CN106757257B - Oxidation trough aluminium ion and retrieval of sulfuric acid and shortening oxidation pole span energy conserving system and technique - Google Patents

Abstract

The present invention disclose a kind of oxidation trough aluminium ion and retrieval of sulfuric acid and shortens oxidation pole span energy conserving system and technique, during for solving the problem of existing oxidized aluminum alloy at oxygenation level the high oxidation film meltage of oxidizing temperature it is big with aoxidize high energy consumption.Shorten oxidation pole span energy saver and include oxidation trough, refrigeration machine, titanium exchanger, No.1 pump, overflow launder and pipeline；Removable dynamic oxidation polar plate device is further included, including multiple driving motors, running fix device, swap cathode cooling tube, anode conducting seat and negative conductive device.Aluminium ion crystalline product recovery system, sulfuric acid oxidation liquid recovery system, gas agitating system and except defrosting system are further included using the oxidation pond slot aluminium ion and the energy saving total system of retrieval of sulfuric acid that shorten oxidation pole span energy saver.Include oxidation solution circulating cooling step, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycling step, gas agitating step and defrosting step using the oxidation trough aluminium ion and retrieval of sulfuric acid technique of above-mentioned energy saving total system.

Description

Oxidation trough aluminium ion and retrieval of sulfuric acid and shortening oxidation pole span energy conserving system and technique

Technical field

The present invention relates to aluminum alloy processing technology fields, and in particular to oxidation trough aluminium ion is aoxidized with retrieval of sulfuric acid and shortening Pole span energy conserving system and technique.

Background technology

Aluminium alloy forms the oxidation film characterized by porosity after anodized, in aluminium material surface, it is necessary to pass through Sealing pores to ensure the physical and chemical performances such as the corrosion resistance of aluminium alloy anode oxide product, weatherability and wearability, obtain Durable performance.

Building alumilite process liquid refers to the tank liquor used in aluminium alloy anode oxide.During fluting, anodizing solution H2SO4 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 section bar per ton was about 3.84Kg/T (400m2/T).With the accumulation of aluminium molten in tank liquor, Al3+ to H+ and The footprint of SO42- increases, and serious that H+ is hindered to be moved to cathode, the SO42- Ghandler motion that faces south, tank liquor electric conductivity declines.When aluminium from When sub- concentration reaches more than 20g/L, tank liquor resistance is too big, and according to constant voltage technique, current density is substantially reduced, and causes film layer Thickness is insufficient, transparency declines or even white spot or the non-uniform phenomenons such as striped or the trace of other shapes occurs；If it adopts With constant current technique, and voltage can be caused to increase, power consumption increase becomes after being also possible that film layer burn and closing when serious Phenomena such as black.

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 ranges, and the oxidation film corrosion resistance that is obtained at this time, wearability are best.But in view of medicament into Sheet and environmental protection pressure, aluminium ion concentration general control is in 15-20g/L sections in actual production.

In view of aluminium ion concentration variation and coating mass and oxidation energy consumption are just like this important relationship, aluminium processing enterprise one As using two methods control aluminium ion.

First, the method for slot, i.e., when aluminium ion concentration is more than 20g/L, outwell a part of tank liquor, it is dense to reduce aluminium ion Degree, supplement sulfuric acid continue to produce to 180g/L.Produce 100000 tons of anodic oxidation aluminium section bars 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 resource.

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 special materials of the due to being equipped with cation exchange in knockout drum in knockout drum Material, quickly and efficiently detaches sulfuric acid with aluminium ion, and aluminium ion is discharged except solution, sulfuric acid is sent back in oxidation trough and continues to make 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 is without needing to change tank liquor.Theoretically, which can make aluminium material oxidation Film thickness and stay in grade, and it is energy saving, also good oxidation film basis is provided to stablize section bar 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 careful user can discharge water outlet in Fig. 4 It measures, it is found that wherein sulfur acid 15-30g/L, aluminium ion 5-10g/L. have monthly discharged nearly 30 tons of sulfuric acid！Monthly so Water consumption power consumption, the effect of acquisition have 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 part oxidation tank liquor is answered.

Modern aluminum processing enterprise, there is that anodic oxidation waste liquid is in need of immediate treatment, and existing processing method is too simple.It is first, straight Run in and put wastewater treatment center into, not only increase processing cost, but also waste bauxite resource, also generate 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, obtained at this time Oxidation film corrosion resistance, wearability it is best, oxidation low energy consumption.At present, the aluminium ion concentration in anodizing tank, each enterprise are basic Control is between 15-20g/L, far beyond optium concentration section.Aluminium ion concentration is high, and resistance is big, high energy consumption, aoxidizes film quality Amount is poor, these are industry common recognitions.But the environmental protection pressure of processing oxidation spent acid is limited by, 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 are Al3+, H+ and SO42-, when not having added electric field, motion mode of these three ions in oxidation solution is Two kinds：Vibrations and drift.By taking Al3+ as an example, motion mode is：

(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 Section is referred to as shaken in domain；

(2), next equalization point is floated to from an equalization point, then proceedes to shake, drift motion is named in this migration；Drift Shifting is unordered, and vibrations are eternal；

After added electric field, each ion is in addition to drift and vibrations, and also along the directed movement in power line direction, concentration gradually forms Gradient is distributed：

(3), to anode movement after SO42- added electric fields, forming anode, nearby concentration is high, and cathode nearby divide by the low gradient of concentration Cloth；In anode, following electrochemical reaction is formed：

SO42--2e=2O+SO2 ↑ (losing electronics, discharge oxygen atom) (1)

2Al+3O=Al2O3 (aluminium oxide alloy, oxygenerating film) (2)

Al2O3+3H+=2Al3++3OH- (oxidation film dissolving) (3)

(4), to cathode motion after Al3+, H+ 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+ reaches cathode surface prior to Al3+, and due to current potential difference, and H+ preferentially obtains electricity Son, Al3+ can only be rested in oxidation solution and constantly be accumulated.By (1) (4) formula it is found that the conductive capability at the two poles of the earth is by anode What the concentration of the H+ at SO42- and cathode determined.With continuing for electrolysis, the ion near the two poles of the earth constantly consumes, and needs distal end SO42- and H+ be continuously replenished, oxidation is made to continue to carry out.At this moment, the complexity that SO42- and H+ is moved to the two poles of the earth determines slot The key problem of liquid conductive capability size, is directly determined by aluminium ion concentration.Assuming that in oxidation solution, it is parallel to a certain of the two poles of the earth Area is the section of A, and the number at aluminium ion vibrations center passed through is N, each aluminum ions concussion section is S, then this section On face aluminum ions total footprint for NS, SO42- and H+ by the section when, influenced smaller significant surface by aluminium ion interception Product is A-NS.It follows that aluminium ion concentration is higher, N is bigger, and effective area A-NS is smaller, SO42- and H+ by difficulty get over Greatly, tank liquor resistance is bigger.But according to (3) formula, aluminium ion concentration is reduced, reacts and is moved to the right, oxidation film dissolving is accelerated, therefore aluminium Ion concentration cannot be too low.Production practices prove that oxidation trough aluminium ion optium concentration is 3-8g/L, this section film layer is best, slot Liquid resistance is smaller, and low energy consumption, and low energy consumption and high film quality, it is necessary to assure aluminium ion concentration is less than 8g/L.It is for that purpose it is necessary to right The aluminium ion of oxidation trough carries out specially treated, not only reduces aluminium ion, but also recycling sulfur acid oxidation solution and byproduct containing aluminium, thoroughly solves The drawbacks of a part of oxidation solution being outwelled when certainly aluminium ion is more than 20g/L.

