CN108250147A - A kind of medicament and resource utilization method for ternary precursor waste water ammonia recycling - Google Patents

A kind of medicament and resource utilization method for ternary precursor waste water ammonia recycling Download PDF

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Publication number
CN108250147A
CN108250147A CN201810034212.XA CN201810034212A CN108250147A CN 108250147 A CN108250147 A CN 108250147A CN 201810034212 A CN201810034212 A CN 201810034212A CN 108250147 A CN108250147 A CN 108250147A
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ammonia
waste water
medicament
ternary precursor
resource utilization
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邓敏
侯瑞
王政强
邱世威
李大维
高卓
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Yibin Guang Yuan Lithium Electric Material Co Ltd
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Yibin Guang Yuan Lithium Electric Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
    • 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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • 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
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/03—Pressure
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention belongs to gas separation and purification techniques field, a kind of medicament and resource utilization method for ternary precursor waste water ammonia recycling is specifically disclosed, and the medicament is made of the anion of the cation and boracic of imidazoles or pyridine and its derivatives, phosphonium ion.The medicament passes through the Hyarogen-bonding between cation and ammonia molecule, anion and the intermolecular Van der Waals force collective effect of ammonia, realize the high efficiente callback to ammonia, the medicament absorptive capacity is big, physico-chemical property is stable simultaneously, long lifespan, recyclable regenerative use, it is utilized for lithium electricity industry Ammonia recovery and provides a kind of New Absorbent, and a kind of ternary precursor waste water ammonia resource utilization method is provided simultaneously, the ammonia nitrogen in high density in ternary precursor waste water can be recycled in the form of ammonia and ammonium hydroxide.

Description

A kind of medicament and recycling profit for ternary precursor waste water ammonia recycling Use method
Technical field
The invention belongs to gas separation and purification techniques field, and in particular to one kind is used for lithium battery tertiary presoma waste water The medicament and resource utilization method of ammonia recycling.
Background technology
Anode material of lithium battery obtains national science policy ＆ technology policy and industrial policy always as a kind of important new energy materials Support, and be put into national related industry development plan and catalogue.Tertiary cathode material is since energy density is high, cost is opposite Relatively low, the features such as cycle performance is excellent, be current volume production positive electrode in a kind of most promising material of potentiality maximum.
Ternary anode material precursor in the market is mainly hydroxide nickel cobalt manganese and nickel cobalt aluminum hydroxide, synthesis path For：By in nickel sulfate, cobaltous sulfate and manganese sulfate or aluminum sulfate input reaction kettle, add in sodium hydroxide pellets agent and be complexed with ammonium hydroxide Agent obtains mother liquor and hydroxide nickel cobalt manganese and nickel cobalt aluminum hydroxide crude product, mother liquor waste water and crude product after reaction by centrifugation In containing the foreign ions such as the complete raw material of unreacted and sulfate radical, sodium ion, ammonium ion, ammonia density is 8000~ 12000mg/L, crude product obtain wash water and finished product after pure water, and finished product is after drying, mixed batch, the screening/except magnetic, packaging To hydroxide nickel cobalt manganese and nickel cobalt aluminum hydroxide product, after wash water is concentrated and mother liquor waste water is mixed into mother liquor pond, mother liquor pond In ammonium root cation recycled in the form of ammonia or ammonium hydroxide through deamination process for raw material or other processes, in deamination Mother liquor Heavy metal ion is recycled with precipitation form, and deamination obtains byproduct anhydrous sodium sulfate with removing the mother liquor after weighing, concentrated crystallization.
In ternary precursor synthesis, ammonium hydroxide is as a kind of complexing agent, to producing high-density spherical hydroxide precursor It plays an important role.Using a large amount of ammonium hydroxide in presoma production, necessarily resulting in the wash water for rinsing presoma has higher ammonia Values of nitrogen might, the recycling and utilization of ammonia not only contribute to reduce the input of ammonium hydroxide raw material, are also beneficial to jean-washing wastewater system reuse, protect Water resource.For ammonia-containing water processing, current method is first to reduce waste water ammon amount, then adopt using the method for physics, chemistry It is degraded with the method for biology.Chemical method is in high ph-values, and the free ammonia in waste water is changed into ammonia with steam and is escaped, is made Ammonia is absorbed with acidic absorbent, becomes formulation fertilizer containing nitrogen, reduces ammonia density in waste water, but mostly there are volatility and corruption for absorbent The shortcomings of corrosion.Water absorption method is used as current most common Physical Absorption method, although technology maturation, application is relatively broad, There are recovery ammonia utilization rate is not high, concentrating regenerative water is volatile to cause consumption big, and high energy consumption, ammonia-containing water discharge capacity is more, ring The problems such as border is seriously polluted.Therefore, research is a kind of has ammonia highly dissoluble and self property stabilization, energy can be recycled New Absorbent becomes current hot spot.
