CN105541043A - MBR and A2/O based treatment method of waste lithium battery electrolyte and electrolyte waste water - Google Patents
MBR and A2/O based treatment method of waste lithium battery electrolyte and electrolyte waste water Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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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
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
Abstract
The invention discloses MBR and A2/O based treatment method of waste lithium battery electrolyte and electrolyte waste water. Three treatment units are adopted for treatment. The treatment method comprises the steps of firstly treating waste electrolyte, then carrying out absorption by introducing a waste gas generated in the reaction of the electrolyte into waste water, so to remove the waste gas in a waste water treatment process, adopting Fenton oxidation to treat lithium battery waste water, so as to increase the biodegradability of the waste water, removing reaction sediment by sediment flocculation, using an A2/O and MBR membrane separation and combination process to treat waste electrolyte , finally enabling effluent to pass through an RO (reverse osmosis) unit to ensure the effluent quality, and as for the concentrated water generated by RO, adopting a powdered activated carbon adsorption-ultrafiltration combined technology to remove organic pollutants in the concentrated water, so as to enable the treated water to reach the requirement of high-quality reuse water of RO. The treatment method overcomes the imperfection of a technic of recycling and treating a waste lithium battery in the past, and realizes reduction, harmlessness, reclamation of waste electrolyte waste water treatment.
Description
The present patent application is the divisional application of parent application " a kind for the treatment of process recycling waste lithium cell electrolytic solution and electrolytic solution waste water ", and the application number of parent application is 2013105625669, and the applying date of parent application is on November 12nd, 2013.
Technical field
The present invention relates to each process of the recovery of lithium battery electrolytes and electrolytic solution waste water, harmless treatment, more particularly, relate to a kind for the treatment of process recycling waste lithium cell electrolytic solution and electrolytic solution waste water.
Background technology
Lithium cell is since realizing commercialization around nineteen ninety, because volume is little, lightweight, the advantage such as charge velocities is fast, use temperature scope is wide and service life cycle is long, thus be widely used in pick up camera, mobile telephone, notebook computer, carry survey meter etc., it is also the high capacity power source of following electromobile first-selection.The positive electrode material of current lithium cell forms by as the pure aluminum foil (thickness is 0.01mm) of collector and the positive active material coating (thickness is about 0.08mm) of black.About containing the positive pole material of lithium cobalt acid of about 88% or single cobalt, nickel, lithium manganate, the acetylene black conductor of about 8% and the PVD binding agent of 4% of modified cobalt acid lithium (with lithium nickelate or lithium manganate substituting cobalt acid lithium) or three component system in black coating.Reclaim waste lithium cell, not only can eliminate the pollution of objectionable impurities to environment, and can make full use of cobalt and the nickel of useful resource, particularly resource scarcity, thus economic benefit and social benefit are very remarkable.In existing process waste lithium cell or waste material, the method for Separation and Recovery is more, mainly contains:
Chinese Patent Application No. 200810178835.0 discloses one " method from the recovery valuable metal of the lithium cell containing Co, Ni, Mn ", it adopts cobalt, nickel, manganese in 250g/L hydrochloric acid mechanical stirring leaching anode material of lithium battery, or with sulfuric acid and hydrogen peroxide agitation leach, reclaim cobalt, nickel, the manganese in cell positive material.The method adopts dissolving with hydrochloric acid cobalt acid lithium (lithium manganate or lithium nickelate) to release chlorine, all has larger impact to environment and labor condition; Although adopt sulfuric acid+hydrogen peroxide to leach feasible process, hydrogen peroxide consumes high, and processing cost is high.Chinese Patent Application No. 200810030494.2 discloses " a kind of acid leaching-extraction process of recycling used batteries of environmental protection ", the method is: cell positive material adopts multistage hydrogen peroxide+sulfuric acid leaching, raffinate returns leaching and to write letter enriching lithium, and leached mud returns roasting and takes off acetylene black (charcoal) and return leaching again.By repeatedly counterflow leaching, raffinate returns leaching, leaches incomplete battery and return leaching again after roasting, Call Provision, nickel and lithium.The method adopts multistage to leach, and raffinate returns leaching enriching nickel, and slag roasting takes off acetylene black and returns leaching, although cobalt, nickel, lithium are all recyclable, long flow path, complex process, it is very inconvenient to operate.Chinese Patent Application No. 200810028730.7 discloses " a kind of method reclaiming from waste lithium cell, prepare cobalt acid lithium ", positive electrode material pulverizes roasting alkali solution-off aluminium, add Quilonum Retard calcining and produce cobalt acid lithium, although technique is simple, but dealuminzation is not exclusively de-, be difficult to or can not ensure quality product at all, actual production can only as carrying cobalt intermediate raw material.
