cathode material produces waste water, the technological process that the processing method is combined using UF membrane, separation of solid and liquid and evaporative crystallization first：First, using sulfuric acid solution as absorbent, use UF membrane that for ammonium sulfate, mineralized nitrogen in waste water is realized into deamination；Because the pH of early stage is alkalescence, a large amount of metal contact breaks and precipitated in waste water with alkali formation after waste water deaminizing, filtering removes the heavy metal precipitation in solution；Supernatant obtains sodium sulphate by evaporative crystallization after filtering.The processing method of the present invention carries out advanced treatment and reclamation to tertiary cathode material production waste water, effectively solves the process problem that tertiary cathode material produces waste water, reclaims ammonia, heavy metal and sodium sulphate resource in waste water, and Water Sproading rate is high, realizes zero-emission.
Description
Technical field
The invention belongs to Sewage advanced treatment technical field, more particularly to a kind of tertiary cathode material produces the place of waste water
Reason method and processing system.
Background technology
With gradually decreasing and huge environmental pollution that traditional energy is brought for petroleum resources, renewable green energy resource is developed
And energy storage material turns into the important directions of global evolution.Lithium rechargeable battery has high-energy-density, stable work in work, matter
The advantage such as light is measured, is the emphasis of high-power power battery exploitation.
At present, the anode material for lithium-ion batteries of successful commercialization has cobalt acid lithium, LiMn2O4 and LiFePO4.Cobalt acid lithium and
LiMn2O4 specific discharge capacity is small, and chemical stability is poor, it is difficult to be used as the positive electrode of high-power dynamic lithium battery.LiFePO4
The shortcomings of well still there is small theoretical and actual specific capacity and poor electric conductivity in heat endurance.Nickel-cobalt-manganternary ternary anode material is made
For Olivine-type Cathode Material in Li-ion Batteries, high with discharge capacity, cycle life is good, safe, the advantages of with low cost, is
Most potential positive electrode.
The preparation method of ternary material positive electrode mainly has high temperature solid-state method, sol-gal process, chemical coprecipitation, hydro-thermal
Synthetic method, spray drying process etc., wherein coprecipitation synthesis product component uniformity is good, and condition is easily controlled, operation letter
It is single, industrially mass produce.Chemical coprecipitation is usually that chemical raw material is mixed with solution state, and into solution
Appropriate precipitating reagent is added, makes each component well mixed in solution be co-precipitated out according to metering ratio, or in the solution
First reaction precipitation goes out a kind of intermediate product, then its calcining and decomposing is prepared fine powder.Chemical coprecipitation is being washed and divided
A large amount of alkaline waste water (pH can be produced from process>9), ammonia-nitrogen content is up to tens of gram per liters and forms complex compound with heavy metal.
Further, since containing substantial amounts of sodium sulfate salt, except being still unable to qualified discharge after ammonia, and can waste of resources is caused.
Therefore, in order to which the qualified discharge and recycling of realizing such waste water are reclaimed, it is badly in need of a kind of for tertiary cathode material
The zero-emission processing method and processing system of material production waste water.
The content of the invention
The present invention gives up for the technological deficiency that prior art described above is present there is provided a kind of production of tertiary cathode material
The processing method and processing system of water.What the processing method was combined using UF membrane, separation of solid and liquid and evaporative crystallization first
Technological process：First, using sulfuric acid solution as absorbent, use UF membrane that for ammonium sulfate, mineralized nitrogen in waste water is realized into deamination；
Because the pH of early stage is alkalescence, a large amount of metal contact breaks and precipitated in waste water with alkali formation after waste water deaminizing, filtering is removed in solution
Heavy metal precipitation；Supernatant obtains sodium sulphate by evaporative crystallization after filtering.The processing method of the present invention is to tertiary cathode material
Material production waste water carries out advanced treatment and reclamation, effectively solves the process problem that tertiary cathode material produces waste water, reclaims in waste water
Ammonia, heavy metal and sodium sulphate resource, Water Sproading rate are up to more than 99%, realize zero-emission.
The present invention is achieved by the following technical solutions：
First aspect present invention provides the processing method that a kind of tertiary cathode material produces waste water, comprises the following steps：
1) tertiary cathode material is produced into the shell side that waste water is passed through UF membrane, absorbing liquid is passed through the tube side of UF membrane, described
Absorbing liquid is sulfuric acid, obtains ammonium sulfate and deamination waste water；
Gaseous ammonia can mutually enter from the waste water of shell side through the micropore on film surface and manage in tertiary cathode material production waste water
The acid of journey absorbs phase, is absorbed by acid solution and becomes ammonium sulfate
2) by step 1) obtained deamination waste water filtering, obtain supernatant and precipitation；
The complexing destruction of deamination heavy metal ions in wastewater forms precipitation；
3) by step 2) obtained supernatant, through evaporative crystallization, obtains sodium sulphate.
