CN105821463B - Free-floride is without treatment agent and its use in face of ammonium four-in-one sand - Google Patents
Free-floride is without treatment agent and its use in face of ammonium four-in-one sand Download PDFInfo
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- CN105821463B CN105821463B CN201610186264.XA CN201610186264A CN105821463B CN 105821463 B CN105821463 B CN 105821463B CN 201610186264 A CN201610186264 A CN 201610186264A CN 105821463 B CN105821463 B CN 105821463B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/36—Alkaline compositions for etching aluminium or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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Abstract
Free-floride is without treatment agent in face of ammonium four-in-one sand and its use and medicament recovery system, and free-floride is without treatment agent in face of ammonium four-in-one sand, including following components：30 50g/L of sodium hydroxide, 100 200g/L of sodium chloride, 1.5 3.5g/L of sodium thiosulfate, 1.5 3.5g/L of surfactant, 1.5 3.5g/L of sorbierite, 1.5 3.5g/L of sodium gluconate, surplus is water.Its medicament recovery system, including four-in-one slot and non-mobile water washing trough subsystem, the non-mobile water washing trough subsystem integral inverted are in series setting, and the beginning in its water flowing direction is equipped with water supplement port, and the water outlet of terminal is series at the four-in-one slot.The present invention proposes a kind of floride-free without treatment agent in face of ammonium four-in-one sand, have the function of oil removing, acid etching, alkaline etching, neutralize four slots, efficiently solve fluorine and the ammonium pollution of aluminium alloy anode oxide pre-treatment, in addition the above-mentioned floride-free medicament recovery system without treatment agent in face of ammonium four-in-one sand is used, it is used by the restriction of medicament and the recycling to medicament, greatly reduce enterprise's pollution treatment amount, reduce production cost, improves effect.
Description
Technical field
The present invention relates to aluminium material surface processing technology field, more particularly to it is floride-free without treatment agent in face of ammonium four-in-one sand and
It is used.
Background technology
Treatment process is broadly divided into alkaline etching, acid etching and mechanical sandblasting three categories in face of aluminium alloy sand.
Large-scale application more than 20 years needs tradition machinery blasting craft although having the advantages that aluminium consumption is low, medicine consumption is low
Special sand-blast shop is configured, is transported to oxidation workshop after sandblasting again, efficiency is low, easily abrades surface and forms waste product.By aluminium shape
Shape limits, and sand blasted surface is difficult uniform, and uneven after coloring to be amplified, rejection rate ramps.
Our previous application (200510101420.X) bright acid etching technology for aluminium alloy, discloses to existing acid etching work
The improvement of skill, arranges reactive tank in the following manner：
(Chinese patent 200510101420.X) is arranged in 1 bright acid etching technology for aluminium alloy slot position of table
Each slot function is：
1# removes oil dewaxing slot：Major function is oil removing at normal temperatures, dewaxing, de- natural oxide film, and is had both to a certain degree
Cryogenic polishing ability；
3# blast acid etching slots：The modified of common acid etching slot, the dusting that has a common acid etching slot is fast, goes mechanical line ability
By force, aluminium consumes the advantages that low and sand grains is uniform；
4# sand mirror polish slots：Remove acid etching ash and sand plane materiel cryogenic polishing.Although aluminium from 3# blast acid etching slots taking-up after,
Most of acid etching ash has been eliminated, but a small amount of remaining ash is still plain stubborn, and conventional method is difficult to remove；Other than acid etching ash,
How to make sand plane materiel light, and one of the core missions to be solved in the prior art.4# sand mirror polish slots are exactly completion
Above-mentioned two main tasks and it is well-designed.In this slot, two major classes function ingredients, i.e. deashing agent and cryogenic polishing agent are added with, are increased
Bright acid etching material is after the processing of this slot, and surface is ashless, metallochrome, and has comparable brightness.Furthermore, it is contemplated that environmental protection and medicament damage
It losing, this slot is designed as being compatible with 3# blast acid etching slots, i.e. aluminium is after the processing of 3# slots, and directly into 4# slots, centre does not set rinsing bowl,
Not only medicament has been saved, but also has been good for the environment；
7# zero diopter polishing troughs：The cryogenic polishing of the smart ash disposal peace finish of sand plane materiel.Aluminium is handled through 1#, 3# and 4# slot
Afterwards, had comparable brightness, surface can directly carry out anodic oxidation without line, fine sand and very clean.But some export orders,
Rolled Aluminum Material Surface Quality requires very high, optional advanced 7# slots, the smart ash disposal of progress, and further polishes, and then carries out anodic oxygen again
Change.For not requiring dusting and removing the zero diopter material of mechanical line, since 3# slots and 4# slots are all easy dusting,
Zero diopter material cannot be produced, the setting of 7# slots just compensates for above-mentioned deficiency, and zero diopter material can be carried out using 1# and 7# slots
Cryogenic polishing.
Nearly 10, the industrialization of patent of the present invention produces a large amount of high-end sand faces aluminium, exports to all over the world.But from
From the point of view of emphasizing today that cleaning is carried out production strictly in line with rules and regulations, which exists following apparent insufficient：
1, medicament is fluorine-containing：1# slots contain NH4HF220g/L, 3# slot 100g/L containing ammonium fluoride, fluoboric acid 65g/L, 4# slot are fluorine-containing
Boric acid contains 28g/L, NH4HF230g/L, HF18g/L, 7# slot contain NH4HF210g/L.These fluorides strictly disable now.
2, contain chromic anhydride：7# slots contain CrO335g/l is more impermissible for using in this way.
3, contain a large amount of ammonia nitrogens：1# slots contain NH4HF220g/L, 3# slot 100g/L containing ammonium fluoride, 4# slot contain NH4HF230g/L,
7# slots contain NH4HF210g/L, HNO3200g/L.When being avoided that, it should as few as possible to use nitrogen compound containing ammonia.
