CN109137034A - The configuration and method of existing oxidation trough recycling anodizing solution is transformed - Google Patents
The configuration and method of existing oxidation trough recycling anodizing solution is transformed Download PDFInfo
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- CN109137034A CN109137034A CN201810843751.8A CN201810843751A CN109137034A CN 109137034 A CN109137034 A CN 109137034A CN 201810843751 A CN201810843751 A CN 201810843751A CN 109137034 A CN109137034 A CN 109137034A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/005—Apparatus specially adapted for electrolytic conversion coating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
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Abstract
The invention discloses the configurations that existing oxidation trough recycling anodizing solution is transformed, including oxidation solution collection system, oxidation solution circulating cooling system, oxidation liquid treating system, oxidation liquid separation system and oxidation solution recycling and recrystallization system.The invention also discloses the methods of the configuration recycling anodizing solution using the existing oxidation trough recycling anodizing solution of above-mentioned transformation, including collect oxidation solution, circulating cooling oxidation solution, processing and separation oxidation solution, oxidation solution recycling and recrystallization process.Arrangements and methods of the invention realize that aluminium ion can crystallize precipitation online, oxidation solution is recycled, and oxidation solution resistance is effectively reduced, and realize low-cost and high-quality production.
Description
Technical field
The present invention relates to configurations and method that existing oxidation trough recycling anodizing solution is transformed, belong to aluminium manufacture field.
Background technique
In the anodizing solution of oxidation trough, the aluminium alloy with conductive surface is placed in anode, under the action of an external electric field,
The process that surface forms oxidation film is known as anodic oxidation, and generated film is anode oxide film or electrochemical conversion film.
Alumilite process liquid refers to tank liquor used in aluminium alloy anode oxide.When fluting, anodizing solution sulfuric acid concentration exists
Between 160-200g/L, there is no aluminium ion in tank liquor, it is stronger to oxidation film solvability.Usual anodizing time is 40-60
Minute, temperature is 18-22 DEG C, and the molten aluminum amount of profile per ton is about 3.84Kg/T (400m2/T).With the accumulation of aluminium molten in tank liquor,
Al3+To H+And SO4 2-Footprint increase, seriously hinder H+To cathode, SO4 2-Ghandler motion is dynamic on the sunny side, the decline of tank liquor electric conductivity.
When aluminium ion concentration reaches 20g/L or more, tank liquor resistance is too big, and according to constant voltage technique, current density is substantially reduced, and makes
Film forming layer thickness is insufficient, transparency decline, or even white spot occurs or striped or the trace of other shapes etc. are unevenly existing
As；According to constant current technique, and voltage can be caused to increase, power consumption increase, be also possible that when serious film layer burn and
After closing phenomena such as blackening.
Aluminium ion in anodizing solution directly affects the electric conductivity of tank liquor, determines oxidation energy consumption and film quality, most
Good controlled concentration should be between 3-8g/L range, and the oxidation film corrosion resistance that is obtained at this time, wearability are best.But in view of medicament at
This and environmental protection pressure, aluminium ion concentration general control is in the section 15-20g/L in actual production.
In view of aluminium ion concentration variation with coating mass and oxidation energy consumption just like this important relationship, aluminium processing enterprise one
As using following two method control aluminium ion:
First is that the method for slot outwells a part of tank liquor that is, when aluminium ion concentration is more than 20g/L, it is dense to reduce aluminium ion
Degree supplements sulfuric acid to 180g/L, continues to produce.Produce 100000 tons of anodic oxidation aluminum profiles per year, the molten aluminum amount of oxidation solution is 400 tons of left sides
The right side, 20000 tons or so of the oxidation waste liquid poured out every year, wherein containing 3600 tons of sulfuric acid, 400 tons of aluminium.Not only medicament is wasted, but also is born
The environmental protection pressure of the so a large amount of spent acid of processing and waste residue, also has lost more than 400 tons of recyclable aluminum metals.
Second is that retrieval of sulfuric acid machine is aluminum ions stabilising arrangement using retrieval of sulfuric acid machine, pumped using acid by the sulphur of oxidation trough
The mixed liquor of acid and aluminum sulfate is pumped into knockout drum.Since knockout drum is provided with the special material of cation exchange, rapidly and efficiently
Ground separates sulfuric acid with aluminium ion, and aluminium ion is discharged except solution, sulfuric acid is sent back in oxidation trough and is continued to use, is made in production
Except the aluminium ion discharge solution constantly generated, stablize the aluminium ion concentration in tank liquor in certain processing range, and can purification tank
The sundries such as organic matter in liquid, longtime running no replacement is required tank liquor.Theoretically, which can make aluminium material oxidation film thickness and product
Matter is stablized, and energy conservation, also provides good oxidation film basis to stablize profile coloring process.But in actual operation, problem
Much.Existing retrieval of sulfuric acid machine need to consume water about 1.5M3/ H consumes electricity about 3KW/H, i.e. monthly 1080 tons of water consumption, power consumption
2160 degree, if measuring from 1080 tons of water that water outlet is discharged, find wherein sulfur acid 15-30g/L, aluminium ion 5-10g/L,
Nearly 30 tons of sulfuric acid is monthly discharged.The effect of monthly such water consumption power consumption, acquisition has few improvement than slot.It is returned in view of sulfuric acid
The using effect of the above-mentioned bad luck of receipts machine, most of aluminium processing enterprise gradually deactivate the device, have restored a part of oxidation trough
The conventional method of liquid.
Modern aluminum processing enterprise is disposed if there is anodic oxidation waste liquid in need of immediate treatment generally according to both ways:
First is that direct emission not only increases processing cost into wastewater treatment center, but also bauxite resource is wasted, also generates a large amount of Industry Waste
Slag；Second is that professional treatment producer is asked to pull away.These treatment plants, if the oxidation acid pickle of single-item handling magnanimity, need to consume magnanimity
Lye, society can pay expensive processing cost thus.
As previously mentioned, the aluminium ion in anodizing solution, optium concentration should be controlled within the scope of 3-8g/L, be obtained at this time
Oxidation film corrosion resistance, wearability it is best, oxidation low energy consumption.Currently, the aluminium ion concentration in anodizing tank, each enterprise is basic
Control is between 15-20g/L, far beyond optium concentration section.Aluminium ion concentration is high, and resistance is big, and energy consumption is high, aoxidizes film quality
It is poor to measure, these are industry common recognitions.But it is limited by the environmental protection pressure of processing oxidation spent acid, enterprise is forced selection and improves aluminium ion control
The upper limit using sacrificial oxidation film quality, increases oxidation energy consumption as cost, to reduce the discharge of oxidation spent acid.