Summary of the invention
Technical purpose of the present invention is to overcome the deficiencies in the prior art, overcomes the not thorough of existing recovery technology, processes incomplete problem, provide a kind for the treatment of process recycling waste lithium cell electrolytic solution and electrolytic solution waste water.
Technical purpose of the present invention is achieved by following technical proposals:
Recycle a treatment process for waste lithium cell electrolytic solution and electrolytic solution waste water, carry out according to following step:
Step 1, utilizes first module to be processed by waste and old electrolytic solution
In treating processes in described step 1, select that waste and old electrolytic solution is placed in encloses container and carry out rectification under vacuum, to obtain carbonate based organic solvent;
In treating processes in described step 1, select in electrolytic solution, add sal enixum (KHSO
4), the interpolation quality of described sal enixum is 8:1 with the ratio of waste and old electrolyte quality, then high-temperature calcination (such as calcining 5h under 500 degrees Celsius) is carried out, dissolve calcining the product obtained rear (such as adopting 90 degrees Celsius of deionized water and stirring to dissolve) after cooling, obtain remaining electrolyte component, after adding the saturated KF aqueous solution wherein by crystallization to reclaim LiF crystal, adopt HF and 5-10 degree Celsius of deionized water washing LiF crystal of 0.01mol/L; The addition of the described saturated KF aqueous solution is 10-50% of residue electrolyte component volume, preferably 30-50%;
In above-mentioned waste and old electrolytic solution treating processes, produce waste gas, adopt waste gas to pass into electrolytic solution waste water and absorb, thus remove in wastewater treatment process.
Step 2, utilizes second unit to be processed by electrolytic solution waste water
In technical solution of the present invention, the waste and old electrolytic solution of process is the electrolytic solution in waste lithium cell, the electrolytic solution waste water of process mainly refers to is disassembling the waste water produced in the parts such as lithium cell Cleaning Process electrode and Footwall drift process, and the waste gas that waste lithium cell electrolytic solution produces after the process of step 1 is passed into electrolytic solution waste water absorb, thus remove in wastewater treatment process, after electrolytic solution remainder after simultaneously step 1 being processed mixes with electrolytic solution waste water, second unit is together utilized to carry out electrolytic solution wastewater treatment, often containing higher COD in waste water, the organism of metal ion and difficult degradation.
In treating processes in described step 2, first described electrolytic solution waste water enter equalizing tank, then the first mixed precipitation pond and the second mixed precipitation pond is entered successively, preferably Fenton oxidation treating pond is set between equalizing tank and the first mixed precipitation pond, wherein said equalizing tank is used for homogenizing water quality and the water yield, precipitates to avoid suspended substance;
Due to the pH meta-alkalescence (pH is 7-10) of electrolytic solution waste water, when adopting Fenton (fenton) oxide treatment lithium battery electrolytes waste water, sulfuric acid was added before electrolytic solution waste water enters Fenton oxidation treating pond, regulate wastewater pH <3.5, hydrogen peroxide and ferrous ion is added in Fenton oxidation treating pond, organism in difficult degradation in catalyzed degradation waste water, increases wastewater biodegradability, the Fe simultaneously generated
3+large amount of organic is removed by coagulating sedimentation.
Electrolytic solution waste water through Fenton oxidation process presents acidity, add alkali entering in the first mixed precipitation pond forward direction waste water, such as sodium hydroxide or potassium hydroxide, alkalescence (pH>7) is presented to make electrolytic solution waste water, in the first mixed precipitation pond, with the mass ratio of electrolytic solution waste water and calcium oxide 19:1, drop into calcium oxide, remove the fluorion (F in electrolytic solution waste water of lithium-ion electrolyte waste water
-concentration is generally 136mg/L-318mg/L), hydraulic detention time is 2h at least, preferably 2-4h.