It is energy saving in order to aoxidize, 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 improves 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 the distance between anode, cathode plate during 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 absorbed by oxidation solution, and tank liquor is caused to heat up, and the optimum oxidation temperature of aluminium alloy is 18-22 DEG C, in order to ensure continuous life Production, 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 shortens pole plate spacing and improves oxidation solution conductivity, has the huge energy saving space.

Coolant generally enters from the bottom of oxidation trough, and upper surface both 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 during actual production, oxidation current generally takes 1.1-1.5A/dm2, and oxidization time generally takes 40-60 Minute.By (3) formula, while aluminium alloy anode oxide, generation 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 section bar per ton is about 3.84Kg/T (400m2/T).I.e. The aluminium surface of 400m2 loses 3.84Kg aluminium, and it is 3.56 microns to be converted into fine aluminium thickness.Oxidation film has double-layer structure, close to matrix Metal be one layer of densification and it is thin, thickness is 0.01-0.05 μm of pure AL2O3 films, this layer is barrier layer；Outer layer is porous oxygen Change film layer, be made of the AL2O3 with the crystallization water, dissolved is AL2O3 oxidation films rather than fine aluminium with the crystallization water, therefore by The oxide thickness numerical value of dissolving can also increase, at least at 3.56 microns or more.The type of cooling of oxidation trough is improved, oxidation solution is transformed Solvability, by reducing the meltage of oxidation film come energy saving, shorten oxidization time, improve 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 requirements 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 during actual motion, corresponding pipeline, valve and pump are also required to defrost, therefore must do local directed complete set, will remove defrosting system and set To defrost to entire cooling system rather than defrosting only for titanium exchanger.It is provided by Chinese patent 201410126857.8 Method, it is recyclable 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, reduce the meltage of oxidation film, further expand the energy saving space.

Invention content

It is an object of the invention to be directed to shortcoming of the prior art, a kind of oxidation trough aluminium ion is provided and is returned with sulfuric acid It receives and shortens the shortening oxidation pole span energy saver in the oxidation energy saving total system of pole span, the heat of aluminium surface, drop can be taken away rapidly The oxidizing temperature of suboxides interface reduces the meltage of oxidation film, reduces oxidation energy consumption, while program reasonable design, behaviour Make easy, precise control.

It is another object of the present invention to the oxidation trough aluminium ions proposed using above-mentioned shortening oxidation pole span energy saver Total system energy saving with retrieval of sulfuric acid and technique by extracting the aluminium in oxidation solution, recycle sulfuric acid, oxidation solution resistance are reduced, in oxygen Change in liquid and add corrosion inhibiter, reduce the meltage of oxidation film to realize that oxidation is energy saving.

For this purpose, the present invention uses following technical scheme：A kind of oxidation trough aluminium ion and retrieval of sulfuric acid and shortening oxygen Change the shortening oxidation pole span energy saver in the energy saving total system of pole span, including oxidation trough, refrigeration machine, titanium exchanger, No.1 pump, overflow Chute and pipeline, circular be set to the oxidation trough one week of the overflow launder, the refrigeration machine coordinate the titanium exchanger to rise To refrigeration, the tank liquor in the overflow launder is imported the titanium exchanger by the No.1 pump, by the titanium exchanger system Cold oxidation solution is directed back through pipeline again to the oxidation trough；

Removable dynamic oxidation polar plate device is further included, the removable dynamic oxidation polar plate device includes multiple driving motors, movement Positioning device, swap cathode cooling tube, anode conducting seat and negative conductive device；

The swap cathode cooling tube is provided with multiple liquid micropores, and the oxidation solution of the titanium exchanger refrigeration is through the shifting Dynamic cooled cathode pipe enters in the oxidation trough；

The negative conductive device is set on the oxidation trough front and rear sides, is provided for the swap cathode cooling tube negative Pole power supply；

The multiple driving motor is set to the running fix device on the oxidation trough；The anode conducting seat is set It is placed on the oxidation trough；The swap cathode cooling tube is set on the driving motor, and driving motor can drive described Swap cathode cooling tube is moved along the running fix device towards anode conducting seat.

Further description, the swap cathode cooling tube includes two supervisors and is in charge of with a plurality of, described to be in charge of arrangement Be set between two supervisors, and it is described be in charge of be respectively communicated in two supervisors, the liquid micropores are distributed in described point Guan Shang.

Further description, there are four the running fix device settings, is correspondingly arranged in described oxidation trough or so two On end and rear and front end；

Running fix device includes driving guide rail, electricity drives gear, stent, positions gear and positioning track；

The driving guide rail is set to above the oxidation trough, and the electricity drives gear and passed with the driving guide rail intermeshing Dynamic, electricity described in the output shaft of the driving motor drives gear connection, and the electricity is driven to drive gear rotation so as to fulfill driving motor Move left and right；

The positioning guide rail is set to the lower end of the oxidation trough leading flank or trailing flank, and the positioning gear is set to Transmission realization is intermeshed on the positioning guide rail with it to move left and right；

Described stent one end is connect with the driving motor, and the other end is connect with the positioning gear；

Swap cathode cooling tube driving motor connection corresponding on the front and rear sides, driving motor output shaft After rotating through conversion, the swap cathode cooling tube can be driven to be moved towards the anode conducting seat.

It illustrates further, conductive head, the conductive head triangular shape is additionally provided on the stent；

The swap cathode cooling tube is electrically connected with the conductive head, and the conductive head is inserted into the negative conductive device In, provide negative power supply for swap cathode cooling tube；

The swap cathode cooling tube is equipped with insulation silk screen towards anode conducting seat side.

It illustrates further, there are two the negative conductive device settings, and correspondence is set on the oxidation trough front and rear sides It puts, the negative conductive device accesses negative power supply；

The negative conductive device includes conductive column and cathode conducting seat；

The conductive column is set on the face of the oxidation trough front and rear sides；

Conductive column upper end both sides are symmetrically arranged with cathode conducting seat, and the cathode conducting seat is equipped with v-notch, notch Top is additionally provided with spring so that the v-notch flexiblely can spring back and be tensioned；

The v-notch of the conductive head and the cathode conducting seat mutually agrees with, and is provided for the swap cathode cooling tube Negative power supply.