In oxidation solution, there is Al3+、H+And SO4 2-, when not having added electric field, motion mode of these three ions in oxidation solution is two
Kind: vibration and drift.With Al3+For, motion mode are as follows:
(1), it is shaken in the spherical section centered on a certain equalization point, the maximum cross-section by the centre of sphere is its zone of influence
Domain, referred to as concussion section；
(2), next equalization point is floated to from an equalization point, then proceedes to shake, drift motion is named in this migration；Drift
Shifting be it is unordered, vibration is eternal；After added electric field, each ion is in addition to drift and vibration, and there are also the orientations along power line direction
Movement, concentration gradually form gradient distribution；
(3)、SO4 2-To anode movement after added electric field, forming anode, nearby concentration is high, and cathode nearby divide by the low gradient of concentration
Cloth；In anode, following electrochemical reaction is formed:
SO4 2-- 2e=2O+SO2↑ (losing electronics, release oxygen atom) (1)
2Al+3O=Al2O3(exothermic reaction, oxygenerating film) (2)
Al2O3+3H+=2Al3++3OH-(oxidation film dissolution) (3)
(4)、Al3+、H+To cathode motion after added electric field, forming cathode, nearby concentration is high, the low gradient of concentration near anode
Distribution；In cathode, following electrochemical reaction is formed:
2H++ 2e=H2↑ (obtaining electronics, discharge hydrogen) (4)
Due to ionic radius difference, H+Prior to Al3+Cathode surface is reached, and due to current potential difference, H+It is preferential to obtain electronics,
Al3+It can only rest in oxidation solution and constantly accumulate.By (1) (4) formula it is found that the conductive capability at the two poles of the earth is the SO by anode4 2-
With the H at cathode+Concentration determine.With continuing for electrolysis, the ion near the two poles of the earth is constantly consumed, and needs the SO of distal end4 2-
And H+It is continuously replenished, makes to aoxidize lasting progress.At this moment, SO4 2-And H+The complexity mobile to the two poles of the earth, determines tank liquor conductive capability
The key problem of size, is directly determined by aluminium ion concentration.Assuming that a certain area for being parallel to the two poles of the earth is A's in oxidation solution
Section, the number at the aluminium ion vibration center passed through are N, each aluminum ions concussion section is S, then aluminium ion on the section
Total footprint be NS, SO4 2-And H+When by the section, being influenced lesser effective area by aluminium ion interception is A-NS.By
, it is found that aluminium ion concentration is higher, N is bigger for this, and effective area A-NS is smaller, SO4 2-And H+By difficulty it is bigger, tank liquor resistance
It is bigger.But according to (3) formula, aluminium ion concentration is reduced, reacts mobile to the right, oxidation film dissolution is accelerated, therefore aluminium ion concentration is not
It can be too low.Production practices prove that oxidation trough aluminium ion optium concentration is 3-8g/L, this section film layer is best, and tank liquor resistance is smaller,
Low energy consumption, and low energy consumption and high film quality, it is necessary to assure aluminium ion concentration is lower than 8g/L.For that purpose it is necessary to the aluminium of oxidation trough
Ion carries out specially treated, not only reduces aluminium ion, but also recycling sulfur acid oxidation solution and byproduct containing aluminium, avoids the aluminium ion from being more than
The drawbacks of a part of oxidation solution is outwelled when 20g/L.
Chinese patent 201320875536.9 is proposed with the method that in mould liquid and anodizing solution recycles aluminium hydroxide is stewed, really
The aluminium hydroxide for meeting national standard GB4294-2010 requirement can be recycled in fact.But the method sacrifices the oxidation of this recoverable
Sulfuric acid in liquid, it is tangible unfortunate.By Chinese patent 201410126857.8,201611043945.7,201611042044.6,
201610995717.3,201611038294.2,201611002760.1 method provided, can be chemically from oxidation solution
Individually crystallization aluminium ion, produces alum, and sulfuric acid all recycles.But the recovery system that these patents of invention provide is matched
It sets, needs to configure a large amount of reactor tanks, crystallizing tank and solid-liquid separating equipment, in addition to increasing equipment investment, take up an area a large amount of place problems
It is more prominent；In addition, although having taken up an area a large amount of places, the volume of these equipment, the total volume of the oxidation solution relative to aluminum material factory,
Still too small, often there is the drawbacks of high load with small power.
Summary of the invention
The purpose of the present invention is to solve the shortcomings of the prior art place, provides transformation existing oxidation trough recycling anodic oxidation
The resistance of anodizing solution is effectively reduced for the configuration of liquid, greatly improves the rate of recovery of aluminium ion and sulfuric acid, reduce investment at
This, reduces occupied area.
It is another object of the present invention to the configurations proposed using the existing oxidation trough recycling anodizing solution of above-mentioned transformation
The method for recycling anodizing solution, production can carry out simultaneously with processing recycling, simplify reclaimer, greatly improve aluminium ion and sulphur
It can ensure that the aluminium alloy quality of production while rate of recovery of acid again, realize environmentally friendly continuous production.
To achieve this purpose, the present invention adopts the following technical scheme:
The configuration of existing oxidation trough recycling anodizing solution, including oxidation solution collection system, oxidation solution circulating cooling is transformed
System, oxidation liquid treating system, oxidation liquid separation system and oxidation solution recycling and recrystallization system；
Oxidation solution collection system includes that oxidation trough, overflow launder, No.1 pump and pipeline, overflow launder surround and be set to oxidation trough
One week, overflow launder was connected with No.1 pump, and No.1 is pumped for the oxidation solution in overflow launder to be pumped into oxidation solution circulating cooling system；
Oxidation solution circulating cooling system is for cooling the oxidation solution being pumped into；
Aoxidizing liquid treating system includes No. two receivers, No. two pumps, reactive tank and pipeline, and reactive tank is by the existing oxygen of oxidation line
Change slot to be transformed, reactive tank is connected to No. two pumps, and No. two receivers are connected with No. two pumps, and No. two receivers are used for reaction cartridge
Liquid, No. two pumps are for driving reaction solution to enter reactive tank；
Aoxidizing liquid separation system includes No. three pumps, continuous filter press and pipeline, and the inlet of No. three pumps is connected with reactive tank,
The liquid outlet of No. three pumps is connected with continuous filter press, and No. three pumps are for being pumped into continuous filter press for the solidliquid mixture in reactive tank
Machine；
Oxidation solution recycling and recrystallization system include that No. four pumps, crystallization tank, No. five pumps and pipeline, crystallization tank are showed by oxidation line
There is oxidation trough to be transformed, No. four pumps, crystallization tank and No. five pumps are sequentially connected by pipeline, and the inlet of No. four pumps passes through pipeline
It is connected with continuous filter press, the liquid outlet of No. five pumps is connected by pipeline with continuous filter press.
It is reactive tank and crystallization tank by the transformation existing oxidation trough of oxidation line, remains its original capacious advantage,
Cost of investment is greatly reduced, improves treatment effeciency, reduce occupied area；Existing oxidation trough recycling anodizing solution is entirely transformed
Configuration completes the efficient process and recycling that generated anodizing solution is produced to aluminium alloy, passes through rich in anodizing solution
The aluminium ion contained is reacted with reaction solution, generates micro-soluble material and crystallization is precipitated, so that aluminium ion and sulfuric acid are able to recycle benefit again
With the resistance of anodizing solution saves resource.
Further, oxidation solution circulating cooling system includes ice maker and pipeline, and No.1 pump, ice maker and reactive tank pass through pipeline
It is sequentially connected, ice maker is connected with oxidation trough.
Ice maker cools down oxidation solution, is delivered to reactive tank, at low temperature with reaction solution reactive crystallization；Cooling simultaneously
Oxidation solution is delivered in oxidation trough, takes away the heat of aluminium surface rapidly, reduces the oxidizing temperature at oxygenation level, reduces oxidation film
Meltage.
Further, the configuration of existing oxidation trough recycling anodizing solution is transformed, further includes crystallization removing system, crystallization is clear
Except system includes No.1 receiver and pipeline, for filling crystallization remover, the slot bottom of reactive tank is provided with multiple No.1 receiver
Reactive tank dreg-drawing pipe, the slot bottom of crystallization tank are provided with multiple crystallization tank dreg-drawing pipes, and No.1 receiver and overflow launder are pumped with No.1
It is connected, reactive tank dreg-drawing pipe, crystallization tank dreg-drawing pipe are connected with ice maker respectively, crystallization remover of the No.1 pump for that will draw simultaneously
Ice maker, reactive tank dreg-drawing pipe are pumped into, in crystallization tank dreg-drawing pipe with oxidation solution.
