CN108193214A - A kind of Aluminum subtracts the oil removing of slag and chromaking medicament is stablized and compatible method - Google Patents
A kind of Aluminum subtracts the oil removing of slag and chromaking medicament is stablized and compatible method Download PDFInfo
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- CN108193214A CN108193214A CN201711471771.9A CN201711471771A CN108193214A CN 108193214 A CN108193214 A CN 108193214A CN 201711471771 A CN201711471771 A CN 201711471771A CN 108193214 A CN108193214 A CN 108193214A
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- chromaking
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- degreasing
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Abstract
Subtract the oil removing of slag the invention discloses a kind of Aluminum and chromaking medicament is stablized and compatible method, including degreasing tank and chromaking slot, there is degreasing fluid in the degreasing tank, there is chromaking liquid in the chromaking slot, the degreasing fluid is nitric acid and the solution of hydrofluoric acid, the chromaking liquid is the solution of chromic anhydride, hydrofluoric acid and nitric acid, and the degreasing fluid and chromaking liquid are compatible, and the degreasing tank and chromaking slot generate in During Process of Long-term Operation without precipitation.Stable component is selected to ensure that degreasing tank and chromaking slot longtime running do not generate precipitation, aluminium material surface is not easy dust, is not likely to produce crystallization precipitate.Degreasing fluid is compatible with chromaking liquid, when degreasing fluid is inevitably carried in chromaking liquid by aluminium, does not influence the operation of chromaking liquid, does not influence aluminium chromaking effect, and chromaking slot is interior without precipitated crystal.
Description
Technical field
The present invention relates to field of metal surface treatment technology more particularly to a kind of Aluminum subtract slag oil removing and chromaking medicament it is steady
Determine and compatible method.
Background technology
Aluminium and aluminium alloy have many advantages, such as that processing performance is excellent, corrosion resistance is good, surface aesthetic, the rate of recovery are high, in building, hand over
The industries such as logical transport, machinery, electric power are applied widely, and it is more obvious to expand aluminium application trend for steel in recent years with aluminium.Aluminium
Processing industry is conventional industries, even more the rising industry full of vitality.According to statistics, year consumes aluminium per capita for European and American developed countries
More than 32kg, and China only has 13kg or so per capita, only 1/3rd or so of developed country, domestic aluminium consumption are also huge
Big growth space, but the problem of under economic new normality, energy consumption is high, total amount of pollutants discharged is big, resource recycling rate is low
As the bottleneck and obstacle of industry development.
Aluminium industry production includes the processes such as electrolysis, founding, pressure processing, surface treatment, and each process can difference during production
Degree generates waste water, waste residue.A large amount of aluminium ash is generated when electrolysis and founding, extrusion process has alkaline etching alkaline waste liquor, is surface-treated
Process generates all kinds of waste water and dregs containing the complicated components such as acid, alkali, treatment agent and chromium, nickel heavy metal ion.
Modern aluminum processing enterprise, there is that spraying pretreated waste water waste residue is in need of immediate treatment, and existing processing method is too simple,
Chromaking technique generates chromate waste water waste residue, and Chromeless process generates fluoride waste waste residue, faces and handles these toxic wastewater waste residues
Environmental protection pressure.These waste residues are handled, society will pay expensive processing cost thus.
Spray the oil removing of pretreatment and the toxic waste residue containing chromium of chromaking generation, such waste residue Zhan Lv processing enterprises surface treatment
The 20% of waste residue total amount.
Powder spray aluminium section bar is because having many advantages, such as surface aesthetic, rich in color, anti-corrosion and good weatherability, it has also become aluminium profiles
The maximum surface treatment kind of material, accounts for more than the 60% of total amount.Section bar will carry out surface preparation before spraying, pass through chemistry
Reaction generates one layer of fine and close conversion film in aluminium material surface, and conversion film has certain antiseptic property, it is often more important that can incite somebody to action
Together with base material and sprayed coating firm connection.
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, i.e., with 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, alkali and flocculant is added to make Cr3+It is formed
Cr(OH)3Precipitation, by flocculating, settling, filter-press dehydration formation chromium hydroxide (trivalent chromium) chromium slag.Chromate waste water process flow is shown in
Fig. 3.Chromium slag belongs to hazardous waste, it is necessary to which legal transfer is disposed to qualified third-party institution's specification.
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 ".
The pollution problem come to solve chromaking process bands has carried out a large amount of Chromeless process replacement and has ground both at home and abroad for many years
Study carefully, and be widely used in aluminum profile industry.Chromeless process mainly has two technology paths, when 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 non-chromium inactivating technique.The technique is blunt
The requirement of GB 5237 can be reached, but be not so good as chromium in terms of certain indexs and overall stability substantially by changing film and sprayed coating quality
Change film, and do not live through outdoor long-term inspection.And non-chromium inactivating technique control requirement is tight, 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 ensure 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, still using toxicity
Very strong Chrome-free chemical agent 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
, there is the technique of pollution in generation nor optimal selection.
In all chemical composition coatings, the corrosion resistance of chromaking film is best, and has the function of " self-regeneration ", this and membrane structure
Middle reservation Cr VI is related, and the level of chromaking film is also not achieved in the antiseptic property of other chemical composition coatings.Therefore, as long as solving
The hexavalent chromium wastewater residue contamination problem of chromaking technique, chromaking technique is still irreplaceable.
Chromate chemical conversion processing is most common aluminium pretreating process, has applied many decades both at home and abroad, technology into
Ripe, technique is easily controllable, and chromizing film layer is high-quality, and sprayed coating quality is highly stable.But contain in chromaking treatment fluid and conversion film
Cr VI have very strong toxicity, national governments formulated a series of policies certain fields limit use such technique,
In most importantly：On 2 13rd, 2003, European Union by " about in electric/electronic device limitation use 6 kinds of Cr VI etc.
The RoHS instructions of poisonous and harmful substance ", this instruction is primarily directed to electric/electronic device product.But in other fields,
Such as in space flight and aviation, building aluminum alloy doors and windows and curtain wall field, there is presently no see external relevant policies report.In America and Europe,
The spraying pretreatment of aluminium section bar and curtain wall aluminium plate is also largely using chromaking treatment process.