Ionic liquid has unique physico-chemical property as a kind of Green absorption solvent：Extremely low ground vapour pressure, fusing point be low, Dissolubility is big and property is stablized etc..Patent (106310931 A of CN) proposes that a kind of iron-containing glyoxaline ion liquid removes at present Ammonia；Patent (104740975 A of CN) proposes that a kind of cobalt complex that contains is anion ion liquid absorbing ammonia；Patent (CN 106914102 A) chloride of the proposition containing Cu, Sn, Mn, Ni, Co, Cd, Zn be anionic ion liquid absorption ammonia, may be inhale Receipts system is added to metal magnetic substance.The doping of magnetisable material has a significant impact to presoma quality, the anode material of synthesis Expect in use there are great security risk, therefore the recycling medicament of ammonia will be as far as possible without magnetic in wash water in presoma production Property, magnetisable material is not added additionally.
Invention content：
For the problem of waste water, the present invention proposes one kind by imidazoles or pyridine and its spreads out in lithium electric material ternary precursor The medicament of the cation and boracic of biology, the anion composition of phosphonium ion, available for lithium battery tertiary presoma waste water ammonia resource Change.
Technical scheme is as follows：
A kind of medicament for ternary precursor waste water ammonia recycling, the general structure of the medicament are as follows：
Wherein R1With R4Respectively independently take CnH2n+1(1≤n≤8, n are integer), R2General structure is CmH2m+1(0≤m≤4, M is integer), R3、R5、R6、R7Respectively independently take CkH2k+1(0≤k≤4, k are integer), the ionic liquid anion Y are BF4 -、 PF6 -。
Wherein R1、R2、R4、R6It respectively can independently take CiH2iSO3(0≤i≤4, i are integer), R1、R2、R4、R6It can respectively solely It is vertical to take CjH2jOH (0≤j≤4, j are integer).
A kind of ternary precursor waste water ammonia resource utilization method, includes the following steps：
(1) Wastewater Pretreatment for producing lithium electricity positive electrode ternary precursor is passed through the ammonia purification of the critical film containing multiphase In equipment, side is passed through production waste water, and control pH is 9~13, and pressure is in 0.1~5.0Mpa；Opposite side is passed through medicament, control temperature 10~100 DEG C of degree, counter current contacting；
(2) in waste water free state NH3Hydrophobic microporous film surface is diffused to by concentration boundary layer in waste water side, is then existed Film both sides NH3Under the promotion of partial pressure difference, NH3Gasification enters fenestra at waste water and microporous membrane interface, diffuses to medicament side and is inhaled It receives, the poor ammonia waste water after absorption, through inorganic acid pickling, obtains low ammonia nitrogen purification by the ammonia cleaning equipment of two sections of critical films of multiphase Water, into next workshop section；
(3) rich ammonia medicament enters analyzing device, and recycling medicament recycles, and obtains high-purity ammon, ammonium hydroxide.
Ammonia nitrogen mass percent concentration is 8000~12000mg/L in step (1) waste water.
Step (1) pretreatment is that lithium electricity positive electrode ternary precursor production waste water is gone removing heavy metals multiple times of filtration again.
The critical film of the multiphase has selective penetrated property in step (1), only allows NH3Pass through, sodium ion and sulfate ion It is trapped.
Ammonia nitrogen value≤15mg/L of low ammonia nitrogen purified water in step (2).
Inorganic acid is selected from sulfuric acid in step (2).
Recycling medicament recycles in step (3), which can be regenerated, then the carded sliver by way of heating or depressurizing Part：30~250 DEG C, 0.006~1.2MPa.
