CN109534549A - Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration - Google Patents
Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration Download PDFInfo
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- CN109534549A CN109534549A CN201811544950.5A CN201811544950A CN109534549A CN 109534549 A CN109534549 A CN 109534549A CN 201811544950 A CN201811544950 A CN 201811544950A CN 109534549 A CN109534549 A CN 109534549A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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Abstract
Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration, 1# degreasing tank hydrofluoric acid containing and phosphonobutane tricarboxylic acid；6# chromaking slot hydrofluoric acid containing, phosphonobutane tricarboxylic acid and chromic anhydride.On the basis of 1# degreasing tank is compatible to 6# chromaking slot medicament, 2# slot, 3# slot, 4# slot, 5# slot are designed as non-mobile water washing trough by the present invention, differential concatenation moisturizing, tap water enters from 5# slot, through 5# slot → 4# slot → 3# slot → 2# slot → 1# slot reverse flow, degreaser is recycled, oil removing medicament and water for cleaning are saved；7# drains the chromaking liquid of slot collection, is pumped into 6# chromaking slot through pump 1, recycles chromaking liquid, realizes waste water and dregs zero-emission, and production and environmentally friendly cost is greatly reduced.
Description
Technical field
The present invention relates to aluminum alloy processing technology field more particularly to Al alloy powder spraying pretreatment chromaking line waste water are useless
Slag zero-emission configuration.
Background technique
Chromate waste water is generated after spraying chromaking pretreatment, chromium belongs to a class of pollutant, and processing must be collected separately in waste water, gives up
Water is up to standard can just to be discharged.Chromyl waste water is usually to be handled using oxide-reduction method, that is, uses ferrous sulfate, Jiao Ya
The reducing agents such as sodium sulphate are by Cr in waste water6+It is reduced into Cr3+, then wastewater pH is transferred to 7-8, add alkali and flocculant to make Cr3+Form Cr
(OH)3Precipitating forms chromium hydroxide (trivalent chromium) chromium slag by flocculation, sedimentation, filter-press dehydration.Chromium slag belongs to hazardous waste, must
Palpus legal transfer is standardized to the qualified third-party institution and is disposed.
In short, the processing cost of disposal of chromate waste water waste residue is high, business burden weight has environmental hazard, either political affairs
Mansion or enterprise's " talking chromium discoloration ".
To solve the bring pollution problem of chromaking technique, a large amount of Chromeless process substitution is carried out both at home and abroad for many years and has ground
Study carefully, and is widely used in aluminum profile industry.Chromeless process mainly has two technology paths, first is that titanium zirconium system, second is that
Silane systems, Chinese aluminium section bar plant using it is more be titanium zirconium system fluotitanic acid, fluorine zirconic acid passivation technology.The technique passivating film
And spray coating quality can achieve the requirement of GB/T 5237.4-2017 substantially, but in terms of certain indexs and overall stability not
Such as chromaking film, and outdoor long-term inspection is not lived through.And Chromeless process control requires sternly, and conversion film does not have color, existing
Field is difficult to judge film quality, careless slightly, it is possible to cause product unqualified.To guarantee product quality, F-C paint spary coating type
Material and curtain wall veneer still use chromaking technique.More crucially fluotitanic acid, fluorine zirconic acid Chrome-free medicament are fluorine-containing, very strong using toxicity
Chrome-free chemical agent still can bring the pollution problem of fluorine." wolf is driven at front door, and back door is into tiger ", is replaced with technique equally not environmentally
In generation, has the technique of pollution to be also not optimal selection.
Existing Chinese patent " a kind of Aluminum subtracts the oil removing of slag and chromaking medicament is stable and compatible method "
2017114771.9), " a kind of Aluminum subtracts the oil removing of slag and chromaking medicament is compatible and water-saving system " (201711472761.7),
" a kind of Aluminum subtract slag oil removing and chromaking medicament it is compatible and subtract dirty spray system " (201711471764.9) propose 1# degreasing tank
The compatible method with 4# chromaking slot, the stabilization of two pharmacy slot ingredients are compatible, medicament is independent of each other after bringing into pharmacy slot
Property and ability to work.On this basis, non-mobile water washing trough is configured, realizes waste water and dregs zero-emission.Wherein, 1# degreasing tank works
Index are as follows: nitric acid (68wt.%) 40-60g/L, hydrofluoric acid (50wt.%) 5-15g/L, acidity value 1.5-2.0 equivalent are (with 50%
Hydrofluoric acid tune acidity value), 20-35 DEG C of temperature；The Con trolling index of chromaking slot are as follows: chromic anhydride CrO32.5-3.5g/L, hydrofluoric acid
(50wt.%) 0.4-0.8g/L, nitric acid (68wt.%) 5-7g/L, pH 1.8-2.2,20-35 DEG C of temperature.
Production run shows that degreasing tank selects nitric acid (68wt.%) 40~60g/L and hydrofluoric acid (50wt.%) 5-15g/
L, degreasing tank and rinsing bowl are highly stable, and nitric acid is passivation ingredient, limit the molten aluminum amount of degreasing tank, meanwhile, the dissolution of nitric acid is special
Property, it is suppressed that the precipitation of fluoride keeps degreasing tank and rinsing bowl clear, does not decompose, do not precipitate；But the passivation ability of nitric acid is too
By force, after the increase of degreasing tank aluminium ion, the etching power of hydrofluoric acid is inadequate, seriously affects the etching power of degreasing tank；Chromaking flowing current separation
With chromic anhydride CrO32.5-3.5g/L, hydrofluoric acid (50wt.%) 0.4-0.8g/L, nitric acid (68wt.%) 5-7g/L, nitric acid participate in oxygen
Change trivalent chromium be Cr VI, decompose be precipitated nitrogen dioxide, be easy to cause concentration of nitric acid inadequate, chromaking slot be easy to produce aluminum fluoride and
The precipitating such as charomic fluoride；After configuring water for cleaning zero-emission, these problems are more prominent.
Summary of the invention
It is an object of the invention to propose Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration, utilize
1# the degreasing tank chelating and corrosion inhibiting ability superpower to the compatible unique design of 6# chromaking slot medicament and PBTCA, chelated mineral sun
Ion, 1#-7# slot is not muddy, does not precipitate, and by degreasing tank ejected wash water differential concatenation to degreasing tank, recycles degreaser；7# drains slot
The chromaking agent of collection is recycled to 6# chromaking slot；It realizes waste water and dregs zero-emission, production and environmentally friendly cost is greatly reduced.
To achieve this purpose, the present invention adopts the following technical scheme:
Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration, comprising: 1# degreasing tank, non-mobile water are washed
Group slot, 6# chromaking slot, 7# drain slot, pump 1 and water inlet；
The 1# degreasing tank, non-mobile water wash a group slot, 6# chromaking slot, 7# and drain that slot is adjacent to be configured in order；
The non-mobile water washes group slot differential concatenation in the 1# degreasing tank；
The 7# drains slot, the pump 1 is connected with 6# chromaking slot differential concatenation；
The non-mobile water washes group slot and connects water inlet；
Contain degreaser in the 1# degreasing tank, the chemical constituent of the degreaser includes: hydrofluoric acid and phosphinylidyne butane
Tricarboxylic acids；
Contain chromaking agent in the 6# chromaking slot, the chemical constituent of the chromaking agent includes: hydrofluoric acid, phosphinylidyne butane three
Carboxylic acid and chromic anhydride.