After the first mixed precipitation pond process, in water outlet, add sulfuric acid, enter the second mixed precipitation pond after regulating electrolytic solution waste water to present acid pH <3.5, add the FeCl that massfraction is 8%-15%
3the aqueous solution, dosage is 2%-4% of electrolytic solution wastewater quality, and hydraulic detention time is 2h at least, preferably 2-4h.
Step 3, utilizes Unit the 3rd to be processed by electrolytic solution waste water
The electrolytic solution waste water processed through step 2 is carried out Unit the 3rd process, successively by anaerobic pond, anoxic pond, Aerobic Pond and membrane bioreactor (MBR), and active sludge is set respectively, to realize the deep purifying to electrolytic solution waste water, deep phosphorous removal denitrogenation, improves the water quality of water outlet.
Namely A is adopted
2/ O and MBR combination process is further processed electrolytic solution waste water, forms A by anaerobic pond, anoxic pond and Aerobic Pond
2/ O, and in each treating pond, active sludge is set respectively, active sludge in MBR membrane sepn trap water and larger molecular organics, the microorganism that the reservation generation cycle is longer, can realize deep purification of waste water, Simultaneous Nitrification bacterium can fully breed in system, deep phosphorous removal denitrogenation, improves the water quality of water outlet.By methyl alcohol for anoxic pond provides carbon source, by air for Aerobic Pond provides oxygen, the pipeline of returned sluge is set between membrane bioreactor and anaerobic pond simultaneously, to realize the backflow of active sludge; The pipeline of backflow mixed liquor is set between the water outlet and the water-in of anoxic pond of Aerobic Pond, to realize A
2the backflow of mixed solution in/O.
Anaerobic pond: raw waste water and the phosphorous returned sluge from MBR discharge synchronously enter this reactor, and its major function is release phosphorus, carries out ammonification to partial organic substances simultaneously; Anoxic pond: sewage enters this reactor through anaerobic reactor, its premiere feature is denitrogenation, and nitric nitrogen is sent here by aerobic reactor by internal recycle, and the mixing liquid measure of circulation is comparatively large, is generally 2Q (Q---raw waste water amount); Aerobic Pond, is aeration tank: mixed solution enters this reactor by anoxic reacter, and its function is multiple, remove BOD, nitrated and absorb phosphorus all carry out in this reactor, these three reflections are all important, in mixed solution contain NO
3-N, containing superfluous phosphorus in mud, the BOD (or COD) in sewage is then removed, and flow is that the mixed solution of 2Q is from being back to anoxic reacter here.
Prevent under special circumstances, such as, under thump load, MBR water outlet is difficult to the requirement meeting reuse, adopt reverse osmosis (RO) technology with at A
2/ O, MBR technique combine: described membrane bioreactor is connected with reverse-osmosis treated unit, the dense water (enrichment sewage) obtained through reverse-osmosis treated unit enters (powder) charcoal absorption uf processing unit and processes, and be back to reverse-osmosis treated unit and membrane bioreactor respectively by pipeline, the water outlet obtained through reverse-osmosis treated unit meets reuse requirement, can discharge.
Selection arranges RO unit, last one barrier of or reuse up to standard as effluent quality.Now utilize the high efficiency separation effect of RO unit, by the organism regulating YIN and YANG ion rejection in waste water, guarantee that water outlet reaches the requirement of reuse.Finally water outlet is guaranteed effluent quality by RO reverse osmosis units, produce dense water for RO, adopt powder electroless plating-ultrafiltration combination technique removal organic pollutant wherein, make the water after process reach the requirement of the high-quality reuse water of RO.It should be noted that RO unit is while the high-quality reuse water of acquisition, produces the dense water of about 60%-70%.For the dense water of RO, adopt powder electroless plating-ultrafiltration combination technique removal organic pollutant wherein, the water after process is made to reach the water quality requirement of RO water inlet, and powder electroless plating-ultra filtration unit effluent recycling is in RO water inlet, and Powdered Activated Carbon can be back in MBR in this unit, utilize the remaining loading capacity of Powdered Activated Carbon to adsorb organic pollutant in MBR further, thus improve the utilization ratio of Powdered Activated Carbon, reduce processing costs simultaneously; Also can select to adsorb directly to directly adding Powdered Activated Carbon in MBR.