In recent years, national environmental protection supervision is more and more tighter, and domestic many local governments consider traditional chromating
Middle Cr VI and trivalent chromium to the environmental hazard of waste water and waste residue and administer and the difficulty of supervision, launched respectively tight
Lattice limitation uses the environmental protection policy of traditional technique containing chromium passivating.Foshan is the region that national aluminium is most concentrated, and aluminum profile industry is
One of pillar industry of Foshan City, how positive and science copes with National Environment Policy Act Laws ＆ Regulations, and guiding enterprise seizes the opportunity
Transition and upgrade, accelerates to promote and apply and does not generate the spraying pretreating process of waste water and dregs, and environmental protection benefits future generations offspring, is value
Obtain the problem of government and enterprise inquire into and think deeply jointly.
In the prior art, spraying pretreating process flow is：Dress extension workpiece → acid etching oil removing → water cleaning → water cleaning →
Chromaking processing → water cleaning → water cleaning → draining → drying → application.Coatings of the aluminium profiles Pretreatment Line be divided into vertical line and
Horizontal 2 kinds of line, vertical line use fully-automatic sprinkling mode；Horizontal line uses intermittent full impregnation method, as shown in Figure 6.
1# acid deoiling slots generally select sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid, sodium fluoride, ammonium fluoride, hydrogen fluoride
Ammonium and proper amount of surfactant oil removing.During aluminium oil removing, aluminium occurs to chemically react as follows in the degreasing fluid containing mixed acid and fluorine：
1st, natural oxide film is removed
Al2O3+6H+=2Al3++3H2O (1)
2nd, molten aluminium, deburring
2Al+6H+=2Al3++3H2↑ (2)
3rd, aluminium is complexed by fluorine, stablizes degreasing fluid
6Al3++F-+H2O=AlF6 3-+Al(OH)F5 3-+Al(OH)2F4 3-
+Al(OH)3F3 3-+Al(OH)4F2 3-+Al(OH)5F3-+6H+ (3)
4th, it is passivated aluminium surface, reduces molten aluminium
2Al+3NO3 -=Al2O3+3NO2 - (4)
By (1) (2) two formula, acid concentration is higher, and molten aluminium speed is faster；By (3) (4) formula, aluminium material surface passivation, molten aluminum amount by
It restricts, reduces the pressure that crystal is precipitated in tank liquor；The presence of high concentration nitric acid simultaneously, aluminium is with the shape of fluoaluminic acid and hydroxyl fluoaluminic acid
Formula exists rather than with aluminum fluoride or aluminum phosphate Precipitation, and tank liquor is stablized, do not decomposed, non-scaling, can longtime running.
4# chromaking slots, general CrO containing chromic anhydride3, potassium bichromate K2Cr2O 7, sodium fluoride, nitric acid, potassium ferricyanide K3Fe(CN)6、
Sodium metasilicate Na2SiO3, hydrofluoric acid, boric acid, sodium molybdate, stabilizer (2 kinds of organic acids allotment be composed) containing carboxyl, hydroxyl
Deng.During aluminium chromaking, one layer is formed in metal surface and is insoluble in water, using chromate as the passivating film that mainly forms.4# slot chromaking
Film forming procedure is more complicated, and reaction mechanism is as follows：
1st, aluminium is dissolved, hydrogen is precipitated in aluminium material surface
2Al+6HF=2AlF3+3H2↑ (5)
AlF3It is reacted by (3), generates fluoaluminic acid and hydroxyl fluoaluminic acid
2nd, 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↓ (6)
3rd, chromium hydroxide colloid forms the oxide of trivalent chromium and Cr VI in conjunction with Cr VI in aluminium surface
2Cr(OH)3+CrO3=Cr (OH)3·Cr(OH)·CrO4↓
+H2O=Cr (OH)3·Cr(OH)2·HCrO4↓ (7)
4th, 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
2Al3++6OH-=2Al (OH)3↓=Al2O3↓+3H2O (8)
5th, 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↓ (9)
6th, make oxidisability accelerating agent with molybdate, molybdate forms aluminium molybdate complex in aluminium surface with aluminium ion and protects
Film
3H2MoO4+2Al3+=Al2(MoO4)3↓+6H+ (10)
7th, with potassium ferricyanide K3Fe(CN)6Make oxidisability accelerating agent, the potassium ferricyanide forms iron cyaniding with aluminium ion in aluminium surface
Aluminium compound protective film
Fe(CN)6 3-+Al3+=AlFe (CN)6↓ (11)
8th, 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.
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 dry
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.
By Fig. 6, chromaking aluminium is produced, longtime running is found, degreasing tank slot bottom has crystal, and chromaking slot slot bottom has containing chromium dirt
Mud needs periodic cleaning, and sludge contains hypertoxic Cr VI, and operation is abnormally dangerous.
Ammonium fluoride, ammonium acid fluoride, sodium fluoride, phosphoric acid in acid deoiling slot are to make the easy dust of aluminium material surface, be also easy to produce knot
The component of brilliant precipitate.Ammonium fluoride, ammonium acid fluoride ammonium ion when bath acidity value is inadequate, aluminium material surface is also easy to produce acid etching
Ash influences deoiling effect；Sodium ion in sodium fluoride easily generates cryolite precipitation, needs to clear up tank liquor；Phosphoric acid easily generates phosphoric acid
Aluminum precipitation, tank liquor need clear bottom.
Potassium bichromate K in chromaking slot2Cr2O 7, sodium fluoride, potassium ferricyanide K3Fe(CN)6, sodium metasilicate Na2SiO3, molybdic acid
Sodium is the component for making the easy dust of aluminium material surface, being also easy to produce crystallization precipitate.These component potassium containing sodium easily generate cryolite and fluorine
Potassium aluminate precipitates, and needs clear slot；Meanwhile these products make tank liquor unintelligible, the easy dust of chromaking film influences chromaking quality.
Stabilizer in chromaking slot is composed of 2 kinds of organic acids allotment containing carboxyl, hydroxyl, is unstable in chromaking liquid
Determine, easily by the component of oxygenolysis.These are reducing agent components, containing chromic anhydride (CrO3), hydrofluoric acid, nitric acid, boric acid tank liquor
In, agent decomposition is oxidized easily, influences the stability of chromaking liquid.
