CN106367790B - Oxidation trough aluminium ion and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving system - Google Patents
Oxidation trough aluminium ion and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving system Download PDFInfo
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- CN106367790B CN106367790B CN201611042044.6A CN201611042044A CN106367790B CN 106367790 B CN106367790 B CN 106367790B CN 201611042044 A CN201611042044 A CN 201611042044A CN 106367790 B CN106367790 B CN 106367790B
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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
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- 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
- C25D21/02—Heating or cooling
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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
- C25D21/10—Agitating of electrolytes; Moving of racks
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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
Oxidation trough aluminium ion and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving system, its oxidation solution inhibition and cooling and energy conserving device include oxidation trough, refrigeration machine, titanium exchanger, No.1 pump, overflow launder and pipeline, circular one week for being set to oxidation trough of the overflow launder, the refrigeration machine cooperation titanium exchanger plays refrigeration, tank liquor in overflow launder is imported titanium exchanger by No.1 pump, is directed back again through pipeline to oxidation trough by the oxidation solution that titanium exchanger freezes；The two sides of oxidation trough are respectively arranged with the cooled cathode pipe through entire oxidation trough, and cooled cathode pipe is provided with multiple liquid outlet microporess.The present invention proposes oxidation solution inhibition cooling and energy conserving system, the heat of aluminium surface can be taken away rapidly, reduce the oxidizing temperature at oxygenation level, reduce the meltage of oxidation film, reduce oxidation energy consumption, in addition the oxidation trough aluminium ion and retrieval of sulfuric acid technique and its total system using it are also proposed, aoxidizes energy conservation by reducing oxidation solution resistance, reducing the meltage of oxidation film to realize.
Description
Technical field
Aluminum alloy processing technology field of the present invention more particularly to oxidation trough aluminium ion and retrieval of sulfuric acid and oxidation solution
Inhibition and cooling and energy conserving system.
Background technique
Aluminium alloy forms the oxidation film characterized by porosity after anodized, in aluminium material surface, it is necessary to pass through
Sealing pores are obtained with physical and chemical performances such as the corrosion resistances, weatherability and wearability that guarantee aluminium alloy anode oxide product
Durable service performance.
Building alumilite process liquid refers to tank liquor used in aluminium alloy anode oxide.When fluting, anodizing solution H2SO4It is dense
Degree does not have aluminium ion between 160-200g/L in tank liquor, stronger to oxidation film solvability.Usual anodizing time is
40-60 minutes, the molten aluminum amount of profile per ton was about 3.84Kg/T (400m2/T).With the accumulation of aluminium molten in tank liquor, Al3+To H+With
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.Work as aluminium ion
When concentration reaches 20g/L or more, tank liquor resistance is too big, and according to constant voltage technique, current density is substantially reduced, and causes film layer thick
Degree is insufficient, transparency decline, or even white spot or the non-uniform phenomenons such as striped or the trace of other shapes occurs；According to
Constant current technique, and voltage can be caused to increase, power consumption increases, and blackening after film layer burn and closing is also possible that when serious
Phenomena such as.
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 two methods 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 bauxite resources.
Second is that using retrieval of sulfuric acid machine, as shown in Figure 4.Retrieval of sulfuric acid machine is aluminum ions stabilising arrangement, will using acid pump
The sulfuric acid of oxidation trough and the mixed liquor of aluminum sulfate are pumped into knockout drum since knockout drum is provided with the special material that cation exchanges
Material, quickly and efficiently separates sulfuric acid with aluminium ion, and aluminium ion is discharged except solution, sulfuric acid is sent back to and continues to make in oxidation trough
With, make except the aluminium ion constantly generated in production discharge solution, stablize the aluminium ion concentration in tank liquor in certain processing range,
And the sundries such as organic matter in tank liquor can be purified, longtime running no replacement is required tank liquor.Theoretically, which can make aluminium material oxidation
Film thickness and stay in grade, and energy conservation also provide good oxidation film basis to stablize profile coloring process.
But in actual operation, problem is many.In Fig. 4, certain model retrieval of sulfuric acid machine need to consume water about 1.5M3/H, consumption
Electricity about 3KW/H, i.e. monthly 1080 tons of water consumption, 2160 degree of power consumption.1080 tons of water that water outlet in Fig. 2 can be discharged in careful user
It measures, wherein sulfur acid 15-30g/L, aluminium ion 5-10g/L. have monthly discharged nearly 30 tons of sulfuric acid for discovery！Monthly so
The effect of water consumption power consumption, acquisition has few improvement than slot.
The using effect of the mirror such as above-mentioned bad luck of retrieval of sulfuric acid machine, most of aluminium processing enterprise gradually deactivates the device, extensive
The conventional method of a part oxidation tank liquor is answered.
Modern aluminum processing enterprise has anodic oxidation waste liquid in need of immediate treatment, and existing processing method is too simple.First is that straight
Run in and put wastewater treatment center into, not only increase processing cost, but also waste bauxite resource, also generates a large amount of industrial residue；Two
It 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 the lye of magnanimity,
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, increase 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 directed movement along power line direction, concentration is gradually formed
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, discharge oxygen atom) (1)
2Al+3O=Al2O3(aluminium oxide alloy, 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, and it is super thoroughly to solve aluminium ion
The drawbacks of outwelling a part of oxidation solution when crossing 20g/L.
In order to aoxidize energy conservation, other than reducing oxidation solution aluminium ion concentration, it is also necessary to oxidation trough configuration and oxidation solution sheet
Body carries out inhibition transformation, further increases energy-saving effect.
Existing oxidation trough is equipped with fixed negative pole plate and ice maker cooling system.The distance between two cathode plates according to groove width and
Fixed, general 1.6 meters or so, aluminium is fixed as 0.8 meter as anode, the distance between cathode plate when oxidation.Input oxidation trough
Energy, a part to aluminium do work, aoxidize aluminium, be converted to the chemical energy for preparing oxidation film；A part is produced because of tank liquor resistance
Heat energy is oxidized liquid absorption, tank liquor is caused to heat up, and the optimum oxidation temperature of aluminium alloy is 18-22 DEG C, in order to guarantee continuous life
It produces, it is necessary to freeze, additionally increase energy consumption.The energy consumption heating of tank liquor resistance, need to consume energy refrigeration cool-down, dual energy consumption.Reduce tank liquor electricity
Resistance, i.e. shortening pole plate spacing and raising oxidation solution conductivity, have the huge energy saving space.
