CN109250803A - A kind of electroplating waste processing equipment and processing method - Google Patents
A kind of electroplating waste processing equipment and processing method Download PDFInfo
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- 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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- C02F1/763—Devices for the addition of such compounds in gaseous form
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of electroplating waste processing equipment and processing methods, including wastewater storage tank, the wastewater storage tank is connected with oxidation reaction pond, agitating device is equipped in oxidation reaction pond, oxidation reaction pond is connected with mixed reaction pond, mixed reaction pond is connected with filtering ponds, and carbon dioxide access equipment is equipped in the mixed reaction pond.Discarded lithium battery and electroplating wastewater are combined, pass through the content of each metal in regulation waste water, reach the requirement of lithium battery, without individually removing the aluminium in waste battery, it is reacted using carbon dioxide with sodium metaaluminate and the nickle cobalt lithium manganate of generation is coated, improve the chemical property of lithium battery, while final electroplating wastewater qualified discharge.
Description
Technical field
The present invention relates to electroplating wastewater processing fields, and in particular to a kind of electroplating waste processing equipment and processing method.
Background technique
The waste water and waste liquid that electroplating wastewater is mainly discharged by electroplating facility or workshop form, such as plating piece rinse water, useless tank liquor,
Component cooling water and the flushing surface water etc..Since plating is more, technique is cumbersome, and water quality is complicated, and ingredient is not easy to control, and plating is useless
Water mainly contains the heavy metal ion such as chromium, nickel, copper and cyanide etc., these electroplating wastewaters belong to carcinogenic, teratogenesis, mutagenic play
Noxious material causes great injury to the living environment of the mankind and other biological.
Electroplating wastewater can be generally divided into three classes, and the first kind is electroplating wastewater of chromium, the chromium ion in this electroplating wastewater
Concentration is higher, and the second class is cyanide-containing electroplating water, and the cyanide ion concentration in this waste water is higher, and third class is general plating
Waste water, this waste water mainly contain a large amount of heavy metal ion.
Such as a kind of compound for treatment of electroplating wastes heavy metal recovery utilization side containing heavy metal Chinese patent 201110431946X
Method discloses a kind of compound for treatment of electroplating wastes heavy metal recovery containing heavy metal using method, step are as follows: will contain heavy metal ion
Low concentration electroplating wastewater by ion exchange resin, so that heavy metal ion contained in electroplating wastewater is adsorbed in ion friendship completely
It changes resin and isolates clean water, until the absorption of ion exchange resin reaches saturation, eluent, which is added, to be made to be adsorbed in ion
The heavy metal ion of exchanger resin is detached from the electroplating wastewater of ion exchange resin and output high concentration, then useless to high concentration plating
Reducing agent is added in water and carries out reduction reaction, obtains the reduzate not soluble in water containing heavy metal ion, and flocculant is added and adds
Fast reduzate coagulation, separates sediment finally by the methods of filtering or centrifugation, and recycle heavy metal by high-temperature calcination
Substance is as the useful raw material of industry.
Alloy plating is the key areas of electroplating technology, because the advantages of alloy can integrate single metal, and have single
The new characteristic, such as hardness, corrosion resistance, functionality etc. that one metal does not have.
Galvanoplastic manufacture diamond bit is the electro-deposition by metal, and loose diamond particles are fixedly arranged at electroplated layer
In, make diamond particles that there is cutting function, since the manufacture of electroplated diamond bit carries out at normal temperature, diamond is not
It is lost by high temperature, while diamond bit is secured, process of drill bit manufacture is simple, and equipment investment is few, one-pass molding.Diamond bit
Working life be heavily dependent on the property of carcass, therefore diamond bit proposes extremely the performance of carcass material
Strict requirements, the more ternary alloy coating of diamond bit is nickel-cobalt-manganese ternary alloy at present.
Electroplating wastewater industry average annual waste water yield in China's is up to 4,000,000,000 tons, accounts for the 1/6 of total discharged volume of industrial waste water, due to
The complexity of electroplating wastewater causes the waste component generated complicated and changeable.Reality of the current most of electroplate factories to phosphorus-containing wastewater
Processing mode is lime chemical precipitation method, but the water outlet phosphorus concentration usually after precipitation process is still maintained at 5-10mg/L, it is difficult to
Reach standard.