4, contain COD：1# slots 6.5g/L containing sorbierite, 4# slot 40g/L containing sorbierite, it should the change containing COD as few as possible
Close object.
Applicant four work nest of another application for a patent for invention (201010515738) aluminium alloy unification medicament full recycling and
Wastewater zero discharge surface pretreatment system capable of combining discloses the section medicine water-saving method for replacing four pharmacy slots of acid etching with a pharmacy slot.
Slot position is arranged as shown in figure 5, its each work nest and system function are as follows：
1# four-in-one sand face slot
This slot is alkaline tank liquor, function is degreasing, go natural oxide film, go line, dusting, adjustment aluminium alloy background color, dedusting,
Medium temperature polishes；1# four-in-one sand face slot：NaOH 60g/L,Na2SO4 10g/L,Na3PO45g/L, sorbierite 5g/L, dodecane
Base sodium sulfonate 0.3g/L, excess water；Operating temperature is 65 DEG C, and processing time is 8 minutes, drip 1 minute；
2# zero diopter slots
1# slot medicaments are retained, precipitated aluminium hydroxide and aluminum phosphate are decomposed, regeneration recycling lye carries out low temperature throwing to frosted material
Light, produces zero diopter material and sweeps line material, and liquid level is supplemented to 1# slots；
3#, 4# wash entrapping tank
It further retains medicament, decompose precipitated aluminium hydroxide and aluminum phosphate, regeneration recycling lye；
5# washes entrapping tank
The 4# lye taken out of of washing entrapping tank and 6# washings wait for the acid solution of the reversed moisturizing of hopper in this slot is online and, make place
The aluminium of reason smoothly transits to acid tank liquor by alkaline tank liquor；
6# washings wait for hopper
This slot is connected to the 8# rinsing bowls after oxidation, and tank liquor is acidity.Aluminium in this slot is further and, ash disposal, in acid
It waits expecting under the conditions of property, spot corrosion and hickie can be prevented；Enter 7# oxidation troughs after acid washing, saves oxidation solution；
7# oxidation troughs
This slot is regular oxidation, and the oxidation solution taken out of is retained by 8# washing entrapping tanks, supplements 8# and 6# slot acid solutions, maintain 6#
Slot acidity；
8# washes entrapping tank
This slot is rinsing bowl after oxidation, with 6# differential concatenations, retains oxidation solution, maintains the acidity value of 6# slots.
Each system function is as follows：
Slag pumping system
By 2# slots, 3# slots, 4# slots and 5# slots and 1# pairs slot and 2# pairs slot, centrifuge, clean solution tank, 2# valves, 3# valves, 4#
Valve, 5# valves, 7# valves, 8# valves, 10# valves, 11# valves, 12# valves, 13# valves and 1# take out pulp pump, 2# clear liquid pumps,
3# pipeline pumps, 4# pipeline pumps and 5# pipeline pumps composition.2# slots, 3# slots, 4# slots and 5# slots are in parallel, slot bottom nozzle equipped with 2# valves,
3# valves, 4# valves and 5# valves are connected by 3# pipeline pumps, 4# pipeline pumps with 5# pipeline pumps between slot, 3# pipeline pumps and 2# valves
Outlet is connected with threeway, and another by-pass line connection 1# of this threeway takes out pulp pump, through 8# valves to 2# pair slots.Secondary trench bottom is equipped with 10#
Valve, 11# valves, 12# valves and 13# valves connect centrifuge.Centrifuge connects clean solution tank, and clean solution tank is connected by 2# clear liquid pumps
Connect 2# pair slots.1# slots do not have sediment, are not required to take out slag, but require supplementation with liquid level.Therefore 1# pairs slot is connected to 2# pair slots, centre is equipped with 7#
Valve is equipped with 1# valves between 1# pairs slot and 1# major troughs.When 2# slots take out slag, 2# valves and 8# valves are opened, other slot valves are closed
Door, the slags of 2# slots can be taken out to 2# pair slots by opening 1# and taking out pulp pump, and tank liquor overflows back 2# slots；Open 7# valves between 1# pairs slot and 2# pair slots
Door, 2# pair slot tank liquors flow into 1# pair slots.When scarfing cinder, 10# valves, 11# valves, 12# valves and 13# valves, alkaline residue are opened respectively
Centrifuge dewatering, scarfing cinder are flowed into, liquid flows into clean solution tank, 2# pair slots are pumped back to by 2# clear liquids.After scarfing cinder, 2# slots need replenisher
2# valves and 3# valves are opened in position, close other valves, open 3# pipeline pumps, you can take out the sediment of 3# slots and liquid together
To 2# slots.Not only 2# tank liquors position, but also recycling 3# slot medicaments had been supplemented, 3# slot sediments are also extracted into.4# slots are extracted into 3# slots, and 5# slots are extracted into 4# slots
Slag is taken out to analogize.
Medicament recovery system
It is made of 1# slots, 1# valves and slag pumping system, while cleaning reaction aluminium slag, recycles medicament.Medicine when due to production
Agent is only added to 1# slots, and 1# slots maintain strong basicity, and 2# slots, 3# slots, 4# slots and 5# slots are medicament entrapping tank, and basic agent comes from
1# slots, concentration is from high to low.By Bayer process, the sodium metaaluminate generated in 1# slots decomposes in 2# slots, 3# slots, 4# slots and 5# slots,
Generate sediment aluminium hydroxide and lye sodium hydroxide.Sediment is handled by slag pumping system, and lye is reversed to recycle to take out in a manner of slag, 2#
Secondary slot mends 1# slots through 1# pair slots, and 3# slots mend 2# slots, and 4# slots mend 3# slots, and 5# slots mend 4# slots.