Invention content
It is an object of the invention to propose a kind of Aluminum subtract slag oil removing and chromaking medicament stablize and compatible method, have
The characteristics of degreasing fluid and compatible chromaking liquid.
It is an object of the invention to propose it is a kind of using Aluminum subtract slag oil removing and chromaking medicament stablize and compatible method
System, have degreasing fluid and chromaking liquid compatible, the characteristics of without clear slot.
For this purpose, the present invention uses following technical scheme：
A kind of Aluminum subtract slag oil removing and chromaking medicament stablize and compatible method, it is described including degreasing tank and chromaking slot
In degreasing tank there is degreasing fluid, there is chromaking liquid, the degreasing fluid is the solution of nitric acid and hydrofluoric acid, described in the chromaking slot
Chromaking liquid is the solution of chromic anhydride, hydrofluoric acid and nitric acid, and the degreasing fluid and chromaking liquid are compatible, the degreasing tank and chromaking slot
It is generated in During Process of Long-term Operation without precipitation.
Further, the Con trolling index of degreasing fluid is：40~60g/L of 68wt% nitric acid, 5~15g/L of 50wt% hydrofluoric acid,
1.0~1.5 equivalent of acid concentration.
Further, medicament is added in degreasing tank During Process of Long-term Operation as nitric acid and the solution of hydrofluoric acid, the degreasing tank
Addition medicament in 68wt% nitric acid/50wt% hydrofluoric acid=1.5~2.5.
Further, the Con trolling index of chromaking liquid is：Chromic anhydride CrO32.5~3.5g/L, 50wt% hydrofluoric acid 0.4~
5~7g/L of 0.8g/L, 68wt% nitric acid, pH 1.8~2.2.
Further, medicament is added in chromaking liquid During Process of Long-term Operation as nitric acid and the solution of hydrofluoric acid, the chromaking liquid
Addition medicament 68wt% nitric acid/50wt% hydrofluoric acid=8~12.
Further, degreasing fluid with chromaking liquid is compatible refers to：
When the part degreasing fluid in the degreasing tank is brought into chromaking slot, chromaking slot is run without influence, to chromaking liquid
Chromaking ability without influence；
When the part chromaking liquid in the chromaking slot is brought into degreasing tank, degreasing tank is run without influence, to degreasing fluid
Oil removing ability without influence.
Spraying pretreating process flow is：Dress hangs workpiece → acid etching oil removing → water cleaning → water cleaning → chromaking processing → water
Cleaning → water cleaning → draining → drying → application.
Beneficial effects of the present invention are：
1st, degreasing fluid selects stable component to ensure that degreasing fluid longtime running does not generate heavy using nitric acid and the solution of hydrofluoric acid
It forms sediment, aluminium material surface is not easy dust, is not likely to produce crystallization precipitate.
2nd, chromaking liquid uses the solution of chromic anhydride, hydrofluoric acid and nitric acid, and stable component is selected to ensure chromaking liquid longtime running not
Precipitation is generated, aluminium material surface is not easy dust, is not likely to produce crystallization precipitate.Also, generation cryolite, potassium fluoroaluminate is avoided to sink
It forms sediment and organic matter decomposes, need clear slot risk.
3rd, selection ensures that degreasing tank longtime running does not influence the stability component of chromaking slot meticulously.Degreasing fluid and chromaking liquid are simultaneous
Hold, when degreasing fluid is inevitably carried in chromaking liquid by aluminium, do not influence the operation of chromaking liquid, do not influence aluminium chromaking
Effect, chromaking slot are interior without precipitated crystal.
4th, selection ensures the stability component that chromaking slot is compatible with degreasing tank meticulously.The present invention passes through selected chromaking liquid first
Each component, under the premise of making tank liquor homeostasis, not precipitated crystal, component selected by concern is to the compatibility of degreasing fluid for the first time.
5th, the ratio between two acid of degreasing tank additive are selected meticulously.Chromaking aluminium is produced, longtime running is found, even if degreaser
Containing only nitric acid and hydrofluoric acid, degreasing tank slot bottom also has the risk that aluminum fluoride is precipitated, and needs periodic cleaning, and sludge is fluorinated containing severe toxicity
Object, operation are abnormally dangerous.The present invention by control the weight ratio of 68wt% nitric acid and 50wt% hydrofluoric acid in degreasing fluid 1.5~
2.5, thoroughly eliminate the risk that degreasing tank generates precipitation.
6th, the ratio between two acid of chromaking slot additive are selected meticulously.Chromaking aluminium is produced, longtime running is found, even if chromaking agent
Containing only chromic anhydride, nitric acid and hydrofluoric acid, chromaking slot slot bottom also has the risk that aluminum fluoride and fluoaluminic acid chromium is precipitated, needs periodic cleaning,
Sludge contains hypertoxic fluoride and Cr VI, operation are abnormally dangerous.The present invention is by controlling in chromaking liquid 68wt% nitre in additive
For the weight ratio of acid and 50wt% hydrofluoric acid between 8~12, thorough eliminationization slot generates the risk of precipitation.
Description of the drawings
Fig. 1 aluminium ash component examining reports；
Fig. 2 large size aluminum material factories Aluminiferous waste slag source；
Fig. 3 chromate waste water process flows；
Fig. 4 nickel-containing waste water process flows；
Fig. 5 waste water and dregs process flows；
Fig. 6 conventional spray paint chromaking processing technological flows and slot position layout drawing.
Specific embodiment
Aluminum of the invention subtracts the oil removing of slag and chromaking medicament stablizes and compatible method, is to fully realize aluminium processing enterprise
The production puzzlement of industry, through researching and developing for many years, the spraying big to existing aluminium processing enterprise waste water and dregs amount, environmental protection pressure is huge pretreatment
Technique, after having carried out unprecedented system research, a new process of birth.
First, the quantitative and qualitative analysis with compatible medicament is stablized in oil removing with chromaking.