Ice maker all can during circulating cooling oxidation solution and during reactive tank and crystallization tank persistently take out slag
Gradually accumulation crystallization will lead to line clogging after crystallization accumulation to a certain extent, at this moment starting crystallization removing system, benefit
Heat production, the knot of dissolution ice maker, crystallization tank dreg-drawing pipe and reactive tank dreg-drawing pipe with the diluting effect of crystallization remover chance oxidation solution
Crystalline substance, the ice maker and dreg-drawing pipe of dredge blockage, resumes production rapidly.
Further, the slot bottom of reactive tank is equipped at least one reactive tank reaction kettle, and reactive tank reaction kettle is in back taper,
One end of reactive tank dreg-drawing pipe is connected with the bottom of reactive tank reaction kettle, and the other end of reactive tank dreg-drawing pipe is connected with No. three pumps；
The slot bottom of crystallization tank is equipped at least one crystallization tank reaction kettle, and crystallization tank reaction kettle is in back taper, and the one of crystallization tank dreg-drawing pipe
End is connected with the bottom of crystallization tank reaction kettle, and the other end of crystallization tank dreg-drawing pipe is connected with No. five pumps.
Reactive tank is responsible for adding reaction solution, so that it is generated chemical reaction and generates crystallization；Crystallization tank is responsible for recrystallization recycling oxygen
Change liquid, prevents aluminium dust.The crystallization that reactive tank and crystallization tank generate is received by reactive tank reaction kettle and crystallization tank reaction kettle respectively
Collection is gone out by No. three pumps and No. five pumpings in time, so that crystallization does not stop accumulation, slot bottom is avoided to block.
Further, reactive tank is provided at least one recycling oxidation solution discharge pipe, recycling oxidation solution discharge pipe and crystallization
Slot is connected, and crystallization tank is provided at least one regenerating oxidation liquid discharge pipe, and regenerating oxidation liquid discharge pipe is connected to overflow launder.
The supernatant of top in reactive tank is discharged into crystallization tank by recycling oxidation solution discharge pipe, passes through regenerating oxidation liquid
The supernatant of crystallization tank is discharged into overflow launder by discharge pipe, can reduce separation of solid and liquid total amount, is more suitable for system on a large scale
Industrial production demand, while being conducive to prevent oxidation solution from substantially heating up.
Further, reactive tank is connected with circulation pipe, and circulation pipe is connected to No. two pumps, and No. two receivers are connected with No. two pumps
Logical, No. two pumps are for the oxidation solution in circular response slot.
Make liquid circulation by reactive tank, No. two pumps and circulation pipe, forms negative pressure, open the pipeline valve of No. two receivers
Door, reaction solution are sucked out by suction function, by No. two pumps and circulation pipe, into reactive tank, are realized the dosing in circulation, are made
Oxidation solution is uniformly mixed with reaction solution, and reaction is abundant.
Using the method for the configuration recycling anodizing solution of the existing oxidation trough recycling anodizing solution of above-mentioned transformation, including with
Lower step:
(1) collect oxidation solution: the liquid of oxidation trough overflows into overflow launder, starting No.1 pump, by overflow launder be collected into wait locate
It manages oxidation solution and imports ice maker；
(2) circulating cooling oxidation solution: starting ice maker, using No.1 pump motive force, circulating cooling reactive tank, crystallization tank,
The oxidation solution of overflow launder, oxidation trough；
(3) it handles and separates oxidation solution: first starting No. three pumps and continuous filter press, the oxidation solution in reactive tank continues from slot
Bottom extraction starts No. two pumps when temperature < 5 DEG C in reactive tank, and reaction solution is driven by No. two pumps to be entered in circulation pipe, later
Into in reactive tank, reaction solution and oxidation solution occur chemical reaction and form solidliquid mixture, and solidliquid mixture is pumped by No. three pumps
Continuous filter press isolates recycling oxidation solution and crystallization；
(4) oxidation solution recycling and recrystallization: when temperature < 12 DEG C in crystallization tank, starting No. four pumps, will recycling oxidation liquid pump
Enter crystallization tank be precipitated again crystallization form solidliquid mixture, start No. five pumps, the solidliquid mixture in crystallization tank be pumped into continuously
Filter press isolates crystallization and regenerating oxidation liquid.
React generate crystallization with the reduction of temperature and solubility reduce, therefore, by oxidation solution in reactive tank temperature < 5
It mixes under conditions of DEG C with reaction solution, is reacted under low temperature, more polycrystalline is precipitated, while ensuring temperature < 12 DEG C of crystallization tank, recycle
Oxidation solution recrystallization repeats to be separated by solid-liquid separation operating process, so that the crystal in regeneration recovered liquid is sufficiently precipitated and separates, further
The rate of recovery is improved, oxidation solution when regenerating oxidation liquid is delivered to overflow launder through regenerating oxidation liquid discharge pipe thereafter with 18~22 DEG C connects
It is unsaturated solution when the regenerating oxidation liquid for touching and heating up, therefore sending back to is utilized, avoids aluminium dust, it is ensured that aluminium processing enterprise connects
Continuous safety in production.
In view of first dosing, crystallization is generated, reactive tank reaction kettle and reactive tank dreg-drawing pipe are crystallized the risk of blocking, first start
No.1 pump, ice maker, No. three pumps and continuous filter press, continue cycling through cooling reactive tank, crystallization tank and overflow launder, in reactive tank slot bottom
Under the premise of being continuously in temperature < 5 DEG C in negative pressure and reactive tank, restart No. two pumps, by reaction solution sucting reaction slot, reaction
Crystallization is generated, reactive tank reaction kettle is settled down to, is pumped into continuous filter press in time by No. three pumps, dosing is carried out simultaneously with slag is taken out, kept away
Exempt from crystallization to accumulate in reaction tank bottom, avoids the pipeline and valve of crystalline particle blocking reaction tank bottom.
Further, when Crystallization Plugging, which occur, in ice maker, reactive tank dreg-drawing pipe and crystallization tank dreg-drawing pipe to be influenced to take out slag, into
Step is removed in row crystallization；Crystallize cleaning: crystallization remover is imported ice maker, reactive tank dreg-drawing pipe and knot by starting No.1 pump
Brilliant slot dreg-drawing pipe.Timely thoroughly crystallization of the dredge blockage in ice maker, reactive tank dreg-drawing pipe and crystallization tank dreg-drawing pipe, it is extensive rapidly
Demutation produces.
Further, in step (3), the supernatant of 3 internal upper part of reactive tank is discharged into knot by recycling oxidation solution discharge pipe
It is recrystallized in brilliant slot；In step (4), the supernatant of crystallization tank internal upper part is discharged into overflow launder by regenerating oxidation liquid discharge pipe
It recycles.
Supernatant in reactive tank and crystallization tank is expelled directly out by pipeline, can reduce separation of solid and liquid total amount, make be
System is more suitable for large-scale industrial production demand；It also can be reduced intermediate processing links simultaneously, oxidation solution avoided substantially to heat up.