Compared with prior art, technical scheme the process of the present invention electrolytic solution of waste lithium cell, waste gas and waste water, organism containing higher COD, metal ion and difficult degradation in waste water, adopt Fenton oxidation process lithium cell waste water, increase wastewater biodegradability, remove reaction precipitation thing by flocculation sediment, use A
2the process of/O+MBR membrane sepn combination process, finally water outlet is guaranteed effluent quality by RO reverse osmosis units, produce dense water for RO, adopt powder electroless plating-ultrafiltration combination technique removal organic pollutant wherein, make the water after process reach the requirement of the high-quality reuse water of RO.Instant invention overcomes the imperfection in the past recycling waste lithium cell processing method, realize the minimizing of waste and old electrolytic solution wastewater treatment, innoxious, resource utilization.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of first module in treatment process of the present invention.
Fig. 2 is the process flow sheet of second unit in treatment process of the present invention.
Fig. 3 is the process flow sheet of Unit the 3rd in treatment process of the present invention.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.The waste and old electrolytic solution of process is the electrolytic solution in waste lithium cell, the electrolytic solution waste water of process mainly refers to is disassembling the waste water produced in the parts such as lithium cell Cleaning Process electrode and Footwall drift process, and the waste gas that waste lithium cell electrolytic solution produces after the process of step 1 is passed into electrolytic solution waste water absorb, thus remove in wastewater treatment process, after electrolytic solution remainder after simultaneously step 1 being processed mixes with electrolytic solution waste water, second unit is together utilized to carry out electrolytic solution wastewater treatment, often containing higher COD in waste water, the organism of metal ion and difficult degradation.
As shown in Figure 1, the process flow sheet of first module in treatment process of the present invention, in the treating processes in described step 1, selects that waste and old electrolytic solution is placed in encloses container and carries out rectification under vacuum, to obtain carbonate based organic solvent; In treating processes in described step 1, select in electrolytic solution, add sal enixum (KHSO
4), the interpolation quality of described sal enixum is 8:1 with the ratio of waste and old electrolyte quality, then under 500 degrees Celsius, 5h is calcined, 90 degrees Celsius of deionized water and stirring are adopted to dissolve after cooling, obtain remaining electrolyte component, after adding the saturated KF aqueous solution wherein by crystallization to reclaim LiF crystal, adopt HF and 5-10 degree Celsius of deionized water washing LiF crystal of 0.01mol/L; The addition of the described saturated KF aqueous solution is 10-50% of residue electrolyte component volume, preferably 30-50%; In above-mentioned waste and old electrolytic solution treating processes, produce waste gas, adopt waste gas to pass into electrolytic solution waste water and absorb, thus remove in wastewater treatment process.
As shown in Figure 2, the process flow sheet of second unit in treatment process of the present invention, first described electrolytic solution waste water enter equalizing tank, then enters the first mixed precipitation pond and the second mixed precipitation pond successively, between equalizing tank and the first mixed precipitation pond, arrange Fenton oxidation treating pond.
Due to the pH meta-alkalescence (pH is 7-10) of electrolytic solution waste water, when adopting Fenton (fenton) oxide treatment lithium battery electrolytes waste water, sulfuric acid was added before electrolytic solution waste water enters Fenton oxidation treating pond, regulate wastewater pH <3.5, hydrogen peroxide and ferrous ion is added in Fenton oxidation treating pond, organism in difficult degradation in catalyzed degradation waste water, increases wastewater biodegradability, the Fe simultaneously generated
3+large amount of organic is removed by coagulating sedimentation.
Electrolytic solution waste water through Fenton oxidation process presents acidity, add sodium hydroxide entering in the first mixed precipitation pond forward direction waste water, alkalescence (pH>7) is presented to make electrolytic solution waste water, in the first mixed precipitation pond, with the mass ratio of electrolytic solution waste water and calcium oxide 19:1, drop into calcium oxide, remove the fluorion of lithium-ion electrolyte waste water, hydraulic detention time 2h.