1st, degreasing fluid each component qualitative and quantitative analysis
Acid deoiling liquid in the prior art generally selects sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid, sodium fluoride, fluorination
Ammonium, ammonium acid fluoride and proper amount of surfactant oil removing.Each component quantitative and qualitative analysis is as follows：
Sulfuric acid：Sulfuric acid is the basis of acid deoiling, act as providing acidity value, dissolves natural oxide film, molten aluminium.Sulphur
Acid is mainly used for the free acidity for maintaining degreasing fluid certain, keeps solution-stabilized, promotes the dissolving of aluminium, showing aluminium surface has
Conducive to the active region of chromate film forming.Sulfuric acid content is too low, and the oil removing time is too long, and deoiling effect weakens；Sulfuric acid concentration is too high, molten
Aluminium is too fast, and wastewater treatment pressure is too big.Therefore, sulfuric acid content should be controlled in the range of 10~20g/L (98% sulfuric acid)；
Phosphoric acid：Phosphoric acid is the basis of acid deoiling, act as providing acidity value, dissolves natural oxide film, molten aluminium, phosphorus
Acid is the basis of acid deoiling.Phosphoric acid is mainly used for the free acidity for maintaining degreasing fluid certain, keeps solution-stabilized, promotes
The dissolving of aluminium makes aluminium surface show the active region for being conducive to chromate film forming.Phosphorus acid content is too low, and solvability weakens, and removes
The oily time is too long；Phosphoric acid concentration is too high, and molten aluminium is too fast, occurs the risk of phosphoric acid aluminum precipitation, and wastewater treatment pressure is too big.Cause
This, phosphorus acid content should be controlled in the range of 5~15g/L (85% phosphoric acid)；
Nitric acid：Nitric acid is the basis of acid deoiling, act as providing acidity value, dissolves natural oxide film, molten aluminium.Nitre
Acid is mainly used for the free acidity for maintaining degreasing fluid certain, keeps solution-stabilized, aluminium surface is promoted to be passivated, ash disposal makes aluminium surface
Show the active region for being conducive to chromate film forming.Nitric acid content is too low, and passivation ability weakens, and molten aluminum amount increase has generation phosphorus
The risk of sour aluminium and aluminum fluoride；Concentration of nitric acid is too high, and ammonia nitrogen increases in waste water, and environmental protection treatment pressure is too big.Therefore, nitric acid content
It should control in the range of 20~30g/L (68% nitric acid)；
Hydrochloric acid：Hydrochloric acid is the basis of acid deoiling, act as providing acidity value, dissolves natural oxide film, molten aluminium.Sulphur
Acid is mainly used for the free acidity for maintaining degreasing fluid certain, keeps solution-stabilized, promotes the dissolving of aluminium, showing aluminium surface has
Conducive to the active region of chromate film forming.Content of hydrochloric acid is too low, and the oil removing time is too long, and deoiling effect weakens；Concentration of hydrochloric acid is too high, molten
Aluminium is too fast, the obfuscation of aluminium surface burnt hair, and wastewater treatment pressure is too big.Therefore, content of hydrochloric acid should be controlled in the range of 5~10g/L
(30% hydrochloric acid)；
Hydrofluoric acid (sodium fluoride, ammonium fluoride, ammonium acid fluoride)：Hydrofluoric acid is the activator of degreasing fluid, quick to dissolve nature oxygen
Change film and aluminium, be the essential promotion ingredient of degreasing fluid.Hydrofluoric acid is mainly used for the free acidity for maintaining solution certain, keeps
It is solution-stabilized, promote the dissolving of aluminium, Al is complexed3+, aluminium surface is made to show the active region for being conducive to chromate film forming.F-And NO3-
Content there are certain proportionate relationship, F-/NO3 -Optimum ratio range be 0.25~0.35, ratio size, which seriously affects, to be removed
The stability of oily effect and tank liquor.F-The oil removing reaction time is longer when content is too low, and aluminium surface dissolving is uneven；F-Too high levels
When it is violent with reactive aluminum liberation of hydrogen, reduce the glossiness of aluminium shape surface, molten aluminum amount is too big, is susceptible to fluorination aluminum precipitation.Therefore,
The content of hydrofluoric acid should be strict controlled in the range of 5~15g/L (50% hydrofluoric acid)；
Surfactant：Surfactant is the basis of acid deoiling, act as emulsification aluminium material surface oil stain, it is ensured that
Surface is uniform, a concentration of 0.005~0.010g/L
Acidity value：The acidity value of degreasing fluid has a significant impact deoiling effect.If the acidity value of degreasing fluid is low, aluminium alloy
Solution rate is slow, and deoiling effect is poor；The acidity value of degreasing fluid is high, and the solution rate of aluminium alloy is fast, and deoiling effect is good.Therefore, it removes
The acidity value of fluid should be strict controlled in 1.0~1.5 equivalent weight ranges；
Except oil temperature：Degreasing fluid temperature has deoiling effect certain influence.When temperature is less than 5 DEG C, reaction speed is too slow, removes
Oily decreased effectiveness；When temperature is higher than 40 DEG C, film forming speed is too fast, and molten aluminium is too fast.Therefore, degreasing fluid temperature be preferably controlled in 10~
In the range of 30 DEG C, under normal circumstances room temperature is sufficient.