Obtain mass percent concentration >=99.0% of high-purity ammon in step (3), the mass percent concentration of ammonium hydroxide >= 21%.
Above-mentioned absorption conditions warrant no moisture by or residual.
Advantageous effect
(1) present invention provides a kind of medicament available for lithium electricity positive electrode ternary precursor waste water ammonia recycling, By the Hyarogen-bonding between cation and ammonia molecule, anion and the intermolecular Van der Waals force collective effect of ammonia are real Now to the high efficiente callback of ammonia, ammonia nitrogen in waste water is reduced, high-purity ammon, ammonium hydroxide are applied to other workshop sections or as raw material, realize life Produce the recycling of waste water recycling and ammonia.1. the medicament absorptive capacity is big, physico-chemical property is stable, long lifespan, recyclable regenerative It uses；2. the medicament is nonmagnetic, magnetisable material is not added additionally, is utilized for lithium electricity industry Ammonia recovery and is provided a kind of novel suction Receive agent.
(2) present invention simultaneously provides a kind of ternary precursor waste water ammonia resource utilization method, ternary precursor can be given up Ammonia nitrogen in high density in water is recycled in the form of ammonia and ammonium hydroxide.1. it is former as reaction will to recycle obtained high concentration ammonium hydroxide Material uses, and cuts operating costs；2. effective guarantee employee working environment effectively prevents occupational health disease.
Description of the drawings
Fig. 1：Deamination medicament absorbing ammonia schematic diagram；
Fig. 2：Inorganic acid absorbing ammonia schematic diagram；
Fig. 3：Ternary precursor waste water ammonia recycling schematic diagram.
Reference numeral：1- absorbs medicament main body；2- absorbs drug concentration boundary layer；3- hydrophobic microporous film surfaces；4- fenestras； 5- waste strengths boundary layer；6- waste bodies；7- inorganic acid main bodys；8- inorganic acid concentrations boundary layer；Bis- sections of critical films of multiphase of 9- Surface；10- fenestras；The poor ammonia waste water concentration boundary layers of 11-；The poor ammonia waste water main bodys of 12-；13- waste water inlets；14- deaminations medicament into Mouthful；The poor ammonia waste water outlets of 15-；16- richness ammonia agent outlets；17- inorganic acid imports；The low ammonia waste water outlets of 18-；19- inorganic acid ammoniums Salt exports；20- freezes purified water inlet；21- ammonia imports；22- high strength ammonia water outs；23- ammonia recycling absorption plants；24- is rich Ammonia medicament regenerating unit；Two sections of absorption plants of 25- inorganic acids；26- high strength ammonia water preparation apparatus.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is described in further detail.It should be appreciated that specific embodiment described herein does not limit only to explain the present invention In the present invention.
Embodiment 1：
(1) it in the self-control absorption plant of Φ 20*200mm, adds in 20mL and absorbs medicament 1- (2- ethoxys) -3- methyl miaows Azoles hexafluorophosphate, and be placed on balance, the pure ammonia of 100L/h is passed through, it is 27 DEG C to absorb temperature, and pressure is the item of 0.1Mpa Absorption experiment is carried out under part, absorption dynamic equilibrium is reached after about 70min, balance registration is stablized, calculated under the described conditions, pure Uptake in the ammonia medicament is 0.024g ammonia/g medicaments.
(2) it in the self-control absorption plant of Φ 20*200mm, adds in 20mL and absorbs medicament 1- butyl imidazole tetrafluoroborates, And be placed on balance, the pure ammonia of 100L/h is passed through, it is 27 DEG C to absorb temperature, and pressure absorb real under conditions of being 0.1Mpa It tests, absorption dynamic equilibrium is reached after about 60min, balance registration is stablized, calculated under the described conditions, the suction in the pure ammonia medicament Receipts amount is 0.014g ammonia/g medicaments.
(3) it in the self-control absorption plant of Φ 20*200mm, adds in 20mL and absorbs medicament 1- sulfo group -2- ethoxys pyridine six Fluorophosphate, and be placed on balance, the pure ammonia of 100L/h is passed through, it is 25 DEG C to absorb temperature, under conditions of pressure is 0.1Mpa Absorption experiment is carried out, absorption dynamic equilibrium is reached after about 70min, balance registration is stablized, calculated under the described conditions, and pure ammonia should Uptake in medicament is 0.064g ammonia/g medicaments.