Water circularly purifying processing system
It is made of 8# slots, 7# slots and 6# slots, moisturizing pond, filtering ponds, scum filtering collecting bag, 9# valves and 6# circulating pumps.
The acid water of moisturizing pond is evacuated to high-order filtering ponds by 6# circulating pumps, after sock filtration, overflows to 8# slots and 6# slots, then overflow
Pond is covered, circulating filtration is completed.7# slots provide acid solution for system, keep tank liquor clear.
Reversed moisturizing neutralized system
It is made of 6# valves, water circularly purifying processing system and slag pumping system, the water consumption of reversed replenishment system.Moisturizing
When, 6# valves are opened, the acid water of 6# slots passes through surface overflow to 5# slots.1# slots, 2# slots, 3# slots, 4# slots supplement liquid level press medicine
Agent way of recycling carries out.
Recycling and wastewater zero discharge surface pretreatment system capable of combining pass through nearly 5 to above-mentioned four work nest of application aluminium alloy unification medicament entirely
Year operation, be entirely capable of replacing four slots with a slot, produce sand plane materiel, medication can be greatly reduced and with water, and realize medicament recycling,
But there is the problem of following several respects to need to improve：
1, the chemical formulation of 1# four-in-ones sand face slot needs to improve：This flowing current separation NaOH 60g/L, Na2SO4 10g/L,
Na3PO45g/L, sorbierite 5g/L, dodecyl sodium sulfate 0.3g/L, excess water；Operating temperature is 65 DEG C, processing time 8
Minute, drip 1 minute.It is found in production following insufficient：
(1) complexing agent sorbierite is selected improper, and complexing power is inadequate.When the aluminium quantity of production increases, aluminium ion is not
Disconnected to rise, when aluminium ion is more than 100g/L, tank liquor decomposes, and aluminium hydroxide is precipitated, is suspended in tank liquor；Tank liquor viscosity rises,
Liquid level rises when production, and when temperature is high or drug concentration is high, tank liquor is easy to overflow；
(2) sand face agent Na3PO4It is improper to select, and dusting ability is inadequate.Phosphoric acid dusting is too thin, and aluminium background color is too bright；
(3) polishing agent Na2SO4It is improper to select, sand plane materiel background color should burnt hair obfuscation, client do not like shinny background color；
(4) dodecyl sodium sulfate is selected improper, and liquid level rises too fast.Tank liquor was originally very glutinous, added dodecyl sodium sulfate
Afterwards, liquid level rises faster, it is easier to which overflow slot.
2, slag pumping system is excessively complicated, and product line worker is not suitable with complex operations.Existing oxidation line is early molded, existing
It directly constructs on line, add equipment, aluminum material factory is beyond affordability.
3, medicament recovery system technical thought is very good, both reduces water consume, by reducing Drug consumptions, also reduces pollution, one action is more
.But in actual production, since the complexing agent ability of 1# four-in-one slots is inadequate, takes medicament out of and decomposed in 2#, 3#, 4#, 5# slot
Too fast, each groove groove wall fouling is very troublesome when clear bottom.
4, water circularly purifying processing system thinking is fine, in-line purification, but product line worker is not suitable with complex operations.Together
Sample, existing oxidation line is early molded, beyond affordability in both wired direct construction, addition equipment, aluminum material factory.
5, reversed moisturizing neutralized system both supplements liquid level, and by recycling medicament, technical concept is very good.But need 1# slots powerful
Complexing agent cooperation, could realize.
For above-mentioned earlier application file there are the problem of, applicant has done it further research, and is solved
The certainly technical solution of the above problem.The complicated, work for traditional alkaline etching (as shown in Figure 3), acid etching (as shown in Figure 4) and blasting craft
Make slot and rinsing bowl be too many, work efficiency is low, dosing is more, wastewater discharge is big, the cost of processing fluorine, COD and ammonia nitrogen it is too high with
And the drawbacks of sandblasting efficiency is too low, high rejection rate, take into account Chinese patent 200510101420.X bright acid etching technology for aluminium alloy and
201010515738 aluminium alloy of Chinese invention patent, four work nest unifies medicament recycling and wastewater zero discharge surface pretreatment system entirely
The pros and cons of system, the water-saving aluminium alloy sand surface treatment technique of a set of section medicine for specially designing, also act most basic purpose：Save medicine
Water-saving mesh.
Invention content
It is a kind of floride-free without treatment agent in face of ammonium four-in-one sand it is an object of the invention to propose, there is oil removing, acid etching, alkali
Erosion, the function of neutralizing four slots efficiently solve fluorine and the ammonium pollution of aluminium alloy anode oxide pre-treatment, greatly reduce enterprise's pollution treatment
Amount.
It is another object of the present invention to propose the above-mentioned floride-free application method without treatment agent in face of ammonium four-in-one sand,
Its index for using parameter is limited, the effect of its medicament is made good can to play.
It is another object of the present invention to propose using the above-mentioned floride-free medicament without treatment agent in face of ammonium four-in-one sand
Recovery system is used while being realized by the restriction of medicament the recycling to medicament, greatly reduces enterprise's pollution treatment amount, reduction is produced into
This, improves effect.
For this purpose, the present invention uses following technical scheme：
Free-floride is without treatment agent in face of ammonium four-in-one sand, including following components：Sodium hydroxide 30-50g/L, sodium chloride 100-
200g/L, sodium thiosulfate 1.5-3.5g/L, surfactant 1.5-3.5g/L, sorbierite 1.5-3.5g/L, sodium gluconate
1.5-3.5g/L, surplus are water.
Further description, the surfactant are sodium tripolyphosphate.
Further description is placed in the slot of four-in-one sand face, and operating temperature is 65 DEG C, and processing time is 8 minutes, drip
1 minute.