Coolant liquid generally enters from the bottom of oxidation trough, and upper surface two sides are overflowed, and takes heat out of to ice maker, completes cooling and follow
Ring.By (2) formula, aluminium alloy is oxidized to exothermic reaction, when oxidation solution temperature is 20 DEG C, aluminium alloy and oxidation solution interface
Temperature is higher than 20 DEG C, related with oxidate current beyond being worth.Current density is higher, and the temperature of aluminium material surface is higher, works as surface
When temperature is more than 30 DEG C (although just 20 DEG C of tank liquor temperature), oxidation film is burned.The temperature of interface aluminium material surface, limits oxygen
Galvanic current density cannot be too high, and when actual production, oxidation current generally takes 1.1-1.5A/dm2, oxidization time generally takes 40-60
Minute.By (3) formula, aluminium alloy anode oxide, while generate oxidation film, partial oxide film is dissolved.Interface temperature is higher,
Oxidization time is longer, sulfuric acid concentration is higher, and dissolved oxidation film is more.It is counted by large-scale production, 18-22 DEG C, anodic oxygen
Change 40-60 minutes, current density is 1.2 amperes/square decimeter, and the molten aluminum amount of profile per ton is about 3.84Kg/T (400m2/T).I.e.
400m2Aluminium surface, lose 3.84Kg aluminium, be converted into fine aluminium with a thickness of 3.56 microns.Oxidation film has double-layer structure, close to matrix
Metal be one layer of densification and it is thin, with a thickness of 0.01-0.05 μm of pure AL2O3Film, this layer are barrier layer；Outer layer is porous oxygen
Change film layer, by the AL with the crystallization water2O3Composition, that dissolved is the AL with the crystallization water2O3Oxidation film, rather than fine aluminium, thus it is molten
The oxide thickness numerical value of solution also will increase, at least at 3.56 microns or more.The type of cooling for improving oxidation trough, is transformed oxidation solution
Solvability, by reduce oxidation film meltage come it is energy saving, shorten oxidization time, raising effect, be to have very much strategic prospect
Research topic.
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.It, can be chemically from oxidation solution by the method that Chinese patent 201410126857.8 provides
Individually crystallization aluminium ion, produces ammonium alum, and sulfuric acid all recycles.But the invention is set as only removing titanium exchanger except defrosting system
Frost, and when actual motion, corresponding pipeline, valve and pump are also required to defrost, therefore must do local directed complete set, will be arranged except defrosting system
To defrost to entire cooling system, rather than defrost only for titanium exchanger.It is provided by Chinese patent 201410126857.8
Method, can be recycled whole oxidation solutions, prevent down slot from this.Just because of not fall tank liquor, can trust and oxidation solution is audaciously transformed, increase
Add its corrosion inhibiting ability, reduces the meltage of oxidation film, further expand the energy saving space.
Summary of the invention
It is an object of the invention to propose oxidation solution inhibition and cooling and energy conserving device, the heat of aluminium surface can be taken away rapidly,
The oxidizing temperature at oxygenation level is reduced, the meltage of oxidation film is reduced, reduces oxidation energy consumption.
It is another object of the present invention to propose using the aluminium alloy of above-mentioned oxidation solution inhibition and cooling and energy conserving device sun
Pole oxidation trough aluminium ion and retrieval of sulfuric acid technique and its total system recycle sulfuric acid, reduce oxidation by extracting the aluminium in oxidation solution
Liquid resistance, adds corrosion inhibiter in oxidation solution, reduces the meltage of oxidation film to realize oxidation energy conservation.
To achieve this purpose, the present invention adopts the following technical scheme:
Oxidation solution inhibition and cooling and energy conserving device, including oxidation trough, refrigeration machine, titanium exchanger, No.1 pump, overflow launder and pipe
Road, circular one week for being set to the oxidation trough of the overflow launder, the refrigeration machine cooperate the titanium exchanger to play refrigeration work
With the tank liquor in the overflow launder is imported the titanium exchanger by the No.1 pump, the oxidation freezed by the titanium exchanger
Liquid is directed back again to the oxidation trough through pipeline；
The two sides of the oxidation trough are respectively arranged with the cooled cathode pipe through the entire oxidation trough, the cooled cathode
Pipe is provided with multiple liquid outlet microporess, and the oxidation solution of the titanium exchanger refrigeration enters the oxidation trough through the cooled cathode pipe
It is interior.
Further description, the cooled cathode pipe include two supervisor and it is a plurality of is in charge of, it is described be in charge of be arranged
Between two supervisors, and it is described be in charge of be respectively communicated in two supervisors, the liquid outlet micropores is distributed in described be in charge of.
Further description, the No.1 pump is variable frequency pump.
It is slow using the oxidation trough aluminium ion of above-mentioned oxidation solution inhibition and cooling and energy conserving device and retrieval of sulfuric acid and oxidation solution
The total system of erosion and cooling and energy conserving, further includes aluminium ion crystalline product recovery system, sulfuric acid oxidation liquid recovery system, gas agitating system
Unite and remove defrosting system；
The aluminium ion crystalline product recovery system includes reactor tank, centrifuge and pipeline, the feed inlet of the reactor tank
It is connected to by pipeline with No.1 pump, the discharge port of the reactor tank is connected to by pipeline with the centrifuge, the centrifugation
Machine is provided with water inlet pipe and water outlet, and the centrifuge is for separating and recovering crystalline solid；
The sulfuric acid oxidation liquid recovery system includes oxidation solution collecting pit, No. two pumps and pipeline, the oxidation solution collecting pit
Feed inlet be connected by pipeline with the centrifuge, the discharge port of the oxidation solution collecting pit passes through pipeline and described No. two
Pump connection, it is described No. two pump for by the oxidation solution of the oxidation solution collecting pit back to the oxidation trough；
The gas agitating system connectivity is in the reactor tank；
The defrosting system that removes includes the water inlet pipe that the drain into the titanium exchanger is pumped through the No.1, is exchanged from the titanium
The liquid of device outflow is transported in the oxidation trough.