The chemical component of the 1# degreasing tank is compatible to the chemical component of the 6# chromaking slot, and the degreaser is brought into described
After 6# chromaking slot, the chromaking ability and stability of the 6# chromaking slot are not influenced.
It further explains, in the 1# degreasing tank, the hydrofluoric acid (50wt.%): the phosphonobutane tricarboxylic acid
(50wt.%)=3:1.
It further explains, in the 6# chromaking slot, the hydrofluoric acid (50wt.%): the phosphonobutane tricarboxylic acid
(50wt.%): the chromic anhydride=0.2:1:1.
It further explains, it includes: the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, 4# that the non-mobile water, which washes a group slot,
Non-mobile water washing trough and 5# non-mobile water washing trough；
Water inlet is connected in the 5# non-mobile water washing trough；
The 5# non-mobile water washing trough, the washing trough of 4# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 2# non-mobile water and 1# are removed
The connection of oil groove differential concatenation.
It further explains, the water source of the water inlet is tap water.
It further explains, the concentration of the degreaser is controlled in 20-30g/L, acidity value 0.5-1.0.
It further explains, the chromaking agent concentration control is in 6.0-8.0g/L.
It further explains, the pH of the 6# chromaking slot is controlled in 1.5-2.5.
It further explains, the chromaking time of the 6# chromaking slot is 60-120 seconds.
It further explains, the chromaking temperature of the 6# chromaking slot is 5-35 DEG C.
It further explains, the 2# non-mobile water washing trough is equipped with one-way valve 7 to the 1# degreasing tank, and the 3# does not flow
Rinsing bowl is equipped with one-way valve 6 to the 2# non-mobile water washing trough, and the 4# non-mobile water washing trough is to the 3# non-mobile water washing trough
Equipped with one-way valve 5, the 5# non-mobile water washing trough is equipped with one-way valve 4, the 5# non-mobile water to the 4# non-mobile water washing trough
Washing trough is equipped with valve 3 at the connection water source；The both ends of the pump 1 are respectively equipped with valve 1 and valve 2；
The tap water of supplement is successively through the 5# non-mobile water washing trough, the washing trough of 4# non-mobile water, the washing trough of 3# non-mobile water, 2#
Non-mobile water washing trough and 1# degreasing tank reverse flow supplement 1# degreasing tank liquid level, recycle degreaser；7# drains slot and 6# chromaking slot
Differential concatenation recycles chromaking agent.
Beneficial effects of the present invention:
1, the present invention simplifies by selecting meticulously and removes oil ingredient, rejecting those reduces chromaking slot ability to work or influence chromium
Change slot stability component, degreasing tank component is designed as it is completely compatible to chromaking slot, thoroughly release except oil ingredient damage chromaking
The risk of slot.
2, special corrosion inhibiter PBTCA is selected, is adsorbed on positively charged aluminium using its electronegative phosphono and three carboxyls
Alloy surface, the function that tank liquor is isolated, slow down corrosion, reduce molten aluminum amount, keep tank liquor stable operation.
3, it directly selects hydrofluoric acid and chromic anhydride as main film-forming components for the first time, the stability of tank liquor is significantly increased.This
Invention eliminates bichromate and fluorine-containing salt from the stability of chromaking liquid, directly selection hydrofluoric acid and chromic anhydride, avoids
Generate the risk of villiaumite precipitating.
4, it makes full use of medicament compatible for the first time and Stability of Bath Solution principle, cleaning sink 2#-5# slot is designed as not flowing
Rinsing bowl, differential concatenation configuration, tap water enter from 5# slot, through 5# → 4# → 3# → 2# → 1# slot reverse flow, supplement 1# slot
Liquid level recycles degreaser, reduces 5# slot drug concentration, realizes waste water and dregs zero-emission.
Detailed description of the invention
Fig. 1 is Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration；
Fig. 2 is PBTCA molecular structure.
Specific embodiment
Pass through specific embodiment to further illustrate the technical scheme of the present invention with reference to the accompanying drawing.
Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration, as shown in Figure 1, comprising: 1# degreasing tank,
Non-mobile water washes a group slot, 6# chromaking slot, 7# and drains slot, pump 1 and water inlet；
The 1# degreasing tank, non-mobile water wash a group slot, 6# chromaking slot, 7# and drain that slot is adjacent to be configured in order；
The non-mobile water washes group slot differential concatenation in the 1# degreasing tank；
The 7# drains slot, the pump 1 is connected with 6# chromaking slot differential concatenation；
It further explains, it includes: the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, 4# that the non-mobile water, which washes a group slot,
Non-mobile water washing trough and 5# non-mobile water washing trough；
Water inlet is connected in the 5# non-mobile water washing trough；
The 5# non-mobile water washing trough, the washing trough of 4# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 2# non-mobile water and 1# are removed
The connection of oil groove differential concatenation.
Contain degreaser in the 1# degreasing tank, the chemical constituent of the degreaser includes: hydrofluoric acid (HF) and phosphono
Butane tricarboxylic acid (PBTCA)；
Contain chromaking agent in the 6# chromaking slot, the chemical constituent of the chromaking agent includes: hydrofluoric acid, phosphinylidyne butane three
Carboxylic acid and chromic anhydride.
The chemical component of the 1# degreasing tank is compatible to the chemical component of the 6# chromaking slot, and the degreaser is brought into described
After 6# chromaking slot, the chromaking ability and stability of the 6# chromaking slot are not influenced.
It further explaining, 1# degreasing tank of the invention and 6# chromaking slot select phosphonobutane tricarboxylic acid (PBTCA),
Using its unique chemical characteristic, not only when chelating agent, corrosion inhibiter but also when phosphorization filming agent uses, chelated metal ions, and inhibition
Aluminium surface reduces molten aluminum amount, stablizes tank liquor；The metal ion that PBTCA is chelated in 6# chromaking slot, can also be by the phosphono of PBTCA
The effect of base bridge joint, direct phosphating is film-forming components, eliminates the wind of 6# chromaking slot dead slot because of metal ion and PBTCA progressive poisoning
Danger.On the basis of 1# degreasing tank is compatible to 6# chromaking slot chromium-free deactivation slot medicament, the present invention by the washing trough of 2# non-mobile water, 3# not
Flowing rinsing bowl, the washing trough of 4# non-mobile water and 5# non-mobile water washing trough are designed as non-mobile water washing trough, differential concatenation moisturizing, supplement
Tap water (not being pure water) from 5# non-mobile water washing trough enter, not through 5# non-mobile water washing trough → 4# non-mobile water washing trough → 3#
Rinsing bowl → 2# non-mobile water washing trough → 1# degreasing tank reverse flow is flowed, 1# tank liquor position is supplemented, recycles degreaser, saves oil removing
Medicament and water for cleaning；7# drains the chromaking liquid of slot collection, is pumped into 6# chromaking slot through pump 1, recycles chromaking liquid, production is greatly reduced
With environmentally friendly cost, waste water and dregs zero-emission is realized.