Use the above-mentioned floride-free medicament recovery system without treatment agent in face of ammonium four-in-one sand, the medicament recovery system
Including four-in-one slot and non-mobile water washing trough subsystem, the non-mobile water washing trough subsystem integral inverted is in series setting, and its
The beginning in water flowing direction is equipped with water supplement port, and the water outlet of terminal is series at the four-in-one slot.
Further description, the non-mobile water washing trough subsystem are provided with no less than three non-mobile water washing troughs.
Further description, the non-mobile water washing trough subsystem include：The 2# non-mobile waters washing trough of sequence arrangement, 3#
Non-mobile water washing trough and 4# non-mobile water washing troughs；The 4# non-mobile waters washing trough is provided with water supplement port.
Further description, the water supplement port and water outlet of the single groove body of non-mobile water washing trough subsystem are respectively set
In both ends, ejected wash water is flowed into from one end, and the downstream flow rinsing bowl in water flowing direction is flowed out to from the other end.
Further description, the single water supplement port and discharge outlet of the non-mobile water washing trough subsystem are respectively arranged at 4#
Non-mobile water washing trough and 2# non-mobile water washing troughs, ejected wash water are filled into from 4# non-mobile water washing troughs, are flowed into from 2# non-mobile water washing troughs
The four-in-one slot.
The above-mentioned drawback of traditional acid etching, alkaline etching oxidation line, basic reason are the following aspects：
1, configuration design concept in slot position is defective.Design excessive work nest, it is necessary to be equipped with twice of rinsing bowl；Each work
Different chemical agents will be consumed by making slot, and have acid to have alkali, although by massive laundering, also unavoidable mutual consumption,
Keep total chemical consumption further up.A large amount of medicine consumption, a large amount of water consume, huge wastewater treatment pressure is brought to aluminium processing enterprise.
Work nest is reduced as much as possible, is reduced medicine consumption to the maximum extent, is reduced water consume, be only the development side of the following process for treating surface
To；
2, the design concept of tank liquor formula is defective.In tank liquor, there is fluorine ion, limits waste water recycling；There are COD and ammonia
Nitrogen, limits discharge of wastewater, and producer has to the waste water for handling fluorine-containing, COD and ammonia nitrogen, need to pay huge environmentally friendly cost.
3, independent cleaning sink design concept is defective.5 pharmacy slots of alkaline etching oxidation line, each pharmacy slot configuration are a set of
Independent rinsing bowl, whole oxidation line configure 5 sets of washings, and independent mutually, ejected wash water 5 into 5 goes out；6 pharmacy slots of acid etching oxidation line,
Each pharmacy slot configures a set of independent rinsing bowl, and whole oxidation line configures 6 sets of washings, and independent mutually, ejected wash water 6 into 6 goes out.It will
Rinse bath differential concatenation, and the work nest reagent combination that flow upstream is compatible with downstream is researched and developed, it is the water-saving basic side of oxidation line
To.
Aluminium alloy free-floride is without treatment process in face of ammonium four-in-one sand and medicament recycling and compatible and rinse bath differential concatenation section
Water system is on the basis for fully realizing traditional alkaline etching, acid etching and sandblasting drawback, through Chinese patent 200510101420.X
Bright acid etching technology for aluminium alloy and 201010515738 aluminium alloy of Chinese invention patent, four work nest unification medicament are recycled and are given up entirely
The two sets of patented technology large-scale production operations of water zero discharge surface pretreatment system capable of combining, one to be constantly born after summary, adjustment are new
Technique.
First, present invention process has fully drawn traditional alkaline etching and acid etching uses fluorine-containing and ammonia nitrogen chemicals lesson,
Nickel fluoride, ammonium acid fluoride and the nitric acid continued to use for many years have been abandoned, has made sand face technique free-floride without ammonium, to make enterprise thoroughly break away from
Worker, etching apparatus and the predicament for discharging fluorine, ammonium waste water are endangered in hydrogen fluoride gas pollution workshop；Free-floride is without ammonium in waste water
Aluminum fabrication plant fully recycles, cycling use of water, and wastewater zero discharge solves maximum problem；
Secondly, present invention process has drawn the lesson that traditional handicraft function trough is too many, technique is too complicated, medicine consumption is too high, will
Oil removing, acid etching, alkaline etching, the function of four slots of neutralization combine in a slot, and the unification of four slots eliminates three functions of original acid etching process
Slot, reagent consumption amount are reduced to 60-80 kgs/tonne of material by 130-150 kgs/tonne of material of acid etching process, less use medicament 50% with
On；
Third, present invention process have drawn traditional handicraft aluminium and have gone out the directly too high lesson of washing, Drug consumptions after pharmacy slot,
3 non-mobile water washing troughs, retention, reuse medicament are set after four-in-one slot；
4th, present invention process just considers oxidation line waste water slant acidity in design, it is necessary to carry out alkali neutralization processing
Aluminium alloy free-floride is designed to alkaline tank liquor, the alkaline tank liquor that rinsing bowl is taken out of by feature without four slot of ammonium unification slot sand surface treatment liquid
Just anodic oxidation rinsing bowl meta-acid waste water is neutralized, when online washing takes into account ash disposal neutralization；
5th, present invention process is special through Chinese patent 200510101420.X bright acid etching technology for aluminium alloy and Chinese invention
Sharp 201010515738 aluminium alloy four work nests unification medicament recycles entirely and two sets of patents of wastewater zero discharge surface pretreatment system capable of combining
Technology large-scale production operation, fully summarizes the pros and cons of this two patents, carries out extensive medicament and system configuration adjustment, more
Suit produce reality, be easy to auxiliary facility construction, worker is easier to manage and operate.