2nd, chromaking slot each component quantitative and qualitative analysis
Chromaking slot generally CrO containing chromic anhydride in the prior art3, potassium bichromate K2Cr2O 7, sodium fluoride, potassium ferricyanide K3Fe
(CN)6, sodium metasilicate Na2SiO3, hydrofluoric acid, nitric acid, boric acid, sodium molybdate, stabilizer (two kinds of organic acid tune containing carboxyl, hydroxyl
With being composed) etc..Each component quantitative and qualitative analysis is as follows：
Chromic anhybride：Chromic anhydride is the basis of passivation, is oxidant in chromaking liquid, content is to the formation speed of chromaking film
Great influence is suffered from presentation quality.Film forming speed is slower when chromic anhydride content is too low, and film is thin imperfect, and color is partially light, corrosion resistant
Lose hydraulic performance decline；Reaction speed is too fast during chromic anhybride too high levels, and film layer crystallizes coarse, loose not fine and close, easy dusting, and color and luster is inclined
It is deep, with reference to force difference, increase environmental pollution and waste water treatment expense.Therefore, chromic anhydride content control is 1.5~4.0g/L；
Hydrofluoric acid：Hydrofluoric acid is the activator of chromaking liquid, has catalytic action to film formation reaction, be to form chromaking film must can not
Few promotion ingredient.Hydrofluoric acid is mainly used for the free acidity for maintaining solution certain, keeps solution-stabilized, promotes the dissolving of aluminium,
Al is complexed3+, aluminium surface is made to show the active region for being conducive to chromate film forming.F-There are certain ratio passes with the content of CrO3
System, F-/CrO3Optimum ratio range be 0.05~0.15, ratio size seriously affects the adhesion of chromate conversion coating and resistance to
Corrosion.F-The film formation reaction time is longer when content is too low, and film layer is relatively thin, and corrosion resistance is poor or even cannot form a film；F-During too high levels
It is violent with reactive aluminum liberation of hydrogen, the glossiness of aluminium shape surface is reduced, makes film layer coarse, loose, adhesive force declines, while chromaking liquid
It is unstable, easily chromium-bearing sludge is formed in slot bottom.Therefore, the content of hydrofluoric acid should be strict controlled in the range of 0.5~1.0g/L；
Nitric acid：Nitric acid is the basis of chromaking liquid, act as providing acidity value, dissolving chromaking ash dissolves chromaking slot
Slot bottom sludge prevents crystallization to be precipitated, and aoxidizes trivalent chromium.Nitric acid is mainly used for the free acidity for maintaining chromaking liquid certain, keeps molten
Liquid is stablized, and aluminium surface is promoted to be passivated, ash disposal, and aluminium surface is made to show the active region for being conducive to chromate film forming.Nitric acid content mistake
Low, solvability weakens, and molten aluminum amount increase has the risk for generating slot bottom chromaking sludge；Concentration of nitric acid is too high, and chromaking film is too thin,
Ammonia nitrogen increases in waste water, and environmental protection treatment pressure is too big.Therefore, nitric acid content should control in the range of 5~10g/L that (nitric acid refers to
Weight fraction is 68% nitric acid)；
Boric acid：Boric acid mainly plays cushioning effect in chromaking liquid, and the pH value of solution is made to keep relative stability.Boric acid can be continuous
Hydrogen ion is ionized out, supplements the hydrogen ion consumed in process of production, so as to which the hydrogen ion concentration for preventing solution drastically reduces,
Solution ph is avoided, which significantly to increase, causes solution unstable.Meanwhile boric acid can control the oxidation reaction speed of solution and improve film
Layer appearance makes conversion film uniform, fine and close.Boric acid content is too low, and cushioning effect is weaker, acts on unobvious；Boric acid content is too high, meeting
Slow down film formation reaction speed, Film color is made to shoal.The dosage of boric acid is advisable with 0.3~1.2g/L；
Sodium molybdate：Sodium molybdate is the accelerating agent to form chromaking film, shows strong oxidizing property in acidic chromate medium, is risen
To cathodic depolarization effect is accelerated, the current density of micro cell is improved, so as to accelerate film forming speed, reduces reaction temperature, contracting
Short film formation time.In addition, sodium molybdate also participates in film formation reaction, generation aluminium molybdate complex is deposited on chromate film, is made up
The leakiness of chromate film, so as to improving the corrosion resistance of chromate conversion coating.Molybdic acid sodium content is low, and film forming speed is slow,
Film is relatively thin, of light color；Molybdic acid sodium content is high, and film forming speed is fast, and color is deep, and corrosion resistance is good, but cost increases.The content of sodium molybdate
It should control in the range of 0.2~0.8g/L；
Stabilizer：Stabilizer is composed of two kinds of organic acids allotment containing carboxyl, hydroxyl, and main function is and mistake
The Al of amount3+Form stable chelate, moreover it is possible to it controls, reduce film formation reaction speed, the interference of impurity, raising chromium in masking solutions
Change the stability of liquid.Meanwhile can be by physics and chemical action absorption on aluminum substrate surface, the synergistic effect of the two makes it have
Higher coverage so as to improve corrosion mitigating effect, effectively inhibits Al3+Generation, reduce the generation of sediment, avoid workpiece surface
Dust.Stabiliser content is too low, and chelate effect is poor, does not have the effect for inhibiting sediment；Stabiliser content is excessively high, can hinder chromaking
Film formation reaction is normally carried out.The content of stabilizer is generally 0.7~2.5g/L；
Chromaking pH value：The pH value of chromaking liquid has a significant impact the formation of chromaking film and quality.If the pH value of solution is relatively low,
The solution rate of metal increases, and film formation reaction is accelerated, and film layer is coarse, loose, poor adhesive force；If the pH value of solution is higher, metal
Solution rate reduce, film formation reaction slows down, and film layer is relatively thin, of light color, and corrosion resistance is poor.Therefore, the pH value of chromaking liquid should be stringent
Control is in the range of 1.8~2.2, the general pH value using nitric acid or ammonium hydroxide adjustment chromaking liquid；
Chromaking temperature：Solution temperature has larger impact to the performance of chromaking film.When temperature is less than 5 DEG C, reaction speed is too slow,
Film layer is relatively thin, of light color or even cannot form a film, and corrosion resistance is poor；When temperature is higher than 40 DEG C, film forming speed is too fast, and film is coarse, thin
Pine easily plays powder, poor adhesive force.Therefore, solution temperature is preferably controlled in the range of 20~35 DEG C, under normal circumstances room temperature is sufficient.
2nd, oil removing and chromaking are stablized and compatible medicament quantitative experiment.
1st, the selection scheme that degreasing fluid medicament is stablized
Acid deoiling liquid of the prior art generally selects sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid, sodium fluoride, fluorination
Ammonium, ammonium acid fluoride and proper amount of surfactant oil removing.Dosage component selection scheme is：
Selection aluminium material surface is not easy dust, the component for being not likely to produce crystallization precipitate：Sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and
Proper amount of surfactant；
Reject the easy dust of aluminium material surface, the component for being also easy to produce crystallization precipitate：Ammonium fluoride, ammonium acid fluoride, sodium fluoride, phosphorus
Acid.Ammonium fluoride, ammonium acid fluoride ammonium ion when bath acidity value is inadequate, aluminium material surface be also easy to produce acid etching ash, influence oil removing effect
Fruit；Sodium ion in sodium fluoride easily generates cryolite precipitation, needs to clear up tank liquor；Phosphoric acid easily generates phosphoric acid aluminum precipitation, and tank liquor needs
Clear bottom is wanted, therefore the angle stablized from deoiling effect and tank liquor, by ammonium fluoride, ammonium acid fluoride, sodium fluoride and phosphoric acid from oil removing
It is rejected in component.