(4) it in the self-control absorption plant of Φ 20*200mm, adds in 20mL and absorbs medicament 1- hydroxyl -2- sulfoethyls pyridine four Borofluoride, and be placed on balance, the pure ammonia of 100L/h is passed through, it is 27 DEG C to absorb temperature, under conditions of pressure is 0.1Mpa Absorption experiment is carried out, absorption dynamic equilibrium is reached after about 70min, balance registration is stablized, calculated under the described conditions, and pure ammonia should Uptake in medicament is 0.036g ammonia/g medicaments.
Embodiment 2：
Lithium electricity positive electrode ternary precursor is produced into waste water after removing heavy metals and multiple segment filters, is passed through critical containing multiphase In the ammonia cleaning equipment of film, side by produce waste water (ammonia nitrogen value be 9500mg/L, pH be 11~12, pressure 0.1Mpa), Opposite side passes through 1- (2- ethoxys) -3- methylimidazoles hexafluorophosphate (temperature is 30 DEG C), counter current contacting.Waste water free state NH3Hydrophobic microporous film surface is diffused to by concentration boundary layer in waste water side, then in film both sides NH3Under the promotion of partial pressure difference, NH3Gasification enters fenestra at waste water and microporous membrane interface, diffuses to medicament side and is absorbed, the poor ammonia waste water (ammonia after absorption Values of nitrogen might is 165mg/L) by the ammonia cleaning equipment of two sections of critical films of multiphase, through sulfuric acid washing, obtain low ammonia nitrogen purified water (ammonia nitrogen It is worth for 12mg/L), into next workshop section；Rich ammonia medicament enters analyzing device (regeneration condition：55 DEG C, 0.009MPa), recycle medicine Agent recycles, and obtains using as raw material with ammonium hydroxide (21.1%).
Embodiment 3：
Lithium electricity positive electrode ternary precursor is produced into waste water after removing heavy metals and multiple segment filters, is passed through critical containing multiphase In the ammonia cleaning equipment of film, side by produce waste water (ammonia nitrogen value be 9800mg/L, pH be 11~12, pressure 0.1Mpa), Opposite side passes through 1- butyl imidazoles tetrafluoroborate (temperature is 31 DEG C), counter current contacting.The NH of waste water free state3Lead in waste water side Over-richness boundary layer diffuses to hydrophobic microporous film surface, then in film both sides NH3Under the promotion of partial pressure difference, NH3In waste water and micropore Gasification enters fenestra at membrane interface, diffuses to medicament side and is absorbed, and the poor ammonia waste water (ammonia nitrogen value is 170mg/L) after absorption is logical The ammonia cleaning equipment of two sections of critical films of multiphase is crossed, through inorganic acid pickling, obtains low ammonia nitrogen purified water (ammonia nitrogen value is 13mg/L), into Enter next workshop section；Rich ammonia medicament enters analyzing device (regeneration condition：50 DEG C, 0.009MPa), recycling medicament recycles, and obtains High-purity ammon (99.2%) is applied to other workshop sections.
Embodiment 4：
Lithium electricity positive electrode ternary precursor is produced into waste water after removing heavy metals and multiple segment filters, is passed through critical containing multiphase In the ammonia cleaning equipment of film, side by produce waste water (ammonia nitrogen value be 10000mg/L, pH be 11~12, pressure 0.1Mpa), Opposite side passes through 1- sulfo group -2- ethoxy pyridines hexafluorophosphate (temperature is 30 DEG C), counter current contacting.The NH of waste water free state3 Hydrophobic microporous film surface is diffused to by concentration boundary layer in waste water side, then in film both sides NH3Under the promotion of partial pressure difference, NH3 Gasification enters fenestra at waste water and microporous membrane interface, diffuses to medicament side and is absorbed, and (ammonia nitrogen value is for poor ammonia waste water after absorption 152mg/L) by the ammonia cleaning equipment of two sections of critical films of multiphase, through inorganic acid pickling, obtaining low ammonia nitrogen purified water, (ammonia nitrogen value is 10mg/L), into next workshop section；Rich ammonia medicament enters analyzing device (regeneration condition：50 DEG C, 0.009MPa), recycling medicament follows Ring uses, and obtains using as raw material with ammonium hydroxide (21.3%).