1# degreasing tank and the flowing current separation of 6# chromaking special corrosion inhibiter and chelating agent PBTCA, using its electronegative phosphono and
The function that three carboxyls are adsorbed on positively charged aluminum alloy surface, tank liquor is isolated, slows down corrosion, reduces molten aluminum amount, chelating it is positive from
Son keeps 1# degreasing tank, 6# chromaking slot and non-mobile water to wash a group flute length phase stable operation.
1# degreasing tank medicament is designed as completely compatible to 6# chromaking slot medicament by the design, prevents to bring 6# chromium into except oil component
After changing slot, the damage to 6# chromaking slot ability to work and stability.The present invention simplifies by selecting meticulously and removes oil ingredient, reject
Those reduce 6# chromaking slot ability to work or influence the component of 6# chromaking slot stability, are hydrogen fluorine by 1# degreasing tank component selection
Acid and PBTCA, it is completely compatible to 6# chromaking slot, thoroughly release the wind except oil ingredient damage chromaking slot chromaking ability and stability
Danger.
It further explains, in the 1# degreasing tank, the hydrofluoric acid (50wt.%): the phosphonobutane tricarboxylic acid
(50wt.%)=3:1.
It further explains, 1# degreasing tank also adds in addition to addition etches ingredient hydrofluoric acid (50wt.%) 15-22.5g/L
Special chemical constituent PBTCA (50wt.%) 5-7.5g/L has both inhibition using PBTCA and chelates unique chemical property, chela
Aluminium ion is closed, inhibition aluminium surface reduces molten aluminum amount, keeps 1# degreasing tank, the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, 4#
Non-mobile water washing trough and 5# non-mobile water washing trough production run steady in a long-term, do not decompose, are not muddy, fluoride is not precipitated.
It further explains, in the 6# chromaking slot, the hydrofluoric acid (50wt.%): the phosphonobutane tricarboxylic acid
(50wt.%): the chromic anhydride=0.2:1:1.
It further explains, 6# chromaking slot is except addition film forming component hydrofluoric acid (50wt.%) 0.5-1.0g/L, chromic anhydride 2.5-
Outside 5.0g/L, special chemical constituent PBTCA (50wt.%) 2.5-5.0g/L is also added, has both inhibition, chelating using PBTCA
With the unique chemical property of phosphorization filming, inhibition aluminium surface reduces molten aluminum amount, chelated metal ions, ion chelate complex phosphatization
Film forming thoroughly eliminates 6# chromaking slot because metal ion and PBTCA are accumulated due to the risk of the dead slot of aging；The addition of PBTCA, it is ensured that
6# chromaking slot, 7# drain the operation of flute length phase steady production, do not decompose, is not muddy, fluoride is not precipitated.
It further explains, the water source of the water inlet is tap water.
PBTCA is except effectively blocking Al3+、Cr3+Decomposition be precipitated, to keep tank liquor run steadily in the long term outer, also effectively chelating is certainly
Ca in water2+、Mg2+Plasma, the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# do not flow
Rinsing bowl is cleaned using not flowing running water, abandons traditional pure water cleaning, production and environmentally friendly cost is greatly reduced.
It further explains, in 20-30g/L, acidity value is 0.5-1.0 equivalent for the concentration control of the degreaser.
It further explains, the chromaking agent concentration control is in 6.0-8.0g/L.
It further explains, the pH of the 6# chromaking slot is controlled in 1.5-2.5.
It further explains, the chromaking temperature of the 6# chromaking slot is 5-35 DEG C.
It further explains, traditional chromaking slot pH value operation interval is 1.8-2.2, the choosing of corrosion inhibiter and chelating agent PBTCA
With, pH value hydrofluoric acid (50wt.%) is expanded downwards to 1.5 and to be not concerned about molten aluminum amount too big, influence passivating solution and stablize；Use ammonia
Water (10wt.%) be improved upwards to 2.5 and be not concerned about fluoride decompose precipitating, greatly improve the stability of passivating solution.
It further explains, the chromaking time of the 6# chromaking slot is 60-120 seconds.
It further explains, the design can be greatly reduced chromaking lowest temperature, substantially shorten the chromaking time.PBTCA's adds
Add, phosphono is combined into chromaking film, is similar to phosphatization, is greatly improved the chromaking ability of 6# chromaking slot；Butane is free on chromaking film
Surface after powder spray, with resin-bonded, greatly improves adhesive force.Traditional chromaking temperature is room temperature, phosphatization component PBTCA's
It selects, chromaking new process of the present invention normally forms qualified chromaking film at 5 DEG C or more, when being lower than room temperature without heating, section
The about energy reduces production cost；Traditional chromaking time is 120-240 seconds, and the selection of phosphatization component PBTCA, the present invention is by chromaking
Time shorten to 60-120 seconds, substantially shortens the chromaking time, improves work efficiency.
It further explains, the 2# non-mobile water washing trough is equipped with one-way valve 7 to the 1# degreasing tank, and the 3# does not flow
Rinsing bowl is equipped with one-way valve 6 to the 2# degreasing tank, and the 4# non-mobile water washing trough is equipped with one-way valve 5 to the 3# degreasing tank,
The 5# non-mobile water washing trough is equipped with one-way valve 4 to the 4# degreasing tank, and the 5# non-mobile water washing trough is in the connection water source
Place is equipped with valve 3, and the both ends of the pump 1 are respectively equipped with valve 2 and valve 1.
The tap water of supplement is successively through the 5# non-mobile water washing trough, the washing trough of 4# non-mobile water, the washing trough of 3# non-mobile water, 2#
Non-mobile water washing trough and 1# degreasing tank reverse flow supplement 1# degreasing tank liquid level, recycle degreaser, reduce 5# slot drug concentration；
7# drains slot and 6# chromaking slot differential concatenation, recycles chromaking agent；Realize the waste water and dregs zero-emission of powder spray chromaking line.
In research and development of the invention, pilot scale and process of producing product, it is all made of hydrofluoric acid-chromic anhydride-chelating agent-corrosion inhibiter-phosphorus
The chromaking liquid of agent compound prescription, chromaking liquid are recycled, reduce the discharge of pollution, prevent the generation of pollutant from source.