Use the oxidation pond slot aluminium ion and retrieval of sulfuric acid of the shortening oxidation pole span energy saver described in above-mentioned any one The energy saving total system of pole span is aoxidized with shortening, further includes aluminium ion crystalline product recovery system, sulfuric acid oxidation liquid recovery system, gas mixing Mix system and except defrosting system；

The aluminium ion crystalline product recovery system includes retort, centrifuge and pipeline, the feed inlet of the retort It is connected by pipeline with No.1 pump, the discharge port of the retort is connected by pipeline with the centrifuge, the centrifugation Machine is provided with water inlet pipe and water outlet, and the centrifuge is used to separate and recover 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 retort；

The water inlet pipe including pumping the drain into the titanium exchanger through the No.1 except defrosting system, exchanges from the titanium The liquid of device outflow is transported in the oxidation trough.

Using the oxidation trough aluminium ion of above-mentioned energy saving total system and retrieval of sulfuric acid technique, walked including oxidation solution circulating cooling Suddenly, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycling 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：Oxidation solution is imported into retort, sulfuric acid is added in into retort Ammonium aluminum sulfate crystal is precipitated after ammonium, the material in retort then is imported centrifugation in centrifuge obtains the solid after separation of solid and liquid And liquid；

The sulfuric acid oxidation liquid recycling step includes：The oxidation solution after crystallization treatment is collected, oxidation solution is carried out at regeneration Oxidation trough recycling is delivered to after reason；

The gas agitating step includes：Ammonium sulfate is added in into the retort for fill oxidation solution, stirring makes its reaction abundant；

The defrosting step includes：It dissolves and cleans the crystalline material in exchanger, cleaning solution is imported in oxidation trough.

Further description, the regeneration treatment in the sulfuric acid oxidation liquid recycling step are organic to be added into oxidation solution Sustained release agent；The process of separation of solid and liquid carries out under the conditions of spray in the aluminium ion crystalline product recycling step.

Further description, the organic slow-release agent are organic acid or low mass molecule alcohol.

Further description, a concentration of 30-50g/L of addition of the organic slow-release agent.

Beneficial effects of the present invention：1st, the heat of aluminium surface can be taken away rapidly, reduced the oxidizing temperature at oxygenation level, subtracted The meltage of few oxidation film reduces oxidation energy consumption；

2nd, oxidate current is improved, shortens oxidization time, reduces the meltage of oxidation film, reduces oxidation energy consumption；

3rd, setting activity cathode, shortening oxidation pole span, reduction oxide capacitance, reduction cooling are consumed energy, and are reduced and are aoxidized energy consumption；

4th, organic acid is added in oxidation solution, utilizes it on the basis of crystallization aluminium ion, whole recycling oxidation solutions for the first time Corrosion inhibiting ability reduces the dissolving of oxidation film, realizes oxidation energy saving more than 20%.

Description of the drawings

The present invention is further described with reference to the accompanying drawings and examples.

Fig. 1 is the structure diagram of the oxidation solution circulating cooling system of one embodiment of the present of invention；

Fig. 2 is the structure diagram of one embodiment of the swap cathode cooling tube of the present invention；

Fig. 3 is the system structure diagram of one embodiment of the present of invention；

Fig. 4 is the structure diagram for the retrieval of sulfuric acid machine that prior art oxidation trough is equipped with；

Fig. 5 is the front view of the removable dynamic oxidation polar plate device of the present invention；

Fig. 6 is the left view of the removable dynamic oxidation polar plate device of the present invention.

Wherein：Oxidation trough 1, overflow launder 1-1, swap cathode cooling tube 11, liquid micropores 111, refrigeration machine 2, titanium exchanger 3, No.1 pump 4, retort 5, centrifuge 6, oxidation solution collecting pit 7, No. two pumps 8, No.1 valve 01, No. two valves 02, No. three valves 03, four Number valve 04, No. five valves 05, No. six valves 06, No. seven valves 07, No. eight valves 08, No. nine valves 09, No. ten valves 010, removable dynamic oxidation pole plate Device 9, driving motor 91, running fix device 92, anode conducting seat 93, negative conductive device 94, conductive column 941, cathode is led Electric seat 942, v-notch 943, spring 944 drive guide rail 921, and electricity drives gear 922, and stent 923 positions gear 924, and positioning is led Rail 925, conductive head 926, insulate silk screen 927.

Specific embodiment

Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.

As shown in Fig. 1, Fig. 5 and Fig. 6, a kind of oxidation trough aluminium ion and retrieval of sulfuric acid and the shortening oxidation energy saving total system of pole span In shortening oxidation pole span energy saver, including oxidation trough 1, refrigeration machine 2, titanium exchanger 3, No.1 pump 4, overflow launder 1-1 and pipe Road, circular be set to the oxidation trough 1 one week of the overflow launder 1-1, the refrigeration machine 2 coordinates the titanium exchanger 3 to play Refrigeration, the tank liquor in the overflow launder 1-1 is imported the titanium exchanger 3 by the No.1 pump 4, by the titanium exchanger The oxidation solution of 3 refrigeration is directed back through pipeline again to the oxidation trough 1；

Further include removable dynamic oxidation polar plate device 9, the removable dynamic oxidation polar plate device 9 include multiple driving motors 91, Running fix device 92, swap cathode cooling tube 11, anode conducting seat 93 and negative conductive device 94；

The swap cathode cooling tube 11 is provided with multiple liquid micropores 111, the oxidation solution warp that the titanium exchanger 3 freezes The swap cathode cooling tube 11 enters in the oxidation trough 1；

The negative conductive device 94 is set on 1 front and rear sides of oxidation trough, is the swap cathode cooling tube 11 Negative power supply is provided；

The multiple driving motor 91 is set to the running fix device 92 on the oxidation trough 1；The anode is led Electric seat 93 is set on the oxidation trough 1；The swap cathode cooling tube 11 is set on the driving motor 91, driving motor 91 can drive the swap cathode cooling tube 11 to be moved along the running fix device 92 towards anode conducting seat 93.

Cancel the cooling tube that tradition runs through 1 trench bottom of oxidation trough, be changed to swap cathode cooling tube 11；Preferably, it is mobile cloudy The area of pole cooling tube 11 is set for twice by aluminium area to be oxidized, is 316L stainless steels with material；

The oxidation solution cooled down through refrigeration machine 2, from 04 entrance of No. four valves swap cathode cooling tube 11, through swap cathode The liquid micropores 111 of cooling tube 11 directly blow to aluminum alloy surface, bring the heat of oxidation at interfacial oxide film into oxidation solution rapidly, The oxidation solution overflow of these heats is carried to overflow launder 1-1, then, through No.1 valve 01, No.1 pump 4, No. two valves 02 are handed over into titanium Parallel operation 3 freezes, then through No. four 04, valves, recycles into swap cathode cooling tube 11, complete oxidation solution cooling cycle；

Previous coolant was up blown from slot bottom, was changed to the swap cathode cooling tube 11 directly to oxidation film surface inward It blows, the heat of aluminium surface can be taken away rapidly, reduce the oxidizing temperature at interfacial oxide film, reduce the meltage of oxidation film. Under conditions of sulfuric acid concentration is constant, oxidized aluminum alloy surface temperature is higher, and oxidation film dissolving is more；Time is longer, and oxidation film is molten Xie Yue is more.