For the electroplating wastewater containing heavy metal and a large amount of phosphorus, main methods are the precipitation method at present, and this method is main
There is following defect: complex process, high to subsequent treatment process and environmental requirement, purification efficiency is not high, it is difficult to reach state's household electrical appliances
The discharge standard of waste electroplating, and input cost is high, needs more treatment process steps and processing unit, consumes during processing
Take a large amount of chemical reagent, the heavy metal in waste water is easy waste, can not turn waste into wealth.
Summary of the invention
The invention proposes a kind of electroplating waste processing equipment and processing method, by phosphorous, aluminium, cobalt, manganese electroplating wastewater into
Row processing, recycles with waste and old nickel-cobalt-manganese ternary lithium battery, the nickel-cobalt lithium manganate material of alumina-coated is finally prepared,
To improve the rate of recovery of heavy metal out of electroplating wastewater and old and useless battery.
It realizes the technical scheme is that a kind of electroplating waste processing equipment, including wastewater storage tank, the waste water store up
It deposits slot to be connected with oxidation reaction pond, agitating device is equipped in oxidation reaction pond, oxidation reaction pond is connected with mixed reaction pond, mixes
Reaction tank is connected with filtering ponds, and carbon dioxide access equipment is equipped in the mixed reaction pond.
The oxidation reaction pond is connected with chlorine dioxide tank, dioxygen water pot and sodium hypochlorite tank.
The method of the processing waste water of the electroplating waste processing equipment, steps are as follows:
(a) phosphorous, aluminium, cobalt, manganese electroplating wastewater, storage to wastewater storage tank are collected;
(b) sodium hydroxide solution is added into waste water, adjusts wastewater pH, compound oxidant is added, carries out oxygen in oxidation reaction pond
Change reaction;
(c) waste and old nickel-cobalt-manganese ternary lithium battery anode piece is immersed in acid solution, to positive electrode active materials and aluminum foil current collector point
From rear, taking-up aluminium foil, reducing agent is added in acid solution, filtrate is obtained by filtration to tertiary cathode material dissolution in heating stirring;
(d) step (b) waste water and step (c) filtrate are mixed, it is 1.5-5.0 that pH is adjusted in mixed reaction pond, and regulation is mixed
Nickel, cobalt, manganese content in liquid are closed, molecular formula LiNi is complied withxCoyMn1-x-yO2, wherein x>0, y>0, x+y<1 are regulated original
Liquid;
(e) sodium hydroxide solution is added into step (d) regulation stoste to be reacted, CO is passed through after reaction2Gas works as mixed base
Aluminium content in liquid stops logical CO when being lower than 50ppm2Gas obtains solid material;
(f) solid material for obtaining step (e) is filtered, washs, dries, and lithium carbonate is added after dry and is uniformly mixed progress
High-temperature calcination obtains the nickel-cobalt lithium manganate material of alumina-coated after calcining.
The mass concentration of sodium hydroxide solution is 15-25wt% in the step (b), and pH value is adjusted to 7-9.
Compound oxidant is that chlorine dioxide, hydrogen peroxide and liquor natrii hypochloritis mix in the step (b), wherein titanium dioxide
The mass ratio of the material of chlorine, hydrogen peroxide and sodium hypochlorite is 1:(1-2): (2-5).
Acid solution includes hydrochloric acid or sulfuric acid in the step (c), and acid strength is 0.1-10 mol/L;With the waste and old nickel cobalt of 10g
On the basis of manganese ternary lithium battery anode piece, acid solution dosage is 0. 5-1 L.
Reducing agent is hydrogen peroxide, sulphite, bisulfites, thiosulfate in the step (c), and reducing agent is dense
Degree is 0.1-5 mol/L;On the basis of the waste and old nickel-cobalt-manganese ternary lithium battery anode piece of 10g, the additive amount of reducing agent is 0.25-
0.5L。
Heating temperature is 30-100 DEG C in the step (c), and mixing time is 40-120 min.
The mass ratio of regulation stoste and sodium hydroxide solution is (20-30): (70-80), sodium hydroxide in the step (e)
The mass concentration of solution is 15-25wt%.
Calcination temperature is 680-720 DEG C in the step (e), calcination time 9-12h.