(1) the new formulating of chromaking liquid
Traditional chromaking flowing current separation uses hydrofluoric acid and chromic anhydride as main chromaking ingredient, and ionization, hydrolysis are reacted with chromaking are as follows:
1, aluminium is dissolved, hydrogen is precipitated in aluminium material surface；Aluminium is complexed by fluorine, generates hydroxyl fluoaluminic acid
2Al+6HF=2AlF3+3H2↑6Al3++21F-+15H2O=AlF6 3-+Al(OH)F5 3-+Al(OH)2F4 3-+Al(OH)3F3 3-+Al(OH)4F2 3-+Al(OH)5F3-+15H+ (1)
2, the hydrogen reducing Cr VI being precipitated is trivalent chromium, due to the pH value liter at aluminium alloy and chromaking liquid two-phase interface
Height, trivalent chromium are just deposited on aluminium surface in the form of chromium hydroxide colloid
3H2+2CrO3=2Cr (OH)3↓ (2)
3, chromium hydroxide colloid forms trivalent chromium and Cr VI product in aluminium surface in conjunction with Cr VI
2Cr(OH)3+CrO3=Cr (OH)3·Cr(OH)·CrO4↓+H2O=Cr (OH)3·Cr(OH)2·HCrO4↓ (3)
4, the pH value at aluminium alloy and chromaking liquid two-phase interface increases, and aluminium ion and hydroxyl is made to generate gelatinous hydrogen-oxygen
Change aluminium, aluminium hydroxide is dehydrated to form the pellumina for being insoluble in water in aluminum alloy surface when drying
2Al3++6OH-=2Al (OH)3↓=Al2O3↓+3H2O (4)
5, Electro Sorb is reacted in the fluoaluminic acid root of aluminum alloy surface with trivalent chromium, generates fluoaluminic acid chromium film
Cr3++AlF6 3-=CrAlF6↓ (5)
6, make oxidisability promotor, molybdate and aluminium ion with molybdate and form the protection of aluminium molybdate complex in aluminium surface
Film
3H2MoO4+2Al3+=Al2(MoO4)3↓+6H+ (6)
7, with potassium ferricyanide K3Fe(CN)6Make oxidisability promotor, the potassium ferricyanide and aluminium ion and forms iron cyaniding in aluminium surface
Aluminium compound protective film
Fe(CN)6 3-+Al3+=AlFe (CN)6↓ (7)
8, make tank liquor stabilizer and deashing agent with nitric acid, remove the empty ash of aluminum section bar chromizing film surface, limit chromaking slot sludge
It is precipitated, oxidation trivalent chromium to Cr VI
Cr3++3NO3 -+6H+=Cr6++3H2O+3NO2↑ (8)
The composition of chromate conversion coating substantially CrAlF6·AlFe(CN)6·Al2(MoO4)3·Cr(OH)3·Cr
(OH)2·CrO4·Al2O3·H2O, newly-generated conversion film exist with the state of colloid, and hardness and wear resistance is poor, after drying
Conversion film dehydration is hardened, and has hydrophobicity, preferable with aluminium basal body binding force and corrosion resistance, is the good bottom of organic coating.
Longtime running discovery, traditional chromaking slot slot bottom have chromium-bearing sludge, need periodic cleaning, and sludge contains hypertoxic Cr VI,
Operation is abnormally dangerous.
Potassium bichromate K in chromaking slot2Cr2O7, sodium fluoride, potassium ferricyanide K3Fe(CN)6, sodium metasilicate Na2SiO3, sodium molybdate
It is the component for making the easy dust of aluminium material surface, being also easy to produce crystallization precipitate.These component potassium containing sodium, cryolite and fluorine aluminium easily generated
Sour potassium precipitating, needs clear slot；Meanwhile these products keep tank liquor unintelligible, chromaking film is easy dust, influences chromaking quality；This
Outside, (8) formula is pressed, tank liquor stabilizer nitric acid easily decomposes, and increases the risk that muddy object is precipitated in chromaking liquid.The present invention rejects chromaking slot
In be also easy to produce sodium molybdate, the potassium ferricyanide, potassium bichromate, sodium fluoride, ammonium fluoride, ammonium acid fluoride of sediment etc. (reject containing sodium,
The component of potassium, ammonium ion), it only selects hydrofluoric acid and chromic anhydride is chromaking film-forming components；Easy decomposition components nitric acid is rejected, is selected
PBTCA, corrosion inhibiter, chelating agent and bonderite as chromaking slot.
In order to guarantee that aluminium alloy is used for a long time, it is necessary to carry out chromaking and spray treatment.The purpose of chromaking spraying is to mention
The corrosion resistance of high aluminium, fast light, weatherability, contamination resistance, the adhesive force of chromaking is highly important technical indicator.At present
The technique generally used both at home and abroad is the Cr VI chromaking liquid based on chromic anhydride, chromaking process conditions are as follows:
PH value: 1.8-2.2
Temperature: 25-35 DEG C
Time: 120-240s
CrO3: 2.5-5.0g/L (9)
But hydrofluoric acid and chromic anhydride how are made good use of, chromaking slot do not decompose, do not precipitate, unclear bottom, and technical difficulty is very big.
By (1) formula, aluminum fluoride and hydrogen, the interface pH raising of aluminium and chromaking liquid, the hydrogen reducing six of precipitation are generated
Valence chromium is trivalent chromium, generates chromium hydroxide, and aluminum fluoride and chromium hydroxide keep powder on chromaking film, chromaking tank liquor muddy；It is molten rejecting
After the component nitric acid for solving these muddy objects, chromaking slot bottom is also easy to produce chromium-bearing sludge, need to add special cheating components, blocks muddy
The generation of object.
For this purpose, selecting corrosion inhibiter, chelating agent and film forming agent, with hydrofluoric acid and chromic anhydride compatibility, powder and slot on aluminium alloy are solved
The problem of liquid muddiness.
Corrosion inhibiter refers to a kind of medicament that hydrofluoric acid corrosive power can be effectively reduced.In view of chromaking film strips positive charge, originally
Invention selects electronegative carboxyl to be adsorbed on aluminum alloy surface, and tank liquor is isolated, slows down corrosion.The selection of corrosion inhibiter, it is necessary to meet
Four requirements: first is that reducing the meltage of aluminium alloy, it is clean to enable aluminum alloy to surface, no pollen；Second is that film forming can be actively engaged in, keep away
Exempt from corrosion inhibiter building up in chromaking slot, influences chromaking ability；Third is that not decomposing, under fluorine-containing, low ph value mal-condition certainly
Body is stablized；Fourth is that meeting requirements of the national standard after chromaking.
Chelating agent, refer to can effectively chelated mineral cation, be allowed to be not easy to decompose a kind of medicament of precipitation from tank liquor.It presses
(1)-(2) formula, after chelating agent is added, AlF3With Cr (OH)3Not easily generated in chromaking liquid, tank liquor is stablized, and aluminium alloy is not easy
Powder.Under low ph value, the constantly raised mal-condition of fluorine-containing, aluminium ion, to keep tank liquor clear, chelant ties live in Al3+With
Cr3+, difficulty is really small.When analyzing alkaline etching and oxidation tank liquor, in order to analyze Al3+Concentration generally plus potassium fluoride uses F-It opens
Al3+With the complex bonds of ligand, aluminium ion concentration is just measured.So in hydrofluoric acid containing and chromic anhydride tank liquor, due to fluorine-containing, one
As complex compound and chelate, bond energy is inadequate, is not enough to chelate Al3+And Cr3+, tank liquor is easily muddy.It is available in high F-Under the conditions of
Chelate Al3+And Cr3+Chelating agent, selection is limited in scope.
By many experiments, following several big serial chelating agents can be selected:
(1), acetic acid system, such as triethanolamine, ethylenediamine tetra-acetic acid etc.；
(2), phosphate, such as sodium tripolyphosphate, sodium pyrophosphate, sodium metaphosphate, aminotrimethylene phosphate (ATMP)；
(3), phosphate carboxylic serials, such as phosphonobutane tricarboxylic acid (PBTCA).