Further, reaction solution be one of ammonium sulfate, ammonium nitrate, ammonium chloride, potassium sulfate, potassium nitrate or potassium chloride or
It is a variety of；Crystallization is alum or aluminum aluminum sulfate；Regenerating oxidation liquid is the regenerating oxidation liquid of sulfur acid；Crystallization remover is dense sulphur
Acid.
Ammonium sulfate, ammonium nitrate, ammonium chloride, potassium sulfate, potassium nitrate or potassium chloride can be generated with the aluminum sulfate in oxidation solution
Chemical reaction, the alum or aluminum aluminum sulfate that formation is slightly soluble in water are easy to be precipitated crystallization at low ambient temperatures, to separate
The regenerating oxidation liquid for recycling product alum or aluminum aluminum sulfate and sulfur acid out, so that aluminium ion and sulfuric acid all obtain
Regeneration.The concentrated sulfuric acid is mixed with oxidation solution, the concentrated sulfuric acid has heating effect in dilution, has heating to oxidation solution
Effect, be passed into ice maker, reactive tank dreg-drawing pipe and crystallization tank dreg-drawing pipe, dissolution ice maker, reactive tank dreg-drawing pipe and crystallization tank
Plug hidden danger is removed in crystallization inside dreg-drawing pipe.
The beneficial effects of the present invention are:
(1) present invention is by anodic oxidation waste liquid online processing, and whole design recovery system, aluminum profile produces and aluminium ion knot
Brilliant, retrieval of sulfuric acid is not interfere with each other, and is carried out simultaneously；
(2) using the configuration that existing oxidation trough recycling anodizing solution is transformed, tank liquor aluminium ion concentration workspace will be aoxidized
Between turn down to good concentration level, not only optimized oxidized aluminum alloy membrane structure, but also oxidation solution resistance is effectively reduced, realize low cost
High quality of production；
(3) the existing oxidation trough of oxidation line is transformed into reactive tank and crystallization tank for the first time by the present invention, remains its original appearance
The big advantage of product, while cost of investment being greatly reduced again, improves treatment effeciency, reduce occupied area；
(4) present invention heat production using crystallization remover chance oxidation solution diluting effect in crystallization removing system for the first time, from
The crystallization accumulated in dynamic dissolution pipeline and ice maker, the ice maker and dreg-drawing pipe of dredge blockage resume production rapidly, save manpower；
(5) using the method for recycling anodizing solution of the invention, realize that aluminium ion can crystallize online precipitation, oxidation solution follows
Ring uses, and has avoided the huge waste of sulfuric acid and bauxite resource caused by outwelling oxidation solution, reduces and handles these waste liquids and waste residue
Environmentally friendly cost.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the configuration of the existing oxidation trough recycling anodizing solution of transformation of the invention and the structural schematic diagram of method；
Fig. 2 is the structural schematic diagram of the reactive tank of one embodiment of the invention；
Fig. 3 is the structural schematic diagram of the crystallization tank of one embodiment of the invention.
Wherein: oxidation trough 1, overflow launder 2, reactive tank 3, reactive tank reaction kettle 31, reactive tank dreg-drawing pipe 32, crystallization tank 4, knot
Brilliant slot reaction kettle 41, crystallization tank dreg-drawing pipe 42, ice maker 5, continuous filter press 6, No.1 receiver 7, No. two receivers 8, No.1 pump
9, No. two pumps 10, No. three pumps 11, No. four pumps 12, No. five pumps 13, circulation pipe 14, recycling oxidation solution discharge pipe 15, regenerating oxidation liquid
Discharge pipe 16, No.1 valve 01, No. two valves 02, No. three valves 03, No. four valves 04, No. five valves 05, No. six valves 06, No. seven valves 07, No. eight
Valve 08, No. nine valves 09, No. ten valves 010,013, ten No. four valves 014,15 of valve of valve 012,13 of ride on Bus No. 11 valve 011,12
Number valve 019 of valve 018,19 of valve 017,18 of valve 016,17 of valve 015,16, No.1 check-valves 020, No. two only
Return valve 021.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
One, in anodizing solution aluminium ion and retrieval of sulfuric acid theoretical foundation
When oxidized aluminum alloy, (3) formula is pressed, partial oxide film is dissolved, about 4Kg/T (400m2) aluminium dissolve in sulfuric acid oxygen
Change liquid, so that containing Al in oxidation solution3+、H+And SO4 2-, ammonium sulfate, ammonium nitrate, ammonium chloride, sulfuric acid are added in this oxidation solution
Following reaction then occurs for potassium, potassium nitrate, potassium chloride:
Ammonium sulfate is added to oxidation solution:
Al2(SO4)3+(NH4)2SO4+12H2O=2NH4Al(SO4)2·12H2O↓ (5)
Ammonium nitrate, ammonium chloride is added to oxidation solution:
Al2(SO4)3+2NH4 ++SO4 2-+12H2O=2NH4Al(SO4)2·12H2O↓ (6)
Potassium sulfate is added to oxidation solution:
Al2(SO4)3+K2SO4+12H2O=2KAl (SO4)2·12H2O↓ (7)
Potassium nitrate, potassium chloride is added to oxidation solution:
Al2(SO4)3+2K++SO4 2-+12H2O=2KAl (SO4)2·12H2O↓ (8)
The present embodiment preferably sulfuric acid ammonium is as reaction solution, under conditions of sulfuric acid, containing aluminium ion and ammonium ion, the sulphur of generation
Sour aluminium ammonium NH4Al(SO4)2·12H2O, NH4Al(SO4)2·12H2O is micro-soluble material, and pre- low temperature mass crystallization is precipitated；In addition, sulfuric acid
The acid ion that ammonium ionizes out in water is SO4 2-, NH with recovery product4Al(SO4)2·12H2O、H2SO4Acid having the same
Radical ion avoids subsequent dedoping step so that recovery product is more pure.
In other embodiments, reaction solution can also use ammonium nitrate, ammonium chloride, potassium sulfate, potassium nitrate, potassium chloride, occur
The chemical reaction of above-mentioned reaction equation (6), (7), (8) generates NH4Al(SO4)2·12H2O or 2KAl (SO4)2·12H2O slightly soluble
Object realizes aluminum ions recycling.
Two, quantitative analytical experiment result
1 liter of anodizing solution is taken, free sulfuric acid 183.9g/L, Al3+20.20g/L, conductivity 152.5s/m, 25 DEG C of temperature,
Addition ammonium sulfate is tested.Crystallization after twenty minutes, measures sulfuric acid concentration, aluminium ion concentration and the conductivity of tank liquor, knot immediately
Fruit is as shown in table 1:
1 bath parameters of table with various concentration ammonium sulfate changing rule
By (5) formula, every crystallization 1g/L Al3+, need to add 2.45g/L ammonium sulfate, the initial Al of oxidation solution3+20.20g/L,
Ammonium sulfate 49.49g/L need to be consumed by being fully crystallized precipitation.Table 1 and its experiments supporting show:
1, ammonium sulfate is added in oxidation solution, under room temperature, crystallizable precipitation alum in the short time；
2, with the increase of ammonium sulfate additive amount, aluminium ion is gradually reduced, but the range of decrease narrows；
3, as crystallization time increases, aluminium ion is further decreased；
4, solubility of the alum at 30 DEG C is 170g/L in oxidation solution, and solubility at 20 DEG C is 150g/L, 10
DEG C when solubility be 130g/L, as crystallization temperature reduces, aluminium ion concentration reduce；Even if ammonium ion is excessive, low temperature and
It crystallizes for a long time, aluminium ion can not be fully crystallized precipitation；
5, with the increase of ammonium sulfate additive amount, sulfuric acid concentration increases；
6, with the increase of ammonium sulfate additive amount, conductivity increases.
