CN102021595A - Surface pre-treatment system combining four aluminum alloy working grooves into whole for full recovery of medicament and zero emission of wastewater - Google Patents
Surface pre-treatment system combining four aluminum alloy working grooves into whole for full recovery of medicament and zero emission of wastewater Download PDFInfo
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- CN102021595A CN102021595A CN 201010515738 CN201010515738A CN102021595A CN 102021595 A CN102021595 A CN 102021595A CN 201010515738 CN201010515738 CN 201010515738 CN 201010515738 A CN201010515738 A CN 201010515738A CN 102021595 A CN102021595 A CN 102021595A
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Abstract
The invention relates to a surface pre-treatment system combining four aluminum alloy working grooves into a whole for full recovery of medicament and zero emission of wastewater. The surface pre-heated system comprises a No.1 four-in-one sand surface groove, a No.2 matte tank, a No.3 water washing interception groove, a No.4 water washing interception groove, a No.5 water washing interception groove, a No.6 water washing material waiting groove, a No.7 oxidation groove and a No.8 water washing interception groove, as well as a matching slag pumping system, a medicament recovery system, a water circulation purification processing system and a reverse water replenishing neutralization system. As the four working grooves are combined into a whole, and the technical scheme is simultaneously equipped with the full recovery of the medicament and the zero emission of the wastewater, the pollution of fluorine and ammonium in the oxidation pre-treatment of an aluminum alloy anode can be effectively solved, the full recovery of the wastewater in the aluminum alloy surface pre-treatment can be realized, the pollution control of a company can be greatly reduced, and the production cost can be reduced.
Description
Technical field
The invention belongs to aluminum alloy surface treatment technology and green technology, be specifically related to floride-free the no ammonium of institute with medicament, groove position and dispose that four work nests are unified, pharmacy response reclaims entirely and Cleaning Wastewater zero release aluminum alloy surface preprocessing system.
Technical background
The aluminum alloy surface pre-treating technology mainly is divided into alkaline etching and acid etching two big classes.Existing aluminium section bar alkaline etching technology was continued to use more than 100 year, and alkaline etching has high, the drawbacks such as alkaline consumption is high, alkaline residue is many, the difficult control of technology, defective is many, production cost is high, environmental pollution is big of aluminium consumption.The alkaline etching groove position of standard arranges that as shown in Figure 1 1#, 4#, 7#, 11# and 14# groove are work nest, and each work nest is joined two washing baths, adds running water wash and treats hopper, and the oxidation pre-treatment needs 10 groove positions, and wherein 4# alkaline etching groove is a surface treatment groundwork groove.Each groove function is as follows:
The 1# degreasing tank
This groove is a work nest.The purpose of oil removing be remove natural oxide film, finger line and with the coherent dirt of grease, can uniform corrosion to ensure aluminium material surface, and the cleaning of protection alkaline etching groove.Oil removing is bad, and alkaline etching is just inhomogeneous, has piebald, surperficial unequal flaw after the heat-tinting.Electrochemical deoiling can adopt alkalescence, neutrality or acid deoiling agent.
The oil removing of general employing oxidation spent acid adds small cations or amphoterics sometimes, improves oil removal efficiency.
There is following deficiency in existing 1# degreasing tank:
1, to long aluminium of shelf-time, oil removing is bad, and natural oxide film can not take off totally, and alkaline etching is inhomogeneous, and various luster appears in aluminium material surface, and heat-tinting is inhomogeneous;
2, degreasing tank contains 150-200g/L sulfuric acid, brings the alkaline etching groove easily into, in and caustic soda;
In order to strengthen the oil removing ability, part producing producer adds the ammonium bifluoride about 20-30g/L in degreasing tank, thoroughly eliminate oil removing hidden danger, handles fluorine-containing and pressure ammonia nitrogen waste water but increased.
2# and the washing trough of 3# flowing water
2# and 3# are the flowing water washing trough, and tap water is gone into by the 3# concentrated flow, and the 2# concentrated flow goes out, differential concatenation.The purpose that the twice washing is set is to clean the acid solution that the 1# troughed belt goes out, protection alkaline etching groove.The highly basic of aluminium from the strong acid of 1# groove to 4#, the water consumption of middle washing bath are crucial, are generally about 3.0 tons of/ton materials.So the big water yield still has the part acid solution and brings the alkaline etching groove into.
4# alkaline etching groove
This groove is a work nest.The purpose of alkaline etching is a natural oxide film, and further oil removing increases aluminium brightness, or dusting, removes line, and following chemical reaction takes place for aluminium and alkaline etching liquid during alkaline etching:
Al
2O
3+ 2NaOH=2NaAlO
2+ H
2O (removing natural oxide film) (1)
Al+2NaOH+2H
2O=2NaAlO
2+ 3H
2↑ (leveling, dusting) (2)
NaAlO
2+ 2H
2O=Al (OH)
3↓+NaOH (reclaiming alkaline residue, regeneration alkali lye) (3)
2Al (OH)
3=Al
2O
3.3H
2O (cell wall fouling, blocking pipe) (4)
(2)+(3) formula, aluminium is in the nature the reaction of alkali groove
2Al+6H
2O＝2Al(OH)
3↓+3H
2↑ (5)
Be that aluminium is followed the water reaction, when reclaiming alkaline residue, renewable whole sodium hydroxide.Press reaction formula (2)-(5), adopted two kinds of alkaline etching schemes at present, the one, do not add the alkali recovery scheme of complexing agent, the 2nd, the line scheme is gone in the dusting that adds complexing agent.
The alkaline etching technology that Japan adopts, general not doping of alkaline etching groove utilizes Bayer process, carries out alkali and reclaims.The 4# groove is equipped with slag pumping system, when free alkali be controlled at 60g/L, when aluminium ion concentration reaches 30g/L, sodium metaaluminate resolves into aluminium hydroxide and sodium hydroxide, the aluminium hydroxide sediment is handled by slag pumping system, the clear liquid after the scarfing cinder is drawn back the 4# groove, realizes that alkali reclaims.
The alkaline etching technology that Italy adopts in the doping of alkaline etching groove, as sorbyl alcohol, Portugal's sodium etc., is utilized the secondary alcohol groups CHOH complexing aluminum ion in the polyol, and reaction formula is:
C
6H
14O
6+ 3NaAlO
2=Al
3C
6H
11O
9+ 3NaOH (sorbyl alcohol complexing aluminum ion) (6)
3NaC
6H
11O
7+ NaAlO
2+ 2H
2O=Al (C
6H
11O
7)
3+ 4NaOH (Portugal's sodium complexing aluminum ion) (7)
When the dissolving of aluminium and aluminum ions when taking balance out of, aluminium ion concentration can reach 80-120g/L, and tank liquor is stable, unclear groove.The technology of Japan, owing to adopted the alkali recovery, alkaline consumption is low, the good cleaning, neutralizing well is less relatively by the consumption of preceding groove buck.But take out slag, aluminium consumption height, do not remove line, can not do the sand plane materiel, the aluminium stenosis is easily tied the alkali dirt.Gondola technology need not be taken out slag; Because aluminum ion is higher, presses viscous elasticity, the speed of response of aluminium material surface can remove line, can do the sand plane materiel greater than the speed of response of mechanical line bottom of trench.But viscosity tank liquor too high, that take out of is many, alkaline consumption is high, bad washing, water consumption is high, neutralizing well consumption is bigger.
5# and the washing trough of 6# flowing water
The purpose that this twice flowing water washing trough is set is to clean alkali lye, the protection neutralizing well.Equally, tap water advances from the 6# groove, and the 5# groove goes out, differential concatenation.Aluminium needs massive laundering from highly basic to strong acid, general water consumes and is about 4.0 tons of/ton materials, and after the 4# groove added the alkaline etching agent, viscosity was bigger, and washing pressure is bigger, and it is unavoidable that part alkali lye is brought the 7# neutralizing well into, consumes the neutralizing well acid solution.