The beneficial effects of the present invention are:
(1) the invention firstly uses compound oxidants to the phosphorus removing in phosphorous short concentration waste water, so that Phosphorus From Wastewater is dense
Degree is reduced to 2-5mg/L, and the sodium metaaluminate generated in later-stage utilization sodium hydroxide adjustment process can adsorb a part again
P, so that water outlet total phosphorus concentration meets discharge standard;
(2) present invention combines discarded lithium battery and electroplating wastewater, by the content of each metal in regulation waste water, makes it
The requirement for reaching lithium battery react pair without individually removing the aluminium in waste battery using carbon dioxide and sodium metaaluminate
The nickle cobalt lithium manganate of generation is coated, and the chemical property of lithium battery, while final electroplating wastewater qualified discharge are improved.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is schematic structural view of the invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
A kind of electroplating waste processing equipment, including wastewater storage tank 1, the wastewater storage tank 1 and 2 phase of oxidation reaction pond
Even, it is equipped with agitating device in oxidation reaction pond 2, oxidation reaction pond 2 is connected with mixed reaction pond 3, mixed reaction pond 3 and filtering ponds
4 are connected, and are equipped with carbon dioxide access equipment 5 in the mixed reaction pond 3.
The oxidation reaction pond 2 is connected with chlorine dioxide tank 6, dioxygen water pot 7 and sodium hypochlorite tank 8.
Embodiment 1
A kind of electroplating wastewater comprehensive processing technique, steps are as follows:
(1) phosphorous, aluminium, cobalt, manganese electroplating wastewater are collected;Wherein the content of phosphorus is 48.9mg/L, total manganese content in electroplating wastewater
18.2 mg/L, total 6.3 mg/L of cobalt content, total 7.38 mg/L of aluminium content;
(2) it is 15wt% morning sodium hydroxide solution that mass concentration is added into waste water, adjusts wastewater pH 7, and compounding oxidation is added
Agent, compound oxidant are that chlorine dioxide, hydrogen peroxide and liquor natrii hypochloritis mix, wherein chlorine dioxide, hydrogen peroxide and hypochlorous acid
The mass ratio of the material of sodium is 1:1:2, carries out oxidation reaction;
(3) waste and old nickel-cobalt-manganese ternary lithium battery anode piece is immersed in the hydrochloric acid solution that concentration is 0.1mol/L, it is waste and old with 10g
On the basis of nickel-cobalt-manganese ternary lithium battery anode piece, acid solution dosage is 0.5 L;It is separated to positive electrode active materials with aluminum foil current collector
Afterwards, aluminium foil is taken out, is added in acid solution in the hydrogen peroxide that concentration is 0.1 mol/L, heats 30 DEG C of stirring 120 min to three
First positive electrode dissolution, is obtained by filtration filtrate;On the basis of the waste and old nickel-cobalt-manganese ternary lithium battery anode piece of 10g, reducing agent
Additive amount is 0.25 L;
(4) step (2) waste water and step (3) filtrate are mixed, adjusting pH is 1.5, regulates and controls nickel, cobalt, manganese in mixed liquor and contains
Amount, complies with molecular formula LiNi0.5Co0.2Mn0.3O2, it is regulated stoste;
(5) sodium hydroxide solution is added into step (4) regulation stoste to be reacted, regulates and controls the matter of stoste and sodium hydroxide solution
For amount than being 20:80, the mass concentration of sodium hydroxide solution is 15wt%, is passed through CO after reaction2Gas, when in mixed alkali liquor
Aluminium content stops logical CO when being lower than 50ppm2Gas obtains solid material;
(6) solid material that step (5) obtains is filtered, washed, dried, lithium carbonate is added after dry and is uniformly mixed progress
High-temperature calcination, calcination temperature are 680 DEG C, and calcination time 12h obtains the nickel-cobalt lithium manganate material of alumina-coated after calcining,
Lithium content reaches 8wt% in the nickel-cobalt lithium manganate material of alumina-coated.
The performance of the nickel-cobalt lithium manganate material of alumina-coated prepared by embodiment 1
The content of Phosphorus From Wastewater can be reduced to 0.5mg/L in the present embodiment hereinafter, reaching discharge standard for electroplating pollutants, given up
The content of underwater gold category ion can recycle, final discharged wastewater met the national standard.