It is slow using the oxidation trough aluminium ion of above-mentioned oxidation solution inhibition and cooling and energy conserving device and retrieval of sulfuric acid and oxidation solution
Erosion and cooling and energy conserving technique, including oxidation solution circulating cooling step, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycle
Step, gas agitating step and defrosting step；
The oxidation solution circulating cooling step includes: using titanium exchanger by the oxygen in the anodizing tank for handling aluminium alloy
Change liquid cooling；
The aluminium ion crystalline product recycling step includes: that oxidation solution is imported reactor tank, and sulfuric acid is added into reactor tank
Ammonium aluminum sulfate crystal is precipitated after ammonium, then the material in reactor tank is imported in centrifuge to the solid being centrifuged after being separated by solid-liquid separation
And liquid；
The sulfuric acid oxidation liquid recycling step includes: the oxidation solution collected after crystallization treatment, is carried out at regeneration to oxidation solution
Oxidation trough recycling is delivered to after reason；
The gas agitating step includes: that ammonium sulfate is added into the reactor tank for fill oxidation solution, and stirring keeps its reaction abundant；
The defrosting step includes: dissolution and cleans the crystalline material in exchanger, and cleaning solution is imported in oxidation trough.
Further description, the regeneration treatment in the sulfuric acid oxidation liquid recycling step be added into oxidation solution it is organic
Corrosion inhibiter.
Further description, the organic inhibitor are organic acid or low mass molecule alcohol.
Further description, the addition concentration of the organic inhibitor are 30-50g/L.
Further description, the process being separated by solid-liquid separation in the aluminium ion crystalline product recycling step is under the conditions of spray
It carries out.
Beneficial effects of the present invention: 1, can take away rapidly the heat of aluminium surface, reduce the oxidizing temperature at oxygenation level, subtract
The meltage of few oxidation film reduces oxidation energy consumption；
2, organic acid is added in oxidation solution, utilizes it on the basis of crystallizing aluminium ion, all recycling oxidation solutions for the first time
Corrosion inhibiting ability reduces the dissolution of oxidation film, realizes 20% or more oxidation energy conservation.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the oxidation solution circulating cooling system of one embodiment of the present of invention；
Fig. 2 is the structural schematic diagram of one embodiment of cooled cathode pipe of the invention；
Fig. 3 is the system structure diagram of one embodiment of the present of invention；
Fig. 4 is the structural schematic diagram for the retrieval of sulfuric acid machine that prior art oxidation trough is equipped with.
Wherein: oxidation trough 1, overflow launder 1-1, cooled cathode pipe 11, liquid outlet micropores 111, refrigeration machine 2, titanium exchanger 3, one
Number pump 4, reactor tank 5, centrifuge 6, oxidation solution collecting pit 7, two pumps 8,03, No. four valve of valve of valve 02, three of No.1 valve 01, two
04, No. five 09, No. ten valves 010 of valve of valve 08, nine of valve 07, eight of valve 06, seven of valve 05, six.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
As shown in Figure 1, oxidation solution inhibition and cooling and energy conserving device, including oxidation trough 1, refrigeration machine 2, titanium exchanger 3, No.1
Pump 4, overflow launder 1-1 and pipeline, circular one week for being set to the oxidation trough 1 the overflow launder 1-1, the refrigeration machine 2 cooperate
The titanium exchanger 3 plays refrigeration, and the tank liquor in the overflow launder 1-1 is imported the titanium exchanger by the No.1 pump 4
3, it is directed back again through pipeline to the oxidation trough 1 by the oxidation solution that the titanium exchanger 3 freezes；
The two sides of the oxidation trough 1 are respectively arranged with the cooled cathode pipe 11 through the entire oxidation trough 1, the cathode
Cooling tube 11 is provided with multiple liquid outlet microporess 111, and the oxidation solution that the titanium exchanger 3 freezes enters through the cooled cathode pipe 11
In the oxidation trough 1.
Cancel the cooling tube that tradition runs through 1 slot bottom of oxidation trough, is changed to cooled cathode pipe；1 two sides of oxidation trough, which are configured with, to be run through
Entire oxidation trough 1 cooled cathode pipe 11 with holes, it is preferred that the area of cooled cathode pipe 11 is set by twice of aluminium area to be oxidized
It sets, is 316L stainless steel with material.
Enter cooled cathode pipe 11 through the cooling oxidation solution of refrigeration machine 2, from No. four valves 04, goes out liquid through cooled cathode pipe 11
Micropore 111 directly blows to aluminum alloy surface, brings the heat of oxidation at interfacial oxide film into oxidation solution rapidly, carries these heats
Then oxidation solution overflow pumps 4, No. two valves 02 through No.1 valve 01, No.1, freezes into titanium exchanger 3, then pass through to overflow launder 1-1
No. four valves 04 recycle into cooled cathode pipe, complete oxidation solution cooling cycle.
It is blown inward for two sides cooled cathode pipe 11 towards oxidation film surface in addition, coolant liquid is up blown from slot bottom, it can be rapidly
The heat of aluminium surface is taken away, the oxidizing temperature at interfacial oxide film is reduced, reduces the meltage of oxidation film.It is constant in sulfuric acid concentration
Under conditions of, oxidized aluminum alloy surface temperature is higher, and oxidation film dissolution is more；Time is longer, and oxidation film dissolution is more.
Further description, as shown in Fig. 2, the cooled cathode pipe 11 includes that two supervisors are in charge of with a plurality of, it is described
Be in charge of and be arranged between two supervisors, and it is described be in charge of be respectively communicated in two supervisors, the liquid outlet micropores 111 is divided
It is distributed in described be in charge of.Two are responsible for parallelly distribute on up and down, are in charge of longitudinal arrangement and are set between two supervisors, and cooling oxidation is accelerated
The oxidizing temperature of each interface of film, can effectively reduce the meltage of oxidation film.
Further description, the No.1 pump 4 is variable frequency pump.