Preferably, step 1) in, Na in tertiary cathode material production waste water2SO4Concentration is 50-150g/L, NH3- N concentration
For 500-10000mg/L, M2+Concentration is 50-500mg/L, M2+Concentration is Ni2+、Co2+And Mn2+Total concentration, pH be 10~14.
Preferably, step 1) in, one or more in also including the following features：
1) UF membrane uses hydrophobic hollow fiber film；
2) membrane separation process condition is：30~45 DEG C of temperature, operation relative pressure is 0.1~0.25MPa；
3) pH value of absorbing liquid is 0~5；
4) it is 1 that tertiary cathode material, which produces waste water and the volume flow ratio of absorbing liquid,：2.5~5；
5) step 1) obtained ammonium sulfate concentration is 15-30wt%；
6) step 1) obtained ammonium sulfate is back in tertiary cathode material production technology.
Preferably, one or more in also including the following features：
1) step 2) sulfuric acid dissolution is used after obtained precipitation press filtration, in tertiary cathode material production technology；
2) step 2) obtained precipitation is discharged into concentration liquid bath, and concentrate trench bottom underflow is molten with sulfuric acid after plate compression
Solution, in tertiary cathode material production technology；
3) step 2) in, described be filtered into is separated by liquid filter.
Preferably, step 3) in, by step 2) obtained supernatant enters oven heats to more than solution boiling point, and such as 70
~125 DEG C, subsequently into being evaporated in vaporization chamber to supersaturation, sodium sulphate is finally separated out in crystallizing tank, through centrifugal drying,
Obtain sodium sulphate.
It is highly preferred that the indirect steam that vaporization chamber is produced is back to heating chamber after being compressed continue heating stepses 2) obtain
Supernatant, without live steam add.
Preferably, the indirect steam, which is back to after heating chamber, obtains evaporation condensed water, and the condensed water, which is used to separate, to be inhaled
Receive in liquid preparation or tertiary cathode material production technology.
Second aspect present invention provides the processing system that a kind of tertiary cathode material produces waste water, including：
Membrane separation device, deamination waste water is obtained for tertiary cathode material production waste water to be carried out into UF membrane；
Equipment for separating liquid from solid, for deamination waste water filtering to be obtained into supernatant and precipitation, the equipment for separating liquid from solid and film
Separator is connected；
Evaporated crystallization device, for supernatant evaporative crystallization to be obtained into sodium sulphate, the evaporated crystallization device and solid-liquid point
From device connection.
Hydrophobic hollow fiber film can be used in the membrane separation device.
The equipment for separating liquid from solid is liquid filter, can be Sean filter, such as Sean CNII2200 filters.
Preferably, one or more in also including the following features：
1) membrane separation device, which is provided with, is used to enter the shell side that tertiary cathode material produces waste water input membrane separation device
Mouth, the shell-side outlet for deamination waste water to be discharged to membrane separation device, the tube-side inlet for sulfuric acid to be inputted to membrane separation device
Exported with the tube side for ammonium sulfate to be discharged to membrane separation device, tube side outlet and the separation of solid and liquid of membrane separation device
Device is connected；During the ammonium sulfate for exporting discharge from tube side can be back to tertiary cathode material production technology；
2) processing system also include be used for store tertiary cathode material produce waste water wastewater trough, the wastewater trough with
Membrane separation device is connected；
3) flow container and solid-liquid after flow container after deamination of the processing system also including being used to store deamination waste water, the deamination
Separator is connected；
4) processing system also includes concentration liquid bath and plate and frame filter press, and the equipment for separating liquid from solid goes out including supernatant
Mouth and precipitation outlet, the precipitation is exported to be connected with concentration liquid bath, and the concentration liquid bath is connected with plate and frame filter press, the sheet frame
Filter press is provided with filtrate (liquid and sludge outlet, and the filtrate (liquid of the plate and frame filter press is connected or institute with equipment for separating liquid from solid
The filtrate (liquid for stating plate and frame filter press is connected with flow container after deamination；
5) evaporated crystallization device includes heating chamber, vaporization chamber and the crystallizing tank being sequentially communicated；
6) processing system also includes flow container before evaporation, and the equipment for separating liquid from solid is connected with flow container before evaporation；
7) processing system also includes the NaOH solution tank NaOH for being used to store ammonium sulfate, the NaOH solution tank NaOH and membrane separation device
Connection.