Three, the configuration and method of the existing oxidation trough recycling anodizing solution of transformation of the invention
It is practical in conjunction with oxidation line quantity-produced according to reaction equation (5) and the experimental result of table 1, retrieval of sulfuric acid, byproduct
When collection, since the solubility of alum is very sensitive to temperature, solubility of the alum at 30 DEG C is in oxidation solution
170g/L, solubility at 20 DEG C are 150g/L, and solubility at 10 DEG C is 130g/L；At 5 DEG C or less, alum solubility
Lower than 100g/L.When recovery system works long hours, the temperature of summer recovered liquid is likely to be breached 30 DEG C, and at this moment alum is molten
Xie Du is 170g/L, and as oxidation solution is recycled into oxidation trough, temperature is reduced to 20 DEG C, and at this moment alum solubility is 150g/
L, part of sulfuric acid aluminium ammonium are crystallized in oxidation trough and are precipitated, and a part is deposited in slot bottom, and a part is attached to oxidation material surface, is formed and hung
Ash causes to stop production；If recovery system configures refrigeration equipment, (be lower than oxidation trough temperature) recrystallization alum, simultaneously at low temperature
Send recovered liquid back to oxidation trough at low temperature, then because oxidation solution temperature is relatively high, what is sent back to is alum unsaturation slot
Crystallization will not be precipitated in liquid, can keep the safety in production.
In view of alum recrystallization needs biggish volume, cooling long period, a large amount of reaction kettles are needed to configure, are accounted for
The a large amount of site areas in ground, in addition to increasing equipment investment, aluminum material factory is difficult to provide the place for assembling these equipment, pushes away to be of the invention
Higher threshold is preset in wide application.Oxidation line is transformed in the present invention, transform two oxidation troughs as reactive tank and crystallization tank, borrows oxidation
The big volume of slot configures cooling system, is responsible for tying again at low temperature to the oxidation solution to be processed refrigeration in reactive tank and crystallization tank
It is brilliant, it is ensured that send overflow launder back to is alum unsaturation oxidation solution.The present invention is exactly based on well-designed, and existing oxidation is transformed
Slot, replace aluminium ion and retrieval of sulfuric acid crystallizing tank, reactor tank, while greatly improving recycling ability, be greatly reduced investment at
This, reduces land occupation site area, simplifies reclaimer, improve recovery efficiency.
This recovery system is by the aluminium oxide profile design for producing 100000 tons per year.It produces 100000 tons of aluminum profiles per year, generates oxidation waste liquid
20000 tons, molten aluminum amount is 400 tons or so.
In order to realize the target of 20000 tons of oxidation waste liquids of processing, transformation oxidation trough is reactive tank, is responsible for addition medicament, raw
At alum；Transformation oxidation trough is crystallization tank, is responsible for recrystallization recovered liquid, prevents aluminium dust；Configure a continuous filter press
Machine is responsible for separation of solid and liquid.Individually oxidation waste liquid should be arranged in the characteristics of being not easy long-distance pipeline in view of oxidation solution, this system
Processing region facilitates treated recovered liquid directly returning crystallization tank with pipeline close to oxidation workshop.
Slot, pump, valve and the pipeline contacted with oxidation waste liquid, it is necessary to press acidproof design；Acid-proof pump is selected, from overflow launder stringing
And valve, oxidation waste liquid is evacuated to reactive tank and crystallization tank, by two trench bottoms by slag requirement is taken out, carries out special technique transformation.
As shown in Figures 1 to 3, the configuration of existing oxidation trough recycling anodizing solution, including oxidation solution collection system, oxygen is transformed
Change liquid circulating cooling system, oxidation liquid treating system, oxidation liquid separation system and oxidation solution recycling and recrystallization system；
Oxidation solution collection system includes that oxidation trough 1, overflow launder 2, No.1 pump 9 and pipeline, overflow launder 2 surround and be set to oxidation
One week of slot 1, overflow launder 2 are connected with No.1 pump 9, and No.1 pump 9 is cold for the oxidation solution in overflow launder 2 to be pumped into oxidation solution circulation
But in system.No.1 valve 01 is connected between overflow launder 2 and No.1 pump 9.Overflow launder 2 is surrounded on 1 surrounding of oxidation trough, automatic to collect
The oxidation solution that overflow launder 2 is collected into is delivered to ice maker 5 by the oxidation solution overflowed from oxidation trough 1, No.1 pump 9.
Oxidation solution circulating cooling system includes ice maker 5 and pipeline, and No.1 pump 9, ice maker 5 and reactive tank 3 pass through pipeline successively
It is connected, ice maker 5 is connected with oxidation trough 1.No. two valves 02, ice maker 5 and two oxidation troughs 1 are provided between ice maker 5 and reactive tank 3
It is respectively arranged with ten No. five valve 015 and ten No. six valves 016.Ice maker 5 cools down the oxidation solution that No.1 pump 9 is pumped into, and is delivered to
Liquid treating system is aoxidized, is cooled down to reactive tank 3, at low temperature reactive crystallization；Cooling oxidation solution is delivered to oxidation trough 1
It is interior, it is appropriate to reduce by 1 temperature of oxidation trough, the heat of aluminium surface is taken away rapidly, reduces the oxidizing temperature at oxygenation level, reduces oxidation
The meltage of film；Meanwhile oxidation is returned to by No.1 pump 9 and ice maker 5 again after the oxidation solution of the collection oxidation trough 1 of overflow launder 2
In slot 1, the circulation between 1 oxidation solution of oxidation trough and 2 oxidation solution of overflow launder is formed.
Aoxidizing liquid treating system includes No. two receiver 8, two pumps 10, reactive tank 3 and pipeline, and reactive tank 3 is by oxidation line
Existing oxidation trough is transformed, and reactive tank 3 is connected with circulation pipe 14, and circulation pipe 14 be connected to No. two pumps 10, No. two receivers 8 and
No. two pumps 10 are connected, and No. two receivers 8 are used for reaction cartridge liquid, and No. two pumps 10 are for the oxidation solution and band in circular response slot 3
Dynamic reaction solution enters reactive tank 3.No. five valves 05 and No. two check-valves 021 are connected between No. two receivers 8 and No. two pumps 10, are followed
Two nozzles of endless tube 14 are set to the both ends of reactive tank.Make liquid circulation by reactive tank 3, two pumps 10 and circulation pipe 14,
Negative pressure is formed, the pipeline valve of No. two receivers 8 is opened, reaction solution is sucked out by suction function, by No. two pumps 10 and circulation
Pipe 14 makes it generate chemical reaction at low ambient temperatures with oxidation solution into reactive tank 3, generates crystallization, realizes in circulation
Dosing is uniformly mixed oxidation solution with reaction solution, and reaction is abundant.
As shown in Fig. 2, the slot bottom of reactive tank 3 is equipped at least one reactive tank reaction kettle 31, reactive tank reaction kettle 31 is in
One end of back taper, reactive tank dreg-drawing pipe 32 is connected with the bottom of reactive tank reaction kettle 31, the other end of reactive tank dreg-drawing pipe 32
It is connected with No. three pumps 11.Reactive tank 3 is responsible for addition reaction solution, so that it is generated chemical reaction and generates crystallization；The knot that reactive tank 3 generates
Crystalline substance is collected by reactive tank reaction kettle 31, avoids slot bottom from blocking so that crystallization does not stop accumulation by No. three 11 extractions of pump in time；Instead
It answers slot 3 to be transformed by the existing oxidation trough of oxidation line, remains its original capacious advantage, while investment being greatly reduced again
Cost improves treatment effeciency, reduces occupied area.