The 7# neutralizing well
This groove is a work nest.The purpose that the 7# neutralizing well is set is to remove to residue in grey shape dirt settling on the aluminium, molten going at alloying element or impurity such as the insoluble manganese of alkali groove, copper, iron, to obtain the metallic surface of light, simultaneously in and the residual alkali lye of aluminium material surface.If dust does not have Ex-all, will cause the gloss obfuscation of painted back.
The existing aluminium section bar plant a very long time is adopted single sulfuric acid neutralization, and the section bar that impurity is few can reach specification of quality with single sulfuric acid, both can utilize the oxidation spent acid, also can avoid crossed contamination, and cost is low.With the many enterprises of aluminium scrap, iron, copper, manganese severe overweight in the section bar have the thick grey black of one deck on the aluminium material surface after the alkaline etching for some, and at this moment only sulfuric acid is difficult to Ex-all.Many producers adopt the sulfuric acid of 150-200g/L, and the nitric acid of 30-50g/L mixes, thoroughly ash disposal.Another benefit of adding nitric acid is to utilize its passivation, and the protection aluminium does not produce spot corrosion and flakes corrosion during making its washing before oxidation wait to expect.But the use of nitric acid needs massive laundering, in case bring oxidation trough into; The waste water that contains nitrate radical has increased the pressure of handling ammonia nitrogen.
8# and 9# washing bath
The purpose that this twice washing bath is set is in cleaning and tank liquor, the protection oxidation trough.Equally, tap water advances from the 9# groove, and the 8# groove goes out, differential concatenation.Aluminium needs massive laundering from the neutralizing well to the oxidation trough, reduce the risk that nitric acid is brought oxidation trough into, and general water consumption is about 3.0 tons of/ton materials.
Hopper is treated in the 10# washing
Aluminium goes out the 9# groove, has finished surperficial pre-treatment.Need wait the oxidation trough dead slot, treat hopper so the 10# running water wash is set, and aluminium is immersed in the mobile clear water, wait for oxidation.This groove water consumption is about 2.0 tons of/ton materials.If the supply delay time is long, aluminium is easy to generate spot corrosion or flakes corrosion.
The 11# oxidation trough
This groove is a work nest.The function of this groove is the oxygenerating film.Along with the increase of amount of oxidation, the aluminum ion of oxidation trough constantly rises, and when aluminium ion concentration surpassed 20g/L, oxide film was loose, and some oxidation liquid are outwelled by part producer, and part producer adopts resins exchange.The former wastes a large amount of sulfuric acid, and the latter wastes a large amount of waters.In addition, the oxidizing temperature of this groove is controlled at 18-22 ℃, needs refrigeration, and resistance is big under the low temperature, and current consumption is big, and under the standard film, ton material current consumption is 1200 degree, and very big energy-saving and cost-reducing space is arranged.The oxidizing temperature of oxidation trough, specific conductivity, pole plate distance and aluminum ions method are handled and are needed improvement badly.
12# and the washing trough of 13# flowing water
The purpose that this twice washing bath is set is to clean the acid solution that oxidation trough is taken out of, tamper seal hole slot.Equally, tap water advances from the 13# groove, and the 12# groove goes out, and differential concatenation, water consumption are that water loss is not only big about 3.0 tons of/ton materials, and what discharge is acid-bearing wastewater, increases environmental protection treatment pressure.
14# sealing of hole groove
This groove is a work nest.The purpose that this groove is set is to seal the micropore of oxide film, guarantees its corrosion resistance nature.Also available electrophoresis chamber replaces the sealing of hole groove.Method for sealing is divided into high temperature, middle gentle normal-temperature hole sealing by working temperature.The high temperature sealing of hole is that aluminium is handled in 95-100 ℃ pure water, and sealing quality is better, but the energy consumption height, evaporated quantity of water is big, easy dust, and the easy foreign ion of tank liquor is poisoned, and needs often to change tank liquor; In warm sealing of hole generally adopt the additivated method of nickel acetate, handle down at 50-60 ℃, sealing of hole speed is fast, few dust is not split film, but nickeliferous, is unfavorable for environmental protection; Normal-temperature hole sealing adopts nickelous fluoride doping method, handles down at 25-35 ℃, and sealing of hole speed is very fast, few dust, and energy consumption is low, and is easy to use.But easily split film, and fluorine-containing and nickel is unfavorable for environmental protection.Now, be main methods with middle gentle normal-temperature hole sealing, consider not have the research and development of nickel sealing of hole from the angle of environmental protection.
15# and the washing trough of 16# flowing water
The purpose that this twice washing bath is set is to clean residual medicaments such as fluorine that the sealing of hole troughed belt goes out and nickel, is not corroded after the protection aluminium dispatches from the factory.Equally, tap water advances from the 16# groove, and the 15# groove goes out, and differential concatenation, water consumption are that water loss is big about 3.0 tons of/ton materials, and what discharge is fluorine-containing and waste water nickel, increases environmental protection treatment pressure.
Aluminium can be packed and dispatch from the factory after handling through 16 groove positions, finishes anodic oxidation treatment.
Existing most of aluminum fabrication plant adopts Italian technology, but slightly improves at 1# groove and 7# groove.The 1# degreasing tank generally is added with the ammonium bifluoride about 20-30g/L, and the 7# neutralizing well is added with the nitric acid about 30-50g/L, and purpose is that oil removing and ash disposal are more thorough.
Use through last 100 years, the drawback of alkaline etching technology is completely exposed already.Particularly emphasize to clean the today of carrying out production strictly in line with rules and regulations, there is following disadvantage in this cover technology:
1, suggestion of process design is unreasonable.1# and 7# are the strongly-acid tank liquor, and 4# is the strong basicity tank liquor, and aluminium needs from strong acid to highly basic, handles from highly basic to strong acid, although the centre respectively is provided with the twice washing bath, and also unavoidable channelling, the medicament of work nest consumes mutually;
2, complex process, the groove position is many.The oxidation trough front is 10 groove positions altogether, 3 work nests, and 7 washing baths, too numerous and diverse;
3, effect is low.Will be before the aluminium material oxidation through 10 grooves, wherein 3 work nests also will take the reaction times, and a general extension material is washed from the 1# degreasing tank to 10# and is treated that hopper needs 25-30 minute.Length consuming time has seriously restricted the production capacity of oxidation line;
4, work nest is many, and the chemical consumption amount is big.1#, 4#, 7# and 11# work nest, total reagent consumption amount is 130-150 kilogram/ton material, for processing contains the waste water of these chemical agents, the aluminum material factory will spend bigger cost;
5, washing bath is many, and water consumption is big.7 washing baths, total water consumption is 10.0-13.0 ton/ton material.Except that the water cost, cost need be additionally paid in the processing of these water and discharging;
6, the 1# groove is fluorine-containing, has hindered waste water recycling;
7,1# and 7# groove contain ammonia nitrogen, and the difficulty of wastewater treatment is made the matter worse.Fluoride waste can not reuse, and nitrogen-containing wastewater can not discharge again, and producer is absorbed in the quagmire that ammonia nitrogen is handled.
Acid etching technology is to grow up on the basis of alkaline etching technology, has used nearly 10 years.Existing acid etching groove position arranges that as Fig. 2 acid etching is to insert the acid etching groove to form between the degreasing tank of former alkaline etching technology and alkaline etching groove.4# acid etching groove is a work nest, and its function is as follows:
This groove is added with the ammonium bifluoride of 60-100g/L, utilizes the fluorion dusting, removes mechanical line, and reaction mechanism is:
3F
-+ Al
3+=AlF
3(molten aluminium, dusting, remove line) (8)
6F
-+ Al
3++ 3NH
+ 4=(NH
4)
3AlF
6(covering, assist to go line) (9)
Acid etching goes mechanical line mechanism different with alkaline etching.Acid etching is not to utilize viscous elasticity, aluminum ion to remove mechanical line in the concentration difference on mechanical line bottom of trench and ditch surface, but utilizes covering theory, presses reaction formula (9), and the complex ion electronegativity of fluoaluminate indissoluble, fluorine is stronger, and fluorochemical covers mechanical line fully.Press reaction formula (8), mechanical groove surface is dissolved, is close in the ditch with medicament to completely cut off, and speed of response is very slow, and both speed of response are poor, and decision goes line very fast.Acid etching than the dusting of alkaline etching, go line speed fast again, the aluminium consumption is 25% of an alkaline etching, and the sand grains uniform and smooth.