It is highly preferred that one or more in also including the following features：
1) feature 4) in, the filter residue that the processing system is also included for plate and frame filter press to be obtained carries out the acid of sour dissolving
Fluid bowl, the sour fluid bowl is connected with the sludge outlet of plate and frame filter press；
2) feature 5) in, the evaporated crystallization device also includes vapour compression machine, and vaporization chamber is provided with steam (vapor) outlet and satiety
And taphole, the steam (vapor) outlet of the vaporization chamber connected with vapour compression machine, and the vapour compression machine is connected with heating chamber again,
The supersaturated solution outlet of the vaporization chamber is connected with crystallizing tank；Vaporization chamber produce steam be compressed be back to heating chamber after
Continuous heating, is added without live steam, and obtained evaporation condensed water can be used for separate absorbent liquid to prepare or tertiary cathode material
In production technology；
3) feature 5) in, the processing system also includes the centrifuge and drier being sequentially communicated, and the crystallizing tank is provided with
Solid sodium sulfate is exported and taphole, and the solid sodium sulfate outlet of crystallizing tank is connected with centrifuge, the liquid outlet of crystallizing tank
Connected with heating chamber.
Compared with prior art, processing method of the invention has following technique effect：
(1) technological process that the present invention is combined by using UF membrane, separation of solid and liquid and evaporative crystallization, to tertiary cathode
Material production waste water carries out advanced treatment and reclamation, reclaims ammonia, heavy metal and sodium sulphate resource in waste water, and Water Sproading rate is high, realizes
Zero-emission；
(2) membrane separating process method is simple and easy to apply in the present invention, and energy consumption is low；MVR evaporative crystallizations only need very small amount steam,
Operating cost is greatly dropped, environmental pollution is reduced；There is no waste hot steam discharge, energy-saving effect is very notable；
(3) present invention investment is small, and operating cost is low, and equipment is simple, it is easy to safeguard；
(4) present invention is produced without harmful byproduct, non-secondary pollution.
Brief description of the drawings
Fig. 1 is the processing method that tertiary cathode material of the present invention produces waste water；
Fig. 2 is the processing system that tertiary cathode material of the present invention produces waste water.
Reference：
1- membrane separation devices；
2- equipment for separating liquid from solid；
3- evaporated crystallization devices；31- heating chambers；32- vaporization chambers；33- crystallizing tanks；34- vapour compression machines；
4- wastewater troughs；
Flow container after 5- deaminations；
6- concentrates liquid bath；
7- plate and frame filter press；
8- acid fluid bowls；
9- centrifuges；
10- driers；
Flow container before 11- evaporations；
12- NaOH solution tank NaOHs.
Embodiment
Illustrate technical scheme below by way of specific instantiation.It should be understood that the present invention mention one or
Multiple method and steps, which do not repel before and after the combination step, also has other method step or the step specifically mentioned at these
Other method step can also be inserted between rapid；It should also be understood that these embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Moreover, unless otherwise indicated, the numbering of various method steps is only the convenient tool for differentiating various method steps,
Rather than ordering or restriction enforceable scope of the invention, the change of its relativeness or tune for limitation various method steps
It is whole, in the case of without essence change technology contents, when being also considered as enforceable category of the invention.