In the present embodiment, a recycling oxidation solution discharge pipe 15, recycling oxidation solution discharge are provided on reactive tank 3
Pipe 15 is connected with crystallization tank 4, recycles and is equipped with No. three valves 03 on oxidation solution discharge pipe 15.Enough reduce is separated by solid-liquid separation total amount, makes
System is more suitable for large-scale industrial production demand；It is easy to maintain the low temperature of recycling oxidation solution, crystallization tank 4 is enabled to reach obvious
Cooling effect.
In other embodiments, recycling oxidation solution discharge pipe 15 is settable one or more, is separately mounted to anti-
On the different height for answering slot 3, it is connected with crystallization tank 4.Recycling oxidation solution discharge pipe 15, can be according to reality in the setting of different height
Supernatant on border situation selection proper height is discharged, and can also be selected more recycling oxidation solution discharge pipes 15 simultaneously, be increased
The velocity of discharge of big supernatant.
Aoxidizing liquid separation system includes No. three pumps 11, continuous filter press 6 and pipeline, the inlet and reactive tank of No. three pumps 11
3 are connected, and the liquid outlet of No. three pumps 11 is connected with continuous filter press 6, and No. three pumps 11 are for pumping the solidliquid mixture in reactive tank 3
Enter continuous filter press 6 to be separated by solid-liquid separation, is crystallized and recycled oxidation solution.It is arranged between No. three pumps 11 and continuous filter press 6
There are No. nine valves 09.
In present embodiment, as shown in Fig. 2, there are three reactive tank reaction kettle 31 and three are anti-for the slot bottom setting of reactive tank 3
Slot dreg-drawing pipe 32 is answered, reactive tank reaction kettle 31 is connected one by one with reactive tank dreg-drawing pipe 32, and reactive tank dreg-drawing pipe 32 imports No. three pumps
In 11,3 slot bottom solidliquid mixture of extraction slot.06, No. seven valve of No. six valves is separately installed on three reactive tank dreg-drawing pipes 32
07 and No. eight valves 08.
In other embodiments, reactive tank reaction kettle 31 and reactive tank dreg-drawing pipe 32 by the needs of actual recovered difference
Be set as one or more than one.
Oxidation solution recycling and recrystallization system include No. four pumps 12, crystallization tank 4, five pumps 13 and pipeline, and crystallization tank 4 is by oxygen
Change the existing oxidation trough of line to be transformed, No. four pumps 12, crystallization tank 4 and No. five pumps 13 are sequentially connected by pipeline, and No. four pump 12
Inlet is connected by pipeline with continuous filter press 6, and the liquid outlet of No. five pumps 13 is connected by pipeline with continuous filter press 6.Four
Number pump 12 and continuous filter press 6 between be provided with No. ten valves 010.Ten No. four are provided between No. five pumps 13 and continuous filter press 6
Valve 014.Oxidation solution recycling and recrystallization system repeat to be separated by solid-liquid separation operating process, obtain crystallization and regenerating oxidation liquid again.
As shown in figure 3, the slot bottom of crystallization tank 4 is equipped at least one crystallization tank reaction kettle 31, crystallization tank reaction kettle 31
In back taper, one end of crystallization tank dreg-drawing pipe 32 is connected with the bottom of crystallization tank reaction kettle 31, crystallization tank dreg-drawing pipe 32 it is another
End is connected with No. five pumps 13.Crystallization tank 4 is responsible for recrystallization recycling oxidation solution, prevents aluminium dust；Crystallization tank 4 generate crystallization by
Crystallization tank reaction kettle 41 is collected, and avoids slot bottom from blocking so that crystallization does not stop accumulation by No. five 13 extractions of pump in time；Crystallization tank 4
Be transformed by the existing oxidation trough of oxidation line, remain its original capacious advantage, at the same be greatly reduced again cost of investment,
It improves treatment effeciency, reduce occupied area.
In present embodiment, crystallization tank 4 is provided with a root regeneration oxidation solution discharge pipe 16, regenerating oxidation liquid discharge pipe 16 with
Overflow launder 2 is connected to, and is equipped with No. four valves 04 on regenerating oxidation liquid discharge pipe 16.It can reduce separation of solid and liquid total amount, make system more
Suitable for large-scale industrial production demand；Intermediate processing links are reduced, so that regenerating oxidation liquid is in the case where maintaining low temperature
It is transported to overflow launder 2, it is ensured that be unsaturated solution when regenerating oxidation liquid is utilized again, it is ensured that aluminium product quality.
In other embodiments, regenerating oxidation liquid discharge pipe 16 is settable one or more, is separately mounted to tie
On the different height of brilliant slot 4, it is connected with overflow launder 2.Regenerating oxidation liquid discharge pipe 16, can be according to reality in the setting of different height
Supernatant on border situation selection proper height is discharged, and can also be selected more root regeneration oxidation solution discharge pipes 16 simultaneously, be increased
The velocity of discharge of big supernatant.
In present embodiment, as shown in figure 3, there are three crystallization tank reaction kettles 41 and three knots for the slot bottom setting of crystallization tank 4
Brilliant slot dreg-drawing pipe 42, crystallization tank reaction kettle 41 are connected one by one with crystallization tank dreg-drawing pipe 42, and crystallization tank dreg-drawing pipe 42 imports No. five pumps
In 13,4 slot bottom solidliquid mixture of crystallization tank is extracted out.Ride on Bus No. 11 valve 011,12 is separately installed on three crystallization tank dreg-drawing pipes 42
Number valve 012 and ten No. three valve 013.
In other embodiments, crystallization tank reaction kettle 41 and crystallization tank dreg-drawing pipe 42 by the needs of actual treatment difference
Be set as one or more than one.
The configuration that existing oxidation trough recycling anodizing solution is transformed further includes crystallization removing system, and crystallization removing system includes
No.1 receiver 7 and pipeline, No.1 receiver 7 pump 9 with No.1 for filling crystallization remover, No.1 receiver 7 and overflow launder 2
It is connected, reactive tank dreg-drawing pipe 32, crystallization tank dreg-drawing pipe 42 are connected with ice maker 5 respectively, crystallization of the No.1 pump 9 for that will draw simultaneously
Remover and oxidation solution are pumped into ice maker 5, reactive tank dreg-drawing pipe 32, in crystallization tank dreg-drawing pipe 42.No.1 receiver 7 and No.1 pump 9
Between be provided with ten No. seven valves 017 and No.1 check-valves 020, be provided with ten No. three valves 013, ice between ice maker 5 and No. five pumps 13
Ten No. nine valves 019 are provided between machine 5 and No. three pumps 11.Ice maker 5 is during circulating cooling oxidation solution and reactive tank 3
During persistently taking out slag with crystallization tank 3, crystallization all can be gradually accumulated, after crystallization accumulation to a certain extent, will lead to pipe
Road blocking, at this moment starts No.1 pump 9, and the oxidation solution of the crystallization remover and overflow launder 2 of extraction No.1 receiver 7 utilizes crystallization
Remover meets oxidation solution and dilutes heat production, to dissolve the crystallization of ice maker 5, crystallization tank dreg-drawing pipe 42 and reactive tank dreg-drawing pipe 32, dredges
The ice maker and dreg-drawing pipe of pass blocking plug, resume production rapidly.