As shown in figure 3, using the oxidation trough aluminium ion and retrieval of sulfuric acid of above-mentioned oxidation solution inhibition and cooling and energy conserving device
And oxidation solution inhibition and cooling and energy conserving total system, further include aluminium ion crystalline product recovery system, sulfuric acid oxidation liquid recovery system,
Gas agitating system and remove defrosting system；
The aluminium ion crystalline product recovery system includes reactor tank 5, centrifuge 6 and pipeline, the charging of the reactor tank 5
Mouth is connected to by pipeline with No.1 pump 4, and the discharge port of the reactor tank 5 is connected to by pipeline with the centrifuge 6, described
Centrifuge 6 is provided with water inlet pipe and water outlet, and the centrifuge is for separating and recovering crystalline solid；
The sulfuric acid oxidation liquid recovery system includes oxidation solution collecting pit 7, two pumps 8 and pipeline, and the oxidation solution is collected
The feed inlet in pond 7 is connected by pipeline with the centrifuge 6, and the discharge port of the oxidation solution collecting pit 7 passes through pipeline and institute
8 connection of No. two pumps is stated, No. two pumps 8 are used for the oxidation solution of the oxidation solution collecting pit 7 back to the oxidation trough 1；
The gas agitating system connectivity is in the reactor tank；
The defrosting system that removes includes the water inlet pipe through the drain into the titanium exchanger 3 of No.1 pump 4, is handed over from the titanium
The liquid that parallel operation 3 flows out is transported in the oxidation trough 1.
No.1 pump 4 is connected to titanium exchanger 3, overflow launder 1-1 and reactor tank 5 by triple valve, in order to ensure hereafter
Describe clearly errorless, now enabling 4 valve that communicates with titanium exchanger 3 of No.1 pump is No. two valves 02, No.1 pump 4 and overflow launder 1-1's
Valve is No.1 valve 01, and No.1 pump 4 is No. three valves 03 with the valve of reactor tank 5, is provided with No. ten valves on the water inlet pipe of centrifuge
010, the valve between No. two pumps 8 and oxidation trough 1 is No. seven valves 07, and the valve between oxidation solution collecting pit 7 and No. two pumps 8 is six
Number valve 06, the valve between titanium exchanger 3 and oxidation trough 1 are No. four valves 04, and the valve between reactor tank 5 and centrifuge 6 is five
Number valve 05, the valve between gas agitating system and reactor tank 5 are No. eight valves 08.
It is specific:
(1), oxidation solution circulating cooling step: it is responsible for circulating cooling oxidation solution；Operating procedure are as follows: close No. three valves and No. nine
The valve of valve, the valve for opening 01, No. two valve 02 of No.1 valve and No. four valves 04 and starting No.1 pump 4 and refrigeration machine 2, make to aoxidize
Slot 1 cools down；Enter cooled cathode pipe 11 through the cooling oxidation solution of refrigeration machine 2, from No. four valves 04, through cooled cathode pipe 11
Liquid outlet micropores 111 directly blows to aluminum alloy surface, brings the heat of oxidation at interfacial oxide film into oxidation solution rapidly, carries these heat
The oxidation solution overflow of amount is to overflow, 1-1, then, pumps 4, No. two valves 02 through No.1 valve 01, No.1, freezes into titanium exchanger 3,
Again through No. four valves 04, recycles into cooled cathode pipe, complete oxidation solution cooling cycle.
(2), aluminium ion crystallization auxiliary Product recycling step: it is responsible for collecting storage oxidation waste liquid, in the condition of addition ammonium sulfate
Under, alum is precipitated in crystallization, and the separation of solid and liquid of alum byproduct is carried out under the conditions of spray.Operating procedure are as follows: a,
The valve for opening No. three valves 03 closes the valve of No. two valves 02 and No. nine valves 09, after 30M3 oxidation solution is evacuated to reactor tank, opens
No. two valves 02 close No. three valves 03；No. eight valves 08 for opening gas agitating system, start to stir；By 2.5 times of weights of aluminium ion concentration
Amount adds ammonium sulfate, stirring while adding；Ammonium sulfate adds, and closes No. eight valves 08 after continuing stirring 30 minutes, stands 2 hours；b,
No. five valves 05 are opened, crystalline solid enters centrifuge.Centrifuge 6 is opened, is separated by solid-liquid separation；No. ten valves 010 are opened, to centrifugation
Solid in machine 6 sprays repeatedly, when the pH value of 6 water outlet recovered liquid of centrifuge is greater than 4.5, closes No. ten valves 010, stops spray
Leaching and centrifuge 6 recycle alum byproduct；
(3), sulfuric acid oxidation liquid recycling step: being responsible for collecting the oxidation solution after crystallization treatment, and is delivered to oxidation trough circulation
It uses.Operating procedure are as follows: 06, No. seven valve 07 of No. six valves and No. two pumps 8 are opened, sends the oxidation solution of reclaiming back to oxidation trough 1,
Complete retrieval of sulfuric acid；
(4), gas agitating step: it is responsible for sulfuric acid oxidation liquid and ammonium sulfate mixed dissolution, sufficiently reacts.Operating procedure are as follows: beat
No. eight valves 08 of gas agitating are opened, start to stir；By 2.5 times of weight of aluminium ion concentration, ammonium sulfate is added, it is stirring while adding；Sulfuric acid
Ammonium adds, and closes No. eight valves 08 after continuing stirring 30 minutes, stands 2 hours；
(5), defrosting step: it is responsible for cleaning dissolution No.1 pump 4, the valve 04 of valve 02, four of No.1 valve 01, two, titanium exchanger 3
And the alum crystallization of pipeline, restore heat exchanger effectiveness, and cleaning solution is delivered to oxidation trough 1, supplement oxidation tank liquor position.Behaviour
Make step are as follows: close refrigeration machine 2 and No.1 pump 4；01, No. three valve 03 of No.1 valve is closed, 09, No. two valve 02 and four of No. nine valves is opened
Number valve 04 is crystallized with the alum that tap water cleans cooling titanium tube surface in dissolution No.1 pump 4 and titanium exchanger 3, improves heat
Exchange efficiency, and cleaning solution is delivered to oxidation trough 1, (alum contains 12 crystallizations water, oxidation solution to supplement 1 liquid level of oxidation trough
Position dehydration is serious, cleaning cooling system just moisturizing).
The present invention relies on the setting of above-mentioned total system, the oxidation waste liquid of aluminum fabrication plant magnanimity is delivered to reactor tank, by 2.5
Times aluminium ion concentration weight adds ammonium sulfate, and alum is precipitated in crystallization, realizes that sulfuric acid oxidation liquid recycles completely, and recycles a large amount of
Alum byproduct.Aluminum ions crystallization precipitation, the recycling of oxidation solution, have avoided sulfuric acid caused by outwelling oxidation solution
With the huge waste of bauxite resource, reduce the environmentally friendly cost for handling these waste liquids and waste residue.The present invention will aoxidize tank liquor aluminium ion
Concentration operation interval is turned down by 15-20g/L to optimal 3-8g/L, has not only optimized oxidized aluminum alloy membrane structure, but also reduce oxidation solution
7.7% or more resistance, ton aoxidize material and economize on electricity 77 degree or more.