Embodiment 5：
Lithium electricity positive electrode ternary precursor is produced into waste water after removing heavy metals and multiple segment filters, is passed through critical containing multiphase In the ammonia cleaning equipment of film, side by produce waste water (ammonia nitrogen value be 9700mg/L, pH be 11~12, pressure 0.1Mpa), Opposite side passes through 1- hydroxyl -2- sulfoethyl pyridinium tetrafluoroborates salt (temperature is 31 DEG C), counter current contacting.The NH of waste water free state3 Hydrophobic microporous film surface is diffused to by concentration boundary layer in waste water side, then in film both sides NH3Under the promotion of partial pressure difference, NH3 Gasification enters fenestra at waste water and microporous membrane interface, diffuses to medicament side and is absorbed, and (ammonia nitrogen value is for poor ammonia waste water after absorption 160mg/L) by the ammonia cleaning equipment of two sections of critical films of multiphase, through inorganic acid pickling, obtaining low ammonia nitrogen purified water, (ammonia nitrogen value is 11mg/L), into next workshop section；Rich ammonia medicament enters analyzing device (regeneration condition：50 DEG C, 0.009MPa), recycling medicament follows Ring uses, and obtains using as raw material with ammonium hydroxide (21.1%).

Claims (10)

1. a kind of medicament for ternary precursor waste water ammonia recycling, it is characterised in that：The medicament general structure is as follows：
Wherein R1With R4Respectively independently take CnH2n+1(1≤n≤8, n are integer), R2General structure is CmH2m+1(0≤m≤4, m are whole Number), R3、R5、R6、R7Respectively independently take CkH2k+1(0≤k≤4, k are integer), the ionic liquid anion Y are BF4 -、PF6 -。
2. a kind of medicament for ternary precursor waste water ammonia recycling according to claim 1, it is characterised in that： R1、R2、R4、R6It respectively can independently take CiH2iSO3(0≤i≤4, i are integer), R1、R2、R4、R6It respectively can independently take CjH2jOH(0 ≤ j≤4, j are integer).
3. a kind of ternary precursor waste water ammonia resource utilization method, it is characterised in that：Include the following steps：
(1) Wastewater Pretreatment for producing lithium electricity positive electrode ternary precursor is passed through the ammonia cleaning equipment of the critical film containing multiphase In, side is passed through production waste water, and control pH is 9~13, and pressure is in 0.1~5.0Mpa；Opposite side is passed through medicament, controls temperature 10 ~100 DEG C, counter current contacting；
(2) in waste water free state NH3Hydrophobic microporous film surface is diffused to by concentration boundary layer in waste water side, then in film two Side NH3Under the promotion of partial pressure difference, NH3Gasification enters fenestra at waste water and microporous membrane interface, diffuses to medicament side and is absorbed, Poor ammonia waste water after absorption through inorganic acid pickling, obtains low ammonia nitrogen purified water by the ammonia cleaning equipment of two sections of critical films of multiphase, Into next workshop section；
(3) rich ammonia medicament enters analyzing device, and recycling medicament recycles, and obtains high-purity ammon, ammonium hydroxide.
4. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (1) ammonia nitrogen mass percent concentration is 8000~12000mg/L in waste water.
5. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (1) pretreatment is that lithium electricity positive electrode ternary precursor production waste water is gone removing heavy metals multiple times of filtration again.
6. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (1) the critical film of the multiphase has selective penetrated property in, only allows NH3Pass through, sodium ion is trapped with sulfate ion.
7. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (2) ammonia nitrogen value≤15mg/L of low ammonia nitrogen purified water in.
8. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (2) inorganic acid is selected from sulfuric acid in.
9. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (3) recycling medicament recycles in, which can be regenerated by way of heating or depressurizing, regeneration condition：30~250 DEG C, 0.006~1.2MPa.
10. a kind of ternary precursor waste water ammonia resource utilization method according to claim 2, it is characterised in that：Step (3) mass percent concentration >=99.0% of high-purity ammon, mass percent concentration >=21% of ammonium hydroxide are obtained in.
CN201810034212.XA 2018-01-12 2018-01-12 A kind of medicament and resource utilization method for ternary precursor waste water ammonia recycling Pending CN108250147A (en)

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