Using the method for the configuration recycling anodizing solution of the existing oxidation trough recycling anodizing solution of above-mentioned transformation, including with
Lower step:
(1) collect oxidation solution: the liquid of oxidation trough overflows into overflow launder, starting No.1 pump 9, by overflow launder 2 be collected into
It handles oxidation solution and imports ice maker 5；
(2) circulating cooling oxidation solution: starting ice maker 5 utilizes the motive force of No.1 pump 9, circulating cooling reactive tank 3, crystallization
Slot 4, overflow launder 2, oxidation trough 1 oxidation solution；
(3) it handles and separates oxidation solution: first starting No. three pumps 11 and continuous filter press 6, the oxidation solution in reactive tank 3 continues
It is extracted out from slot bottom, when temperature < 5 DEG C in reactive tank 3, restarts No. two pumps 10, reaction solution is driven to enter and be followed by No. two pumps 10
In endless tube 14, enter in reactive tank 3 later, reaction solution and oxidation solution occur chemical reaction and form solidliquid mixture, No. three pumps 11
Solidliquid mixture is pumped into continuous filter press 6, isolates recycling oxidation solution and crystallization；
(4) oxidation solution recycling and recrystallization: when temperature < 12 DEG C in crystallization tank, start No. four pumps 12, oxidation solution will be recycled
Be pumped into crystallization tank 4 be precipitated again crystallization form solidliquid mixture, start No. five pump 13, by crystallization tank 4 solidliquid mixture pump
Enter continuous filter press 6 and isolates crystallization and recycling oxidation solution.
Further, it influences to take out slag when Crystallization Plugging occur in ice maker, reactive tank dreg-drawing pipe 32 and crystallization tank dreg-drawing pipe 42
When, it carries out crystallization and removes step；Crystallize cleaning: crystallization remover is imported ice maker 5 by starting No.1 pump 9, reactive tank takes out slag
Pipe 32 and crystallization tank dreg-drawing pipe 42.The thoroughly crystallization of dredge blockage accumulation in time, resumes production rapidly.
Further, in step (3), the supernatant of 3 internal upper part of reactive tank is discharged by recycling oxidation solution discharge pipe 15
It is recrystallized in crystallization tank 4；In step (4), the supernatant of 4 internal upper part of crystallization tank is discharged into excessive by regenerating oxidation liquid discharge pipe 16
It is utilized in chute 2.It can reduce separation of solid and liquid total amount, system made to be more suitable for large-scale industrial production demand.
Further, reaction solution be one of ammonium sulfate, ammonium nitrate, ammonium chloride, potassium sulfate, potassium nitrate or potassium chloride or
It is a variety of；Crystallization is alum or aluminum aluminum sulfate；Regenerating oxidation liquid is the regenerating oxidation liquid of sulfur acid；Crystallization remover is dense sulphur
Acid.
Ammonium sulfate, ammonium nitrate, ammonium chloride meet water power separate out ammonium root son and strong acid radical ion (sulfate radical, nitrate anion, chlorine from
Son), potassium sulfate, potassium nitrate, potassium chloride meet water power and separate out potassium ion and strong acid radical ion (sulfate radical, nitrate anion, chloride ion), when
Ammonium root or potassium ion generate chemical reaction after mixing with the aluminum sulfate in oxidation solution, form the alum or sulphur for being slightly soluble in water
Sour aluminium potassium is easy to be precipitated crystallization at low ambient temperatures, to isolate recycling product alum or aluminum aluminum sulfate, Yi Jihan
The regenerating oxidation liquid of sulfuric acid, so that aluminium ion and sulfuric acid have all obtained regeneration.The concentrated sulfuric acid is mixed with oxidation solution, it is dense
Sulfuric acid has heating effect in dilution, dissolves the crystallization of ice maker and pipeline accumulation, removes plug hidden danger.
Steps are as follows for specific method:
1. collecting oxidation solution: the liquid of oxidation trough 1 overflows into overflow launder 2, opens No.1 valve 01, starting No.1 pump 9, by overflow
The oxidation solution to be processed that slot 2 is collected into imports ice maker 5；
2. circulating cooling oxidation solution: opening No. two 04, ten No. five valve 015 and ten No. six valve of valve of valve 03, four of valve 02, three
016, start ice maker 5, using the motive force of No.1 pump 9, circulating cooling reactive tank 3, crystallization tank 4, overflow launder 2 and oxidation trough 1
Oxidation solution；
3. processing and separation oxidation solution: No. six valves 08 of valve 07, eight of valve 06, seven and No. nine valves 09 are opened, start No. three
11 and continuous filter press 6 are pumped, the oxidation solution in reactive tank 3 continues to extract out from slot bottom, when temperature < 5 DEG C in reactive tank 3, beats
No. five valves 05 and No. two check-valves 021 to be opened, No. two pumps 10 are started, reaction solution is driven by No. two pumps 10 to be entered in circulation pipe 14, it
Enter in reactive tank 3 afterwards, reaction solution and oxidation solution occur chemical reaction and form solidliquid mixture, and No. three pump 11 for solidliquid mixture
It is pumped into continuous filter press 6, isolates recycling oxidation solution and crystallization；
4. oxidation solution recycling and recrystallization: No. two valves 02 of adjustment control reactive tank 3,2 systemic circulation of crystallization tank 4 and overflow launder
Flow, keep 4 temperature < 12 DEG C of crystallization tank, close No. nine valves 09, open 011, ten No. two No. ten valves 010, ride on Bus No. 11 valve valve
012, ten No. three valve 013 and ten No. four valves 014 start No. four pumps 12, recycling oxidation solution are pumped into crystallization tank 4, crystallization is precipitated again
Solidliquid mixture is formed, starts No. five pumps 13, the solidliquid mixture in crystallization tank 4 is pumped into continuous filter press 6 and isolates crystallization
With recycling oxidation solution；
5. crystallizing cleaning: opening ten No. seven valves 017, six valve 06, seven valve 07, No. eight valve 08, ride on Bus No. 11 valves
011, ten No. two 018, ten No. nine valves 019 of the valve of valve 013,18 of valve 012,13 and No.1 check-valves 020, close No. two valves
02, ten No. four valves 016 of valve 015,16 of valve 014,15 and No. nine valves 09, starting No.1 pump 9, crystallization remover is imported
Ice maker 5, reactive tank dreg-drawing pipe 32 and crystallization tank dreg-drawing pipe 42.The thoroughly crystallization of dredge blockage accumulation in time, restores rapidly life
It produces.
The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain of the invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, the technology of this field
Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within
Within protection scope of the present invention.