It is slow using the oxidation trough aluminium ion of above-mentioned oxidation solution inhibition and cooling and energy conserving device and retrieval of sulfuric acid and oxidation solution
Erosion and cooling and energy conserving technique, including oxidation solution circulating cooling step, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycle
Step, gas agitating step and defrosting step；
The oxidation solution circulating cooling step includes: will be in the anodizing tank that handle aluminium alloy using titanium exchanger 3
Oxidation solution cooling；
The aluminium ion crystalline product recycling step includes: that oxidation solution is imported reactor tank 5, and sulphur is added into reactor tank 5
Ammonium aluminum sulfate crystal is precipitated after sour ammonium, then will be centrifuged in the material importing centrifuge 6 in reactor tank 5 after being separated by solid-liquid separation
Solid and liquid；
The sulfuric acid oxidation liquid recycling step includes: the oxidation solution collected after crystallization treatment, is carried out at regeneration to oxidation solution
The recycling of oxidation trough 1 is delivered to after reason；
The gas agitating step includes: that ammonium sulfate is added into the reactor tank for fill oxidation solution, and stirring keeps its reaction abundant；
The defrosting step includes: dissolution and cleans the crystalline material in exchanger, and cleaning solution is imported in oxidation trough.
Solid after separation of solid and liquid is ammonium aluminum sulfate crystal, and liquid is the oxidant of sulfur acid.
Further description, the regeneration treatment in the sulfuric acid oxidation liquid recycling step be added into oxidation solution it is organic
Corrosion inhibiter.
Using the corrosion inhibition of organic inhibitor, under identical oxidizing condition, by reducing the meltage of oxidation film, increase
2 microns of oxide thickness or more, ton material economizes on electricity 200 degree or more.On the basis of crystallizing aluminium ion, all recycling oxidation solutions,
Organic acid is added in oxidation solution, using its corrosion inhibiting ability, reduces the dissolution of oxidation film, realizes oxidation energy conservation.
Further description, the organic inhibitor are organic acid or low mass molecule alcohol.Organic acid can be tartaric acid, Portugal
Grape saccharic acid, lactic acid, oxalic acid or citric acid etc., low mass molecule alcohol can be sorbierite or ethylene glycol.
Further description, the addition concentration of the organic inhibitor are 30-50g/L.
Further description, the process being separated by solid-liquid separation in the aluminium ion crystalline product recycling step is under the conditions of spray
It carries out.
The aluminum ions recycling of the application is by following theoretical foundation, quantitative analysis, waste liquid crystallization processing and aluminium ion and sulphur
Acid recovery system configuration is realized.
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.Ammonium sulfate is added in this oxidation solution, then following reaction occurs:
Al2(SO4)3+(NH4)2SO4+12H2O=2NH4Al(SO4)2·12H2O↓(3)
Under the conditions of 160-200g/L sulfuric acid, ammonium are excessive, alum NH4Al(SO4)2·12H2O crystallization is precipitated, residual
It stays aluminum ions how much related with crystallization temperature and time.
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 in time
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, as crystallization temperature reduces, aluminium ion concentration is reduced；
Even if 5, ammonium ion is excessive, low temperature and long-time crystallize, aluminium ion can not be fully crystallized precipitation；
6, with the increase of ammonium sulfate additive amount, sulfuric acid concentration increases；
7, with the increase of ammonium sulfate additive amount, conductivity increases.
Three, aluminium alloy anode oxide slot aluminium ion and retrieval of sulfuric acid Process configuration
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
The factors such as collection, packaging, and idle place etc., aluminium alloy anode oxide slot aluminium ion recovery process and configuration are set by Fig. 3
Meter.
This recovery system produces 100000 tons of aluminum profiles per year by the aluminium oxide profile design for producing 100000 tons 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, 1 40M is configured in attached drawing 33Oxidation waste liquid reactor tank, 1
A 40M3Oxidation solution collecting pit, a desk centrifuge and matched pipeline, pump and valve.
Individually oxidation liquid waste processing area should be arranged in the characteristics of being not easy long-distance pipeline in view of oxidation solution, this system
Domain facilitates treated oxidation solution directly returning oxidation trough with pipeline close to oxidation workshop.
With oxidation the waste liquid reactor tank, pump, valve and the pipeline that contacts, it is necessary to press acidproof design, it is contemplated that aoxidize waste liquid regardless of
Solution does not block pipeline and valve, selects acid-proof pump, and from oxidation trough stringing and valve, oxidation waste liquid is evacuated to reactor tank.
Gas agitating is only set in reactor tank, allow for chemical reaction it is fairly simple, be uniformly mixed.According to electricity
Machine stirring, not only power consumption, but also it is dangerous, it repairs more troublesome.
Aluminium ion crystallization is precipitated, oxidation solution is recycled, and has avoided the huge of sulfuric acid and bauxite resource caused by outwelling oxidation solution
Big waste, reduces the environmentally friendly cost for handling these waste liquids and waste residue.By table 1, aluminum ions reduction, it is meant that tank liquor resistance
It reduces.In table 1, Al3+When 20.20g/L, conductivity 152.5s/m；Al3+When 9.00g/L, conductivity 164.25s/m.Conductivity
Increase by 7.7%, i.e. oxidation solution resistance reduces by 7.7%.Aluminium processing enterprise aoxidizes one ton of aluminium, consumes about 1000 degree of electricity, reduces
7.7% resistance, it is meant that less with 77 degree of electricity；When passing through in view of electric current, tank liquor resistance makes tank liquor heat up, and also ice maker is needed to cool down
Energy consumption, crystallization aluminium ion reduce tank liquor resistance, reduce cooling energy consumption, and energy-saving index can further improve.