2nd, the selection scheme that chromaking liquid medicament is stablized
Chromaking liquid generally selects chromic anhydride (CrO in the prior art3), potassium bichromate (K2Cr2O 7), sodium fluoride, the potassium ferricyanide
[K3Fe(CN)6], sodium metasilicate (Na2SiO3), hydrofluoric acid, nitric acid, boric acid, sodium molybdate and stabilizer be (by containing carboxyl, hydroxyl
Two kinds of organic acid allotments are composed), dosage component selection scheme is：
A, selection aluminium material surface is not easy dust, the component for being not likely to produce crystallization precipitate：Chromic anhydride, hydrofluoric acid, nitric acid, boron
Acid；
B, the easy dust of aluminium material surface, the component for being also easy to produce crystallization precipitate are rejected：Potassium bichromate, sodium fluoride, the potassium ferricyanide,
Sodium metasilicate, sodium molybdate.These component potassium containing sodium easily generate cryolite and potassium fluoroaluminate precipitation, need clear slot；Meanwhile these
Product makes tank liquor unintelligible, and the easy dust of chromaking film influences chromaking quality, it should be rejected from chromaking liquid component；
C, reject chromaking liquid in it is unstable, easily by the component of oxygenolysis：Stabilizer is had by two kinds containing carboxyl, hydroxyl
Machine acid allotment be composed, these are reducing agent components, containing chromic anhydride, hydrofluoric acid, nitric acid, boric acid tank liquor in, easily by oxygen
Agent is decomposed, and influences the stability of chromaking liquid, it should be rejected from chromaking liquid component.
By above-mentioned selection result, degreasing tank selects sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and proper amount of surfactant；Chromaking slot
Select chromic anhydride, hydrofluoric acid, nitric acid, boric acid.When these selections can ensure oil removing and chromaking, tank liquor is steady in a long-term, unclear slot.
But in actual production, it after aluminium oil removing, flows and washes through twice, into chromaking slot chromaking, part degreasing fluid can
Chromaking slot can be brought into, chromaking effect is influenced and chromaking liquid stablizes or even production precipitation.So for the thorough stabilization of tank liquor, it must
It must carry out medicament compatible design.
3rd, the compositional selecting that degreasing fluid is compatible with chromaking liquid medicament
The component that degreasing fluid stabilization can be selected in degreasing tank is sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and proper amount of surfactant；
These components, aluminium can bring chromaking slot into, influence the steady of chromaking ability and chromaking slot after degreasing tank, two flowing rinsing bowls
It is qualitative, it needs to carry out compatible design, it is ensured that chromaking slot long-term stable operation.Experiment is as follows：
A, in degreasing fluid additive amount be 68wt% nitric acid 30g/L, the concentrated sulfuric acid (weight fraction 98%) 10g/L, hydrochloric acid solution
(weight fraction 30%) 5g/L, 50wt% hydrofluoric acid 10g/L, TX-10 phosphoesterase 30 .001g/L；Additive amount is chromic anhydride in chromaking liquid
3g/L, 50wt% hydrofluoric acid 0.7g/L, 68wt% nitric acid 8.5g/L, boric acid 0.8g/L.Aluminium impregnates oil removing 3 in degreasing fluid and divides
Through twice flowing washing in each 30 seconds, chromaking is carried out 3 minutes through chromaking liquid for clock, then through twice flowing washing in each 30 seconds, is then dried in the air
It is dry, observe aluminium material surface color, record original version number 0#.
Chromaking liquid is in itself containing nitric acid, hydrofluoric acid, therefore the nitric acid and hydrofluoric acid in degreasing fluid can be brought into chromaking liquid, completely
It is compatible；But do not have in the sulfuric acid, hydrochloric acid and TX-10 chromaking liquid in degreasing fluid, carry out compatible experiment, observation sulfuric acid, hydrochloric acid
With influences of the TX-1 0 to chromaking liquid ability to work and stability.
B, take out experiment a in 5 parts of chromaking liquid, be separately added into the concentrated sulfuric acid (98%) 1.0g/L, 2.0g/L, 3.0g/L,
4.0g/L、5.0g/L；Aluminium impregnates oil removing 3 minutes in degreasing fluid, through twice flowing washing in each 30 seconds, through above-mentioned 5 parts of chromaking
Liquid chromaking 3 minutes, then through twice flowing washing in each 30 seconds, then dry, observe aluminium material surface color, record chromaking version number
1#, 2#, 3#, 4#, 5# compare the appearance color of chromaking version 0#~5#, it is found that 1#~5# chromaking version is faded, sulfuric acid seriously affects chromium
Change ability, even if sulfuric acid concentration, down to 1g/L, chromaking film is hardly painted, therefore the sulfuric acid in degreasing fluid is incompatible to chromaking liquid,
Degreasing tank sulfuric acid component should be rejected.
C, take out experiment a in 5 parts of chromaking liquid, be separately added into hydrochloric acid solution (30%) 1.0g/L, 2.0g/L, 3.0g/L,
4.0g/L、5.0g/L；Aluminium impregnates oil removing 3 minutes in degreasing fluid, through twice flowing washing in each 30 seconds, through above-mentioned 5 parts of chromaking
Liquid chromaking 3 minutes, then through the flowing washing in each 30 seconds of # twice, then dry, observe aluminium material surface color, record chromaking version number
6#, 7#, 8#, 9#, 10#, compare chromaking version 0,5#~10# appearance color, it is found that 6#~10# chromaking version is faded, hydrochloric acid is serious
Chromaking ability is influenced, even if concentration of hydrochloric acid, down to 1g/L, chromaking film is hardly painted, therefore the hydrochloric acid of degreasing fluid is not simultaneous to chromaking liquid
Hold, salt acid constituents should be rejected.
D, take out experiment a in 5 parts of chromaking liquid, be separately added into TX-10 0.0001g/L, 0.0002g/L, 0.0003g/L,
0.0004g/L、0.0005g/L；Aluminium oil removing 3 minutes in degreasing fluid, through twice flowing washing in each 30 seconds, through above-mentioned 5 parts of chromium
Change liquid chromaking 3 minutes, then through twice flowing washing in each 30 seconds, then dry, observe aluminium material surface color, record chromaking version number
11#, 12#, 13#, 14#, 15#, compare chromaking version 0,10~15# appearance color, it is found that 11#~15# chromaking versions are colour-fast；Spray
After powder, curing, then boiling, cupping, impulse detection are carried out, it is found that chromaking film adhesive force is inadequate, detection is unqualified.So TX-10
The adhesive force of chromaking film is seriously affected, even if concentration, down to 0.0001g/L, chromaking film adhesive force is also unqualified, therefore in degreasing fluid
TX-10 it is incompatible to chromaking liquid, surface active agent composition should be rejected.