Although consumption that acid etching technology has aluminium is low, leveling is effective, the characteristics of sand face exquisiteness, environmental issue is more outstanding.The deleterious severe corrosive hydrogen fluoride gas of overflowing during acid etching pollutes production environment, harm workers ' health; The acid sludge amount is too many, tank liquor clarification constantly, press filtration, slagging-off; In addition, the aluminium material surface obfuscation although prolonged alkaline etching and bright dipping, but still has the acid etching ash behind the acid etching.Both increase operation, lost surface luster again, also increased environmental burden.Acid etching technology is more than the alkaline etching drawback, mainly comprises:
1, technology is more complicated, and the groove position is more.The oxidation trough front is 13 groove positions altogether, 4 work nests, and 9 washing baths, more numerous and diverse;
2, effect is low.Will be before the aluminium material oxidation through 13 grooves, wherein 4 work nests also will take the reaction times, and a general extension material is washed from the 1# oil removing to 13# and is treated that hopper needs 20-25 minute.Time is long, has seriously restricted the production capacity of oxidation line;
3, work nest is many, and the chemical consumption amount is big.1#, 4#, 7#, 10# and 13# are work nest, and total reagent consumption amount is 150-170 kilogram/ton material, and for processing contains the waste water of these chemical agents, the aluminum material factory will spend bigger cost;
4, washing bath is more, and water consumption is bigger.9 washing baths, total water consumption is 13.0-15.0 ton/ton material.Except that the water cost, the processing of these waste water and discharging all will additionally be paid cost;
5,1# groove content of fluoride ion is 10-15g/L, and 4# groove content of fluoride ion is 30-50g/L, the hydrogen fluoride gas harm workers ' health that discharges in the production, etching apparatus, atmosphere pollution.The fluorion that contains high density in the waste water needs special disposal, and waste water can not reuse;
6,1#, 4# and 10# groove contain ammonia nitrogen, and the difficulty of wastewater treatment is made the matter worse.Fluoride waste can not reuse, and nitrogen-containing wastewater can not discharge again, and producer could discharge after must handling ammonia nitrogen, additionally pays huge environmental protection cost.
The above-mentioned drawback of acid etching, alkaline etching, basic reason are following two aspects:
At first, the design concept defectiveness of this two covers technology.Design too much work nest, must be equipped with the washing bath of twice; Each work nest will consume different chemical agents, and has acid that alkali is arranged, although through massive laundering, also keeps away unavoidable consumption mutually, and total chemical consumption is further risen.A large amount of medicine consumptions, a large amount of water consumptions bring huge wastewater treatment pressure for aluminium processing enterprise.Reduce work nest as much as possible, reduce the medicine consumption to greatest extent, reduce the water consumption, be only the developing direction of following process for treating surface;
Secondly, tank liquor Formula Design theory defectiveness.In the tank liquor, fluorion is arranged, limited waste water recycling; Ammonia nitrogen is arranged, limited discharge of wastewater, producer has to handle fluorine-containing and waste water ammonia nitrogen, need pay huge environmental protection cost.
Summary of the invention
The objective of the invention is at existing alkaline etching and acid etching complex process, work nest and washing bath are many, work efficiency is low, dosing is many, wastewater discharge is big, handle the drawbacks such as cost height of fluorine and ammonia nitrogen, full recovery of a kind of aluminium alloy four work nests unification medicament and wastewater zero discharge surface preprocessing system are provided, the tank liquor prescription is selected the chemical ingredients of floride-free no ammonium for use, the unification of four work nests, be equipped with full recovery of medicament and waste water zero-discharge technology scheme simultaneously, the fluorine and the ammonium that can solve effectively in the aluminium alloy anode oxide pre-treatment pollute, the waste water of realizing the aluminum alloy surface pre-treatment reclaims entirely, significantly reduce enterprise's pollution treatment amount, reduce production costs.
The present invention also aims to provide a kind of aluminium alloy four work nests unification medicament complete reclaim and the surperficial preprocessing system of wastewater zero discharge at chemical sanding material, mechanical sandblast material, zero diopter material with sweep application in the surperficial pre-treatment of line material.
Full recovery of aluminium alloy four work nests unification medicament of the present invention and wastewater zero discharge surface preprocessing system structured flowchart are as shown in Figure 3, comprise that 1# four unification sand face grooves, 2# zero diopter groove, 3#, 4# and the washing of 5# three roads hold back groove, 6# washing and treat that hopper, 7# oxidation trough and 8# washing hold back groove, and supporting slag pumping system, medicament recovery system, water cycle cleaning treatment system and reverse moisturizing neutralized system.Specific as follows:
1# four unification sand face grooves
Oil removing in this groove collection ortho acid etching technique, acid etching, alkaline etching, neutralization four work nests are a groove, and tank liquor is an alkalescence, and function is degreasing, remove natural oxide film, remove line, dusting, adjustment aluminium alloy background color, dedust, middle temperature are polished;
2# zero diopter groove
Hold back 1# groove medicament, decompose precipitated aluminium hydroxide and aluminum phosphate, alkali lye is reclaimed in regeneration, and the frosted material is carried out cryogenic polishing, produces the zero diopter material and sweeps the line material, and the 1# groove is replenished liquid level;
Groove is held back in 3#, 4# washing
Further hold back medicament, decomposition precipitated aluminium hydroxide and aluminum phosphate, regeneration recovery alkali lye;
Groove is held back in the 5# washing
4# washing hold back alkali lye that troughed belt goes out and 6# wash treat the reverse moisturizing of hopper acid solution in the online neutralization of this groove, make the aluminium of processing smoothly transit to acid tank liquor by alkaline tank liquor;
Hopper is treated in the 6# washing
This groove is communicated with 8# washing bath after the oxidation, and tank liquor is acid.Aluminium further neutralizes at this groove, and ash disposal is waited to expect under acidic conditions, can prevent spot corrosion and hickie; Acid washing is laggard goes into the 7# oxidation trough, saves oxidation liquid;
The 7# oxidation trough
This groove is conventional oxidation, and the oxidation liquid of taking out of is held back groove by the 8# washing and held back, and replenishes 8# groove and 6# groove acid solution, keeps 6# groove acidity value;
Groove is held back in the 8# washing
This groove is an oxidation after washing groove, with 6# groove differential concatenation, holds back oxidation liquid, keeps the acidity value of 6# groove.
Full recovery of aluminium alloy four work nests unification medicament of the present invention and wastewater zero discharge surface preprocessing system also comprise following corollary system:
Slag pumping system
Taking out pulp pump, 2# clear liquid pump, 3# in-line pump, 4# in-line pump and 5# in-line pump by the secondary groove of 2# groove, 3# groove, 4# groove and 5# groove and 1# groove and the secondary groove of 2# groove, whizzer, clean solution tank, 2# valve, 3# valve, 4# valve, 5# valve, 7# valve, 8# valve, 10# valve, 11# valve, 12# valve, 13# valve and 1# forms.
Each assembly connects as follows: 2# groove, 3# groove, 4# groove and the series connection of 5# groove, the bottom land mouth of pipe is equipped with 2# valve, 3# valve, 4# valve and 5# valve, be connected by 3# in-line pump, 4# in-line pump and 5# in-line pump between groove, the 3# in-line pump is connected with threeway with the 2# valve export, another by-pass line of this threeway connect 1# take out pulp pump, through the 8# valve to 2# groove pair groove.Secondary trench bottom is equipped with 10# valve, 11# valve, 12# valve and 13# valve, connects whizzer.Whizzer connects clean solution tank, and clean solution tank connects the secondary groove of 2# groove by the 2# clear liquid pump.Secondary groove of 1# groove and the secondary groove of 2# groove are communicated with, and the centre is provided with the 7# valve.