6th, present invention process skill universality is strong, may replace alkali sand material, sour sand material and sandblasting material.The sand face aluminium produced
Material surface is without line, ashless, fine sand, beautiful.Alkaline etching aluminium consumption height, the non-uniform problem of sand grains are not only solved, while also thoroughly being solved
It has determined acid etching fluoride pollution, the non-uniform problem in sandblasting material surface.
Description of the drawings
Fig. 1 is one embodiment of the present of invention slot position layout drawing；
Fig. 2 is that the medicament recovery system of the present invention is applied to the alkaline etching slot position layout drawing of existing aluminium section bar standard；
Fig. 3 is the alkaline etching slot position layout drawing of existing aluminium section bar standard；
Fig. 4 is the acid etching slot position layout drawing of existing aluminium section bar standard；
Fig. 5 is four work nest of prior art aluminium alloy unification medicament recycling and wastewater zero discharge surface pretreatment system capable of combining cloth entirely
Set figure.
Wherein, the second valve 02, the first valve 01.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
As a kind of forward position technique of aluminum alloy surface processing, aluminium alloy free-floride is very big without four slot of ammonium unification slot sand surface treatment
Ground improves aluminum alloy surface quality, is the replacement technology of the traditional handicrafts such as existing common acid etching, alkaline etching and sandblasting, can be effectively
Fluorine and the ammonium pollution for solving aluminium alloy anode oxide pre-treatment, realize that anodic oxidation line is significantly water-saving, greatly reduce enterprise and control
Dirt amount, reduces production cost, improves effect.
As shown in Figure 1, the present invention is by 1# four-in-one sand face slot, tri- non-mobile water washing trough of 2#, 3#, 4#, 5#, 6# circulating water
Washing trough, 7# washings wait for that hopper, 8# oxidation troughs, 9#, 10# flow rinsing bowl, and 11# medium temperature sealing of hole slots and 12#, 13# flow rinsing bowl
It constitutes.Wherein, 1# four-in-ones sand face slot and 2#, 3# and 4# non-mobile water washing trough, form medicament recovery system；1#、2#、3#、4#
Slot by differential concatenation be arranged, for step retention 1# four-in-one slots medicament, 2#, 3# and 4# non-mobile water washing trough clean aluminium,
Medicament, supplement 1# tank liquors position are retained, tap water can be entered by the switch control of the second valve 02 from 4#, through 3#, 2#, into 1#
Slot to realize medicament retention and recycling, and realizes that 1# slots supplement liquid level by the switch of third valve 01；
Differential concatenation water-saving system is made of 5#, 6#, 7#, 9#, 10#, 12#, 13# flowing rinsing bowl, is passed through by tap water
The switch control of first valve 03 can enter from 13# slots, differential concatenation flowing, through 12#, 10#, 9#, 7#, 6# slot, most afterwards through 5#
Slot flows out, and realizes that whole oxidation line rinsing bowl is reversely connected greatly, traditional acid etching oxidation line ejected wash water 6 into 6 is gone out, the design is changed to
1 into 1 go out, water-saving 80% or more；8# oxidation troughs and 11# medium temperature sealing of hole slots form medicament compatible system, are designed as 11# medium temperatures
Sealing of hole slot is compatible with 8# oxidation troughs, i.e. after the medium temperature pore-sealing liquids of 11# slots brings 8# oxidation troughs into, does not influence the ability to work of oxidation solution
With the performance of Process on Aluminum Alloy Oxidation Film；
Medicament compatible system therein is compatibility of the 11# medium temperature sealing of hole slots to 8# oxidation troughs.By tap water from 13# slots into
Enter, differential concatenation flowing is most flowed out through 5# slots afterwards through 12#, 10#, 9#, 7#, 6# slot, and 11# medium temperature sealing of hole slots are clear in 8# oxidation troughs
The upstream of wash water stream, when production, medium temperature pore-sealing liquid brings 13#, 12# slot into, through 12#, 10#, 9#, 7#, 6# slot, most afterwards through 5# slot streams
Go out, 7# washings wait for pore-sealing liquid containing medium temperature in hopper, by 11# medium temperature sealing of hole slots to 8# oxidation trough compatible designs, 11# medium temperature sealing of hole slots
Containing nickel acetate, isobutanol and triethanolamine, nickel ion is conductive salt, is added to 8# oxidation troughs, can reduce tank liquor resistance, improve at
Film speed；Acetic acid and isobutanol are corrosion inhibiter, can reduce molten film speed, improve rate of film build；Triethanolamine can chelate in oxidation solution
Aluminium ion, reduce tank liquor resistance, improve rate of film build.11# medium temperature sealing of hole slot each components are completely compatible to 8# oxidation troughs, bring 8# into
After oxidation trough, the ability to work of oxidation solution and the performance of Process on Aluminum Alloy Oxidation Film are not influenced, to realize that whole oxidation line is reversely gone here and there
Connection connection, is greatly reduced water for cleaning.
The mode of production of different aluminiums is as follows：
(1) mechanical spray sand material
Sandblasting aluminium is directly entered 1# slots, reacts 4-6 minutes, 95-105 DEG C, drip 1 minute, then through 2#, 3#, 4# slot three
Road non-mobile water washing trough is cleaned into 5#, 6#, 7# rinsing bowl；It aoxidizes 45-60 minutes in 8# oxidation troughs, is cleaned through 9#, 10#；
11# slot sealing of holes 10-20 minutes are washed through 12#, 13# rinsing bowl, complete oxidation processes.
(2) chemical sanding material
Aluminium is directly entered 1# slots, reacts 8-12 minutes, 95-105 DEG C, drip 1 minute, then not through 2#, 3#, 4# slot three
Rinsing bowl is flowed, is cleaned into 5#, 6#, 7# rinsing bowl；It aoxidizes 45-60 minutes in 8# oxidation troughs, is cleaned through 9#, 10#；In 11#
Slot sealing of hole 10-20 minutes is washed through 12#, 13# rinsing bowl, completes oxidation processes.