With reference to specific embodiment, the present invention will be further described：
Embodiment 1
By taking certain domestic 6000 tons of ternary precursor manufacturer of annual output as an example, waste water water 350m3/d.Discharge of wastewater pollutes
Thing concentration determination is as follows：
| Pollutant | pH | Na2SO4 | NH3-N | M2+ |
| Concentration (g/L) | 12.95 | 100 | 10.2 | 0.243 |
A kind of tertiary cathode material produces the processing system of waste water, as shown in Fig. 2 including：Membrane separation device 1, for inciting somebody to action
Tertiary cathode material production waste water carries out UF membrane and obtains deamination waste water；The membrane separation device 1, which is provided with, to be used for tertiary cathode
Material production waste water input membrane separation device shell side inlet, for by deamination waste water discharge membrane separation device shell-side outlet,
For sulfuric acid to be inputted to the tube-side inlet of membrane separation device and is exported for the tube side that ammonium sulfate is discharged to membrane separation device,
The tube side outlet of membrane separation device 1 is connected with the equipment for separating liquid from solid 2；The ammonium sulfate for exporting discharge from tube side can reuse
In tertiary cathode material production technology；Hydrophobic hollow fiber film can be used in the membrane separation device, and such as polypropylene (PP) is dredged
Water hollow-fibre membrane；Equipment for separating liquid from solid 2, for deamination waste water filtering to be obtained into supernatant and precipitation, the separation of solid and liquid dress
2 are put to connect with membrane separation device 1；The equipment for separating liquid from solid is liquid filter, can be Sean filter, such as Sean
CNII2200 filters；Evaporated crystallization device 3, for supernatant evaporative crystallization to be obtained into sodium sulphate, the evaporated crystallization device 3
Connected with equipment for separating liquid from solid 2；The evaporated crystallization device 3 includes heating chamber 31, vaporization chamber 32 and the crystallizing tank being sequentially communicated
33；The evaporated crystallization device 3 also includes vapour compression machine 34, and vaporization chamber 32 is exported provided with steam (vapor) outlet and supersaturated solution,
The steam (vapor) outlet of the vaporization chamber 32 is connected with vapour compression machine 34, and the vapour compression machine 34 is connected with heating chamber 31 again, institute
The supersaturated solution outlet for stating vaporization chamber 32 is connected with crystallizing tank 33；The steam that vaporization chamber is produced, which is compressed, is back to heating chamber
Continue to heat, added without live steam, obtained evaporation condensed water can be used for separate absorbent liquid to prepare or tertiary cathode material
In material manufacturing technique；The processing system also includes being used to store the wastewater trough 4 that tertiary cathode material produces waste water, the waste water
Groove 4 is connected with membrane separation device 1；Flow container 5 is with consolidating after flow container 5 after deamination also including being used to store deamination waste water, the deamination
Liquid separating apparatus 2 is connected；Also include concentration liquid bath 6 and plate and frame filter press 7, the equipment for separating liquid from solid 2 includes supernatant outlet
With precipitation outlet, the precipitation outlet is connected with concentration liquid bath 6, and the concentration liquid bath 6 is connected with plate and frame filter press 7, the plate
The filtrate (liquid of frame filter press 7 is connected with flow container after deamination 5；Also include flow container 11 before evaporation, the equipment for separating liquid from solid 2 is with steaming
Flow container 11 is connected before hair；Also include the NaOH solution tank NaOH 12 for being used to store ammonium sulfate, the NaOH solution tank NaOH 12 connects with membrane separation device 1
It is logical.Also include the sour fluid bowl 8 that the filter residue for plate and frame filter press 7 to be obtained carries out sour dissolving, the sour fluid bowl 8 and plate compression
The sludge outlet connection of machine 7；Also include the centrifuge 9 and drier 10 being sequentially communicated, the crystallizing tank 33 is solid provided with sodium sulphate
Body is exported and taphole, and the solid sodium sulfate outlet of crystallizing tank 33 is connected with centrifuge 9, the liquid outlet of crystallizing tank and heating
Room 31 is connected.
A kind of tertiary cathode material produces the processing method of waste water, and process chart is shown in Fig. 1.UF membrane is polypropylene in figure
(PP) hydrophobic hollow fiber membrane, operation relative pressure is 0.1MPa, and temperature is 30 DEG C；Liquid filter filters for CNII2200
Device, separate unit disposal ability 15m3/h；Evaporated crystallization device designed rating be 13.5t/h, 15 DEG C of vapour compression machine designed temperature difference,
Design temperature rises to 105 DEG C from 90 DEG C.
Processing step is as follows：
1. UF membrane：Ternary waste water in waste water tank is pumped into the shell side of UF membrane, is pumped into pH=1's in the tube side of UF membrane
Dilute sulfuric acid is circulated flowing, and the flow of dilute sulfuric acid is 1320m3/d.In waste water gaseous ammonia can through film surface micropore from
The acid that the waste water of shell side mutually enters tube side absorbs phase, is absorbed by acid solution and becomes ammonium sulfate, by constantly supplementing dilute sulfuric acid
Raise ammonium sulfate concentrations, when the concentration for reaching 20wt% is just back in tertiary cathode material production technology.Wherein diluted acid
Preparation can be prepared with evaporation condensed water.
