CN102021595B - 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 PDF

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CN102021595B
CN102021595B CN2010105157383A CN201010515738A CN102021595B CN 102021595 B CN102021595 B CN 102021595B CN 2010105157383 A CN2010105157383 A CN 2010105157383A CN 201010515738 A CN201010515738 A CN 201010515738A CN 102021595 B CN102021595 B CN 102021595B
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groove
valve
medicament
washing
water
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CN102021595A (en
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熊映明
熊朔
刘庆芬
李昌群
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FOSHAN SANSHUI XIONGYING INNOVATIVE CENTER FOR ALUMINUM SURFACE TECHNOLOGIES Co Ltd
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FOSHAN SANSHUI XIONGYING INNOVATIVE CENTER FOR ALUMINUM SURFACE TECHNOLOGIES Co Ltd
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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

Duraluminum four work nests unification medicament is complete to be reclaimed and wastewater zero discharge surface preprocessing system
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 alkali erosion and acid etching two big classes.Existing aluminium section bar alkali etching technique was continued to use more than 100 year, and the alkali erosion has drawbacks such as the aluminium consumption is high, alkaline consumption is high, alkaline residue is many, difficult technique control, defective is many, production cost is high, environmental pollution is big.The alkali erosion groove position of standard is arranged as shown in Figure 1, and 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# alkali erosion groove is a surface treatment groundwork groove.Each groove function is following:
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 alkali erosion groove.Oil removing is bad, and the alkali erosion 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.
Existing 1# degreasing tank exists following not enough:
1, to long aluminium of shelf-time, oil removing is bad, and natural oxide film can not take off totally, and the alkali erosion 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 alkali erosion groove easily into, in and caustic soda;
In order to strengthen the oil removing ability, part producing producer adds the matt salt 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 alkali erosion 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 alkali erosion groove into.
4# alkali erosion groove
This groove is a work nest.The purpose of alkali erosion is a natural oxide film, and further oil removing increases aluminium brightness, or dusting, removes line, and aluminium loses liquid with alkali following chemical reaction takes place during the alkali erosion:
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 alkali erosion 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 alkali etching technique that Japan adopts, the not doping of general alkali erosion 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 white lake and sodium hydroxide, the white lake 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 alkali etching technique that Italy adopts in the doping of alkali erosion groove, like sorbyl alcohol, Portugal's sodium etc., utilizes 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 prone to knot 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 consumption is about 4.0 tons of/ton materials, and after the 4# groove added alkali erosion 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, dissolve to go at alloying element or impurity such as the insoluble manganese of alkali groove, copper, iron, to obtain the metallic surface of light, simultaneously in 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, and oxidation spent acid both capable of using also can be avoided 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 of alkali erosion back 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 during making its washing before oxidation wait to expect and corrodes with flakes.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 accomplished 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, sull 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 sull, 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 energy consumption is high, and evaporated quantity of water is big, is prone to dust, and tank liquor is prone to foreign ion and poisons, 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 the sealing of hole rapid speed, few dust, energy consumption is low, and is easy to use.But be prone to split film, and fluorine-containing and nickel are 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 protecting aluminium to dispatch 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, accomplishes anodize.
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 matt salt 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 alkali etching technique is completely exposed already.Particularly stress today that cleaning is carried 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, from highly basic to strong acid, handles, 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, the processing of these water and discharging need the extra cost of paying;
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 on the basis of alkali etching technique, to grow up, and has used nearly 10 years.Existing acid etching groove position arranges that like Fig. 2 acid etching is between the degreasing tank of former alkali etching technique and alkali erosion groove, to insert the acid etching groove to form.4# acid etching groove is a work nest, and its function is following:
This groove is added with the matt salt of 60-100g/L, utilizes the fluorion dusting, removes mechanical line, and reaction mechanism is:
3F -+ Al 3+=AlF 3(dissolve 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 the alkali erosion.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 alkali erosion, go line speed fast again, the aluminium consumption is 25% of alkali erosion, and the sand grains uniform and smooth.
The characteristics that consumption is low, leveling is effective, the sand face is fine and smooth although acid etching technology has aluminium, 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, aluminium material surface obfuscation behind the acid etching although prolonged alkali erosion and bright dipping, but still has the acid etching ash.Both increase operation, lost surface luster again, also increased environmental burden.Acid etching technology is more than alkali erosion 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 extra cost of paying is all wanted in the processing of these waste water and discharging;
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, extraly pays huge environmental protection cost.