Further description, above-mentioned each slot working mechanism are as follows：
1# four-in-one slots
1, alkaline tank liquor：In view of whole oxidation line waste water slant acidity, this slot is designed as working under alkaline condition, in
With rinsing bowl meta-acid waste water, waste water acid-base balance is realized.After aluminium enters this slot, by galvanic principles, with fine aluminium mutually for anode,
Alloy is mutually cathode, and cation is chemically reacted to alloy phase, anion to fine aluminium phase shift by reaction equation (1) and (2)；
2, striping degreasing：By reaction equation (1), aluminium first removes natural oxide film, while in the table of appropriate concentration into after this slot
Under the activating agent sodium tripolyphosphate effect of face, degreasing and fingerprint can be removed, degreasing tank is saved；
3, line is removed in dusting.This flowing current separation uses sodium chloride to go the main component of line as dusting.By reaction equation (2), fine aluminium is mutually made
It is dissolved for anode, meets with the chlorion attracted by anode；Spot corrosion dusting, and sand grains is uniform, aluminium consumption is low, removes mechanical line
Thoroughly；Reaction equation is：
Al3++3Cl-=AlCl3
2AlCl3+ 2NaOH=Al2(OH)2Cl4+2NaCl (10)
Al2(OH)2Cl4+ NaOH=Al2(OH)3Cl3+NaCl
2AlCl3+ nNaOH=Al2(OH)nCl6-n+nNaCl
Chlorion is combined near anode phase with the aluminium ion of dissolving, and aluminium polychloride is generated, and it is anti-to reduce aluminium surface chemistry
The aluminium ion concentration for answering area accelerates molten aluminium, dusting, the speed for removing line；
4, complexing completely：This slot is added with sodium thiosulfate, sorbierite and the Portugal's sodium of sufficient amount, and sorbierite is by (6) formula, Portugal
Aluminium ion is complexed by reaction equation (7) in sodium, and sodium thiosulfate forms complex compound as the following formula with aluminium ion：
Al3++2S2O3 2-=[Al (S2O3)2]- (11)
By (6), (7), (10) and (11) formula, aluminium ion can be complexed completely, and especially sodium thiosulfate is formed with aluminium
Complex ion, viscosity is extremely low, and tank liquor is limpid, good drip, good to clean, and liquid level rising is limited, it is difficult to the slot that overflows；
5, contain a large amount of Cl in tank liquor-, the grey black of aluminium material surface can pass through Cl-It removes, ash disposal need not be specially set
Slot.
The not flowing grooves of 2#, 3# and 4# tri-
1, aluminium is cleaned.For 1# slots aluminium ion up to 150g/L or more, viscosity is very high.Scavenging period is 2# slots 2 minutes；3# slots
2 minutes；4# slots 1 minute；The medicament that thoroughly cleaning aluminium is taken out of；
2, medicament is retained.Three rinse baths retain step by step.The medicament that 1# slots are carried over, concentration is at terraced distribution；2# slots
Drug concentration is high, and 4# slot drug concentrations are low；
3, medicament, supplement 1# tank liquors position are recycled.In 1# slots, the evaporation and carry-over loss of medicament, liquid level constantly decline, need
Supplement liquid level.The second valve 02 is opened, tap water enters from 4# slots, flows through 3#, 2# slot, finally enter 1# slots, both supplements liquid
Position, and realize the recycling step by step of medicament.
The working index of whole oxidation line is：
1# four-in-one sand face slot：Sodium hydroxide 30-50g/L, sodium chloride 100-200g/L, sodium thiosulfate 1.5-3.5g/
L, sodium tripolyphosphate 1.5-3.5g/L, sorbierite 1.5-3.5g/L, sodium gluconate 1.5-3.5g/L, excess water；Operating temperature
It it is 80-90 DEG C, processing time is 8-12 minutes, drip 1 minute；
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
As shown in Fig. 2, subsequent technique is carried out by existing standard alkaline etching slot, connects its 8# flowing rinsing bowls and start (Fig. 3 institutes
Show), through oxidation after washing, sealing of hole is carried out after oxidation, finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
1# four-in-ones frosted slot removes line ingredient sodium chloride, a concentration of 100-200g/L of Optimization Work added with dusting；Separately
It is added with tank liquor stable elements sodium thiosulfate, a concentration of 1.5-3.5g/L of Optimization Work outside；Except oil component sodium tripolyphosphate,
A concentration of 1.5-3.5g/L of its Optimization Work；Complexing components sorbierite, a concentration of 1.5-3.5g/L of Optimization Work；It is all complexing
Component sugar glucose acid sodium, a concentration of 1.5-3.5g/L of Optimization Work, in addition, 1# four-in-one frosteds slot is also added with hydroxide
Sodium, a concentration of 30-50g/L of Optimization Work；It is useless that the alkaline tank liquor that rinsing bowl is taken out of neutralizes anodic oxidation rinsing bowl meta-acid just
Water, online ash disposal neutralize.