2. separation of solid and liquid：Heavy metals ion complexation form after deamination is destroyed so as to form precipitation, enters
CNII3300 filters are separated.Supernatant suspension is less than 5mg/L after filter is separated, and metal ion is less than 1mg/
L, can be discharged into flow container before evaporation with overflow.The precipitation of filter bottom is periodically discharged into concentration liquid bath, then squeezes into plate and frame filter press
It is dehydrated, after sediment is using dilute sulfuric acid dissolving, tertiary cathode material production system can be back to, sheet frame filtrate then returns to
Filter continues separation of solid and liquid.
3. evaporative crystallization：Evaporated crystallization device includes vaporization chamber, crystallizing tank, heating chamber and vapour compression machine.Given up after deamination
Water is introduced into heating chamber and exchanged heat with the saturated steam that vapour compression machine comes out, and waste water is heated to more than solution boiling point, then
It is evaporated in into vaporization chamber to supersaturation.Then cooling separates out anhydrous sodium sulfate in crystallizing tank, collects after centrifugal drying
Middle disposal.Indirect steam returns to waste water after oven heats deamination after vapour compression machine compresses in vaporization chamber.Evaporative condenser
Water can be back to preparation and the tertiary cathode material production system of UF membrane absorbing liquid.
By whole processing system, 20wt% ammonium sulfate 138.6t/d, heavy metal 85.05kg/d and anhydrous slufuric acid are obtained
Sodium 35t/d, resource is all reclaimed, water also almost 100% reuse.
Embodiment 2
By taking certain domestic 10000 tons of ternary precursor manufacturer of annual output as an example, waste water water 1000m3/d.Discharge of wastewater is dirty
Contaminate thing concentration determination as follows：
| Pollutant | pH | Na2SO4 | NH3-N | M2+ |
| Concentration (g/L) | 11.5 | 75 | 4.5 | 0.07 |
Process flow diagram is shown in Fig. 2.UF membrane is polytetrafluoroethylene (PTFE) (PTFE) hydrophobic hollow fiber membrane in figure, runs phase
It is 0.25MPa to pressure, temperature is 45 DEG C, pH=5 dilute sulfuric acid flow is 3600m3/h；Liquid filter is CNII3300 mistakes
Filter, separate unit disposal ability 30m3/ h, totally 2；Evaporated crystallization device designed rating is 42t/h, designs 2 sets, single set 21t/
H, 18 DEG C of vapour compression machine designed temperature difference, design temperature rises to 113 DEG C from 95 DEG C.
Processing step such as embodiment 1,
By whole processing system, 25wt% ammonium sulfate 139.8t/d, heavy metal 70kg/d and anhydrous sodium sulfate are obtained
75t/d, resource is all reclaimed, water also almost 100% reuse.
Claims (10)
1. a kind of tertiary cathode material produces the processing method of waste water, it is characterised in that comprise the following steps：
1) tertiary cathode material is produced into the shell side that waste water is passed through UF membrane, absorbing liquid is passed through the tube side of UF membrane, the absorption
Liquid is sulfuric acid, obtains ammonium sulfate and deamination waste water；
2) by step 1) obtained deamination waste water filtering, obtain supernatant and precipitation；
3) by step 2) obtained supernatant, through evaporative crystallization, obtains sodium sulphate.
2. processing method as claimed in claim 1, it is characterised in that step 1) in, in tertiary cathode material production waste water
Na2SO4Concentration is 50-150g/L, NH3- N concentration is 500-10000mg/L, M2+Concentration is 50-500mg/L, M2+Concentration is Ni2 +、Co2+And Mn2+Total concentration, pH be 10~14.
3. processing method as claimed in claim 1, it is characterised in that step 1) in, one in also including the following features or
It is multinomial：
1) UF membrane uses hydrophobic hollow fiber film；
2) membrane separation process condition is：30~45 DEG C of temperature, operation relative pressure is 0.1~0.25MPa；
3) pH value of absorbing liquid is 0~5；
4) it is 1 that tertiary cathode material, which produces waste water and the volume flow ratio of absorbing liquid,：2.5~5；
5) step 1) obtained ammonium sulfate concentration is 15-30wt%；
6) step 1) obtained ammonium sulfate is back in tertiary cathode material production technology.
4. processing method as claimed in claim 1, it is characterised in that one or more in also including the following features：
1) step 2) sulfuric acid dissolution is used after obtained precipitation press filtration, in tertiary cathode material production technology；
2) step 2) obtained precipitation is discharged into concentration liquid bath, and concentrate trench bottom underflow uses sulfuric acid dissolution after plate compression, uses
In tertiary cathode material production technology；
3) step 2) in, described be filtered into is separated by liquid filter.