Each groove is taken out the slag operation method: the 1# groove does not have sediment, need not take out slag, but needs to replenish liquid level, so secondary groove of 1# groove and the secondary groove of 2# groove are communicated with, the centre is provided with the 7# valve, is provided with the 1# valve between secondary groove of 1# groove and 1# major trough.When the 2# groove is taken out slag, open 2# valve and 8# valve, close other valves, to open 1# and take out slag that pulp pump can take out the 2# groove to the secondary groove of 2# groove, tank liquor overflows back the 2# groove; Open 7# valve between secondary groove of 1# groove and the secondary groove of 2# groove, the secondary groove tank liquor of 2# groove flows to the secondary groove of 1# groove.During scarfing cinder, open 10# valve, 11# valve, 12# valve and 13# valve respectively, alkaline residue flows into centrifuge dewatering, scarfing cinder, and soup flows into clean solution tank, draws back the secondary groove of 2# groove by the 2# clear liquid pump.After the scarfing cinder, the 2# groove need replenish liquid level, opens 2# valve and 3# valve, closes other valves, opens the 3# in-line pump, the sediment and the soup of 3# groove can be extracted into the 2# groove together.Both replenish 2# tank liquor position, reclaimed 3# groove medicament again, also be extracted into 3# groove sediment.The 4# groove is extracted into the 3# groove, and the 5# groove is extracted into the 4# groove and takes out slag and analogize.
The medicament recovery system
Constitute by 1# groove, 1# valve and slag pumping system.In the time of cleaning reaction aluminium slag, reclaim medicament.Because medicament only adds the 1# groove to when producing, the 1# groove is kept strong basicity, and 2# groove, 3# groove, 4# groove and 5# groove are medicament and hold back groove, and basic agent is from the 1# groove, and concentration from high to low.By Bayer process, the sodium metaaluminate that generates in the 1# groove decomposes in 2# groove, 3# groove, 4# groove and 5# groove, generates sediment aluminium hydroxide and alkali lye sodium hydroxide.Sediment is handled by slag pumping system, and alkali lye oppositely reclaims to take out the slag mode, and the secondary groove of 2# groove is mended 1# tank liquor position through the secondary groove of 1# groove, and the 3# groove is mended 2# tank liquor position, and the 4# groove is mended 3# tank liquor position, and the 5# groove is mended 4# tank liquor position.
The water cycle cleaning treatment system
Filtering collecting bag, 9# valve and 6# recycle pump by 8# groove, 7# groove and 6# groove, moisturizing pond, filtering basin, scum silica frost forms.The 6# recycle pump is evacuated to high-order filtering basin with the sour water in moisturizing pond, after filter bag filters, overflows to the 8# groove, overflows to the 6# groove through the 8# groove, overflows back the moisturizing pond through the 6# groove again, finishes circulating filtration.The 7# groove provides acid solution for system, goes out acid solution by the 7# groove to the 8# troughed belt, keeps system's tank liquor clear.
Reverse moisturizing neutralized system
Form by 6# valve, water cycle cleaning treatment system and slag pumping system, oppositely the water consumption of replenishment system.During moisturizing, open the 6# valve, the sour water of 6# groove replenishes liquid level by surperficial overflow to 5# groove.4# groove, 3# groove, 2# groove, 1# tank liquor position are pressed the medicament way of recycling and are replenished.
The mode of production is as follows:
Chemical sanding material and mechanical sandblast material
Aluminium enters the 1# groove, and temperature 55-65 ℃, reacted 4-8 minute, drip 1 minute enters the 2# groove, and temperature 40-50 ℃, reacted 2-6 minute, drip 1 minute again through 3# groove, 4# groove and the three road non-mobile water washing troughs of 5# groove, enters the 6# washing and treats hopper; Through the oxidation of 7# oxidation trough, the groove washing is held back in the 8# washing, finishes oxide treatment again.
Zero diopter material and sweep the line material
Aluminium directly enters the 2# groove, reacts 2-6 minute, and temperature 40-50 ℃, drip 1 minute again through 3# groove, 4# groove and the three road non-mobile water washing troughs of 5# groove, enters the 6# washing and treats hopper; Through the oxidation of 7# oxidation trough, the groove washing is held back in the 8# washing, finishes oxide treatment again.
Each groove working mechanism is as follows:
1# four unification sand face grooves
1, alkaline tank liquor: consider whole piece oxidation line waste water slant acidity, this groove is designed to work under alkaline condition, with in and meta-acid waste water, realize wastewater zero discharge.After aluminium enters this groove, pressing galvanic principles, is anode with fine aluminium mutually, and alloy phase is a negative electrode, and positively charged ion to the fine aluminium phase shift, carries out chemical reaction by reaction formula (1) and (2) to alloy phase, negatively charged ion;
2, striping degreasing: press reaction formula (1), after aluminium advances this groove, remove earlier natural oxide film, under the tensio-active agent sodium laurylsulfonate effect of appropriate concentration, can remove degreasing and fingerprint simultaneously, save degreasing tank;
3, line is removed in dusting.The main component of line is gone in this flowing current separation as dusting with phosphoric acid salt.Aluminum phosphate is water insoluble, but under alkaline condition certain solubleness is arranged.Press reaction formula (2), fine aluminium is dissolved as anode, and the negatively charged ion phosphate radical that comes with being attracted by anode meets; When aluminum ion and phosphate concentration surpass the solubleness of aluminum phosphate, will carry out following reaction:
Al
3++ PO
4 3-=AlPO
4(dusting, cover, go line) (10)
Aluminum phosphate it is close to tank liquor isolates, and the ditch surface reaction is proceeded, and removes mechanical line rapidly attached to aluminium material surface mechanical line bottom of trench.Compare with ammonium bifluoride, the dusting of this groove is gone the fast 2-5 of line minute, and sand grains is even, and the aluminium consumption is lower, goes mechanical line more thorough;
4, middle temperature polishing: this flowing current separation, is polished down at 55-65 ℃ as the polishing main component with vitriol.Press reaction formula (2), fine aluminium is as anode, and the anion sulfate acid root that comes with being attracted by it meets, and carries out following reaction
SO
4 2--2e=SO
2+ 2O (release active oxygen) (11)
2Al+3O=Al
2O
3(alumina surface, polishing) (12)
Sulfate radical exchanges electronics at anode, decomposites active very strong Sauerstoffatom; Sauerstoffatom and aluminium react rapidly, and the aluminium surface is polished.This groove has thoroughly solved the industry difficult problem of acid etching, the obfuscation of alkaline etching aluminium material surface, the surface brightness of the aluminium of producing, and common alkaline etching, acid etching are incomparable;
5, ash disposal automatically: under tensio-active agent, vitriol and phosphoric acid salt combined action that this groove adds, aluminium material surface is ashless, has saved neutralizing well, can directly carry out anodic oxidation;
6, complexing fully: this groove is added with the sorbyl alcohol of q.s, presses reaction formula (6), and fully the complexing aluminum ion does not decompose, and does not precipitate, and guarantees the tank liquor long term operation.