The above-mentioned drawback of acid etching, alkali erosion, basic reason is 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 to existing alkali erosion 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, provides that a kind of duraluminum four work nests unification medicament is complete to be reclaimed and wastewater zero discharge surface preprocessing system, and the tank liquor prescription is selected the chemical ingredients of the no ammonium of free-floride 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, and realize that the waste water of 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 duraluminum four work nests unification medicament complete reclaim with the surperficial preprocessing system of wastewater zero discharge at chemical sanding material, mechanical sandblast material, zero diopter material with sweep the application in the surperficial pre-treatment of line material.
Full recovery of duraluminum 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, alkali erosion, neutralization four work nests are a groove, and tank liquor be an alkalescence, and function is degreasing, remove natural oxide film, remove line, dusting, adjustment duraluminum background color, dedust, middle temperature are polished;
2# zero diopter groove
Hold back 1# groove medicament, decompose precipitated aluminium hydroxide and phosphagel phosphaljel, 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 phosphagel phosphaljel, 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
8# washing bath after this groove and the oxidation is communicated with, 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, practices thrift 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 duraluminum 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, can the sediment and the soup of 3# groove 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 white lake 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, 3# groove benefit 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, accomplishes circulating filtration.The 7# groove is that system provides acid solution, goes out acid solution by the 7# groove to the 8# troughed belt, keeps system's tank liquor clear.
Reverse moisturizing neutralized system
Form the water consumption of reverse replenishment system by 6# valve, water cycle cleaning treatment system and slag pumping system.During moisturizing, open the 6# valve, the sour water of 6# groove replenishes liquid level through 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 following:
Chemical sanding material and mechanical sandblast material
Aluminium gets into the 1# groove, and temperature 55-65 ℃, reacted 4-8 minute, drip 1 minute gets into 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, gets into the 6# washing and treats hopper; Through the oxidation of 7# oxidation trough, the groove washing is held back in the 8# washing, accomplishes oxide treatment again.
The zero diopter material with sweep the line material
Aluminium directly gets into 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, gets into the 6# washing and treats hopper; Through the oxidation of 7# oxidation trough, the groove washing is held back in the 8# washing, accomplishes oxide treatment again.
Each groove working mechanism is following:
1# four unification sand face grooves
1, alkaline tank liquor: consider whole piece oxidation line waste water slant acidity, this groove is designed under alkaline condition work, with in meta-acid waste water, realize wastewater zero discharge.Aluminium is pressed galvanic principles after getting into this groove, is anode mutually with fine aluminium, 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 staple of line is gone in this flowing current separation as dusting with phosphoric acid salt.Phosphagel phosphaljel 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 phosphagel phosphaljel, will react as follows:
Al 3++ PO 4 3-=AlPO 4(dusting, cover, go line) (10)
Phosphagel phosphaljel 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 matt salt, 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 staple 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 reacts as follows
SO 4 2--2e=SO 2+ 2O (activated oxygen released) (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 that acid etching, alkali erosion aluminium material surface shade, the surface brightness of the aluminium of producing, and conventional base is lost, acid etching is 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, and tank liquor reacts by reaction formula (3), (4) and (10) after bringing into and getting into this groove, decomposites white lake, phosphagel phosphaljel 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, phosphagel phosphaljel 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.Through slag pumping system, 2# groove sediment is extracted into the secondary groove of 2# groove, reclaim white lake and phosphagel phosphaljel;
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 practiced thrift more than 60%;
6, cryogenic polishing: when the free alkali concentration of going into when the 1# troughed belt reaches 30g/L because vitriol and phosphatic existence, but this groove both direct production zero diopter material with sweep the line material, also can polish sand plane materiel and sandblast material that the 1# groove is produced;
7, stop fouling: press reaction formula (4), after the white lake sediment forms, change into the aluminium dirt easily, stop up the dreg-drawing pipe road, appropriate sorbitol concentration in this groove can prevent the formation that aluminium is dirty.
Groove is held back in 3#, 4# and the washing of 5# three roads
Press reaction formula (3), 3#, 4# and the washing of 5# three roads are held back groove and are designed to step and hold 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 is slightly fluctuating near the meta-alkalescence, makes aluminium material surface under the condition of not tying the alkali dirt, gets into tart 6# groove.
Hopper is treated in the 6# washing
This groove is communicated with the 8# groove, and the oxidation flow that the 8# groove is held back is gone into this groove, and tank liquor pH value is below 1.After aluminium gets into this groove, the residual alkali lye that further neutralizes, ash disposal, prevention spot corrosion and hickie guarantee that aluminium gets into the 7# oxidation trough under acid, ashless condition, practice thrift oxidation liquid.