The selection of chelating agent, it is necessary to meet four requirements: first is that effectively chelated mineral cation, it is dry to enable aluminum alloy to surface
Only, no pollen, does not corrode；Second is that tank liquor is clear, do not decompose, does not precipitate；Third is that film forming can be actively engaged in, avoid chelating agent in chromium
Change building up for slot, influences chromaking ability；Fourth is that meeting requirements of the national standard after chromaking.
Film forming agent, the present invention refer to moieties participate in film forming, the organic group that is partially free on chromaking film surface can be with
A kind of medicament that spraying resin mixes.This kind of film forming agent can greatly improve chromaking film quality, shorten the chromaking time, reduce chromaking temperature
Degree enhances chromaking film adhesive force.
The present invention is selected by hydrofluoric acid, chromic anhydride, chelating agent phosphonobutane tricarboxylic acid (PBTCA), corrosion inhibiter phosphono fourth
Alkane tricarboxylic acids (PBTCA) and film forming agent phosphonobutane tricarboxylic acid (PBTCA) form chromaking liquid and are newly formulated, chelating agent, corrosion inhibiter
Same component phosphonobutane tricarboxylic acid is selected with film forming agent, is done based on PBTCA special molecular structure (as shown in Figure 2)
Ingenious selection out:
In Fig. 2, phosphono and three carboxyls are in electronegativity, and there are three types of functions for this structure tool.1, three carboxyls and phosphino-
Sequestering power with super strength can chelate cation, solids is avoided to be precipitated, and stablize tank liquor；2, three carboxyls and phosphono can
It is adsorbed in electropositive aluminum alloy surface, tank liquor is isolated using organic moiety, there is superpower corrosion inhibiting ability；3, chelated sun from
The PBTCA of son, can be used as carrier, and phosphono can also be with positively charged alloy matrix aluminum phosphorization filming, organic portion on the outside of film
Point, it mixes with the spraying resin same sex, the adhesive force of chromaking film can be significantly increased.A kind of only component of PBTCA has both inhibition, chelating
With three kinds of functions of phosphorization filming, the chromaking ability of chromaking agent can be greatly improved, adhesive force is greatly improved, greatly improves the steady of tank liquor
It is qualitative, reagent cost is greatly reduced.PBTCA is not easy that it is steady in a long-term to be able to maintain tank liquor by other chemical agents or bacterial decomposition；This
Outside, phosphonobutane tricarboxylic acid also chelates in addition to chelating aluminium ion, chromium ion, shields the Ca that water for cleaning is brought into2+、Mg2+Deng
Cation, the water for cleaning before and after chromaking slot can replace pure water with tap water, production cost are greatly reduced.
(2) chromaking process dynamics
(1)-(5) formula shows the dynamic (dynamical) overall process of chromaking.(1) formula shows that hydrogen is precipitated in hydrofluoric acid dissolution aluminium, aluminium material surface
Gas；The aluminium of dissolution is complexed by fluorine, generates hydroxyl fluoaluminic acid；(2) formula shows that the hydrogen reducing Cr VI being precipitated is trivalent chromium, in aluminium
Increase pH value at alloy and chromaking liquid two-phase interface, trivalent chromium conversion at chromium hydroxide, aluminium surface is deposited in the form of colloid；
(3) formula shows that chromium hydroxide colloid in conjunction with Cr VI, forms trivalent chromium and Cr VI product in aluminium surface；(4) formula shows aluminium
PH value at alloy and chromaking liquid two-phase interface increases, and aluminium ion and hydroxyl is made to generate gelatinous aluminium hydroxide, hydroxide
Aluminium is dehydrated to form the pellumina for being insoluble in water in aluminum alloy surface when drying；(5) formula shows Electro Sorb in aluminum alloy surface
Fluoaluminic acid root is reacted with trivalent chromium, generates fluoaluminic acid chromium film；The aluminium of chromaking slot dissolution, under conditions of tank liquor is stablized, with fluorine aluminium
The complex status of acid and hydroxyl fluoaluminic acid, is present in chromaking liquid, using the chemical bond of fluoaluminic acid, participates in film forming；In chromaking slot,
Cr6+Reduction, the dissolution of aluminium and the film forming of fluoaluminic acid chromium carry out simultaneously, avoid Cr3+And Al3+It builds up and dead slot；(8)
Formula shows to make tank liquor stabilizer and deashing agent with nitric acid, removes the empty ash of aluminum section bar chromizing film surface, and limitation chromaking slot sludge is precipitated,
Trivalent chromium is aoxidized to Cr VI, while discharging NO2, nitric acid is consumed, increases and loses stabilization because concentration of nitric acid consumes chromaking slot excessively
The risk of property.
(3) chromaking regulation rule is studied
1), influence of the chromaking time to chromaking quality
The chromaking time directly determines chromaking quality.Time is too short, and chromaking is incomplete, and the time is too long, and aluminum alloy surface plays ash
Seriously, the adhesive force of chromaking film is influenced；The chromaking time is the embodiment of chromaking agent chromaking ability, by temperature, pH value, chromaking agent ingredient
With being affected for concentration, additive component and concentration.
2), influence of the chromaking temperature to chromaking quality
Temperature influences chemical reaction velocity, and usually every to increase 10 DEG C of l times of chemical reaction velocities raisings, the chromaking time can contract
It is short by 1 half.According to the chromaking test under different temperatures, the changing rule of hydrofluoric acid and chromic anhydride chromaking quality and temperature can be obtained.When
When temperature increases, ion diffusion velocity is accelerated, and hydrolysis rate is accelerated, and quickening is reacted with aluminium alloy, and chromaking speed improves.Test table
It is bright, when other Con trolling index are in working range, the relationship of chromaking temperature and chromaking speed are as follows: temperature is at 5-10 DEG C, chromaking
Time 180-240s；Temperature is at 10-15 DEG C, chromaking time 120-180；Temperature is at 15-20 DEG C, chromaking time 60-120s,
Temperature at this moment 20 DEG C or more when, the chromaking time is close to 60s.
3), influence of the pH value to chromaking quality
Influence test according to pH value to chromaking quality, can obtain pH value to the affecting laws of chromaking quality.With tank liquor pH value
Rising, hydrofluoric acid and chromic anhydride hydrolysis increase, chromaking Quality advance；But pH value is too high, and Surface of profile is easy to produce a large amount of yellow ashes,
This is primarily due to chromaking liquid loss of stability, a large amount of to hydrolyze；PH value is too low, and chromaking film is dissolved, and chromaking effect is not achieved.pH
Value is by the chemical reaction of (2) (3) (4) (5) formula, the hydrolysis of hydrofluoric acid and chromic anhydride, the film forming of generation to the action principle of chromaking
Electrodeposition substance aluminium surface achievees the purpose that chromaking, the number of deposition directly affect the effect of chromaking.PH value 1.5-2.5 it
Between deposition it is moderate, can reach the purpose of chromaking, pH value chromaking effect in 1.8-2.2 or so is best, and acidity at this moment is non-
Often good control, just in the hydrolysising balance section of hydrofluoric acid and chromic anhydride, pH value is sufficiently stable.