Claims (10)
1. the configuration of existing oxidation trough recycling anodizing solution is transformed, which is characterized in that including oxidation solution collection system, oxidation solution
Circulating cooling system, oxidation liquid treating system, oxidation liquid separation system and oxidation solution recycling and recrystallization system；
The oxidation solution collection system includes oxidation trough, overflow launder, No.1 pump and pipeline, and the overflow launder is described around being set to
One week of oxidation trough, the overflow launder and the No.1 pump are connected, and the No.1 is pumped for by the oxidation solution in the overflow launder
It is pumped into the oxidation solution circulating cooling system；
The oxidation solution circulating cooling system is for cooling the oxidation solution being pumped into；
The oxidation liquid treating system includes that No. two receivers, No. two pumps, reactive tank and pipeline, the reactive tank are showed by oxidation line
There is oxidation trough to be transformed, the reactive tank is connected to No. two pumps, and No. two receivers are connected with No. two pumps,
No. two receivers are used for reaction cartridge liquid, and No. two pumps are for driving the reaction solution to enter the reactive tank；
The oxidation liquid separation system includes No. three pumps, continuous filter press and pipelines, inlets of No. three pumps and described anti-
Slot is answered to be connected, the liquid outlets of No. three pumps are connected with the continuous filter press, and described No. three pump for will be in the reactive tank
Solidliquid mixture be pumped into the continuous filter press；
The oxidation solution recycling and recrystallization system include No. four pumps, crystallization tank, No. five pumps and pipeline, and the crystallization tank is by aoxidizing
The existing oxidation trough of line is transformed, and No. four pumps, crystallization tank and No. five pumps are sequentially connected by the pipeline, No. four pumps
Inlet be connected with the continuous filter press by the pipeline, described No. five liquid outlets pumped pass through the pipeline with it is described
Continuous filter press is connected.
2. the configuration of the existing oxidation trough recycling anodizing solution of transformation according to claim 1, which is characterized in that the oxygen
Changing liquid circulating cooling system includes ice maker and pipeline, and the No.1 pump, ice maker and reactive tank are sequentially connected by the pipeline, institute
Ice maker is stated to be connected with the oxidation trough.
3. the configuration of the existing oxidation trough recycling anodizing solution of transformation according to claim 1 or 2, which is characterized in that also
Including crystallizing removing system, the crystallization removing system includes No.1 receiver and pipeline, and the No.1 receiver is for filling knot
Brilliant remover, the slot bottom of the reactive tank are provided with multiple reactive tank dreg-drawing pipes, and the slot bottom of the crystallization tank is provided with multiple knots
Brilliant slot dreg-drawing pipe, the No.1 receiver and overflow launder are connected with No.1 pump, and the reactive tank dreg-drawing pipe, crystallization tank are taken out
Slag pipe is connected with the ice maker respectively, and the No.1 pump is for being pumped into institute for the crystallization remover and oxidation solution drawn simultaneously
State ice maker, reactive tank dreg-drawing pipe, in crystallization tank dreg-drawing pipe.
4. the configuration of the existing oxidation trough recycling anodizing solution of transformation according to claim 1, which is characterized in that described anti-
Answer the slot bottom of slot that at least one reactive tank reaction kettle is installed, the reactive tank reaction kettle is in back taper, and the reactive tank takes out slag
One end of pipe is connected with the bottom of the reactive tank reaction kettle, the other end of the reactive tank dreg-drawing pipe and No. three pumps phase
Even；
The slot bottom of the crystallization tank is equipped at least one crystallization tank reaction kettle, and the crystallization tank reaction kettle is in back taper, described
One end of crystallization tank dreg-drawing pipe is connected with the bottom of the crystallization tank reaction kettle, the other end of the crystallization tank dreg-drawing pipe with it is described
No. five pumps are connected.
5. the configuration of the existing oxidation trough recycling anodizing solution of transformation according to claim 1, which is characterized in that described anti-
Slot is answered to be provided at least one recycling oxidation solution discharge pipe, the recycling oxidation solution discharge pipe is connected with the crystallization tank, institute
It states crystallization tank and is provided at least one regenerating oxidation liquid discharge pipe, the regenerating oxidation liquid discharge pipe is connected to the overflow launder.
6. the configuration of the existing oxidation trough recycling anodizing solution of transformation according to claim 1, which is characterized in that described anti-
Slot is answered to be connected with circulation pipe, the circulation pipe is connected to No. two pumps, and No. two receivers are connected with No. two pumps,
Oxidation solution of No. two pumps for recycling in the reactive tank.
7. the side of the configuration recycling anodizing solution using the existing oxidation trough recycling anodizing solution of transformation as claimed in claim 3
Method, which comprises the following steps:
(1) collect oxidation solution: the liquid of oxidation trough overflows into overflow launder, starting No.1 pump, the oxygen to be processed that overflow launder is collected into
Change liquid and imports ice maker；
(2) circulating cooling oxidation solution: starting ice maker, the motive force pumped using No.1, circulating cooling reactive tank, crystallization tank, overflow
The oxidation solution of slot, oxidation trough；
(3) it handles and separates oxidation solution: first starting No. three pumps and continuous filter press, the oxidation solution in reactive tank continues to take out from slot bottom
Out, when temperature < 5 DEG C in reactive tank, start No. two pumps, reaction solution is driven by No. two pumps to be entered in circulation pipe, is entered later
In reactive tank, reaction solution and oxidation solution occur chemical reaction and form solidliquid mixture, and solidliquid mixture is pumped into continuously by No. three pumps
Filter press isolates recycling oxidation solution and crystallization；
(4) oxidation solution recycling and recrystallization: when temperature < 12 DEG C in crystallization tank, starting No. four pumps, will recycle oxidation solution and be pumped into knot
Crystallization is precipitated again and forms solidliquid mixture for brilliant slot, starts No. five pumps, the solidliquid mixture in crystallization tank is pumped into continuous filter press
Machine isolates crystallization and recycling oxidation solution.
8. the method for recycling anodizing solution according to claim 7, which is characterized in that when the ice maker, reactive tank are taken out
When slag pipe and crystallization tank dreg-drawing pipe Crystallization Plugging occur and influence to take out slag, carries out crystallization and remove step；The crystallization cleaning:
Start No.1 pump, crystallization remover is imported into ice maker, reactive tank dreg-drawing pipe and crystallization tank dreg-drawing pipe.
9. the method for recycling anodizing solution according to claim 7, which is characterized in that in the step (3), reaction
The supernatant of slot internal upper part is discharged into crystallization tank by recycling oxidation solution discharge pipe and is recrystallized；In the step (4), crystallization tank
The supernatant of internal upper part is discharged into overflow launder by regenerating oxidation liquid discharge pipe and is recycled.
10. the method for recycling anodizing solution according to claim 7 or 8, which is characterized in that the reaction solution is sulfuric acid
One of ammonium, ammonium nitrate, ammonium chloride, potassium sulfate, potassium nitrate or potassium chloride are a variety of；The crystallization is alum or sulfuric acid
Aluminium potassium；The regenerating oxidation liquid is the regenerating oxidation liquid of sulfur acid；The crystallization remover is the concentrated sulfuric acid.
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| CN115432875A (en) * | 2021-06-04 | 2022-12-06 | 祝来宏 | Novel process for recovering aluminum anodic oxidation waste acid |
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| CN106757256A (en) * | 2016-11-11 | 2017-05-31 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Oxidation trough aluminium ion and retrieval of sulfuric acid and use pulse power energy conserving system and technique instead |
| CN107858731A (en) * | 2017-12-04 | 2018-03-30 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of oxidized aluminum alloy liquid recovery and cooling device crystallization removing system and technique |
| CN108130576A (en) * | 2017-12-04 | 2018-06-08 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of oxidized aluminum alloy slot aluminium ion and retrieval of sulfuric acid system and technique |
| CN108149310A (en) * | 2017-12-04 | 2018-06-12 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of oxidized aluminum alloy liquid recycling and recrystallization cooling system and technique |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115432875A (en) * | 2021-06-04 | 2022-12-06 | 祝来宏 | Novel process for recovering aluminum anodic oxidation waste acid |
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