Corrosion inhibiter can be added in oxidation solution, reduces the molten of oxidation film not falling slot under the premise of recycling oxidation solution completely
Xie Liang, further energy conservation.By (3) formula, aluminium alloy anode oxide, while generate oxidation film, partial oxide film is dissolved.Interface
Place's temperature is higher, oxidization time is longer, sulfuric acid concentration is higher, and dissolved oxidation film is more.It is counted by large-scale production, 18-
22 DEG C, anodic oxidation 40-60 minutes, current density was 1.2 amperes/square decimeter, and the molten aluminum amount of profile per ton is about 3.84Kg/T
(400m2/ T), generate 12 μm or so of oxidation film.That is 400m2Aluminium surface, lose 3.84Kg aluminium, be converted into fine aluminium with a thickness of
3.56 micron.Oxidation film has double-layer structure, close to parent metal be one layer of densification and it is thin, it is pure with a thickness of 0.01-0.05 μm
AL2O3Film, this layer are barrier layer；Outer layer is porous oxidation film layer, by the AL with the crystallization water2O3Composition, dissolved is band knot
The AL of brilliant water2O3Oxidation film, rather than fine aluminium, therefore oxide thickness numerical value also will increase, at least at 3.56 microns or more.Dissolution
Oxidation film and the ratio between the oxidation film of generation be (3.56 μm/12 μm) 0.297, can also so understand, that is, collectively generate 15.56
μm oxidation film, wherein 3.56 μm be dissolved, 12 μm remain, dissolving ratio 22.88%.In recycling oxidation solution completely
Under the premise of, corrosion inhibiter, such as tartaric acid, gluconic acid, lactic acid, oxalic acid, citric acid and low molecule can be added in oxidation trough
Alcohol, such as sorbierite, ethylene glycol, using the corrosion inhibition of these organic principles, by reduce the meltage of oxidation film come it is energy saving,
Shorten oxidization time and improves effect.Take free sulfuric acid 206.19g/L, Al3+When 9.00g/L, conductivity 164.25s/m, temperature
20 DEG C, anodizing time 40 minutes, current density was 1.2 amperes/square decimeter, and adding different organic matters, (concentration is
Oxidation control experiment 30g/L) is carried out, detects average film thickness, the results are shown in Table 2:
Table 2 adds influence of the different organic matters to anodic oxidation film thickness
Using oxalic acid as corrosion inhibiter, free sulfuric acid 206.19g/L is taken, when Al3+9.00g/L, conductivity 164.25s/m, temperature
20 DEG C, anodizing time 40 minutes, current density was 1.2 amperes/square decimeter, studied different concentration of oxalic acid to average oxidation
The influence of film thickness, the results are shown in Table 3:
Influence of the different concentration of oxalic acid of table 3 to oxide thickness
Table 3 shows addition organic inhibitor, can increase oxide thickness, wherein tartaric acid, lactic acid, oxalic acid and citric acid
It performs better than.Table 3 shows to increase with concentration of oxalic acid, and oxide thickness increases, when concentration of oxalic acid reaches 40g/L or more, film thickness
Increase it is limited, therefore appropriate organic acid concentration be 30-50g/L.
Add solution rate of the organic matter for reducing oxidation film, identical oxidizing condition, can increase by 2 μm of oxidation film with
On, 200 degree of economize on electricity or more reduces the meltage of oxidation film, is energy-efficient effective way.The present invention passes through crystallization aluminium ion, drop
Low tank liquor resistance, ton material economize on electricity 70 degree or more, and by addition organic acid, reduce the meltage of oxidation film, 200 degree of economize on electricity with
On, it is contemplated that the energy consumption for cooling of reduction due to reducing tank liquor resistance realizes oxidation economize on electricity according to both effective energy conservation measures
20% or more.
Organic acid is added in oxidation solution, protects oxidation film, is reduced meltage, is a traditional energy conservation measure, but so far
Fail popularity, basic reason is that the aluminium ion problem in oxidation solution could not be solved thoroughly.Using retrieval of sulfuric acid machine shown in Fig. 2
Method, organic matter may block permeable membrane in tank liquor, and retrieval of sulfuric acid machine is made to fail；Using partial oxidation liquid method is outwelled, can incite somebody to action
Deliberately be added to oxidation solution, expensive organic acid outwell together, cost is too big, and opposite energy-saving benefit may lose more than gain.Only
Have the technological means that whole oxidation solutions are recycled by crystallization aluminium ion of the invention, could to add in oxidation solution organic acid,
Oxidation film dissolution is reduced, practicable power-saving technology is become.
When actual production, oxidation current generally takes 1.1-1.5A/dm2, oxidization time generally takes 40-60 minutes.Interface
Temperature is higher, oxidization time is longer, sulfuric acid concentration is higher, and dissolved oxidation film is more.Except oxygen is effectively reduced in addition corrosion inhibiter
Outside the solution rate for changing film, cooling recirculation system, raising cooling efficiency, the temperature that aluminium surface at interfacial oxide film is effectively reduced are improved
Degree and then raising current density, shortening oxidization time, a kind of effective oxidation power-economizing method of also can yet be regarded as.Fig. 1 exactly presses this structure
Want that oxidation trough cooling system is transformed.
In order to verify the energy-saving effect after improving the type of cooling, it can adjust the flow of variable frequency pump 1, carry out oxidation experiment.It takes
Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 ampere/square decimeter (A/dm2),
Anodizing time 35 minutes.Close valve 3,9, Open valve 1,2,4, variable frequency pump 1 and refrigeration machine, the oxygen through cryocooled
Change liquid, enter cooled cathode pipe from No. four valves 04, the micropore through cooling tube directly blows to aluminum alloy surface, rapidly by oxidation film circle
The heat of oxidation at face brings oxidation solution into.The internal circulating load for adjusting variable frequency pump 1, from (1 time/h) once every hour to 8 times (8 per hour
Secondary/h), measurement oxide thickness changes, and experimental result is as shown in table 4:
Table 4 increases influence of 1 internal circulating load of variable frequency pump to oxide thickness
Table 4 shows under conditions of other oxidizing conditions are constant, increases the internal circulating load of variable frequency pump 1, and oxide thickness increases
Add；At internal circulating load 1-4 times, oxidation film increases very fast, and at 6-8 time, increase is slower.When internal circulating load is 6 times/h, 13.39 μm of film thickness,
Than 13.10 μm of 1 time/h, increase by 0.29 μm, economize on electricity (0.29 μm/13.10 μm) × 1000 degree=22.14 degree.