2# zero diopter groove
1, alkaline tank liquor: the chemical agent of this groove is gone into by the 1# troughed belt fully, and component is identical, but concentration is much lower, after tank liquor is brought into and entered this groove, reacts by reaction formula (3), (4) and (10), decomposites aluminium hydroxide, aluminum phosphate and sodium hydroxide;
2, hold back medicament: do not establish washing bath between 1# groove and the 2# groove, aluminium after 4-8 minute, directly advances the 2# groove in the reaction of 1# groove, reacts 2-4 minute, advances the 3# washing bath again, and the high density medicament of 1# groove is held back through the 2# groove, and the 3# groove is retained, brought on a small quantity to major part;
3, reclaim sediment: press reaction formula (3) and (10), under the not high condition of alkali and complexing agent concentration, aluminum phosphate is saturated separates out, and sodium metaaluminate decomposites aluminum hydroxide precipitation.Press reaction formula (5), aluminium is aluminium and water reaction in the reacting quintessence of 1# groove and 2# groove; Per kilogram aluminium consumption consumes 2 kg of water.By slag pumping system, 2# groove sediment is extracted into the secondary groove of 2# groove, reclaim aluminium hydroxide and aluminum phosphate;
4, regeneration alkali lye: press reaction formula (3), under the not high condition of alkali and complexing agent concentration, sodium metaaluminate decomposites sodium hydroxide, and this groove alkali concn is constantly raise;
5, replenish the 1# groove:, take a large amount of medicaments out of to this groove owing to do not have degreasing tank, dried aluminium directly to advance the higher 1# groove of viscosity, the 1# groove need replenish liquid level every day, and this groove regenerated alkali lye is after the secondary groove clarification of 1# groove, replenish 1# tank liquor position through the 1# valve, alkali consumption is saved more than 60%;
6, cryogenic polishing: when the free alkali concentration of going into when the 1# troughed belt reached 30g/L, because vitriol and phosphatic existence, but both direct production zero diopter material and sweep the line material of this groove also can polish sand plane materiel and sandblast material that the 1# groove is produced;
7, stop fouling: press reaction formula (4), after the aluminium hydroxide sediment forms, change into the aluminium dirt easily, obstruction dreg-drawing pipe road, appropriate sorbitol concentration in this groove can prevent the formation of aluminium dirt.
Groove is held back in 3#, 4# and the washing of 5# three roads
Press reaction formula (3), the washing of 3#, 4# and 5# three roads is held back groove and is designed to step and holds back medicament, precipitation of aluminium slag, regeneration alkali lye.With soda acid, adjusting pH, the pH of 4# groove fluctuates about 10, is aluminium is smoothly transitted to acid tank liquor, surperficial non-scaling by alkaline tank liquor pass keyway in 4# and the associating of 5# two grooves.The alkaline tank liquor of being gone into by the 4# troughed belt mixes at the 5# groove with the oppositely additional acid tank liquor that contains oxidation liquid of 6# groove, and the online neutralization of soda acid guarantees that 4# groove tank liquor pH value slightly fluctuating near the meta-alkalescence, makes aluminium material surface under the condition of not tying the alkali dirt, enters tart 6# groove.
Hopper is treated in the 6# washing
This groove is communicated with the 8# groove, and the oxidation liquid that the 8# groove is held back flows into this groove, and tank liquor pH value is below 1.After aluminium enters this groove, the residual alkali lye that further neutralizes, ash disposal, prevention spot corrosion and hickie guarantee that aluminium enters the 7# oxidation trough under acid, ashless condition, save oxidation liquid.
The 7# oxidation trough
This groove is common oxidation trough.After the aluminaization, enter the washing of 8# groove, oxidation liquid is trapped, and the acid solution of neutralization and ash disposal is provided for the 6# groove.
Groove is held back in the 8# washing
This groove is an oxidation after washing groove, with the 6# differential concatenation, holds back oxidation liquid, alleviates the spent acid pressure of oxidative work-up, keeps the acidity value of 6# groove.
Each corollary system working mechanism is as follows:
Slag pumping system
Except that the power of the floride-free no ammonium of 1# groove, the unification of four grooves, the supporting of slag pumping system is the successful core place of native system operation.Arrange that from the groove position alkali concn reduces from the 1# groove to 5# groove step successively; Acid concentration raises from the 4# groove to 7# groove gradient; Acid base equilibrium point is between 4# groove and 5# groove.Press reaction formula (3) and (10), when alkali concn reduced, sodium metaaluminate decomposed acceleration, and aluminum phosphate is saturated separates out, easier generation aluminium slag.So the 2#-4# groove progressively decomposites aluminium hydroxide and small amounts of phosphoric acid aluminium, the pH value of 4#-5# groove fluctuates between 4-10, and most of aluminum ion is precipitable to finish.The sediment of 2# groove is after the secondary groove precipitation of 2# groove, centrifuge dehydration, and 2# tank liquor position is not enough, takes out slag to the 2# groove with in-line pump from 3# groove bottom land, has both cleared up 3# groove sediment, replenishes 2# tank liquor position again, also reclaims 3# groove alkali lye.Equally, the 4# groove is extracted into the 3# groove, and the 5# groove is extracted into the 4# groove.Key element that so slag pumping system is this cover system can be cleared up sediment, replenish liquid level, reclaim alkali lye, normally move.
The medicament recovery system
Medicament recovery system of the present invention relies on slag pumping system to realize.Press reaction formula (3), when sodium metaaluminate resolves into aluminium hydroxide, also generate sodium hydroxide.So when oppositely taking out slag step by step, also reclaim alkali lye step by step.The ingenious part of native system is, utilizes the 1# groove to be four unification grooves, to take the characteristics of loss liquid level out of because of chemical reaction and aluminium, and the secondary groove of 1# groove is set, and through the 1# valve, the medicament that reclaims refilled the 1# groove, realizes that alkali reclaims.The alkali reclaiming method that Japan adopts is that the washing bath behind the alkali groove is a running water wash at alkaline etching groove bottom land dress slag pumping system, and the alkali lye of taking out of is all wasted, and seriously polluted.Native system 2#-5# groove is immobilising medicament and holds back groove, and alkali lye is thoroughly held back, and takes limited some alkali lye of 5# groove to, the acid solution of taking out of with oxidation trough in also being used for.Native system has been used the limit with Bayer process.
The water cycle cleaning treatment system
Tradition acid etching and alkaline etching technology, corresponding washing treats that hopper and oxidation after washing groove are running water wash.Washing treats that hopper ton material water loss is 2 tons, and oxidation after washing groove is 2 tons.Treat that hopper is designed to neutrality.Purpose is to prevent that aluminium is corroded during waiting to expect.But production practice show that aluminium exposed, that do not have oxide film is even treating also to be easy to generate spot corrosion and hickie under the hopper neutral environment.For this reason, many producers add the nitric acid of 30-50g/L in neutralizing well, and the passivation aluminium material surface prevents spot corrosion to be expected.In addition, aluminium will treat that the hopper neutral water brings, dilutes oxidation trough into, bring the oxidation liquid of high density into oxidation after washing groove, the only turnover of water, sulfuric acid consumption is about 15 kilograms of/ton materials, and two grooves add up to 4 tons of/ton materials of water, also need handle to contain more than 10 kilogram of these waste water of vitriolic.
This water cycle cleaning treatment system is that 6# and 8# groove are held back fully, does not discharge, and the sulfuric acid reversed flow of holding back is finished filtration and purified sealing and circulating, life-time service, per tour moisturizing by system to the 6# groove.The acidity of system is brought realization balance to emitting with 7# of 5# groove sour water to 8# groove sour water by 6#.After the balance, the sulfuric acid content of system is 20-30g/L, and the sulfuric acid of taking consumption out of of bringing into of 7# oxidation trough water is about 5-7 kilogram/ton material, is with acidiferous water to advance oxidation trough, and it is over half to save sulfuric acid.But the both ash disposal of the acidity of 6# groove also can be protected aluminium, wait to expect also not spot corrosion for a long time.Consider the characteristics of the porousness of oxide film, very strong adsorptive power, the scum silica frost filter bag is set, tank liquor after filtering flows back to the 8# groove, guarantees that flaws such as pin hole do not appear in aftertreatment technology such as painted and electrophoresis.