In addition, the negative conductive device 94 provides negative power supply, driving motor 91 for the swap cathode cooling tube 11 The swap cathode cooling tube 11 can be driven to be moved along the running fix device 92 towards anode conducting seat 93, the shifting Dynamic cooled cathode pipe 11 can move left and right, and when it is moved toward anode conducting seat 93, shorten oxidation pole plate distance, improve two Oxidate current between person, it is further energy saving so as to largely reduce the energy consumption of oxidation and refrigeration.

It illustrates further, is in charge of as shown in Fig. 2, the swap cathode cooling tube 11 includes two supervisors with a plurality of, institute State and be in charge of arrangement and be set between two supervisors, and it is described be in charge of be respectively communicated in two supervisors, the liquid micropores 111 It is distributed in described be in charge of.

Parallel distribution above and below two supervisors, is in charge of longitudinal arrangement and is set between two supervisors, accelerates cooling oxidation film all circles Oxidizing temperature at face can effectively reduce the meltage of oxidation film.

It illustrates further, as shown in Figure 5 and Figure 6, there are four the settings of running fix device 92, is correspondingly arranged in institute It states on 1 left and right ends of oxidation trough and rear and front end；

Running fix device 92 includes driving guide rail 921, electricity drives gear 922, stent 923, positions gear 924 and positioning rail Road；

The driving guide rail 921 is set to 1 top of oxidation trough, and the electricity drives gear 922 and the driving guide rail 921 Intermeshing transmission, electricity described in the output shaft of the driving motor 91 drive gear 922 and connect, and the electricity is driven to drive 922 turns of gear Dynamic moving left and right so as to fulfill driving motor 91；

The positioning guide rail 925 is set to the lower end of 1 leading flank of oxidation trough or trailing flank, the positioning gear 924 be set on the positioning guide rail 925 with its be intermeshed transmission realize move left and right；

Described 923 one end of stent is connect with the driving motor 91, and the other end is connect with the positioning gear 924；

The swap cathode cooling tube 11 driving motor 91 corresponding on the front and rear sides connects, and driving motor 91 is defeated Shaft rotate through conversion after, the swap cathode cooling tube 11 can be driven to be moved towards the anode conducting seat 93.

The driving motor 91 works, and the electricity is driven to drive gear 922 and is driven with the driving intermeshing of guide rail 921, practical At this moment upper driving motor 91 realizes is moved to the left or moves right.In addition, the power moved forward and backward is passed by stent 923 It leads on the positioning gear 924 and positioning guide rail 925, positions gear 924 and positioning guide rail 925 is intermeshed, at this point, positioning The movement of gear 924 and positioning guide rail 925 drives gear 922 with electricity and the driving realization of guide rail 921 is synchronous, stent 923, positioning gear 924 and positioning guide rail 925 enable to stablize the movement of the driving motor 91, in addition people need to only observe positioning gear 924 The position of relative positioning guide rail 925, just can be clear from driving motor 91 be approximately at where, be convenient for people to and time control System and positioning.

More further illustrate, as shown in figure 5, being additionally provided with conductive head 926 on the stent 923, the conductive head 926 is in Triangle；

The swap cathode cooling tube 11 is electrically connected with the conductive head 926, and the conductive head 926 is inserted into the cathode and leads In electric installation 94, negative power supply is provided for swap cathode cooling tube 11；

The swap cathode cooling tube 11 is equipped with insulation silk screen 927 towards 93 side of anode conducting seat；Insulate silk screen 927 Setting, be in order to prevent cathode and anode too close to causing short circuit, damage oxidation power supply.

It illustrates further, as shown in figure 5, there are two the negative conductive device 94 settings, before and after the oxidation trough 1 It is correspondingly arranged on both sides, the negative conductive device 94 accesses negative power supply；

The negative conductive device 94 includes conductive column 941 and cathode conducting seat 942；

The conductive column 941 is set on the 1 front and rear sides face of oxidation trough；

The 941 upper end both sides of conductive column are symmetrically arranged with cathode conducting seat 942, and the cathode conducting seat 942 is equipped with V-type Notch 943, notch top are additionally provided with spring 944 so that the v-notch 943 flexiblely can spring back and be tensioned；

The v-notch 943 of the conductive head 926 and the cathode conducting seat 942 mutually agrees with, and is that the swap cathode is cold But pipe 11 provides negative power supply.

The anode conducting seat 93 releases cation to the oxidation solution, increases cation in oxidation solution, it is anti-to provide quickening The condition answered, the swap cathode cooling tube 11 with it is described when the swap cathode cooling tube 11 moves closer to the anode conducting During seat 93, at this moment the conductive head 926 is stuck in the v-notch 943, and spring 944 therein can be tensioned the connection of the two, Prevent swap cathode cooling tube 11 or so in reaction process from waving, at this moment the negative power supply of the access of the conductive column 941 is through leading Dateline 926 is transmitted on swap cathode cooling tube 11, and swap cathode cooling tube 11 releases anion, at this moment swap cathode cooling tube 11 and anode conducting seat 93 lean on close, shorten oxidation pole span, between oxidate current be greatly improved, reduce Oxide capacitance reduces cooling energy consumption, and smaller energy is inputted than in the past can also realize efficient chemical reaction, accomplish to save The effect that can be lowered consumption.

As shown in figure 3, the oxidation pond slot aluminium ion using the shortening oxidation pole span energy saver described in above-mentioned any one With retrieval of sulfuric acid and the shortening oxidation energy saving total system of pole span, aluminium ion crystalline product recovery system is further included, sulfuric acid oxidation liquid returns Receipts system, gas agitating system and except defrosting system；

The aluminium ion crystalline product recovery system includes retort 5, centrifuge 6 and pipeline, the charging of the retort 5 Mouth is connected by pipeline with No.1 pump 4, and the discharge port of the retort 5 is connected by pipeline with the centrifuge 6, described Centrifuge 6 is provided with water inlet pipe and water outlet, and the centrifuge 6 is used to separate and recover crystalline solid；

The sulfuric acid oxidation liquid recovery system includes 7, No. two pumps 8 of oxidation solution collecting pit and pipeline, the oxidation solution are 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 No. two 8 connections of pump are 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 retort 5；

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 retort 5 by triple valve, in order to ensure hereafter Description is clear errorless, and it is No. two valves 02 now to enable the valve that No.1 pump 4 is communicated with titanium exchanger 3, and No.1 pump 4 is with overflow launder 1-1's Valve is No.1 valve 01, and No.1 pump 4 on the water inlet pipe of the valve of retort 5 for No. three 03 centrifuges 6 of valve with being provided with No. ten valves 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 retort 5 and centrifuge 6 is five Number valve 05, the valve between gas agitating system and retort 5 are No. eight valves 08.