After the first mixed precipitation pond process, in water outlet, add sulfuric acid, enter the second mixed precipitation pond after regulating electrolytic solution waste water to present acid pH <3.5, add the FeCl that massfraction is 5%
3the aqueous solution, dosage is 4% of electrolytic solution wastewater quality, hydraulic detention time 2h.
As shown in Figure 3, the process flow sheet of Unit the 3rd in treatment process of the present invention, the electrolytic solution waste water processed through step 2 is carried out Unit the 3rd process, successively by anaerobic pond, anoxic pond, Aerobic Pond and membrane bioreactor (MBR), and active sludge is set respectively, to realize the deep purifying to electrolytic solution waste water, deep phosphorous removal denitrogenation, improve the water quality of water outlet.Prevent MBR water outlet under thump load to be difficult to meet the requirement of reuse, adopt reverse osmosis (RO) technology with at A
2/ O, MBR technique combine: described membrane bioreactor is connected with reverse-osmosis treated unit, the dense water (enrichment sewage) obtained through reverse-osmosis treated unit enters (powder) charcoal absorption uf processing unit and processes, and be back to reverse-osmosis treated unit and membrane bioreactor respectively by pipeline, the water outlet obtained through reverse-osmosis treated unit meets reuse requirement, can discharge, select in MBR, to add Powdered Activated Carbon to be adsorbed with organic pollutants further simultaneously.
Waste gas, waste water, waste electrolyte generation for following:
Wastewater flow rate
mAX: 10t/d
Exhausted air quantity: 3000m
3/ h
The generation of waste and old electrolytic solution: 8L/d
Influent quality: COD13000-25000mg/L, BOD2000-12000mg/L, pH6-10, TN300-360mg/L, TP70-460mg/L, F
-136-320mg/L
(1) equalizing tank
Adopt rectangle equalizing tank, for homogenizing water quality, the water yield.Hydraulic detention time is 24h, useful volume 10m
3, rectangle, size 2m × 2m × 3m, SUS316 stainless steel.If waste water lifting pump 2,1 is standby with 1, separate unit flow 10m
3/ h, lift 10m, power 0.75kW, material SUS316.Equalizing tank adopts water pump pump circulation, and at the bottom of equalizing tank, establish perforated pipe, perforated pipe is connected with water pump pressure pipe, stirs, strengthen waste water mixed effect and avoid suspended substance to precipitate with pressure water timing.
(2) first mixed precipitation ponds
Adopt mechanical stirring mixing pit, hydraulic detention time 2h, volume 0.08m3, mixing pit diameter D=0.46m, skeleton construction.Bottom water inlet, top water outlet, establishes fast rotational paddle board in pond, perisporium adds fixed dam four pieces, and every block width B adopts 1/10D, and on it, lower edge is all 1/4D at the bottom of standby fluid level and pond.
In fluoride waste, add lime, mix with waste water.Need the unslaked lime 491kg of 95% every day.
Adopt chemical precipitation method, fluorion and calcium ion are reacted and generates calcium fluoride precipitate, make metal ion and OH-form difficulty soluble salt.CaF is removed by solid-liquid separation
2with metal difficulty soluble salt, then add sulfuric acid adjust ph to neutral.
(3) second mixed precipitation ponds
Adopt mechanical stirring mixing pit, hydraulic detention time 2h, volume 0.08m
3, mixing pit diameter D=0.46m, skeleton construction.Bottom water inlet, top water outlet, establishes fast rotational paddle board in pond, perisporium adds fixed dam four pieces, and every block width B adopts 1/10D, and on it, lower edge is all 1/4D at the bottom of standby fluid level and pond.FeCl is added in waste water
3, mix with waste water.Every day needs FeCl
31kg.FeCl
3be hydrolyzed to Fe (OH)
3and carry out coagulation with the pollutent in water.
(4) anaerobic pond, anoxic pond, Aerobic Pond
Anaerobic pond residence time 10h, volume 0.5m
3; A diving mixer is established, power 0.85kW, model in pond
QJB0.85/8-260/3-740。
Anoxic pond residence time 10h, volume 0.5m
3; Add methyl alcohol as carbon source, establish a diving mixer in pond, power 0.85kW, model QJB0.85/8-260/3-740.
Adopt impeller between anaerobic pond and anoxic pond, power is at 5 ~ 8W/m
3.