Reverse moisturizing neutralized system
Reverse moisturizing neutralized system of the present invention relies on 6# valve, medicament recovery system and water cycle cleaning treatment system to realize.Press reaction formula (5), the essence of alkaline etching reaction is the reaction of aluminium and water, and 1 kilogram of aluminium of every consumption needs to consume 2 kg of water.Native system aluminium consumption is about 15 kilograms of/ton materials, and about 30 kilograms of consumption of chemical reaction water produces about 45 kilograms of aluminium hydroxide, moisture about 70%, the 45 kilogram of moisture 105 kg of alkaline residue of the alkaline residue after the dehydration, so aluminium per ton in theory water loss be about 150 kilograms.So, after the scarfing cinder, system's serious water shortage.By 30 tons of calculating of a horizontal oxidation line daily output, need 4.5 tons of moisturizings every day.System needs moisturizing rather than draining, is 6# washing is treated that hopper, 7# oxidation trough and 8# washing hold back the basis that groove is included whole water treatment design in.After slag is taken out step by step by system, the not enough liquid level of 5# groove; Open the 6# valve, the alkaline water that the 4# troughed belt is gone into when the sour water of 6# groove and production is in the online neutralization of this groove, and fully recovering.Sulfate radical can instead be mended the 1# groove with slag pumping system, presses reaction formula (11)-(12), temperature polishing during aluminium is carried out.Another big purpose that 4# and 5# groove are set is the protection aluminium.From groove position layout drawing, the inclined to one side alkali in the whole piece oxidation line left side, the right meta-acid, aluminium directly advance acid tank from alkaline groove, easily fouling of surface, the neutral tank liquor transition of intermediate demand.Traditional acid etching and alkaline etching system are that two washing baths are set behind the alkaline etching groove, and 4 tons of water of ton material consumption clean, and guarantee that aluminium enters neutralizing well under near the neutral condition.PH value between the 4#-5# groove just in time fluctuates near neutral, guarantees the aluminium safe transition.
By the combination of 1# groove and 2# groove, but production frosted material, sandblast material, zero diopter material and sweep the line material.The 1# groove is responsible for oil removing, is removed natural oxide film, dusting, go mechanical line, ash disposal and the polishing of middle temperature, and the 2#-5# groove is responsible for holding back medicament, decomposes aluminium hydroxide, is reclaimed alkali lye.Slag pumping system is responsible for each groove sludge collection is arrived the secondary groove of 2# groove, removes the aluminium slag; The medicament recovery system relies on slag pumping system, reclaims alkali lye, the anti-1# groove of mending; Oppositely the moisturizing neutralized system is responsible for aluminium and is smoothly transitted to acid solution from alkali lye, online in and the soda acid water, and fully recovering; The water cycle cleaning treatment system is responsible for providing reverse moisturizing, in and aluminium, ash disposal, prevention spot corrosion, reduce the oxidation trough sulfuric acid consumption, hold back oxidation liquid.Whole system relies on the ingenious combination of medicament and corollary system, has realized that oxidized aluminum alloy is handled floride-free no ammonium, four grooves are unified, saved medicament, reclaim the ideal state of aluminium slag, waste water zero-emission.
Compare with the common acid alkaline etching, the present invention has following major technological breakthrough:
1, first with modern environmental protection, energy-conservation, reduce discharging, angle that consumption reduction, cleaning are carried out production strictly in line with rules and regulations, change redesign aluminium alloy anode oxide production line significantly;
2, select aluminum alloy surface to handle the chemical agent prescription first meticulously, thoroughly stop composition fluorine-containing, that contain ammonium, guarantee the floride-free no ammonium of whole piece oxidation line, aluminium processing enterprise wastewater zero discharge is become a reality;
3, first abandoning tradition technology by acid to alkali, the laying out slot positions that consumes mutually to acid, medicament by alkali again, adopt chemicals treatment aluminium with a kind of character, channelling not, water-saving is economized medicine;
4, reduce function trough first on a large scale, four function troughs of acid etching technology are reduced to one, reduce the medicine consumption significantly, improve effect;
5, reduce washing bath first on a large scale, and the washing bath after surface treatment and the oxidation is held back fully, online neutralization, fully recovering reduces water 13-15 ton/ton material, and water-saving rate is more than 99%, system's moisturizing, not draining has realized wastewater zero discharge;
6, wide-scale adoption Bayer process first reclaims alkali lye, is only reclaimed at the alkali groove by traditional technology, changes into the multiple-grooved classification and reclaims, and the medicament rate of recovery reaches 100%, all comprehensive utilization;
7, slag pumping system, medicament recovery system, reverse moisturizing neutralized system and water cycle cleaning treatment system are set first, reclaim alkali lye and byproduct aluminium slag, online treatment water, and fully recovering;
8, adopt phosphoric acid salt as main dusting with remove mechanical line master salt first, the online recovery of aluminum phosphate replaces ammonium bifluoride fully, has thoroughly solved the aluminium processing industry difficult problem that fluoride pollution and ammonia nitrogen exceed standard;
9, adopt vitriol as the main salt of polishing first, under alkaline condition, polish aluminium, both reduced polish temperature, significantly reduce the aluminium consumption again, reduce the polishing cost.
Description of drawings
Fig. 1 is an existing alkaline etching groove position layout drawing;
Fig. 2 is an existing acid etching groove position layout drawing;
Fig. 3 is full recovery of aluminium alloy four work nests unification medicament of the present invention and wastewater zero discharge surface preprocessing system structured flowchart;
Fig. 4 is that 1# groove work capacity R in the described system of Fig. 3 is with the change curve of output W;
Fig. 5 is that 2# groove corrosion ability R in the described system of Fig. 3 is with the change curve of output W;
Fig. 6 adopts the change curve of the aluminium waste Δ Al of system of the present invention with output W;
Fig. 7 is that 7# oxidation trough sulfuric acid consumption Δ S in the described system of Fig. 3 is with the change curve of output W;
Fig. 8 is the change curve of the pH value of the 3# groove in the described system of Fig. 3 with output W;
Fig. 9 is the change curve of the pH value of the 4# groove in the described system of Fig. 3 with output W;
Figure 10 is the change curve of the pH value of the 5# groove in the described system of Fig. 3 with output W;
Figure 11 is the change curve of the pH value of the 6# groove in the described system of Fig. 3 with output W;
Figure 12 is that moisturizing pond rate of water make-up in the described system of Fig. 3 is with the change curve of output W.
Embodiment
Embodiment
Full recovery of aluminium alloy four work nests unification medicament and the every excellent function of wastewater zero discharge surface preprocessing system are achieved, be the result of each groove of system of the present invention and corollary system close fit, component and operation index that 1# four unification grooves and 2# zero diopter groove are appropriate are the keys that embodies technical characterictic.
Embodiment 1 (sand plane materiel)
1# four unification sand face grooves: NaOH 60g/L, Na
2SO
410g/L, Na
3PO
410g/L, sorbyl alcohol 5g/L, sodium laurylsulfonate 0.3g/L, excess water; Working temperature is 65 ℃, and the treatment time is 8 minutes, drip 1 minute;
2# zero diopter groove; Drug concentration is 30% of 1# four unification sand face groove concentration, and working temperature is 50 ℃, and the treatment time is 4 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds 1 minute.