Specifically：

(1), oxidation solution circulating cooling step：It is responsible for circulating cooling oxidation solution；Operating procedure is：Close No. three valves 03 and nine The valve of number valve 09, the valve for opening 01, No. two valve 02 of No.1 valve and No. four valves 04 and start No.1 pump 4 and refrigeration machine 2, make Oxidation trough 1 cools down；Oxidation solution through the cooling of refrigeration machine 2 enters swap cathode cooling tube 11 from No. four 04, valves, through movement The liquid micropores 111 of cooled cathode pipe 11 directly blow to aluminum alloy surface, bring the heat of oxidation at interfacial oxide film into oxygen rapidly Change liquid, carry the oxidation solution overflow of these heats to overflow, then, pump 4, No. two valves 02 through No.1 valve 01, No.1, handed over into titanium Parallel operation 3 freezes, then through No. four 04, valves, recycles into swap cathode cooling tube 11, complete oxidation solution cooling cycle.In this process In, the swap cathode cooling tube 11 can move left and right, i.e., when needing in reaction, drive the swap cathode cooling tube 11 It is moved to anode conductive seat 93, is being not required to react, drive the swap cathode cooling tube 11 far from the anode conducting seat 93.

(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 is：a、 The valve of No. three valves 03 is opened, the valve of No. two valves 02 and No. nine valves 09 is closed, after 30M3 oxidation solutions are evacuated to retort 5, opens No. two valves 02 are opened, close No. three valves 03；No. eight valves 08 of gas agitating system are opened, start to stir；By 2.5 times of aluminium ion concentration Weight adds ammonium sulfate, stirring while adding；Ammonium sulfate adds, and closes No. eight 08, valves after continuing stirring 30 minutes, it is small to stand 2 When；B, No. five valves 05 are opened, crystalline solid enters centrifuge 6.Centrifuge 6 is opened, carries out separation of solid and liquid；No. ten valves 010 are opened, Solid in centrifuge 6 is sprayed repeatedly, when the pH value of 6 water outlet recovered liquid of centrifuge is more than 4.5, closes No. ten valves 010, Stop spray and centrifuge 6, recycle alum byproduct；

(3), sulfuric acid oxidation liquid recycling step：It is responsible for collecting the oxidation solution after crystallization treatment, and be delivered to oxidation trough 1 and recycle It uses.Operating procedure is：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, fully reacts.Operating procedure is：It beats 08, the valve of gas agitating eight is opened, starts to stir；By 2.5 times of weight of aluminium ion concentration, ammonium sulfate is added, it is stirring while adding；Sulphur Sour ammonium adds, and closes No. eight 08, valves after continuing stirring 30 minutes, stands 2 hours；

(5), defrosting step：It is responsible for cleaning dissolving 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 1 liquid level of oxidation trough. Operating procedure is：Close refrigeration machine 2 and No.1 pump 4；No.1 01, No. three valve 03 of valve is closed, opens 09, No. two 02 and of valve of No. nine valves No. four valves 04, the alum that cooling titanium tube surface in dissolving No.1 pump 4 and titanium exchanger 3 is cleaned with tap water are crystallized, are improved Heat exchanger effectiveness, and cleaning solution is delivered to oxidation trough 1, (alum contains 12 crystallizations water, oxidation to 1 liquid level of supplement oxidation trough Liquid level dehydration is serious, cleaning cooling system just moisturizing).

The present invention relies on above system setting, the oxidation waste liquid of aluminum fabrication plant magnanimity is delivered to retort 5, 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 is precipitated, the recycling of oxidation solution, avoided sulfuric acid caused by outwelling oxidation solution and The huge waste of bauxite resource reduces the environmentally friendly cost for handling these waste liquids and waste residue.The present invention is dense by 1 liquid aluminium ion of oxidation trough Degree operation interval is turned down by 15-20g/L to best 3-8g/L, has not only optimized oxidized aluminum alloy membrane structure, but also reduces oxidation solution electricity More than 7.7% resistance, ton oxidation material economize on electricity 77 degree or more.

As shown in figure 3, using the oxidation trough aluminium ion of above-mentioned energy saving total system and retrieval of sulfuric acid technique, including oxidation solution Circulating cooling step, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycling step, gas agitating step and defrosting step；

The oxidation solution circulating cooling step includes：It will be in the anodizing tank 1 that handle aluminium alloy using titanium exchanger 3 Oxidation solution cools down；

The aluminium ion crystalline product recycling step includes：Oxidation solution is imported into retort 5, sulphur is added in into retort 5 Ammonium aluminum sulfate crystal is precipitated after sour ammonium, then imports the material in retort 5 in centrifuge 6 after centrifugation acquisition separation of solid and liquid Solid and liquid；

The sulfuric acid oxidation liquid recycling step includes：The oxidation solution after crystallization treatment is collected, oxidation solution is carried out at regeneration Oxidation trough 1 is delivered to after reason to recycle；

The gas agitating step includes：Ammonium sulfate is added in into the retort 5 for filling oxidation solution, stirring fills its reaction Point；

The defrosting step includes：It dissolves and cleans the crystalline material in exchanger, cleaning solution is imported in oxidation trough 1.

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 are organic to be added into oxidation solution Sustained release agent.

Using the corrosion inhibition of organic slow-release agent, under identical oxidizing condition, by reducing the meltage of oxidation film, increase 2 microns of oxide thickness or more, ton material economize on electricity 200 degree or more.On the basis of crystallization aluminium ion, whole recycling oxidation solutions, Organic acid is added in oxidation solution, using its corrosion inhibiting ability, reduces the dissolving of oxidation film, realizes that oxidation is energy saving.

Further description, the organic slow-release agent 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, a concentration of 30-50g/L of addition of the organic slow-release agent.

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.

First, the theoretical foundation of aluminium ion and retrieval of sulfuric acid in anodizing solution

During oxidized aluminum alloy, by (3) formula, partial oxide film is dissolved, and the aluminium of about 4Kg/T (400m2) dissolves 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) 212H2O ↓ (5)

Under conditions of 160-200g/L sulfuric acid, ammonium excess, alum NH4Al (SO4) 212H2O crystallizations are precipitated, residual It stays aluminum ions how much related with crystallization temperature and time.

2nd, quantitative analytical experiment result

Take 1 liter of anodizing solution, 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, 1g/L Al are often crystallized³⁺, 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：

1st, ammonium sulfate is added in oxidation solution, under room temperature, crystallizable precipitation alum in the short time；

2nd, with the increase of ammonium sulfate additive amount, aluminium ion gradually reduces, but the range of decrease narrows；

3rd, as crystallization time increases, aluminium ion further reduces；

4th, as crystallization temperature reduces, aluminium ion concentration reduces；

Even if the 5, ammonium ion is excessive, low temperature and long-time crystallize, aluminium ion can not be fully crystallized precipitation；

6th, with the increase of ammonium sulfate additive amount, sulfuric acid concentration increases；

7th, with the increase of ammonium sulfate additive amount, conductivity increases.