Compared with common acids alkaline etching and sandblasting, the present invention has following major technological breakthrough：
1, the angle carried out production strictly in line with rules and regulations for the first time with modern environmentally friendly, energy saving, emission reduction, consumption reduction, cleaning, is significantly changed, is set again
Count aluminium alloy anode oxide production line；
2, selection aluminum alloy surface meticulously handles chemical agent formula for the first time, thoroughly prevents ingredient fluorine-containing, containing ammonium, it is ensured that
Cost for wastewater treatment is greatly reduced without ammonium in whole oxidation line free-floride；
3, the laying out slot positions that abandoning tradition technique is consumed mutually to alkali, again by alkali to acid, medicament by acid for the first time, using one
Pharmacy slot pre-treatment aluminium, channelling, water-saving do not save medicine；
4, it reduces function trough on a large scale for the first time, four function troughs of acid etching process is reduced to one, medicine is greatly lowered
Consumption improves effect；
5, the medicament recovery system being made of 1# four-in-ones slot and 2#, 3# and 4# non-mobile water washing trough is set for the first time.2#、3#
Aluminium is cleaned with 4# non-mobile water washing troughs, retains medicament step by step；4#, 3#, 2#, 1# differential concatenation, by 4# slot moisturizings, reverse flow
It is dynamic, medicament is recycled to 1# slots step by step, Drug consumptions are greatly reduced in 80% or more the medicament rate of recovery；
The present invention takes 150L sump volume design simulation oxidation lines, each function trough to slot by 100L, and parameters of bath control is as follows
Shown in each embodiment.
Embodiment 1 group-four-in-one sand plane materiel produces
The reagent combination and working index of each slot be：
1# four-in-one sand face slot：Sodium hydroxide, sodium chloride, sodium thiosulfate, sodium tripolyphosphate, sorbierite, gluconic acid
Sodium according to the form below 1 adds, and surplus is water；Operating temperature is 85 DEG C, and processing time is 10 minutes, drip 1 minute；
| Classification | Embodiment 1-1 | Embodiment 1-2 | Embodiment 1-3 |
| Sodium hydroxide | 30g/L | 40g/L | 50g/L |
| Sodium chloride | 100g/L | 100/L | 100g/L |
| Sodium thiosulfate | 2.5g/L | 2.5g/L | 2.5g/L |
| Sodium tripolyphosphate | 2.5g/L | 2.5g/L | 2.5g/L |
| Sorbierite | 2.5g/L | 2.5g/L | 2.5g/L |
| Sodium gluconate | 2.5g/L | 2.5g/L | 2.5g/L |
Table 1
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
As shown in Fig. 2, subsequent technique is carried out by existing standard alkaline etching slot, connects its 8# flowing rinsing bowls and start (Fig. 3 institutes
Show), through oxidation after washing, sealing of hole is carried out after oxidation, finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
Embodiment group 1 can be mass aluminum alloy chemically frosted material, and as naoh concentration increases, reaction speed
Accelerate, can suitably reduce reaction temperature, shortens the reaction time.
Embodiment 2 groups-four-in-one sand plane materiel produces
The reagent combination and working index of each slot be：
1# four-in-one sand face slot：Sodium hydroxide, sodium chloride, sodium thiosulfate, sodium tripolyphosphate, sorbierite, gluconic acid
Sodium according to the form below 2 adds, and surplus is water；Operating temperature is 85 DEG C, and processing time is 10 minutes, drip 1 minute；
| Classification | Embodiment 2-1 | Embodiment 2-2 |
| Sodium hydroxide | 40g/L | 40g/L |
| Sodium chloride | 150g/L | 200g/L |
| Sodium thiosulfate | 2.5g/L | 2.5g/L |
| Sodium tripolyphosphate | 2.5g/L | 2.5g/L |
| Sorbierite | 2.5g/L | 2.5g/L |
| Sodium gluconate | 2.5g/L | 2.5g/L |
Table 2
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
As shown in Fig. 2, subsequent technique is carried out by existing standard alkaline etching slot, connects its 8# flowing rinsing bowls and start (Fig. 3 institutes
Show), through oxidation after washing, sealing of hole is carried out after oxidation, finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
Embodiment group 2, can be mass aluminum alloy chemically frosted material, can be obtained from embodiment 2-1 to 2-2, with sodium chloride
Concentration increases, and dusting speed is accelerated, and sand face is aggravated.Reaction temperature can be suitably reduced, the reaction time is shortened.
Embodiment 3 groups-four-in-one sand plane materiel produces
The reagent combination and working index of each slot be：
1# four-in-one sand face slot：Sodium hydroxide, sodium chloride, sodium thiosulfate, sodium tripolyphosphate, sorbierite, gluconic acid
Sodium according to the form below 3 adds, and surplus is water；Operating temperature is 85 DEG C, and processing time is 10 minutes, drip 1 minute；
| Classification | Embodiment 3-1 | Embodiment 3-2 | Embodiment 3-3 | Embodiment 3-4 |
| Sodium hydroxide | 40g/L | 40g/L | 40g/L | 40g/L |
| Sodium chloride | 100g/L | 100g/L | 100g/L | 100g/L |
| Sodium thiosulfate | 1.5g/L | 3.5g/L | 2.5g/L | 2.5g/L |
| Sodium tripolyphosphate | 2.5g/L | 2.5g/L | 1.5g/L | 3.5g/L |
| Sorbierite | 2.5g/L | 2.5g/L | 2.5g/L | 2.5g/L |
| Sodium gluconate | 2.5g/L | 2.5g/L | 2.5g/L | 2.5g/L |
Table 3
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
As shown in Fig. 2, subsequent technique is carried out by existing standard alkaline etching slot, connects its 8# flowing rinsing bowls and start, after washing
It is oxidized, sealing of hole is carried out after oxidation, finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
Embodiment group 3, can be mass aluminum alloy chemically frosted material, can be obtained from embodiment 3-1 to 3-2, with thio sulphur
Sour na concn increases, and reaction speed reduces, and Stability of Bath Solution increases, and can properly increase reaction temperature, extends the reaction time；From reality
Applying a 3-3 to 3-4 can obtain, and as tripolyphosphate na concn increases, tank liquor aluminium ion complexing power increases, and reaction speed reduces,
Reaction temperature can be properly increased, the reaction time is extended.