4), the influence of hydrofluoric acid and chromium anhydride concentration to chromaking quality
The present invention selects hydrofluoric acid and chromic anhydride as main chromaking substance, and chromaking is to form film forming by hydrofluoric acid and chromic anhydride root
Substance is deposited on what aluminium surface was achieved, and chromaking substance presses the synthesis result of (1)-(5) formula reaction, hydrofluoric acid and chromic anhydride
Content influences chromaking quality very big.The experimental results showed that the control of hydrofluoric acid (50wt.%) concentration is dense in 0.5-1.0g/L, chromic anhydride
Between 2.5-5.0g/L, the aluminium of chromaking can meet national standard testing requirements for degree control.
5), influence of the PBTCA density of corrosion inhibitor to chromaking quality
PBTCA corrosion inhibiter of the present invention is adsorbed on positively charged aluminum alloy surface by electronegative three carboxyl and phosphono,
Tank liquor is isolated, slows down corrosion.Under hydrofluoric acid and chromic anhydride chromaking system, pH value operation interval 1.5-2.5, slant acidity is pressed (1)-(5)
Formula, low ph value are conducive to Al2O3With F-Reaction generates AlF6 3-, Al (OH) F5 3-, Al (OH)2F4 3-, content reaches certain value
When, association, hydrolysis and concentration occur for interionic, are finally translated into stable phase complexing aluminum fluoride Al2(OH)3F3；In aluminium alloy table
Face, Al2(OH)3F3It is pollen；In tank liquor, Al2(OH)3F3It is muddy object.So the molten aluminum amount of tank liquor is too big, on aluminium alloy is easy
Powder, the easily muddy dead slot of tank liquor.The addition of PBTCA corrosion inhibiter reduces molten aluminum amount, extends precisely in order to protecting the not upper powder of aluminium alloy
Tank liquor service life.By experimental result, the concentration ranges of PBTCA corrosion inhibiter are 1.25-2.5g/L.
6), influence of the chelating agent concentrations to chromaking quality
Chelating agent of the present invention selects phosphonobutane tricarboxylic acid (PBTCA), with its powerful chelating bond energy, stablizes Cr3+With
Al3+, it is ensured that tank liquor is not muddy, the not upper powder of aluminium alloy.By (1)-(5) formula, when pH is increased, it is easy to generate Cr (OH)3And Al2(OH)3F3.These goods and materials, if generating in aluminum alloy surface, as powder；If generating in tank liquor, as muddy object.PBTCA chelating agent
It is added, improves Cr (OH)3And Al2(OH)3F3Generation threshold, aluminium alloy is not easy powder, and tank liquor is not easy muddiness.In addition,
Carboxyl and phosphono in PBTCA chelating agent is negatively charged, can be adsorbed on positively charged passivating film, plays corrosion inhibiter, reduces aluminium
The meltage of alloy.Experiment shows that appropriate PBTCA chelating agent concentrations are 1.25-2.5g/L.
7), influence of the special film forming agent concentration to chromaking quality
Film forming agent of the present invention selects phosphonobutane tricarboxylic acid (PBTCA), by its powerful chelating bond energy, chelates Cr3+
And Al3+, it is ensured that tank liquor is not muddy, the not upper powder of aluminium alloy；Using its electronegative phosphono, will chelating body phosphatization into chromaking film,
Phosphatization-chromaking film is formed, metal ion and PBTCA in chromaking slot are consumed, avoids these ingredient excessive accumulations and dead slot.Phosphorus
The formation of change-chromaking film greatly improves chromaking ability, shortens the chromaking time, reduces chromaking temperature, widens chromaking pH value section.
Chelating, inhibition, film forming select same component PBTCA, are significant technology innovations of the invention, have both the PBTCA of three kinds of functions
Total amount is 2.5-5.0g/L, by hydrofluoric acid: chromic anhydride: PBTCA=0.2:1.0:1.0 weight ratio prepares chromaking agent, and chromaking agent is dense
Spend 5.0-8.0g/L, as Con trolling index, production requirement can be met.
8), influence of the foreign ion to chromaking quality
In process of production, washing constantly brings foreign ion into, causes the accumulation of impurity, such as Na+、K+、Ca2+、Mg2+Equal sun
Ion increases, and the consumption of PBTCA chelating agent is accelerated.Therefore, it is most important to hold cleaning pass.In addition, ammonia can be used when tank liquor pH is too low
Water adjusts pH value to 2.0 or so, not adjusted with sodium hydroxide, can effectively prevent Na in this way+Addition, consume PBTCA chela
Mixture.Select hydrofluoric acid and chromic anhydride rather than sodium fluoride and potassium bichromate as main chromaking ingredient, key reason is Na+、
K+Consumption to PBTCA chelating agent.
There are many factor for influencing aluminium alloy chromaking quality, mainly there is hydrofluoric acid and chromium anhydride concentration, density of corrosion inhibitor, chelating agent
Concentration and film forming agent concentration, this five factors are the key that determine aluminium alloy chromaking quality；When the pH value of tank liquor, temperature and chromaking
Between be influence aluminium alloy chromaking quality an important factor for；And improving the cleanliness of tank liquor, reducing the content of impurity is aluminium alloy chromium
Change the important guarantee of quality.
(4) chromaking is newly formulated new process
(9) formula gives the technological parameter of traditional chromic anhydride chromaking liquid, with hydrofluoric acid, chromic anhydride, PBTCA corrosion inhibiter, PBTCA
Chelating agent and PBTCA film forming agent are under the new formulation condition of chromaking liquid of chromaking main component, and technological parameter varies widely:
HF (50wt.%) 0.5-1.0g/L
PBTCA (50wt.%) 2.5-5.0g/L
CrO3 2.5-5.0g/L (10)
5-35 DEG C of chromaking temperature
Chromaking speed 60-240s
Tank liquor pH 1.5-2.5
Comparing (9) and (10) formula, chromaking ability enhances after PBTCA is added, and chromaking lowest temperature is widened by 25 DEG C to 5 DEG C,
Chromaking lower velocity limit raises speed to 60s, tank liquor pH and is widened by 1.8-2.2 to 1.5-2.5.Due to containing a large amount of PBTCA chelating agents, newly match
Side is not high to water quality requirement, and washing, fluting use tap water, contained Ca2+、Mg2+It can be shielded completely by PBTCA chelating agent.
Chromaking liquid hydrofluoric acid containing reduces the corrosive power of fluorine for this purpose, corrosion inhibiter PBTCA is specially arranged in formula.Aluminium ion in chromaking liquid
It is chelated with trivalent chromium by PBTCA, chelating ion phosphatization is stablized into chromaking film, chromaking liquid, and no muddy object is precipitated.