3rd, 1 aluminium ion of aluminium alloy anode oxide slot and retrieval of sulfuric acid Process configuration

According to the experimental result of reaction equation (5) and table 1, with reference to oxidation line quantity-produced reality, retrieval of sulfuric acid, byproduct The factors such as collection, packaging and idle place etc., 1 aluminium ion recovery process of aluminium alloy anode oxide slot and configuration are set by Fig. 3 Meter.

This recovery system is produced per year 100,000 tons of aluminium section bars, is generated oxidation waste liquid by the aluminium oxide profile design for producing 100000 tons per year 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 40M3 oxidation waste liquids retort 5,1 is configured in attached drawing 3 A 40M3 oxidation solutions collecting pit 7, a desk centrifuge 6 and mating pipeline, pump and valve.

The characteristics of being not easy long-distance pipeline in view of oxidation solution, this system should set individually oxidation liquid waste processing area Domain close to oxidation workshop, facilitates treated oxidation solution directly returning oxidation trough 1 with pipeline.

With oxidation the waste liquid retort 5, pump, valve and the pipeline that contacts, it is necessary to by acidproof design, it is contemplated that aoxidize waste liquid regardless of Solution does not block pipeline and valve, selects acid-proof pump, and from 1 stringing of oxidation trough and valve, oxidation waste liquid is evacuated to retort 5.

Gas agitating is only set in retort 5, allow for chemical reaction it is fairly simple, be uniformly mixed.According to Motor stirs, not only power consumption, but also dangerous, and repair is cumbersome.

Aluminium ion crystallization is precipitated, oxidation solution recycles, and has avoided the huge of sulfuric acid caused by outwelling oxidation solution and bauxite resource 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, during Al3+20.20g/L, conductivity 152.5s/m；During Al3+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；In view of electric current by when, 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.

Not fall slot, completely recycle oxidation solution under the premise of, corrosion inhibiter can be added in oxidation solution, reduces the molten of oxidation film Xie Liang, it is further energy saving.By (3) formula, while aluminium alloy anode oxide, generation 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 is 1.2 amperes/square decimeter, and the molten aluminum amount of section bar per ton is about 3.84Kg/T (400m2/T), the oxidation film of 12 μm or so of generation.That is the aluminium surface of 400m2 loses 3.84Kg aluminium, and being converted into fine aluminium thickness is 3.56 micron.Oxidation film has double-layer structure, close to parent metal be one layer of densification and it is thin, thickness is 0.01-0.05 μm pure AL2O3 films, this layer are barrier layer；Outer layer is porous oxidation film layer, is made of the AL2O3 with the crystallization water, dissolved is band The AL2O3 oxidation films rather than fine aluminium of the crystallization water, therefore oxide thickness numerical value can also increase, at least at 3.56 microns or more.It is molten The ratio between the oxidation film of solution and the oxidation film of generation are (3.56 μm/12 μm) 0.297, can also so understand, that is, collectively generate 15.56 μm of oxidation film, wherein, 3.56 μm are dissolved, and 12 μm remain, dissolving ratio 22.88%.In recycling oxygen completely Under the premise of changing liquid, corrosion inhibiter can be added in oxidation trough 1, such as tartaric acid, gluconic acid, lactic acid, oxalic acid, citric acid and Low mass molecule alcohol, such as sorbierite, ethylene glycol, using the corrosion inhibition of these organic principles, by the meltage for reducing oxidation film Carry out energy saving, shortening oxidization time and improve effect.When taking free sulfuric acid 206.19g/L, Al3+9.00g/L, conductivity 164.25s/m, 20 DEG C of temperature, anodizing time 40 minutes, current density are 1.2 amperes/square decimeter, and addition is different organic Object (concentration is 30g/L) carries out oxidation control experiment, 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, when taking free sulfuric acid 206.19g/L, Al3+9.00g/L, conductivity 164.25s/m, temperature 20 DEG C, anodizing time 40 minutes, current density is 1.2 amperes/square decimeter, studies 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 more than 40g/L, film thickness Increase it is limited, therefore appropriate organic acid concentration be 30-50g/L.

Organic matter is added for reducing the solution rate of oxidation film, identical oxidizing condition, can increase by 2 μm of oxidation film with On, it economizes on electricity 200 degree or more, reduces the meltage of oxidation film, be energy-efficient effective way.The present invention is dropped by crystallizing aluminium ion Low tank liquor resistance, ton material economize on electricity 70 degree or more, and pass through addition organic acid, reduce the meltage of oxidation film, economize on electricity 200 degree with On, it is contemplated that the energy consumption for cooling of reduction when reducing tank liquor resistance according to both effective energy conservation measures, realizes oxidation economize on electricity More than 20%.

Organic acid is added in oxidation solution, protects oxidation film, meltage is reduced, 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. 4 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, with respect to energy-saving benefit, may lose more than gain.Only Have the crystallization aluminium ion by the present invention, recycle the technological means of whole oxidation solutions, could cause addition organic acid in oxidation solution, Oxidation film dissolving is reduced, becomes practicable power-saving technology.

During actual production, oxidation current generally takes 1.1-1.5A/dm2, and 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 addition corrosion inhibiter effectively reduces oxygen Outside the solution rate for changing film, cooling recirculation system, the temperature for improving cooling efficiency, effectively reducing aluminium surface at interfacial oxide film are improved It spends and then improves current density, shortens oxidization time, a kind of effective oxidation power-economizing method of also can yet be regarded as.Fig. 1 is exactly by this structure Want 1 cooling system of oxidation trough is transformed.

In order to verify the energy-saving effect after improving the type of cooling, the flow of No.1 pump 4 is can adjust, carries 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.It closes No. three valves 03 and No. nine valves 09, open 01, No. two valve 02 of No.1 valve and No. four valves 04, No.1 pump 4 and refrigeration machine 2, the oxidation solution cooled down through refrigeration machine 2 enter swap cathode cooling tube 11, warp from No. four valves 04 The micropore of cooling tube directly blows to aluminum alloy surface, brings the heat of oxidation at interfacial oxide film into oxidation solution rapidly.Adjust No.1 The internal circulating load of pump 4, from (1 time/h) once every hour to 8 times per hour (8 times/h) measure oxide thickness variation, experimental result As shown in table 4：

Table 4 increases influence of the No.1 pump circulation amount to oxide thickness

Table 4 shows under conditions of other oxidizing conditions are constant, increases the internal circulating load of No.1 pump 4, and oxide thickness increases Add；During 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.

In order to verify improve No.1 pump 4 internal circulating loads after, improve oxidate current, shorten oxidization time energy-saving effect, The different oxidate current of adjustable selection, carries out oxidation experiment.No.1 is taken to pump 4 internal circulating loads 6 times/h, oxalic acid 40g/L, free sulphur Sour 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.It closes No. three valves 03 and No. nine valves 09, open one Number 01, No. two valve 02 of valve and No. nine valves 09, No.1 pump 4 and refrigeration machine 2, the oxidation solution cooled down through refrigeration machine 2, from No. four valves 04 into Enter swap cathode cooling tube 11, the micropore through cooling tube directly blows to aluminum alloy surface, rapidly by the oxidation at interfacial oxide film The torrid zone enters oxidation solution.