Aerobic Pond residence time 10h, volume 0.5m
3; A Root's blower.
(5) membrane bioreactor (MBR)
Residence time 10h, volume 3m
3.Select integral type (immersion) MBR, adopt the ultra-filtration membrane in 0.1-0.4um aperture, membrane module form is hollow fiber form, and material is PVDF (polyvinylidene difluoride (PVDF)), membrane module area 50m
3.
Water-out manners adopts the water outlet of stainless steel vacuum primingpump intermittent type, and MBR working pressure value is at about 160kPa.Aeration mode adopts the perforated pipe aerating regulation producing larger bubble.
(6) Fenton oxidation pond
Fenton oxidation pond design alternative batch reactor, to ensure that chemical agent and waste water fully react under complete admixture.Reaction tank useful volume 2m
3, equipment size 1.5m × 1m × 2m, each total time cycle of operation is 4h, wherein water inlet, reaction precipitation and each 1h of water outlet operation.In reaction tank, be provided with deceleration stirrer fast reaction speed, install the pH value of pH meter to reaction and monitor, supporting have 2 cover medicine systems for oxidizer and catalyzer.
(7) RO reverse-osmosis treated unit and powder electroless plating ultra filtration unit
Both all can adopt existing reverse osmosis technology, select batch reactor, reaction tank useful volume 2m
3, equipment size 1.5m × 1m × 2m, hydraulic detention time 2h, and select deceleration stirrer fast reaction speed is installed in reaction tank, select Powdered Activated Carbon and recirculation water to reflux in the lump when refluxing.
Carry out actual motion with above-mentioned reactive system, effluent quality can reach integrated wastewater discharge standard GB8978-1996 and require: COD100mg/L, BOD20mg/L, pH6 ~ 9, TN15mg/L, TP0.5mg/L, F
-10mg/L.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (6)
1., based on the waste lithium cell electrolytic solution of MBR and A2/O and the treatment process of electrolytic solution waste water, it is characterized in that, carry out according to following step:
Step 1, utilizes first module to be processed by waste and old electrolytic solution
In treating processes in described step 1, select that waste and old electrolytic solution is placed in encloses container and carry out rectification under vacuum, to obtain carbonate based organic solvent;
In treating processes in described step 1, select to add sal enixum in electrolytic solution, the interpolation quality of described sal enixum is 8:1 with the ratio of waste and old electrolyte quality, then under 500 degrees Celsius, 5h is calcined, after the product that calcining obtains being dissolved after cooling, obtain remain electrolyte component, after adding the saturated KF aqueous solution wherein by crystallization to reclaim LiF crystal; The addition of the described saturated KF aqueous solution is 10-50% of residue electrolyte component volume;
Step 2, utilizes second unit to be processed by electrolytic solution waste water
In treating processes in described step 2, first described electrolytic solution waste water enter equalizing tank, then enters the first mixed precipitation pond and the second mixed precipitation pond successively, between equalizing tank and the first mixed precipitation pond, arrange Fenton oxidation treating pond;
When adopting Fenton oxidation process lithium battery electrolytes waste water, sulfuric acid was added before electrolytic solution waste water enters Fenton oxidation treating pond, regulate wastewater pH <3.5, hydrogen peroxide and ferrous ion is added in Fenton oxidation treating pond, organism in difficult degradation in catalyzed degradation waste water, increase wastewater biodegradability, the Fe simultaneously generated
3+remove large amount of organic by coagulating sedimentation, hydraulic detention time is 2h at least;
Electrolytic solution waste water through Fenton oxidation process presents acidity, add alkali entering in the first mixed precipitation pond forward direction waste water, alkalescence is presented to make electrolytic solution waste water, in the first mixed precipitation pond, with the mass ratio of electrolytic solution waste water and calcium oxide 19:1, drop into calcium oxide, remove the fluorion of lithium-ion electrolyte waste water, hydraulic detention time is 2h at least;
After the first mixed precipitation pond process, in water outlet, add sulfuric acid, enter the second mixed precipitation pond after regulating electrolytic solution waste water to present acid pH <3.5, add the FeCl that massfraction is 8%-15%
3the aqueous solution, dosage is 2%-4% of electrolytic solution wastewater quality, and hydraulic detention time is 2h at least;
Step 3, utilizes Unit the 3rd to be processed by electrolytic solution waste water
The electrolytic solution waste water processed through step 2 is carried out Unit the 3rd process, successively by anaerobic pond, anoxic pond, Aerobic Pond and membrane bioreactor, and active sludge is set respectively, to realize the deep purifying to electrolytic solution waste water, deep phosphorous removal denitrogenation, improves the water quality of water outlet; In described Unit the 3rd, by methyl alcohol for anoxic pond provides carbon source, by air for Aerobic Pond provides oxygen, the pipeline of returned sluge is set between membrane bioreactor and anaerobic pond simultaneously, to realize the backflow of active sludge; The pipeline of backflow mixed liquor is set between the water outlet and the water-in of anoxic pond of Aerobic Pond, to realize the backflow of mixed solution; In described Unit the 3rd, described membrane bioreactor is connected with reverse-osmosis treated unit, the dense water obtained through reverse-osmosis treated unit enters charcoal absorption uf processing unit and processes, and be back to reverse-osmosis treated unit and membrane bioreactor respectively by pipeline, the water outlet obtained through reverse-osmosis treated unit meets reuse requirement, can discharge.