Embodiment
Aluminium alloy anode oxide slot aluminium ion and retrieval of sulfuric acid and oxidation solution inhibition and cooling system reducing energy consumption, are foundations
Aluminium processing enterprise generates largely useless oxidation solution every year, not only increases processing cost, but also the status of waste bauxite resource, for the first time online design
The useless oxidation solution of direct crystallization processing, recycles sulfuric acid, aluminium ion is completely converted into the alum of technical grade.It is aluminum ions to subtract
It is few, oxidation solution resistance is reduced, it can be achieved that 7% or more oxidation energy conservation.On the basis of oxidation solution obtains all recycling, the present invention
Organic inhibitor is added in oxidation solution, reduces the dissolution of oxidation film, 20% or more energy conservation.The present invention is changing coolant liquid from slot bottom
It up blows and cools down heat, the reduction oxidation circle that cathode tube blows inward towards oxidation film surface, can take away aluminium surface rapidly for two sides
On the basis of oxidizing temperature at face, the meltage for reducing oxidation film is realized, reduce oxidation energy consumption.
The present invention aoxidizes liquid waste processing and is achieved with byproduct recycling, oxidation energy conservation object, system configuration and section's student movement
Row is successful key.
Embodiment 1 (anodizing solution is cooling)
It closes 03, No. nine valve 09 of No. three valves, open the valve 02, four of No.1 valve 01, two valve 04, variable frequency pump and refrigeration machine,
Oxidation solution through cryocooled enters cooled cathode pipes from No. four valves 04, and the micropore through cooling tube directly blows to aluminium alloy table
Into oxidation solution is brought the heat of oxidation at interfacial oxide film rapidly in face；Carry the oxidation solution overflows of these heats to overflow launder, so
Afterwards, through No.1 valve 01, variable frequency pump, No. two valves 02, freeze into titanium exchanger, then through No. four valves 04, recycle into cooled cathode pipe,
Complete oxidation solution cooling cycle.
Embodiment 2 (online recycling alum)
1, No. three valves 03 are opened, 02, No. nine valve 09 of No. two valves are closed, by 30M3After oxidation solution is evacuated to reactor tank, two are opened
Number valve 02, closes No. three valves 03；No. eight valves 08 of gas agitating are opened, start to stir；By 2.5 times of weight of aluminium ion concentration, addition
Ammonium sulfate, it is stirring while adding；Ammonium sulfate adds, and closes No. eight valves 08 after continuing stirring 30 minutes, stands 2 hours；
2, No. five valves 05 are opened, crystalline solid enters centrifuge.Centrifuge is opened, is separated by solid-liquid separation；Open No. ten valves
010, the solid in centrifuge is sprayed repeatedly, when the pH value of centrifuge water outlet recovered liquid is greater than 4.5, closes No. ten valves
010, stop spray and centrifuge, recycles alum byproduct；
Embodiment 3 (online recycling oxidation solution)
06, No. seven valve 07 of No. six valves and No. two pumps 8 are opened, the oxidation solution of reclaiming is sent back to oxidation trough, completes sulfuric acid
Recycling；
Embodiment 4 (cooling system defrosting)
Close refrigeration machine and variable frequency pump；01, No. three valve 03 of No.1 valve is closed, the valve of valve 02, four of No. nine valves 09, two is opened
04, it is crystallized with the alum that tap water cleans cooling titanium tube surface in dissolution variable frequency pump and titanium exchanger, improves heat exchange effect
Rate, and cleaning solution is delivered to oxidation trough, supplement oxidation tank liquor position；
Embodiment 5 (oxidation solution transformation)
Oxalic acid 10g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 6 (oxidation solution transformation)
Oxalic acid 20g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 7 (oxidation solution transformation)
Oxalic acid 30g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 8 (oxidation solution transformation)
Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 9 (oxidation solution transformation)
Oxalic acid 50g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 10 (oxidation solution transformation)
Tartaric acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 11 (oxidation solution transformation)
Citric acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 12 (oxidation solution transformation)
Lactic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 13 (oxidation solution transformation)
Gluconic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square
Decimetre, anodizing time 35 minutes；
Embodiment 14 (oxidation solution transformation)
Sorbierite 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes；
Embodiment 15 (oxidation solution transformation)
Ethylene glycol 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 amperes/square point
Rice, anodizing time 35 minutes.
Embodiment 16 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density 1.2
Ampere/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment frequency conversion pump discharge to oxygen are opened by embodiment 1
Change liquid to recycle per hour 1 time, measures oxide thickness；
Embodiment 17 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment frequency conversion pump discharge to oxidation are opened by embodiment 1
Liquid recycles 2 times per hour, measures oxide thickness；
Embodiment 18 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment frequency conversion pump discharge to oxidation are opened by embodiment 1
Liquid recycles 3 times per hour, measures oxide thickness；
Embodiment 19 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment frequency conversion pump discharge to oxidation are opened by embodiment 1
Liquid recycles 4 times per hour, measures oxide thickness；
Embodiment 20 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment 1 flow of variable frequency pump to oxygen are opened by embodiment 1
Change liquid to recycle per hour 5 times, measures oxide thickness；
Embodiment 21 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment 1 flow of variable frequency pump to oxygen are opened by embodiment 1
Change liquid to recycle per hour 6 times, measures oxide thickness；
Embodiment 22 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment frequency conversion pump discharge to oxidation are opened by embodiment 1
Liquid recycles 7 times per hour, measures oxide thickness；
Embodiment 23 (influence test of the variable frequency pump internal circulating load to oxidation film)
Oxidizing condition are as follows: oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, current density is 1.2 peaces
Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system, adjustment frequency conversion pump discharge to oxidation are opened by embodiment 1
Liquid recycles 8 times per hour, measures oxide thickness.
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 (8)
1. oxidation solution inhibition and cooling and energy conserving device, it is characterised in that: pumped including oxidation trough, refrigeration machine, titanium exchanger, No.1,
Overflow launder and pipeline, circular one week for being set to the oxidation trough of the overflow launder, the refrigeration machine cooperate the titanium exchanger
Refrigeration is played, the tank liquor in the overflow launder is imported the titanium exchanger by the No.1 pump, by the titanium exchanger
The oxidation solution of refrigeration is directed back again to the oxidation trough through pipeline；
The two sides of the oxidation trough are respectively arranged with the cooled cathode pipe through the entire oxidation trough, and the cooled cathode pipe is set
Multiple liquid outlet microporess are equipped with, the oxidation solution of the titanium exchanger refrigeration enters in the oxidation trough through the cooled cathode pipe；
The cooled cathode pipe include two supervisor and it is a plurality of is in charge of, it is described be in charge of be arranged between two supervisors, and
It is described be in charge of be respectively communicated in two supervisors, the liquid outlet micropores is distributed in described be in charge of.