6 times/the h of internal circulating load of fixed No.1 pump 4, is aoxidized with different current densities, measures oxide thickness variation, Experimental result is as shown in table 5：

Table 5 improves influence of the oxidate current to oxide thickness

5 surface of table under conditions of other oxidizing conditions are constant, increases oxidate current, and oxide thickness increases；Oxygen During galvanic current density 1.0-2.6A/dm2, oxidation film is increased with current density by linear relationship；Current density 2.6-3.4A/dm2 When, oxidation film increase is slower, and the slightly upper powder phenomenon of aluminium surface, needs to increase the internal circulating load of No.1 pump 4.Current density is During 2.6A/dm2,27.32 μm of film thickness, if by this current density aoxidize 11.15 μm of film thickness, it is only necessary to 14 points 30 seconds, aoxidize at this time The meltage of film than aoxidize 35 minutes than much less, be a kind of effective energy saving way.

Embodiment

1 aluminium ion of aluminium alloy anode oxide slot and retrieval of sulfuric acid and oxidation solution inhibition and cooling system reducing energy consumption, be according to It generates largely useless oxidation solution every year according to aluminium processing enterprise, not only increases processing cost, but also the present situation of waste bauxite resource, design for the first time The useless oxidation solution of line 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 oxidation energy saving more than 7%.On the basis of oxidation solution obtains all recycling, the present invention Organic inhibitor is added in oxidation solution, reduces the dissolving of oxidation film, energy saving more than 20%.The present invention is changing coolant from slot bottom It up blows and is blown inward to oxidation film surface for swap cathode cooling tube 11, heat that aluminium surface can be taken away rapidly, reduces oxidation circle On the basis of oxidizing temperature at face, setting activity cathode shortens oxidation pole span, reduces oxide capacitance, reduces cooling energy consumption, subtracts Energy consumption is aoxidized less.

Present invention oxidation liquid waste processing is achieved with byproduct recycling, oxidation energy conservation object, system configuration and section's student movement Row is successful key.

Embodiment 1 (anodizing solution cooling)

It closes 03, No. nine valve 09 of No. three valves, open the No.1 valve 02, four of valve 01, two valve 04, No.1 pump 4 and refrigeration machine 2, the oxidation solution through the cooling of refrigeration machine 2 enters swap cathode cooling tube 11 from No. four valves 04, through the micro- of swap cathode cooling tube 11 Hole directly blows to aluminum alloy surface, brings the heat of oxidation at interfacial oxide film into oxidation solution rapidly；Carry the oxidation of these heats Hydrorrhea flow to overflow launder 1-1, then, pumps 4, No. two valves 02 through No.1 valve 01, No.1, freezes into titanium exchanger 3, then through No. four Valve 04 recycles into swap cathode cooling tube 11, completes oxidation solution cooling cycle.

Embodiment 2 (online recycling alum)

1st, No. three valves 03 are opened, 02, No. nine valve 09 of No. two valves are closed, by 30M³After oxidation solution is evacuated to retort 5, 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；

2nd, No. five 05, valves are opened, crystalline solid enters centrifuge 6.Centrifuge 6 is opened, carries out separation of solid and liquid；Open ten Number valve 010, sprays the solid in centrifuge 6 repeatedly, when the pH value of 6 water outlet recovered liquid of centrifuge is more than 4.5, closes ten Number valve 010 stops spray and centrifuge 6, 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 1, completes sulfuric acid Recycling；

Embodiment 4 (cooling system defrosting)

Close refrigeration machine 2 and No.1 pump 4；No.1 01, No. three valve 03 of valve is closed, opens No. nine valves 02, four of valve 09, two Valve 04, the alum that cooling titanium tube surface in dissolving No.1 pump 4 and titanium exchanger 3 is cleaned with tap water crystallize, improve heat and hand over Efficiency is changed, and cleaning solution is delivered to oxidation trough 1, supplements 1 liquid level of oxidation trough；

Embodiment 5 (oxidation solution transformation)

Oxalic acid 10g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 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 are 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 are 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 are 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 are 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 are 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 are 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 are 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 are 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 are 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 are 1.2 amperes/square point Rice, anodizing time 35 minutes.

Embodiment 16 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：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 is opened by embodiment 1, adjustment No.1 pumps 4 flows extremely Oxidation solution recycles 1 time per hour, measures oxide thickness；

Embodiment 17 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 2 times, measure oxide thickness；

Embodiment 18 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 3 times, measure oxide thickness；

Embodiment 19 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 4 times, measure oxide thickness；

Embodiment 20 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 5 times, measure oxide thickness；

Influence test of the 21 No.1 pump circulation amount of embodiment to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 6 times, measure oxide thickness；

Embodiment 22 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 7 times, measure oxide thickness；

Embodiment 23 (influence test of the No.1 pump circulation amount to oxidation film)

Oxidizing condition is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al³⁺10g/L, 20 DEG C of temperature, current density are 1.2 peaces Training/square decimeter, anodizing time 35 minutes.Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows to oxygen Change liquid to recycle per hour 8 times, measure oxide thickness.

Embodiment 24 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 1.0 amperes/square decimeter, measures oxide thickness；

Embodiment 25 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 1.3 amperes/square decimeter, measures oxide thickness；

Embodiment 26 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 1.6 amperes/square decimeter, measures oxide thickness；

Embodiment 27 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 1.9 amperes/square decimeter, measures oxide thickness；

Embodiment 28 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 2.2 amperes/square decimeter, measures oxide thickness；

Embodiment 29 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 2.5 amperes/square decimeter, measures oxide thickness；

Embodiment 30 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 2.8 amperes/square decimeter, measures oxide thickness；

Embodiment 31 (influence test of the current density to oxidation film)

Cooling recirculation system is opened by embodiment 1, adjustment No.1 pumps 4 flows and recycled per hour to oxidation solution 6 times.Aoxidize item Part is：Oxalic acid 40g/L, free sulfuric acid 180g/L, Al3+10g/L, 20 DEG C of temperature, anodizing time 35 minutes.Adjust electric current Density is 3.1 amperes/square decimeter, measures oxide thickness.

Embodiment 32 (movable swap cathode cooling tube system testing)

A, cooling system is opened, enters 11 He of swap cathode cooling tube through No. four valves 04 through the oxidation solution that refrigeration machine 2 cools down Oxidation trough 1, oxidizing slot 1 cool down；B, loop wheel machine is opened, aluminium alloy to be oxidized is hung in into oxidation trough 1, the copper for aoxidizing conducting beam is led Electrode block is placed on anode conducting seat 93；C, only by taking Fig. 5 as an example, the driving motor 91 on left and right ends is opened, electricity is driven to drive tooth Wheel 922 is moved along driving guide rail 921 towards 93 direction of anode conducting seat, close to anode, when the conductive head 926 is fully inserted into the moon Pole conductive seat 942 and when being clamped by the spring 944, closes driving motor 91, at this moment the swap cathode cooling tube 11 can To connect upper negative power supply.In practical operation, the startup of driving motor 91 synchronous can be carried out with stopping.Insulate silk screen 927 Setting is that the swap cathode cooling tube 11 is too close to anode in order to prevent, to prevent causing short circuit, damage oxidation power supply；d、 Open negative power supply, aluminium oxide alloy；E, negative power supply is disconnected, reversely opens the driving motor 91 of left and right ends on oxidation trough 1, The direction that the swap cathode cooling tube 11 of left and right ends carries anode is moved to 1 wall of oxidation trough, closes driving motor 91；F, it opens Well-oxygenated aluminium alloy is hung out oxidation trough 1 by loop wheel machine, completes aluminium alloy anode oxide processing.