Two, degreasing tank formula is formulated compatible design to chromaking slot
Degreasing tank generally selects sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid, sodium fluoride, ammonium fluoride, ammonium acid fluoride, lemon
Acid, sorbierite, glycerol, ethylene glycol and proper amount of surfactant oil removing.When aluminium oil removing, aluminium is in the degreasing fluid containing mixed acid and fluorine
The middle following chemical reaction of generation:
1, natural oxide film is removed
Al2O3+6H+=2Al3++3H2O (11)
2, molten aluminium, deburring
2Al+6H+=2Al3++3H2↑ (12)
3, aluminium is by fluorine complexing, stable degreasing fluid
6Al3++21F-+15H2O=AlF6 3-+Al(OH)F5 3-+Al(OH)2F4 3-+Al(OH)3F3 3-+Al(OH)4F2 3-+Al
(OH)5F3-+15H+ (13)
4, it is passivated aluminium surface, reduces molten aluminium
2Al+3NO3 -=Al2O3+3NO2 - (14)
By (11) (12) two formula, acid concentration is higher, and molten aluminium speed is faster；By (13) (14) formula, aluminium material surface passivation, molten aluminium
Amount is restricted, and the pressure that crystal is precipitated in tank liquor is reduced；The presence of high concentration nitric acid simultaneously, aluminium is with fluoaluminic acid and hydroxyl fluoaluminic acid
Form exist, rather than with aluminum fluoride or aluminum phosphate Precipitation, tank liquor is stablized, and does not decompose, non-scaling, can longtime running.
By the chromaking tank liquor formula that (10) formula is selected, the tank liquor is kept to run steadily in the long term, the formula of degreasing tank is to chromium
The influence for changing Stability of Bath Solution be can not ignore.When mass production, after aluminium alloy oil removing, generally flows and wash through twice, into chromaking
Slot chromaking, part degreasing fluid bring chromaking slot into, influence chromaking ability and tank liquor is stablized.In degreasing tank, it is necessary to reject those harm
Chromaking ability to work and the stable component of tank liquor, it is ensured that oil removing is run steadily in the long term with chromaking.It is optionally removing in oil ingredient, sulphur
Acid, hydrochloric acid, phosphoric acid and nitric acid influence the ability to work and stability of chromaking slot, it is necessary to reject；The fluorine of sodium ion consumption chromaking slot
Ion generates ice crystal precipitating, it is necessary to reject；Citric acid, sorbierite, glycerol, ethylene glycol are easy to be bacterially decomposed, and make chromaking slot
It is muddy smelly, it is necessary to reject；Degreasing tank ammonium ion cannot too, and aluminium material surface is easy dust, rejects ammonium acid fluoride；Surface-active
The adhesive force of agent influence chromaking material, it is necessary to reject；In addition, degreasing tank dissolves a large amount of aluminium, under conditions of rejecting nitric acid, it is easy
Form AlF3Precipitating；It is needed to add chelating agent, blocks the generation of aluminum fluoride to stablize hydroxyl fluoaluminic acid series by (13 formula)；
In order to reduce molten aluminum amount, degreasing tank ability to work is kept, it is necessary to add corrosion inhibiter.Integrated suites experimental result, it is simultaneous to chromaking slot
The degreasing tank of appearance simplifies formula are as follows:
HF (50wt.%) 10-20g/L
PBTCA (50wt.%) 3.5-7g/L (15)
Acidity value 0.5-1.0 equivalent
Time 3-6 minute
Temperature room temperature
By (10) formula, HF and PBTCA contained by (15) formula is completely compatible to chromaking slot, removes oil component through what rinsing bowl was brought into,
It will not influence the ability to work and stability of chromaking slot completely.(15) in formula, HF is good etching agent, dissolves aluminum alloy surface
Natural oxide film, deburring, it is ensured that certain etch amount；PBTCA is acidity, it is possible to provide certain acidity value increases oil removing
Ability；PBTCA is chelating agent, chelates aluminium ion, blocks the generation of aluminum fluoride, it is ensured that degreasing tank longtime running；Meanwhile PBTCA
Or corrosion inhibiter, electronegative three carboxyl and phosphono are adsorbed on positively charged aluminum alloy surface, and tank liquor is isolated, slows down corruption
Erosion.PBTCA is used for degreasing tank, can perform to its corrosion inhibiting ability and sequestering power ultimate attainment.
Embodiment 1
1# degreasing tank, non-mobile water wash a group slot, 6# chromaking slot, 7# and drain slot, pump 1 and water inlet；The non-mobile water is washed
Group slot differential concatenation is in the 1# degreasing tank；The 7# drains slot, the pump 1 is connected with 6# chromaking slot differential concatenation；It is described not
It flows washing group slot and connects water inlet.
Tap water is pressed in the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# non-mobile water washing trough
Cleaning 60 seconds, is produced for drip 30 seconds.
1# degreasing tank Con trolling index are as follows:
HF (50wt.%) 18g/L, PBTCA (50wt.%) 6g/L；
Time: 4 minutes；
Temperature: room temperature；
6# chromaking slot Con trolling index are as follows:
Hydrofluoric acid (50wt.%) 0.75g/L, chromic anhydride 3.0g/L, PBTCA 3.0g/L；
The chromaking time 150 seconds；
Temperature: room temperature；
PH value: 2.0；
It is produced by above-mentioned Con trolling index, spraying material can meet national standard testing requirements.Increase 1# degreasing tank PBTCA concentration
To 7.5g/L, degreasing tank reaction speed slows down, 1# degreasing tank, the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, 4# non-mobile water
Washing trough and 5# non-mobile water washing trough are apparent；1# degreasing tank PBTCA concentration is reduced to 5g/L, degreasing tank reaction speed is accelerated, 1#
Degreasing tank is clear, and the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# non-mobile water washing trough are slightly muddy
It is turbid, there is a small amount of aluminum fluoride to decompose and is precipitated.Block 1# degreasing tank, the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, 4# non-mobile water
The condition that washing trough and 5# non-mobile water washing trough aluminum fluoride are precipitated is HF (50wt.%): PBTCA (50wt.%)≤3:1 (weight
Than)；Influence in view of reagent cost and to 6# chromaking slot takes HF (50wt.%): PBTCA (50wt.%)=3:1, heavy by this
Amount is than preparing degreaser, the production Con trolling index by degreaser concentration 20-30g/L, as 1# slot.
Embodiment 2
Tap water is pressed in the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# non-mobile water washing trough
Cleaning 60 seconds, is produced for drip 30 seconds.
1# degreasing tank Con trolling index are as follows:
HF (50wt.%) 18g/L, PBTCA (50wt.%) 6g/L；
Time 4 minutes；
Temperature is room temperature；
6# chromaking slot Con trolling index are as follows:
Hydrofluoric acid (50wt.%) 0.75g/L, chromic anhydride 3.0g/L, PBTCA 3.0g/L；
The chromaking time 150 seconds；
Temperature is room temperature；
PH value: 2.0；
It is produced by above-mentioned Con trolling index, spraying material can meet national standard testing requirements.Increase the 6# chromaking slot chromaking time
To 240 seconds, national standard detection was qualified；The 6# chromaking slot chromaking time is reduced to 50 seconds, national standard detection is unqualified once in a while；It can be fitted under room temperature
When shortening the chromaking time, but not below 60 seconds；The chromaking time can be appropriately extended under low temperature, but do not exceed 240 seconds.
Embodiment 3
Tap water is pressed in the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# non-mobile water washing trough
Cleaning 60 seconds, is produced for drip 30 seconds.