The 7# oxidation trough
This groove is common oxidation trough.After the aluminaization, get into 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 following:
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 1# groove to 5# groove step successively; Acid concentration raises from 4# groove to 7# groove gradient; Acid point is between 4# groove and 5# groove.Press reaction formula (3) and (10), when alkali concn reduced, sodium metaaluminate decomposed acceleration, and phosphagel phosphaljel is saturated separates out, and generates the aluminium slag more easily.So the 2#-4# groove progressively decomposites white lake 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 deposition 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 white lake, 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 alkali erosion 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 alkali etching technique, 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 sull 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 accomplished 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 practice thrift 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 sull, 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 technologys 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 alkali erosion 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 white lake, 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.The layout n. from the groove position, 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, and the surface is prone to fouling, the neutral tank liquor transition of intermediate demand.Traditional acid etching and alkali erosion system are behind alkali erosion groove, two washing baths to be set, and 4 tons of water of ton material consumption clean, and guarantee that aluminium gets into 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 white lake, 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; Reverse moisturizing neutralized system is responsible for aluminium and is smoothly transitted to acid solution from alkali lye, online in soda acid water, and fully recovering; The water cycle cleaning treatment system is responsible for providing reverse moisturizing, in 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, practiced thrift medicament, reclaim the ideal state of aluminium slag, waste water zero-emission.
Compare with common soda acid erosion, 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 significantly, design the aluminium alloy anode oxide production line again;
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 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 sub product aluminium slag, in-line treatment water, and fully recovering;
8, adopt phosphoric acid salt as main dusting with remove mechanical line master salt first, the online recovery of phosphagel phosphaljel replaces matt salt 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, the polishing aluminium had both reduced polish temperature under alkaline condition, significantly reduced the aluminium consumption again, reduced the polishing cost.
Description of drawings
Fig. 1 is an existing alkali erosion groove position layout n.;
Fig. 2 is an existing acid etching groove position layout n.;
Fig. 3 is full recovery of duraluminum 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 said system of Fig. 3 is with the change curve of output W;
Fig. 5 is that 2# groove corrosion ability R in the said 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 said 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 said system of Fig. 3 with output W;
Fig. 9 is the change curve of the pH value of the 4# groove in the said system of Fig. 3 with output W;
Figure 10 is the change curve of the pH value of the 5# groove in the said system of Fig. 3 with output W;
Figure 11 is the change curve of the pH value of the 6# groove in the said system of Fig. 3 with output W;
Figure 12 is that moisturizing pond rate of water make-up in the said system of Fig. 3 is with the change curve of output W.
Embodiment
Embodiment
Full recovery of duraluminum four work nests unification medicament and the wastewater zero discharge surface excellent function of preprocessing system each item 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 is balance in the 1.60-1.70 left and right sides, shows that the 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 is balance in the 2.00-2.50 left and right sides, shows that the 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 is balance in the 20-23Kg/T left and right sides, shows that the 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, is 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 balance in the 6.00-8.00Kg/T left and right sides; 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 (9)

1. duraluminum 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 reverse moisturizing neutralized system constitute.
2. according to the said 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;
Groove is held back in the 5# washing: 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 said 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;
1# four unification sand face 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.
4. according to the said system of claim 3, 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 circulating inside reclaims oxidation liquid, does not discharge acid-bearing wastewater.
5. according to the said system of claim 4, 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.
6. according to the said system of claim 5; 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 3# groove slag 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.
7. according to the said system of claim 6, it is characterized in that supporting medicament recovery system is made up of slag pumping system, 1# groove and 1# valve; Medicament recovery system workflow is:
Slag is taken out in A, completion;
B, the secondary groove of clarification 1# groove;
C, unlatching 1# valve replenish 1# tank liquor position, accomplish medicament and reclaim.
8. according to the said system of claim 7, it 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, accomplishes circulating filtration; The 7# groove is that system provides acid solution, 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.
9. said according to Claim 8 system is characterized in that supporting reverse moisturizing neutralized system is made up of slag pumping system, water cycle cleaning treatment system and 6# valve; Reverse moisturizing neutralized system workflow is:
Slag, 5# groove lack of water are taken out in A, completion step by step;
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 accomplished system water supplement.
CN2010105157383A 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 Active CN102021595B (en)

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