Embodiment 2 (sand plane materiel)
1# four unification sand face grooves: NaOH 180g/L, Na
2SO
430g/L, Na
3PO
430g/L, sorbyl alcohol 15g/L, sodium laurylsulfonate 0.6g/L, excess water; Working temperature is 60 ℃, and the treatment time is 6 minutes, drip 1 minute;
2# zero diopter groove; Drug concentration is 40% of 1# four unification sand face concentration, and working temperature is 45 ℃, and the treatment time is 3 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds 1 minute;
Embodiment 3 (sand plane materiel)
1# four unification sand face grooves: NaOH 300g/L, Na
2SO
450g/L, Na
3PO
450g/L, sorbyl alcohol 25g/L, sodium laurylsulfonate 0.9g/L, excess water; Working temperature is 55 ℃, and the treatment time is 4 minutes, drip 1 minute;
2# zero diopter groove; Drug concentration is 50% of 1# four unification sand face groove concentration, and working temperature is 40 ℃, and the treatment time is 2 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds 1 minute;
Embodiment 4 (zero diopter material)
2# zero diopter groove; Drug concentration be 1# four unification sand face groove concentration 40% (1# groove concentration is NaOH 180g/L, Na
2SO
430g/L, Na
3PO
430g/L, sorbyl alcohol 15g/L, sodium laurylsulfonate 0.6g/L, excess water), working temperature is 45 ℃, the treatment time is 4 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds 1 minute;
Embodiment 5 (sweeping the line material)
2# zero diopter groove; Drug concentration be 1# four unification sand face groove concentration 40% (1# concentration is NaOH 180g/L, Na
2SO
430g/L, Na
3PO
430g/L, sorbyl alcohol 15g/L, sodium laurylsulfonate 0.6g/L, excess water), working temperature is 45 ℃, the treatment time is 6 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds 1 minute;
Embodiment 6 (sandblast material)
1# four unification sand face grooves: NaOH 120g/L, Na
2SO
420g/L, Na
3PO
420g/L, sorbyl alcohol 10g/L, sodium laurylsulfonate 0.9g/L, excess water; Working temperature is 65 ℃, and the treatment time is 8 minutes, drip 1 minute;
2# zero diopter groove; Drug concentration is 50% of 1# four unification sand face groove concentration, and working temperature is 50 ℃, and the treatment time is 6 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds 1 minute;
Embodiment 7 (system testing)
Each groove is pressed 1m
3Fluting, addition material is pressed
NaOH 66.27wt.％
Na
2SO
4 13.25wt.％
Na
3PO
4 9.94wt.％
Sorbyl alcohol (solid) 9.94wt.%
Sodium laurylsulfonate 0.6wt.%
Prepare, select the aluminium of 1.2mm standard wall thickness for use, consume 25 kilograms of interpolations by the ton material.
Choose parameters R=free alkali concentration (g/L)/aluminium ion concentration (g/L) as 1# and 2# groove work capacity measurement index.
Choose parameter W=and produce aluminium gross weight (T)/volume of bath solution (m
3) as production index, monitor each tank liquor index with output W (T/m
3) Changing Pattern.
Choose parameter Δ Al=aluminium waste (Kg)/production aluminium weight (T) as weighing aluminium etching extent index.
Choose parameter Δ S=7# sulfuric acid waste (Kg)/production aluminium weight (T) as weighing oxidation liquid indication of consumption.
Choose parameter Δ H
2O=moisturizing pond rate of water make-up (Kg)/production aluminium weight (T) is as weighing the water consumption index.Each groove working index is:
1# four unification sand face grooves: NaOH 180g/L, Na
2SO
430g/L, Na
3PO
430g/L, sorbyl alcohol 15g/L, sodium laurylsulfonate 0.6g/L, excess water; Working temperature is 60 ℃, and the treatment time is 6 minutes, drip 1 minute;
2# zero diopter groove; Drug concentration is 40% of 1# four unification sand face concentration, and working temperature is 45 ℃, and the treatment time is 3 minutes, drip 1 minute;
Groove is held back in the 3# washing; Washed drip 30 seconds (not having medicament during fluting) 1 minute;
Groove is held back in the 4# washing: washed drip 30 seconds (not having medicament during fluting) 1 minute;
Groove is held back in the 5# washing: washed drip 30 seconds (not having medicament during fluting) 1 minute;
Hopper is treated in the 6# washing: washed drip 30 seconds (not having medicament during fluting) 1 minute;
7# oxidation trough: reacted 30 seconds (no power) (H during fluting of drip 1 minute
2SO
4180g/L);
Groove is held back in the 8# washing: washed drip 30 seconds (not having medicament during fluting) 1 minute.
Interpretation of result
1, presses embodiment 1-3, can produce aluminum alloy chemically frosted material in batches; Along with chemical agent concentration raises, can suitably reduce temperature of reaction, shorten the reaction times;
2, press embodiment 1-3,1# groove drug concentration interval is: NaOH 60-300g/L, Na
2SO
410-50g/L, Na
3PO
410-50g/L, sorbyl alcohol 5-25g/L, sodium laurylsulfonate 0.3-0.9g/L; Time is 4-8 minute, and temperature is 55-65 ℃;
3, press embodiment 1-3,2# groove concentration is the 30-50% of 1# groove concentration;
4, press embodiment 4, the treatment time of zero diopter material is 2-6 minute, and temperature is 40-50 ℃;
5, press embodiment 5, the treatment time of sweeping the line material is 4-8 minute, and temperature is 40-50 ℃;
6, press embodiment 6, the sandblast material, 1# groove drug concentration interval is NaOH 120-100g/L, Na
2SO
420-50g/L, Na
3PO
420-50g/L, sorbyl alcohol 10-25g/L, sodium laurylsulfonate 0.6-0.9g/L; Time is 6-8 minute, and temperature is 60-65 ℃;
7,1# groove work capacity R with the Changing Pattern of output W is: the R value is the highest during fluting, is about 4.0, and with the increase of output W, R progressively reduces, and W reaches 12.0T/m when output
3The time, the R value shows that in the 1.60-1.70 left and right sides balance work capacity of tank liquor tends towards stability, the interpolation of medicament, the dissolving of aluminium and take out of and tend to balance Changing Pattern such as Fig. 4.
8,2# groove corrosion ability R with the Changing Pattern of output W is: the R value is the highest during fluting, is about 3.0, and with the increase of output W, R progressively reduces, and W reaches 7.17-9.75T/m when output
3The time, the bounce-back of R value raises, and surperficial sodium metaaluminate begins to decompose, and alkali concn raises; Then, the R value shows that in the 2.00-2.50 left and right sides balance work capacity of tank liquor tends towards stability, the dissolving of the bringing into of medicament, aluminium and separate out and tend to balance Changing Pattern such as Fig. 5.
9, aluminium waste Δ Al with the Changing Pattern of output W is: Δ Al value is the highest during fluting, and for about 50Kg/T, with the increase of output W, Δ Al progressively reduces, and W reaches 10.00T/m when output
3When above, Δ Al value shows that in the 20-23Kg/T left and right sides balance work capacity of tank liquor tends towards stability, and the interpolation of medicament, the dissolving of aluminium and taking out of tends to balance, and the aluminium consumption is stable, Changing Pattern such as Fig. 6.
10,7# oxidation trough sulfuric acid consumption Δ S with the Changing Pattern of output W is: Δ S value is the highest during fluting, for about 13.5Kg/T, be neutrality when showing 6# groove fluting, bring the neutral water dilution oxidation trough of 7# groove into, with the increase of output W, the sulfuric acid that the 8# groove is held back increases, and the acidity of 6# groove increases, Δ S progressively reduces, and W reaches 5.00T/m when output
3When above, Δ S value is in 6.00-8.00Kg/T left and right sides balance, show that the sulfuric acid that oxidation trough is taken out of, the 8# groove is held back sulfuric acid and the anti-5# of the benefit groove of 6# groove, the moisturizing of moisturizing pond consume tends to balance, the acidity value of water cycle cleaning treatment system tends towards stability, Changing Pattern such as Fig. 7.
11, the pH value of 3# groove with the Changing Pattern of output W is: for neutral, the pH value is 7, and is minimum during fluting, and with the increase of output W, the pH value progressively raises, and W reaches 10.00T/m when output
3When above, pH is balance near 13.00, Changing Pattern such as Fig. 8.
12, the pH value of 4# groove with the Changing Pattern of output W is: for neutral, the pH value is 7, and is minimum during fluting, and with the increase of output W, the pH value progressively raises, and W reaches 2.50T/m when output
3When above, pH is balance near 11.00, Changing Pattern such as Fig. 9.