Empirically a~d's as a result, degreasing fluid it is selectable to chromaking liquid compatibility dosage component be：Nitric acid, hydrofluoric acid；
Other components influence the stability of chromaking liquid or influence the quality of chromaking film.
4th, the compositional selecting that chromaking liquid is compatible with degreasing fluid medicament
E, additive amount is 68wt% nitric acid 40g/L, 50wt% hydrofluoric acid 10g/L in degreasing fluid；Additive amount is in chromaking liquid
Chromic anhydride 3g/L, 50wt% hydrofluoric acid 0.7g/L, 68wt% nitric acid 8.5g/L, boric acid 0.8g/L.Aluminium oil removing 3 in degreasing fluid divides
Clock through the flowing washing of each 30 seconds of twice, through chromaking liquid chromaking 3 minutes, then through twice flowing washing in each 30 seconds, is then dried, is seen
Examine aluminium material surface color, record original version number 00#.
It for using water wisely, is cleaned after aluminium chromaking, water for cleaning can carry out degreasing fluid moisturizing, which uses
Water is inevitably containing chromaking liquid ingredient, and therefore, when chromaking liquid is compatible with degreasing fluid, deoiling effect is unaffected.Oil removing
Liquid is in itself containing nitric acid, hydrofluoric acid, therefore the nitric acid and hydrofluoric acid of chromaking liquid and degreasing fluid are completely compatible；But the chromic anhydride and boron of chromaking liquid
Sour degreasing fluid does not have, and carries out compatible experiment, the influence of observation chromic anhydride and boric acid to degreasing fluid ability to work and stability.
F, 5 parts of degreasing fluid in experiment e is taken out, is separately added into CrO3 0.2g/L、0.4g/L、0.6g/L、0.8g/L、
1.0g/L；Aluminium was through oil removing in above-mentioned 5 parts of degreasing fluids 3 minutes, through twice flowing washing in each 30 seconds, through chromaking liquid chromaking 3 minutes,
Again through the flowing washing of each 30 seconds of twice, then dry, observe aluminium material surface color, record chromaking version number 16#, 17#, 18#,
19#, 20# compare the appearance color of chromaking version 00#, 16#~20#, it is found that 16#~20# chromaking versions are colour-fast；It dusts, cure
Afterwards, then boiling, cupping, impulse detection are carried out, it is found that chromaking film adhesive force is unaffected, detection is qualified.So add in degreasing fluid
Enter CrO3The adhesive force of chromaking film, CrO are not influenced3Degreasing fluid is compatible with.
G, take out experiment e in 5 parts of degreasing fluid, be separately added into boric acid 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L,
0.5g/L；Aluminium was through oil removing in above-mentioned 5 parts of degreasing fluids 3 minutes, through twice flowing washing in each 30 seconds, through chromaking liquid chromaking 3 minutes,
Again through the flowing washing of each 30 seconds of twice, then dry, observe aluminium material surface color, record chromaking version number 21#, 22#, 23#,
24#, 25# compare the appearance color of chromaking version 00#, 21~25#, it is found that 21~25# chromaking versions are colour-fast；After dusting, curing,
Boiling, cupping, impulse detection are carried out again, it is found that chromaking film adhesive force is unaffected, detection is qualified.So it is added in degreasing fluid
Boric acid does not influence the adhesive force of chromaking film, and boric acid is compatible with degreasing fluid.But after adding in boric acid, oil removing ability significantly weakens, instead
Speed is answered to slow down, after aluminium oil removing, appearance is bad, can reject boric acid so that chromaking liquid is completely compatible to degreasing fluid.
Empirically a~g, the degreasing fluid selected as compatible with the dosage component of chromaking liquid：
Degreasing fluid takes nitric acid and hydrofluoric acid, and chromaking liquid takes chromic anhydride, nitric acid and hydrofluoric acid.For this purpose, after carrying out medicament compatibility
The national standard detection of the various abilities of chromaking film：
H, additive amount is 68wt% nitric acid 40g/L, 50wt% hydrofluoric acid 10g/L in degreasing fluid；Additive amount is in chromaking liquid
Chromic anhydride CrO33g/L, 50wt% hydrofluoric acid 0.8g/L, 68wt% nitric acid 7g/L.Aluminium oil removing 3 minutes in degreasing fluid, through two
The flowing washing of each 30 seconds of road through chromaking liquid chromaking 3 minutes, then through twice flowing washing in each 30 seconds, then dries, observes aluminium table
Face color, record original version number 001#.
The appearance color of chromaking version 001# is observed, then dusts, cure, then carry out boiling, cupping, impulse detection, is detected
Chromaking film adhesive force, the results showed that every Testing index is all qualified.
Although also there is the risk of generation fluorination aluminum precipitation, it is thus necessary to determine that just containing only nitric acid and hydrofluoric acid in degreasing fluid
When nitric/hydrofluoric section, using the solvability of nitric acid, hinder the generation of aluminum fluoride.Experiment is as follows：
I, additive amount is 68wt% nitric acid 40g/L, 50wt% hydrofluoric acid 10g/L in degreasing fluid；Additive amount is in chromaking liquid
Chromic anhydride CrO33g/L, 50wt% hydrofluoric acid 0.7g/L, 68wt% nitric acid 8.5g/L.Aluminium was in degreasing fluid oil removing 3 minutes, through two
Each 30 seconds of road flowing washing, through chromaking liquid chromaking 3 minutes, then through twice flowing washing in each 30 seconds.The acidity value control of degreasing fluid
For 1.0~1.5 equivalents, annex solution selection 68wt% nitric acid/50wt% hydrofluoric acid weight ratio=1~3：Different medicines in the range of 1
Agent is added, and is tested repeatedly.Although chromaking film is qualified by national standard detection, when 68wt% nitric acid/50wt% hydrofluoric acid weight ratios are low,
Reaction is too fast, and molten aluminium is too many, there is Precipitation in degreasing tank；68wt% nitric acid/50wt% hydrofluoric acid weight ratios are improved, precipitation disappears
It loses；When 68wt% nitric acid/50wt% hydrofluoric acid weight ratios are too high, reaction is slowed down, and deoiling effect is bad.1 degreasing fluid is appropriate to be added
It is 1.5~2.5 that the sour weight ratio of charging two, which is dense (the 68%)/50wt% hydrofluoric acid of nitric acid,.