5. processing method as claimed in claim 1, it is characterised in that step 3) in, by step 2) obtained supernatant enters
Oven heats, subsequently into being evaporated in vaporization chamber to supersaturation, are finally separated out to more than solution boiling point in crystallizing tank
Sodium sulphate, through centrifugal drying, obtains sodium sulphate.
6. processing method as claimed in claim 5, it is characterised in that the indirect steam that vaporization chamber is produced is returned after being compressed
Continue heating stepses 2 to heating chamber) obtained supernatant.
7. processing method as claimed in claim 1, it is characterised in that the indirect steam, which is back to after heating chamber, to be evaporated
Condensed water, the condensed water is used in the preparation of separate absorbent liquid or tertiary cathode material production technology.
8. a kind of tertiary cathode material produces the processing system of waste water, it is characterised in that including：
Membrane separation device (1), deamination waste water is obtained for tertiary cathode material production waste water to be carried out into UF membrane；
Equipment for separating liquid from solid (2), for deamination waste water filtering to be obtained into supernatant and precipitation, the equipment for separating liquid from solid (2) with
Membrane separation device (1) is connected；
Evaporated crystallization device (3), for supernatant evaporative crystallization to be obtained into sodium sulphate, the evaporated crystallization device (3) and solid-liquid
Separator (2) is connected.
9. processing system as claimed in claim 8, it is characterised in that one or more in also including the following features：
1) membrane separation device (1), which is provided with, is used to enter the shell side that tertiary cathode material produces waste water input membrane separation device
Mouth, the shell-side outlet for deamination waste water to be discharged to membrane separation device, the tube-side inlet for sulfuric acid to be inputted to membrane separation device
Exported with the tube side for ammonium sulfate to be discharged to membrane separation device, tube side outlet and the solid-liquid of membrane separation device (1)
Separator (2) is connected；
2) processing system also includes being used to store the wastewater trough (4) that tertiary cathode material produces waste water, the wastewater trough (4)
Connected with membrane separation device (1)；
3) flow container (5) is with consolidating after flow container (5) after deamination of the processing system also including being used to store deamination waste water, the deamination
Liquid separating apparatus (2) is connected；
4) processing system also includes concentration liquid bath (6) and plate and frame filter press (7), and the equipment for separating liquid from solid (2) includes upper
Purified liquor outlet and precipitation are exported, and the precipitation outlet is connected with concentration liquid bath (6), the concentration liquid bath (6) and plate and frame filter press
(7) connect, the plate and frame filter press (7) be provided with filtrate (liquid and sludge outlet, the filtrate (liquid of the plate and frame filter press (7) with
Equipment for separating liquid from solid (2) is connected or the filtrate (liquid of the plate and frame filter press (7) is connected with flow container after deamination (5)；
5) evaporated crystallization device (3) includes heating chamber (31), vaporization chamber (32) and the crystallizing tank (33) being sequentially communicated；
6) processing system also includes flow container (11) before evaporating, and the equipment for separating liquid from solid (2) connects with flow container (11) before evaporation
It is logical；
7) processing system also includes the NaOH solution tank NaOH (12) for being used to store ammonium sulfate, the NaOH solution tank NaOH (12) and UF membrane
Device (1) is connected.
10. processing system as claimed in claim 9, it is characterised in that one or more in also including the following features：
1) feature 4) in, the filter residue that the processing system is also included for plate and frame filter press (7) to be obtained carries out the acid of sour dissolving
Fluid bowl (8), the sour fluid bowl (8) connects with the sludge outlet of plate and frame filter press (7)；
2) feature 5) in, the evaporated crystallization device (3) also includes vapour compression machine (34), and vaporization chamber (32) is provided with steam (vapor) outlet
With supersaturated solution outlet, the steam (vapor) outlet of the vaporization chamber (32) is connected with vapour compression machine (34), the vapour compression machine
(34) connected again with heating chamber (31), the supersaturated solution outlet of the vaporization chamber (32) is connected with crystallizing tank (33)；
3) feature 5) in, the processing system also includes the centrifuge (9) and drier (10) being sequentially communicated, the crystallizing tank
(33) provided with solid sodium sulfate outlet and taphole, the solid sodium sulfate outlet of crystallizing tank (33) is connected with centrifuge (9), is tied
The liquid outlet of brilliant tank is connected with heating chamber (31).
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| CN109721186A (en) * | 2018-12-30 | 2019-05-07 | 沈阳化工研究院有限公司 | A kind of processing method recycling ternary precursor mother liquor in lithium battery active object |
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