Claims (9)

1. oxidation trough aluminium ion and the shortening oxidation pole span energy saver in retrieval of sulfuric acid and the shortening oxidation energy saving total system of pole span, It is characterized in that：Including oxidation trough, refrigeration machine, titanium exchanger, No.1 pump, overflow launder and pipeline, the overflow launder is around setting In one week of the oxidation trough, the refrigeration machine coordinated the titanium exchanger to play refrigeration, and the No.1 pump overflows described Tank liquor in chute imports the titanium exchanger, and the oxidation solution to freeze by the titanium exchanger is directed back again through pipeline to institute State oxidation trough；

Removable dynamic oxidation polar plate device is further included, the removable dynamic oxidation polar plate device includes multiple driving motors, running fix Device, swap cathode cooling tube, anode conducting seat and negative conductive device；

The swap cathode cooling tube is provided with multiple liquid micropores, and the oxidation solution of the titanium exchanger refrigeration is through described mobile cloudy Pole cooling tube enters in the oxidation trough；

The negative conductive device is set on the oxidation trough front and rear sides, and negative electricity is provided for the swap cathode cooling tube Source；

The multiple driving motor is set to the running fix device on the oxidation trough；The anode conducting seat is set to On the oxidation trough；The swap cathode cooling tube is set on the driving motor, and driving motor can drive the movement Cooled cathode pipe is moved along the running fix device towards anode conducting seat；

There are four the running fix device settings, is correspondingly arranged on the oxidation trough left and right ends and rear and front end；

Running fix device includes driving guide rail, electricity drives gear, stent, positions gear and positioning guide rail；

The driving guide rail is set to above the oxidation trough, and the electricity drives gear and is driven with the driving guide rail intermeshing, Electricity described in the output shaft of the driving motor drives gear connection, and the electricity is driven to drive a left side of the gear rotation so as to fulfill driving motor It moves right；

The positioning guide rail is set to the lower end of the oxidation trough leading flank or trailing flank, and the positioning gear is set to described Transmission realization is intermeshed on positioning guide rail with it to move left and right；

Described stent one end is connect with the driving motor, and the other end is connect with the positioning gear；

Swap cathode cooling tube driving motor connection corresponding on the front and rear sides, the rotation of driving motor output shaft After conversion, the swap cathode cooling tube can be driven to be moved towards the anode conducting seat.

2. according to claim 1 shorten oxidation pole span energy saver, it is characterised in that：The swap cathode cooling tube packet Include two supervisors and it is a plurality of be in charge of, it is described to be in charge of arrangement and be set between two supervisors, and it is described be in charge of be respectively communicated in two The supervisor, the liquid micropores are distributed in described be in charge of.

3. according to claim 1 shorten oxidation pole span energy saver, it is characterised in that：It is additionally provided with and leads on the stent Dateline, the conductive head triangular shape；

The swap cathode cooling tube is electrically connected with the conductive head, and the conductive head is inserted into the negative conductive device, is Swap cathode cooling tube provides negative power supply；

The swap cathode cooling tube is equipped with insulation silk screen towards anode conducting seat side.

4. according to claim 3 shorten oxidation pole span energy saver, it is characterised in that：The negative conductive device setting There are two, it is correspondingly arranged on the oxidation trough front and rear sides, the negative conductive device accesses negative power supply；

The negative conductive device includes conductive column and cathode conducting seat；

The conductive column is set on the face of the oxidation trough front and rear sides；

Conductive column upper end both sides are symmetrically arranged with cathode conducting seat, and the cathode conducting seat is equipped with v-notch, notch top It is additionally provided with spring so that the v-notch flexiblely can spring back and be tensioned；

The v-notch of the conductive head and the cathode conducting seat mutually agrees with, and cathode is provided for the swap cathode cooling tube Power supply.

5. use the oxidation pond slot aluminium ion and sulphur of the shortening oxidation pole span energy saver described in any one in claim 1-4 Acid recovery and the shortening oxidation energy saving total system of pole span, it is characterised in that：Further include aluminium ion crystalline product recovery system, sulfuric acid oxygen Change liquid recovery system, gas agitating system and except defrosting system；

The aluminium ion crystalline product recovery system includes retort, centrifuge and pipeline, and the feed inlet of the retort passes through Pipeline is connected with No.1 pump, and the discharge port of the retort is connected by pipeline with the centrifuge, and the centrifuge is set Water inlet pipe and water outlet are equipped with, the centrifuge is used to separate and recover 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 described 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 retort；

The water inlet pipe including pumping the drain into the titanium exchanger through the No.1 except defrosting system, from the titanium exchanger stream The liquid gone out is transported in the oxidation trough.

6. use the oxidation trough aluminium ion of the energy saving total system described in claim 5 and retrieval of sulfuric acid technique, it is characterised in that：Packet It includes oxidation solution circulating cooling step, aluminium ion crystalline product recycling step, sulfuric acid oxidation liquid recycling step, gas agitating step and removes White 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：Oxidation solution is imported into retort, after adding in ammonium sulfate into retort Ammonium aluminum sulfate crystal is precipitated, the material in retort then is imported centrifugation in centrifuge obtains solid and liquid after separation of solid and liquid Body；

The sulfuric acid oxidation liquid recycling step includes：The oxidation solution after crystallization treatment is collected, after carrying out regeneration treatment to oxidation solution It is delivered to oxidation trough recycling；

The gas agitating step includes：Ammonium sulfate is added in into the retort for fill oxidation solution, stirring makes its reaction abundant；

The defrosting step includes：It dissolves and cleans the crystalline material in exchanger, cleaning solution is imported in oxidation trough.

7. oxidation trough aluminium ion according to claim 6 and retrieval of sulfuric acid technique, it is characterised in that：The sulfuric acid oxidation liquid Regeneration treatment in recycling step is adds organic sustained release agent into oxidation solution；

The process of separation of solid and liquid carries out under the conditions of spray in the aluminium ion crystalline product recycling step.

8. oxidation trough aluminium ion according to claim 7 and retrieval of sulfuric acid technique, it is characterised in that：The organic slow-release agent For organic acid or low mass molecule alcohol.

9. oxidation trough aluminium ion according to claim 7 or 8 and retrieval of sulfuric acid technique, it is characterised in that：It is described organic slow Release a concentration of 30-50g/L of addition of agent.