Embodiment 4 groups-four-in-one sand plane materiel produces
The reagent combination and working index of each slot be：
1# four-in-one sand face slot：Sodium hydroxide, sodium chloride, sodium thiosulfate, sodium tripolyphosphate, sorbierite, gluconic acid
Sodium according to the form below 4 adds, and surplus is water；Operating temperature is 85 DEG C, and processing time is 10 minutes, drip 1 minute；
| Classification | Embodiment 4-1 | Embodiment 4-2 | Embodiment 4-3 | Embodiment 4-4 |
| Sodium hydroxide | 40g/L | 40g/L | 40g/L | 40g/L |
| Sodium chloride | 100g/L | 100g/L | 100g/L | 100g/L |
| Sodium thiosulfate | 2.5g/L | 2.5g/L | 2.5g/L | 2.5g/L |
| Sodium tripolyphosphate | 2.5g/L | 2.5g/L | 1.5g/L | 3.5g/L |
| Sorbierite | 1.5g/L | 3.5g/L | 2.5g/L | 2.5g/L |
| Sodium gluconate | 2.5g/L | 2.5g/L | 1.5g/L | 3.5g/L |
Table 4
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
Subsequent technique is carried out by existing standard alkaline etching slot, is connect its 8# flowing rinsing bowls and is started (shown in Fig. 3), to pass through after washing
Oxidation, sealing of hole is carried out after oxidation, and finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
Embodiment group 4, can be mass aluminum alloy chemically frosted material, can be obtained from embodiment 4-1 to 4-2, with sorbierite
Concentration increases, and tank liquor aluminium ion complexing power increases, and reaction speed reduces, and can properly increase reaction temperature, extends the reaction time；
It can be obtained from embodiment 4-3 to 4-4, tank liquor aluminium ion complexing power increases, and reaction speed reduces, and can properly increase reaction temperature,
Extend the reaction time.
Embodiment 5- four-in-one sand plane materiels produce
The reagent combination and working index of each slot be：
1# four-in-one sand face slot：Sodium hydroxide 40g/L, sodium chloride 100g/L, sodium thiosulfate 2.5g/L, sodium tripolyphosphate
2.5g/L, sorbierite 2.5g/L, sodium gluconate 2.5g/L, excess water；Operating temperature is 80 DEG C, and processing time is 10 minutes,
Drip 1 minute；
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
Subsequent technique is carried out by existing standard alkaline etching slot, is connect its 8# flowing rinsing bowls and is started (shown in Fig. 3), to pass through after washing
Oxidation, sealing of hole is carried out after oxidation, and finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
Embodiment 6- four-in-one sand plane materiels produce
In addition to the operating temperature of 1# four-in-one sand face slot is 90 DEG C, the reagent combination and working index of other each slots and implementation
The processing of example 5 is consistent.It can be obtained from embodiment 5 and embodiment 6, as tank liquor temperature increases, reaction speed is accelerated, and can suitably reduce
Drug concentration shortens the reaction time.
Embodiment 7- four-in-one sand plane materiels produce
The reagent combination and working index of each slot be：
1# four-in-one sand face slot：Sodium hydroxide 40g/L, sodium chloride 100g/L, sodium thiosulfate 2.5g/L, sodium tripolyphosphate
2.5g/L, sorbierite 2.5g/L, sodium gluconate 2.5g/L, excess water；Operating temperature is 85 DEG C, and processing time is 8 minutes, drop
Stream 1 minute；
2# non-mobile water washing troughs：Washing 2 minutes, drip 30 seconds；
3# non-mobile water washing troughs：Washing 1.5 minutes, drip 30 seconds；
4# non-mobile water washing troughs：Washing 1 minute, drip 30 seconds；
Subsequent technique is carried out by existing standard alkaline etching slot, is connect its 8# flowing rinsing bowls and is started (shown in Fig. 3), to pass through after washing
Oxidation, sealing of hole is carried out after oxidation, and finally washing is air-dried, packaging, is put in storage, and completes surface treatment.
Embodiment 8- four-in-one sand plane materiels produce
In addition to the processing time of 1# four-in-one sand face slot is 12 minutes, the reagent combination and working index and reality of other each slots
The processing for applying example 7 is consistent.It can be obtained from embodiment 7 and embodiment 8, with the increase in aluminium reaction time in tank liquor, aluminium consumption increases
Add, sand face is aggravated, and drug concentration can be suitably reduced, and shortens the reaction time.
Embodiment 9- medicament recovery systems are tested
The second valve 02 and the first valve 01 are opened, tap water enters 4#, through 3#, 2#, into 1# slots, supplements 1# tank liquors
Position；Realize medicament retention, recycling.1# tank liquors position can be supplemented；Realize medicament retention, recycling.
The technical principle of the present invention is described above in association with specific embodiment.These descriptions are intended merely to explain the present invention's
Principle, and it cannot be construed to limiting the scope of the invention in any way.Based on the explanation herein, the technology of this field
Personnel would not require any inventive effort the other specific implementation modes that can associate the present invention, these modes are fallen within
Within protection scope of the present invention.
Claims (2)
1. free-floride is without treatment agent in face of ammonium four-in-one sand, it is characterised in that：Including following components：Sodium hydroxide 30-50g/L,
Sodium chloride 100-200g/L, sodium thiosulfate 1.5-3.5g/L, surfactant 1.5-3.5g/L, sorbierite 1.5-3.5g/L,
Sodium gluconate 1.5-3.5g/L, surplus are water；The surfactant is sodium tripolyphosphate.
2. using the floride-free method without treatment agent in face of ammonium four-in-one sand described in claim 1, it is characterised in that：It is placed in
In the slot of four-in-one sand face, operating temperature is 65 DEG C, and processing time is 8 minutes, drip 1 minute.
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