1# degreasing tank Con trolling index are as follows:
HF (50wt.%) 18g/L, PBTCA (50wt.%) 6g/L；
Time: 4 minutes；
Temperature is room temperature；
6# chromaking slot Con trolling index are as follows:
Hydrofluoric acid (50wt.%) 0.75g/L, chromic anhydride 3.0g/L, PBTCA 3.0g/L；
The chromaking time: 150 seconds；
Temperature is room temperature；
PH value: 2.0；
It is produced by above-mentioned Con trolling index, spraying material can meet national standard testing requirements.Increase 6# chromaking bath temperature degree to 35
DEG C, national standard detection is qualified；6# chromaking bath temperature degree is reduced to 5 DEG C, national standard detection is unqualified once in a while；At 15-35 DEG C, 6# chromaking slot hydrogen
Fluoric acid (50wt.%) concentration 0.5-1.0g/L, chromium anhydride concentration 2.5-5.0g/L, PBTCA concentration 2.5-5.0g/L, chromaking time is
60-240 seconds, spraying material can meet national standard testing requirements；Under low temperature, at 5-15 DEG C, drug concentration capping, the chromaking time is also taken
The upper limit can satisfy national standard testing requirements.
Embodiment 4
Tap water is pressed in the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# non-mobile water washing trough
Cleaning 60 seconds, is produced for drip 30 seconds.
1# degreasing tank Con trolling index are as follows:
HF (50wt.%) 18g/L, PBTCA (50wt.%) 6g/L；
Time: 4 minutes；
Temperature is room temperature；
6# chromaking slot Con trolling index are as follows:
Hydrofluoric acid (50wt.%) 0.75g/L, chromic anhydride 3.0g/L, PBTCA 3.0g/L；
The chromaking time: 150 seconds；
This room temperature of temperature；
PH value: 2.0；
It is produced by above-mentioned Con trolling index, spraying material can meet national standard testing requirements.46# chromaking slot pH is adjusted with ammonium hydroxide
To 2.5, spraying material national standard detection is qualified；6# chromaking slot pH value is adjusted to 1.5 with hydrofluoric acid, and spraying material national standard detection is qualified；Chromium
Change slot pH and be higher than 2.5, chromaking liquid has the risk decomposed and fluoride is precipitated；Chromaking liquid pH value is lower than 1.5, and molten aluminum amount is too big, chromaking
Liquid equally has the risk decomposed and fluoride is precipitated；The stable pH value control interval of chromaking liquid is 1.5-2.5.
Embodiment 5
The moisturizing of 1# degreasing tank and degreaser way of recycling: opening tap water water inlet valve, and tap water enters 5# and do not flow
Rinsing bowl；Through one-way valve 4, into 4# non-mobile water washing trough；Through one-way valve 5, into 3# non-mobile water washing trough；Through one-way valve 6, into
Enter 2# non-mobile water washing trough；Through one-way valve 7, into 1# degreasing tank；Complete the moisturizing of 1# degreasing tank and degreaser recycling.
Embodiment 6
6# chromaking slot chromaking liquid way of recycling: 1 and 2, valve, valve is opened, pump 1 is opened, 7# is drained to the chromaking of slot collection
Liquid pump enters 6# chromaking slot；Complete the recycling of 6# chromaking slot chromaking liquid.
The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain of the invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, the technology of this field
Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within
Within protection scope of the present invention.
Claims (10)
1. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration characterized by comprising 1# degreasing tank,
Non-mobile water washes a group slot, 6# chromaking slot, 7# and drains slot, pump 1 and water inlet；
The degreasing tank and the non-mobile water wash a group slot differential concatenation, and tap water is washed group slot from the non-mobile water and entered, warp
The non-mobile water washes group slot to the 1# degreasing tank reverse flow, recycles degreaser, saves oil removing medicament and water for cleaning；Institute
The chromaking liquid that 7# drains slot collection is stated, the 6# chromaking slot is pumped into through the pump 1, recycles chromaking liquid, whole chromaking line does not drain
Deslagging；
Contain degreaser in the 1# degreasing tank, the chemical constituent of the degreaser includes: hydrofluoric acid and phosphinylidyne butane tricarboxylic
Acid；
Contain chromaking agent in the 6# chromaking slot, the chemical constituent of the chromaking agent includes: hydrofluoric acid, phosphonobutane tricarboxylic acid
And chromic anhydride；
The chemical component of the 1# degreasing tank is compatible to the chemical component of the 6# chromaking slot, and the degreaser brings the 6# chromium into
After changing slot, the chromaking ability and stability of the 6# chromaking slot are not influenced.
2. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 1, feature
It is, it includes: the washing trough of 2# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 4# non-mobile water and 5# that the non-mobile water, which washes a group slot,
Non-mobile water washing trough；
The water inlet is connected in the 5# non-mobile water washing trough；
The 5# non-mobile water washing trough, the washing trough of 4# non-mobile water, the washing trough of 3# non-mobile water, the washing trough of 2# non-mobile water and 1# degreasing tank
Differential concatenation connection；The 7# drains slot, pump 1 is connect with 6# chromaking slot differential concatenation.
3. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 2, feature
It is, in the 1# degreasing tank, the hydrofluoric acid (50wt.%): phosphonobutane tricarboxylic acid (the 50wt.%)=3:1.
4. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 2 or 3, special
Sign is, in the 6# chromaking slot, the hydrofluoric acid (50wt.%): the phosphonobutane tricarboxylic acid (50wt.%): described
Chromic anhydride=0.2:1:1.
5. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 2, feature
It is, the water source of the water inlet is tap water.
6. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 4, feature
It is, in 20-30g/L, acidity value is 0.5-1.0 equivalent for the concentration control of the degreaser.
7. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 4, feature
It is, the chromaking agent concentration control is in 6.0-8.0g/L.
8. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 2, feature
It is, the pH of the 6# chromaking slot is controlled in 1.5-2.5.
9. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 2, feature
It is, the chromaking time of the 6# chromaking slot is 60-120 seconds, and chromaking temperature is 5-35 DEG C.
10. Al alloy powder spraying pretreatment chromaking line waste water and dregs zero-emission configuration according to claim 2, feature
Be, the 2# non-mobile water washing trough to the 1# degreasing tank be equipped with one-way valve 7, the 3# non-mobile water washing trough to the 2# not
It flows rinsing bowl and is equipped with one-way valve 6, the 4# non-mobile water washing trough is equipped with one-way valve 5 to the 3# non-mobile water washing trough, described
The washing trough of 5# non-mobile water is equipped with one-way valve 4 to the 4# non-mobile water washing trough, and the 5# non-mobile water washing trough is in the connection water
Valve 3 is equipped at source；The both ends of the pump 1 are respectively equipped with valve 1 and valve 2；The tap water of supplement enters 5# non-mobile water from No. three valves
Washing trough, through 5# non-mobile water washing trough → 4# non-mobile water washing trough → 3# non-mobile water washing trough → 2# non-mobile water washing trough → 1# oil removing
Slot reverse flow supplements 1# degreasing tank liquid level, recycles degreaser；The 7# drains slot and 6# chromaking slot differential concatenation, drains liquid
Slot → No.1 valve → valve of pump 1 → bis- → 6# chromaking slot reverse flow is drained through 7#, recycles chromaking liquid；Whole chromaking line not row of setting
The mouth of a river, waste water and dregs zero-emission.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113862655A (en) * | 2021-08-26 | 2021-12-31 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Aluminum alloy chromizing pretreatment spraying room with zero discharge of waste water and waste residues |
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Application publication date: 20190329 |