Embodiment 2
A kind of electroplating wastewater comprehensive processing technique, steps are as follows:
(1) phosphorous, aluminium, cobalt, manganese electroplating wastewater are collected;Wherein the content of phosphorus is 48.9mg/L, total manganese content in electroplating wastewater
18.2 mg/L, total 6.3 mg/L of cobalt content, total 7.38 mg/L of aluminium content;
(2) it is 20wt% morning sodium hydroxide solution that mass concentration is added into waste water, adjusts wastewater pH 8, and compounding oxidation is added
Agent, compound oxidant are that chlorine dioxide, hydrogen peroxide and liquor natrii hypochloritis mix, wherein chlorine dioxide, hydrogen peroxide and hypochlorous acid
The mass ratio of the material of sodium is 1:1.5:3, carries out oxidation reaction;
(3) waste and old nickel-cobalt-manganese ternary lithium battery anode piece is immersed in the hydrochloric acid or sulfuric acid solution that concentration is 5 mol/L, to just
After pole active material is separated with aluminum foil current collector, aluminium foil is taken out, is added in acid solution in the sodium sulfite that concentration is 3 mol/L,
It heats 80 DEG C of 80 min of stirring to dissolve to tertiary cathode material, filtrate is obtained by filtration;With the waste and old nickel-cobalt-manganese ternary lithium battery of 10g
On the basis of anode pole piece, the additive amount of reducing agent is 0.4 L;
(4) step (2) waste water and step (3) filtrate are mixed, adjusting pH is 3.0, regulates and controls nickel, cobalt, manganese in mixed liquor and contains
Amount, complies with molecular formula LiNi0.5Co0.2Mn0.3O2, it is regulated stoste;
(5) sodium hydroxide solution is added into step (4) regulation stoste to be reacted, regulates and controls the matter of stoste and sodium hydroxide solution
For amount than being 25:75, the mass concentration of sodium hydroxide solution is 20wt%, is passed through CO after reaction2Gas, when in mixed alkali liquor
Aluminium content stops logical CO when being lower than 50ppm2Gas obtains solid material;
(6) solid material that step (5) obtains is filtered, washed, dried, lithium carbonate is added after dry and is uniformly mixed progress
High-temperature calcination, calcination temperature are 700 DEG C, and calcination time 10h obtains the nickel-cobalt lithium manganate material of alumina-coated after calcining,
Lithium content reaches 7wt% in the nickel-cobalt lithium manganate material of alumina-coated.
The performance of the nickel-cobalt lithium manganate material of alumina-coated prepared by embodiment 2
The content of Phosphorus From Wastewater can be reduced to 0.48mg/L in the present embodiment hereinafter, reaching discharge standard for electroplating pollutants,
The content of metal ion can recycle in waste water, final discharged wastewater met the national standard.
Embodiment 3
A kind of electroplating wastewater comprehensive processing technique, steps are as follows:
(1) phosphorous, aluminium, cobalt, manganese electroplating wastewater are collected;Wherein the content of phosphorus is 48.9mg/L, total manganese content in electroplating wastewater
18.2 mg/L, total 6.3 mg/L of cobalt content, total 7.38 mg/L of aluminium content;
(2) it is 25wt% morning sodium hydroxide solution that mass concentration is added into waste water, adjusts wastewater pH 9, and compounding oxidation is added
Agent, compound oxidant are that chlorine dioxide, hydrogen peroxide and liquor natrii hypochloritis mix, wherein chlorine dioxide, hydrogen peroxide and hypochlorous acid
The mass ratio of the material of sodium is 1:2:5, carries out oxidation reaction;
(3) waste and old nickel-cobalt-manganese ternary lithium battery anode piece is immersed in the hydrochloric acid or sulfuric acid solution that concentration is 10 mol/L, to
After positive electrode active materials are separated with aluminum foil current collector, aluminium foil is taken out, the bisulfite that concentration is 5 mol/L is added in acid solution
Sodium heats 100 DEG C of 40 min of stirring and dissolves to tertiary cathode material, filtrate is obtained by filtration;With the waste and old nickel-cobalt-manganese ternary lithium of 10g
On the basis of battery positive pole piece, the additive amount of reducing agent is 0.5 L;
(4) step (2) waste water and step (3) filtrate are mixed, adjusting pH is 5.0, regulates and controls nickel, cobalt, manganese in mixed liquor and contains
Amount, complies with molecular formula LiNi0.6Co0.2Mn0.2O2, wherein x>0, y>0, x+y<1 are regulated stoste;
(5) sodium hydroxide solution is added into step (4) regulation stoste to be reacted, regulates and controls the matter of stoste and sodium hydroxide solution
For amount than being 30:70, the mass concentration of sodium hydroxide solution is 25wt%, is passed through CO after reaction2Gas, when in mixed alkali liquor
Aluminium content stops logical CO when being lower than 50ppm2Gas obtains solid material;
(6) solid material that step (5) obtains is filtered, washed, dried, lithium carbonate is added after dry and is uniformly mixed progress
High-temperature calcination, calcination temperature are 720 DEG C, and calcination time 9h obtains the nickel-cobalt lithium manganate material of alumina-coated, oxygen after calcining
Change lithium content in the nickel-cobalt lithium manganate material of aluminium cladding and reaches 7.5wt%.