2. according to claim 1 based on the waste lithium cell electrolytic solution of MBR and A2/O and the treatment process of electrolytic solution waste water, it is characterized in that, in described step 3, select to adsorb directly to adding Powdered Activated Carbon in membrane bioreactor, or be back in membrane bioreactor by the Powdered Activated Carbon in charcoal absorption uf processing unit, the organic pollutant in further adsorption film bio-reactor.
3. according to claims 1 or 2 based on the waste lithium cell electrolytic solution of MBR and A2/O and the treatment process of electrolytic solution waste water, it is characterized in that, hydraulic detention time preferably 2-4h in Fenton oxidation pond.
4. according to claims 1 or 2 based on the waste lithium cell electrolytic solution of MBR and A2/O and the treatment process of electrolytic solution waste water, it is characterized in that, to add alkali in the first mixed precipitation pond forward direction waste water be sodium hydroxide or potassium hydroxide entering.
5. according to claims 1 or 2 based on the waste lithium cell electrolytic solution of MBR and A2/O and the treatment process of electrolytic solution waste water, it is characterized in that, in the first mixed precipitation pond and the second mixed precipitation pond, hydraulic detention time is 2-4h.
6. according to claims 1 or 2 based on the waste lithium cell electrolytic solution of MBR and A2/O and the treatment process of electrolytic solution waste water, it is characterized in that, in described step 1, the addition of the described saturated KF aqueous solution is 30-50% of residue electrolyte component volume.
Priority Applications (1)
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| CN106252780A (en) * | 2016-11-03 | 2016-12-21 | 王坚 | A kind of lithium-ion-power cell disassembles the processing method producing waste water |
| CN107814449A (en) * | 2016-09-13 | 2018-03-20 | 神华集团有限责任公司 | A kind of processing method of brine waste |
| CN109467261A (en) * | 2018-09-29 | 2019-03-15 | 惠州亿纬锂能股份有限公司 | Waste lithium cell electrolyte wastewater treatment method |
| CN115650532A (en) * | 2022-12-28 | 2023-01-31 | 深圳永清水务有限责任公司北京分公司 | Treatment and recovery method for lithium battery electrolyte production wastewater |
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| CN105271612A (en) * | 2015-10-20 | 2016-01-27 | 四川科能锂电有限公司 | Circulating treatment system for lithium battery wastewater |
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| CN106252780A (en) * | 2016-11-03 | 2016-12-21 | 王坚 | A kind of lithium-ion-power cell disassembles the processing method producing waste water |
| CN109467261A (en) * | 2018-09-29 | 2019-03-15 | 惠州亿纬锂能股份有限公司 | Waste lithium cell electrolyte wastewater treatment method |
| CN115650532A (en) * | 2022-12-28 | 2023-01-31 | 深圳永清水务有限责任公司北京分公司 | Treatment and recovery method for lithium battery electrolyte production wastewater |
Also Published As
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| CN104628217B (en) | 2016-09-07 |
| CN105541043B (en) | 2019-05-31 |
| CN104628217A (en) | 2015-05-20 |
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