13, the pH value of 5# groove with the Changing Pattern of output W is: for neutral, the pH value is 7, and is the highest during fluting, and with the increase of output W, the pH value progressively reduces, and W reaches 10.00T/m when output
3When above, pH is balance near 1.25, Changing Pattern such as Figure 10.
14, the pH value of 6# groove with the Changing Pattern of output W is: for neutral, the pH value is 7, and is the highest during fluting, and with the increase of output W, the pH value progressively reduces, and W reaches 12.00T/m when output
3When above, pH is balance near 0.70, Changing Pattern such as Figure 11.
15, moisturizing pond rate of water make-up with the Changing Pattern of output W is: for neutral, sediment is less during fluting, and scarfing cinder is few, and the moisturizing of moisturizing pond is less; With the increase of output W, the scarfing cinder amount progressively increases, and rate of water make-up increases, and W reaches 5.00T/m when output
3When above, near moisturizing pond rate of water make-up balance 150Kg/T, Changing Pattern such as Figure 12.
Claims (10)
1. aluminium alloy four a work nests unification medicament reclaims and wastewater zero discharge surface preprocessing system entirely, it is characterized in that holding back groove, 6# washing by 1# four unification sand face grooves, 2# zero diopter groove, 3#, 4# and the washing of 5# three roads treats that hopper, 7# oxidation trough and 8# washing hold back groove, and supporting slag pumping system, medicament recovery system, water cycle cleaning treatment system and oppositely the moisturizing neutralized system constitute.
2. according to the described system of claim 1, it is characterized in that each groove component and working index are:
1# four unification sand face grooves: NaOH 60-300g/L, Na
2SO
410-50g/L, Na
3PO
410-50g/L, sorbyl alcohol 5-25g/L, sodium laurylsulfonate 0.3-0.9g/L, excess water; Working temperature is 55-65 ℃, and the treatment time is 4-8 minute, drip 1 minute;
2# zero diopter groove: medicine component and 1# groove are identical, and concentration is the 30-50% of 1# four unification sand face groove concentration, and working temperature is 40-50 ℃, and the treatment time is 2-6 minute, drip 1 minute;
Groove is held back in the 3# washing: washed 1 minute, drip 30 seconds does not have medicament during fluting;
Groove is held back in the 4# washing: washed 1 minute, drip 30 seconds does not have medicament during fluting;
5# washes regulating tank: washed 1 minute, drip 30 seconds does not have medicament during fluting;
Hopper is treated in the 6# washing: washed 1 minute, drip 30 seconds does not have medicament during fluting;
7# oxidation trough: H
2SO
4160-200g/L, 18-22 ℃, current density 1.0-1.3A/dm
2, oxidization time is 25-30 minute, drip 30 seconds;
Groove is held back in the 8# washing: washed 1 minute, drip 30 seconds does not have medicament during fluting.
3. according to claim 1 or 2 described systems, it is characterized in that producing chemical sanding material and mechanical sandblast material, sweep the line material by 2# groove production zero diopter material and machinery by 1# groove and the combination of 2# groove.
4. according to the described system of claim 3, it is characterized in that 1# four unification frosted grooves are added with dusting and remove line composition sodium phosphate, polishing composition sodium sulfate, remove oil component sodium laurylsulfonate and complexing components sorbyl alcohol.
5. according to the described system of claim 4, it is characterized in that not adding medicament when the 2# groove is produced, 3# groove, 4# groove and 5# groove are the non-mobile water washing trough, hold back fully, do not discharge to contain alkali waste water, and step decomposes the aluminium slag, and step reclaims medicament; 6# groove and 8# groove water are held back fully, and internal recycling reclaims oxidation liquid, does not discharge acid-bearing wastewater.
6. according to the described system of claim 5, it is characterized in that supporting slag pumping system takes out pulp pump, 2# clear liquid pump, 3# in-line pump, 4# in-line pump and 5# in-line pump by 2# groove, 3# groove, 4# groove and 5# groove and the secondary groove of 1# groove and the secondary groove of 2# groove, whizzer, clean solution tank, 2# valve, 3# valve, 4# valve, 5# valve, 7# valve, 8# valve, 10# valve, 11# valve, 12# valve, 13# valve and 1# and form.
7. according to the described system of claim 6, the mode of connection that it is characterized in that slag pumping system is: 2# groove, 3# groove, 4# groove and the series connection of 5# groove, the bottom land mouth of pipe is equipped with 2# valve, 3# valve, 4# valve and 5# valve, be connected by 3# in-line pump, 4# in-line pump and 5# in-line pump between groove, the 3# in-line pump is connected with threeway with the 2# valve export, another by-pass line of this threeway connect 1# take out pulp pump, through the 8# valve to 2# groove pair groove; The secondary groove of 2# groove is through 7# valve and the secondary groove of 1# groove UNICOM; Secondary trench bottom is equipped with 10# valve, 11# valve, 12# valve and 13# valve, connects whizzer; Whizzer connects clean solution tank, and clean solution tank connects the secondary groove of 2# groove by the 2# clear liquid pump; The workflow of slag pumping system is:
A, take out the 2# groove slag to the secondary groove of 2# groove, open 2# valve and 8# valve, close other groove valves, open 1# and take out pulp pump, take out slag to 2# groove pair groove, tank liquor overflows back the 2# groove; Open 7# valve between secondary groove of 1# groove and the secondary groove of 2# groove, the secondary groove tank liquor of 2# groove flows to the secondary groove of 1# groove; During scarfing cinder, open 10# valve, 11# valve, 12# valve and 13# valve respectively, alkaline residue flows into centrifuge dewatering, scarfing cinder, and soup flows into clean solution tank, draws back the secondary groove of 2# groove by the 2# clear liquid pump;
B, take out the slag of 3# groove to the 2# groove; Open 2# valve and 3# valve, close other valves, open the 3# in-line pump, the sediment and the soup of 3# groove is extracted into the 2# groove together;
C, 4# groove are to the 3# groove, and the 5# groove is taken out slag to the 4# groove and analogized.
8. according to the described system of claim 7, it is characterized in that supporting medicament recovery system is made of slag pumping system, 1# groove and 1# valve; Medicament recovery system workflow is:
A, finish and take out slag;
B, the secondary groove of clarification 1# groove;
C, unlatching 1# valve replenish 1# tank liquor position, finish medicament and reclaim.
9. described according to Claim 8 system is characterized in that supporting water cycle cleaning treatment system filters collecting bag, 9# valve and 6# recycle pump by 8# groove, 7# groove and 6# groove, moisturizing pond, filtering basin, scum silica frost and forms; Its workflow is: the 6# recycle pump is evacuated to high-order filtering basin with the sour water in moisturizing pond, after filter bag filters, overflows to the 8# groove, overflows to the 6# groove through the 8# groove, overflows back the moisturizing pond through the 6# groove again, finishes circulating filtration; The 7# groove provides acid solution for system, goes into acid solution by the 7# groove to the 8# troughed belt, keeps system's tank liquor clear; The water cycle cleaning treatment system is by the moisturizing of moisturizing pond, the dilution system acid solution.
10. according to the described system of claim 9, it is characterized in that supporting reverse moisturizing neutralized system is made up of slag pumping system, water cycle cleaning treatment system and 6# valve; Oppositely moisturizing neutralized system workflow is:
A, finish and take out slag step by step, 5# groove lack of water;
B, unlatching 6# recycle pump start the water cycle cleaning treatment system;
C, unlatching 6# valve replenish 5# tank liquor position;
D, additional moisturizing pit level are finished system water supplement.
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| CN2010105157383A CN102021595B (en) | 2010-10-21 | 2010-10-21 | Surface pre-treatment system combining four aluminum alloy working grooves into whole for full recovery of medicament and zero emission of wastewater |
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| CN2010105157383A CN102021595B (en) | 2010-10-21 | 2010-10-21 | Surface pre-treatment system combining four aluminum alloy working grooves into whole for full recovery of medicament and zero emission of wastewater |
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