The performance of the nickel-cobalt lithium manganate material of alumina-coated prepared by embodiment 3
The content of Phosphorus From Wastewater can be reduced to 0.35mg/L in the present embodiment hereinafter, reaching discharge standard for electroplating pollutants,
The content of metal ion can recycle in waste water, final discharged wastewater met the national standard.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of electroplating waste processing equipment, it is characterised in that: including wastewater storage tank (1), the wastewater storage tank (1) and oxygen
To change reaction tank (2) to be connected, agitating device is equipped in oxidation reaction pond (2), oxidation reaction pond (2) are connected with mixed reaction pond (3),
Mixed reaction pond (3) is connected with filtering ponds (4), is equipped with carbon dioxide access equipment (5) in the mixed reaction pond (3).
2. electroplating waste processing equipment according to claim 1, it is characterised in that: the oxidation reaction pond (2) and dioxy
Change chlorine tank (6), dioxygen water pot (7) is connected with sodium hypochlorite tank (8).
3. the method for the processing waste water using electroplating waste processing equipment described in as claimed in claim 1 or 22, it is characterised in that step is such as
Under:
(a) phosphorous, aluminium, cobalt, manganese electroplating wastewater, storage to wastewater storage tank (1) are collected;
(b) sodium hydroxide solution is added into waste water, adjusts wastewater pH, compound oxidant is added, is carried out in oxidation reaction pond (2)
Oxidation reaction;
(c) waste and old nickel-cobalt-manganese ternary lithium battery anode piece is immersed in acid solution, to positive electrode active materials and aluminum foil current collector point
From rear, taking-up aluminium foil, reducing agent is added in acid solution, filtrate is obtained by filtration to tertiary cathode material dissolution in heating stirring;
(d) step (b) waste water and step (c) filtrate are mixed, it is 1.5-5.0, regulation that pH is adjusted in mixed reaction pond (3)
Nickel, cobalt, manganese content in mixed liquor, comply with molecular formula LiNixCoyMn1-x-yO2, wherein x>0, y>0, x+y<1 are regulated
Stoste;
(e) sodium hydroxide solution is added into step (d) regulation stoste to be reacted, CO is passed through after reaction2Gas works as mixed base
Aluminium content in liquid stops logical CO when being lower than 50ppm2Gas obtains solid material;
(f) solid material for obtaining step (e) is filtered, washs, dries, and lithium carbonate is added after dry and is uniformly mixed progress
High-temperature calcination obtains the nickel-cobalt lithium manganate material of alumina-coated after calcining.
4. the method for processing waste water according to claim 3, it is characterised in that: sodium hydroxide solution in the step (b)
Mass concentration be 15-25wt%, pH value is adjusted to 7-9.
5. the method for processing waste water according to claim 3, it is characterised in that: compound oxidant is in the step (b)
Chlorine dioxide, hydrogen peroxide and liquor natrii hypochloritis's mixing, wherein the mass ratio of the material of chlorine dioxide, hydrogen peroxide and sodium hypochlorite is
1:(1-2): (2-5).
6. the method for processing waste water according to claim 3, it is characterised in that: acid solution includes hydrochloric acid in the step (c)
Or sulfuric acid, acid strength are 0.1-10 mol/L;On the basis of the waste and old nickel-cobalt-manganese ternary lithium battery anode piece of 10g, acid solution is used
Amount is 0. 5-1 L.
7. the method for processing waste water according to claim 3, it is characterised in that: reducing agent is peroxide in the step (c)
Change hydrogen, sulphite, bisulfites, thiosulfate, reductant concentration is 0.1-5 mol/L;With the waste and old nickel cobalt manganese three of 10g
On the basis of first lithium battery anode piece, the additive amount of reducing agent is 0.25-0.5 L.
8. the method for processing waste water according to claim 3, it is characterised in that: heating temperature is 30- in the step (c)
100 DEG C, mixing time is 40-120 min.
9. the method for processing waste water according to claim 3, it is characterised in that: regulation stoste and hydrogen in the step (e)
The mass ratio of sodium hydroxide solution is (20-30): (70-80), and the mass concentration of sodium hydroxide solution is 15-25wt%.
10. the method for processing waste water according to claim 3, it is characterised in that: calcination temperature is in the step (e)
680-720 DEG C, calcination time 9-12h.
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