2. oxidation solution inhibition according to claim 1 and cooling and energy conserving device, it is characterised in that: the No.1 pump is frequency conversion
Pump.
3. using the oxidation trough aluminium ion and retrieval of sulfuric acid and oxygen of oxidation solution inhibition described in claim 1 and cooling and energy conserving device
Change liquid inhibition and cooling and energy conserving total system, it is characterised in that: further include aluminium ion crystalline product recovery system, sulfuric acid oxidation liquid time
Receipts system, gas agitating system and remove defrosting system；
The aluminium ion crystalline product recovery system includes reactor tank, centrifuge and pipeline, and the feed inlet of the reactor tank passes through
Pipeline is connected to No.1 pump, and the discharge port of the reactor tank is connected to by pipeline with the centrifuge, and the centrifuge is set
It is equipped with water inlet pipe and water outlet, the centrifuge is for separating and recovering crystalline solid；
The sulfuric acid oxidation liquid recovery system include oxidation solution collecting pit, No. two pump and pipeline, the oxidation solution collecting pit into
Material mouth is connected by pipeline with the centrifuge, and the discharge port of the oxidation solution collecting pit is connected by pipeline and No. two pumps
It is logical, No. two pumps for by the oxidation solution of the oxidation solution collecting pit back to the oxidation trough；
The gas agitating system connectivity is in the reactor tank；
The defrosting system that removes includes the water inlet pipe that the drain into the titanium exchanger is pumped through the No.1, from the titanium exchanger stream
Liquid out is transported in the oxidation trough.
4. using the oxidation trough aluminium ion and retrieval of sulfuric acid and oxygen of oxidation solution inhibition as claimed in claim 3 and cooling and energy conserving device
Change the oxidation trough aluminium ion and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving technique of liquid inhibition and cooling and energy conserving total system,
It is characterized in that: including oxidation solution circulating cooling step, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycling step, gas
Whipping step and defrosting step；
The oxidation solution circulating cooling step includes: using titanium exchanger by the oxidation solution in the anodizing tank for handling aluminium alloy
Cooling；
The aluminium ion crystalline product recycling step includes: that oxidation solution is imported reactor tank, after ammonium sulfate is added into reactor tank
Ammonium aluminum sulfate crystal is precipitated, then the material in reactor tank is imported in centrifuge to the solid and liquid being centrifuged after being separated by solid-liquid separation
Body；
The sulfuric acid oxidation liquid recycling step includes: the oxidation solution collected after crystallization treatment, after carrying out regeneration treatment to oxidation solution
It is delivered to oxidation trough recycling；
The gas agitating step includes: that ammonium sulfate is added into the reactor tank for fill oxidation solution, and stirring keeps its reaction abundant；
The defrosting step includes: dissolution and cleans the crystalline material in exchanger, and cleaning solution is imported in oxidation trough.
5. oxidation trough aluminium ion according to claim 4 and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving technique,
Be characterized in that: the regeneration treatment in the sulfuric acid oxidation liquid recycling step is that organic inhibitor is added into oxidation solution.
6. oxidation trough aluminium ion according to claim 5 and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving technique,
Be characterized in that: the organic inhibitor is organic acid or low mass molecule alcohol.
7. oxidation trough aluminium ion according to claim 5 or 6 and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving technique,
It is characterized by: the addition concentration of the organic inhibitor is 30-50g/L.
8. oxidation trough aluminium ion according to claim 4 and retrieval of sulfuric acid and oxidation solution inhibition and cooling and energy conserving technique,
Be characterized in that: the process being separated by solid-liquid separation in the aluminium ion crystalline product recycling step carries out under the conditions of spray.
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| CN108034980B (en) * | 2017-11-27 | 2019-04-26 | 福建奋安铝业有限公司 | Aluminium shape surface coating apparatus, with the device to the method for aluminium shape surface plated film |
| CN109112597B (en) * | 2018-07-27 | 2020-03-24 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Configuration and method for reforming oxidation line to recover oxidation liquid and protect mono-nickel salt coloring tank |
| CN112391670A (en) * | 2019-08-19 | 2021-02-23 | 永州市瑞祥锌材料有限公司 | Application of titanium heat exchanger in electrolytic zinc liquid circulating cooling system |
| CN112391655A (en) * | 2019-08-19 | 2021-02-23 | 永州市瑞祥锌材料有限公司 | Electrolyte cooling system |
| CN112144100B (en) * | 2020-09-24 | 2022-07-05 | 内蒙古新达科技股份有限公司 | Recovery method of electroplating solution in electroplating bath |
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| JPS51131430A (en) * | 1975-05-12 | 1976-11-15 | Sumitomo Electric Industries | Continuous anodic oxidation process |
| JPS57171695A (en) * | 1981-04-17 | 1982-10-22 | Nippon Kentetsu Co Ltd | Washing method of anode oxide film |
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| CN101186282B (en) * | 2007-11-23 | 2011-05-18 | 浙江苏泊尔股份有限公司 | Method for reclaiming waste sulfuric acid in hard anode oxidation process |
| ITPR20100047A1 (en) * | 2010-05-21 | 2011-11-22 | Massimiliano Gazzani | METHOD AND PLANT FOR ANODIZING AN ALUMINUM PROFILE OR ITS ALLOYS |
| CN201809467U (en) * | 2010-07-27 | 2011-04-27 | 郑松秋 | Tank solution cooling system used in aluminum fabrication |
| EP2489448B1 (en) * | 2011-02-16 | 2013-12-25 | Constellium Extrusions Deutschland GmbH | In-line surface treatment for obtaining aluminium extrusions coated with a corrosion-resistant layer |
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| KR101418407B1 (en) * | 2012-11-02 | 2014-07-11 | 삼일금속주식회사 | Apparatus for removing carbonate from zinc plating refrigeratory |
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| CN103911651B (en) * | 2014-03-28 | 2016-08-17 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Aluminium alloy anode oxide groove aluminium ion and the process units of retrieval of sulfuric acid technique |
| CN203947172U (en) * | 2014-06-10 | 2014-11-19 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of aluminium alloy anode oxide device |
| CN104726918A (en) * | 2015-03-09 | 2015-06-24 | 张小可 | Spray-type nonferrous metal surface treatment technique and device |
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