As degreasing fluid, although also there is generation aluminum fluoride and fluorine containing only chromic anhydride, nitric acid and hydrofluoric acid in chromaking liquid
The risk of aluminic acid chromium precipitation, it is thus necessary to determine that appropriate nitric/hydrofluoric section using the solvability of nitric acid, hinders aluminum fluoride
With the generation of fluoaluminic acid chromium precipitation：
J, additive amount is 68wt% nitric acid 40g/L, 50wt% hydrofluoric acid 10g/L in degreasing fluid；Additive amount is in chromaking liquid
Chromic anhydride 3g/L, 50wt% hydrofluoric acid 0.7g/L, 68wt% nitric acid 8.5g/L.Aluminium oil removing 3 minutes in degreasing tank, it is each through twice
Flowing washing in 30 seconds, through chromaking liquid chromaking 3 minutes, then through twice flowing washing in each 30 seconds.The acidity value control of degreasing fluid is 1.0
~1.5 equivalents, chromium anhydride concentration control two selection 68wt% nitric acid ÷ of addition in 2.5~3.5g/L, chromaking liquid in chromaking liquid
50wt% hydrofluoric acid weight ratio=5~15：Different agents addition in the range of 1, is tested repeatedly.Although chromaking film is detected by national standard
Qualification, but when 68wt% nitric acid/50wt% hydrofluoric acid weight ratios are low, chromaking is too fast, and chromaking slot has aluminum fluoride or fluoaluminic acid chromium to sink
Precipitation goes out, and improves 68wt% nitric acid/50wt% hydrofluoric acid weight ratios, and precipitation disappears；68wt% nitric acid/50wt% hydrofluoric acid weight
Than it is too high when, chromaking film lighter, film lightens again, chromaking film national standard detection it is unqualified.Appropriate two acid of additive of chromaking liquid
Weight ratio is that 68wt% nitric acid/50wt% hydrofluoric acid is 8~12.
3rd, degreasing fluid and chromaking liquid medicament are stablized and compatible design analysis of experimental results
Empirically a~j and testing result can do following analysis：
1st, degreasing fluid ingredient selects nitric acid and hydrofluoric acid, and tank liquor is stablized, compatible with chromaking liquid.In the additive of degreasing fluid
68wt% nitric acid/50wt% hydrofluoric acid weight ratio should be controlled between 1.5~2.5, be able to maintain that degreasing fluid is run steadily in the long term,
Fluorination aluminum precipitation is not generated.
2nd, chromaking liquid ingredient selects chromic anhydride, nitric acid and hydrofluoric acid, and tank liquor is stablized, compatible with degreasing fluid.The addition of chromaking liquid
68wt% nitric acid/50wt% hydrofluoric acid weight ratio should be controlled between 8~12 in material, be able to maintain that degreasing fluid is transported steadily in the long term
Row does not generate aluminum fluoride and fluoaluminic acid chromium precipitation.
Below in conjunction with the accompanying drawings and the technical solution that further illustrates the present invention of specific embodiment.
The present invention provides a kind of Aluminum subtract slag oil removing and chromaking medicament stablize with compatible method, including degreasing tank with
Chromaking slot, the degreasing tank is interior to have degreasing fluid, has chromaking liquid in the chromaking slot, and the degreasing fluid is nitric acid and hydrofluoric acid
Solution, the chromaking liquid be chromic anhydride, hydrofluoric acid and nitric acid solution, the degreasing fluid and chromaking liquid are compatible, described to remove
Oil groove and chromaking slot generate in During Process of Long-term Operation without precipitation.
Degreasing fluid selects stable component to ensure that degreasing fluid longtime running does not generate heavy using nitric acid and the solution of hydrofluoric acid
It forms sediment, aluminium material surface is not easy dust, is not likely to produce crystallization precipitate.
Chromaking liquid uses the solution of chromic anhydride, hydrofluoric acid and nitric acid, and stable component is selected to ensure that chromaking liquid longtime running does not produce
Raw precipitation, aluminium material surface are not easy dust, are not likely to produce crystallization precipitate.Also, avoid generation cryolite, potassium fluoroaluminate precipitation
It is decomposed with organic matter, needs clear slot risk.
Degreasing fluid with chromaking liquid is compatible refers to：When the part degreasing fluid in the degreasing tank is brought into chromaking slot,
Chromaking slot is run without influence, on the chromaking ability of chromaking liquid without influence；When the part chromaking liquid in the chromaking slot is brought into
During degreasing tank, degreasing tank is run without influence, on the oil removing ability of degreasing fluid without influence.
Selection ensures that degreasing tank longtime running does not influence the stability component of chromaking slot meticulously.Degreasing fluid and chromaking liquid are simultaneous
Hold, when degreasing fluid is inevitably carried in chromaking liquid by aluminium, do not influence the operation of chromaking liquid, do not influence aluminium chromaking
Effect, chromaking slot are interior without precipitated crystal.Selection ensures the stability component that chromaking slot is compatible with degreasing tank meticulously.The present invention is first
By selected chromaking liquid each component, make tank liquor homeostasis, not precipitated crystal under the premise of, for the first time concern selected by component to oil removing
The compatibility of liquid.
Further, the Con trolling index of degreasing fluid is：40~60g/L of 68wt% nitric acid, 5~15g/L of 50wt% hydrofluoric acid,
1.0~1.5 equivalent of acid concentration.
Further, medicament is added in degreasing tank During Process of Long-term Operation as nitric acid and the solution of hydrofluoric acid, degreasing tank adds
68wt% nitric acid ÷ 50wt% hydrofluoric acid=1.5~2.5 in adding medicine.The ratio between two acid of selection degreasing tank additive meticulously.It is logical
It crosses the weight ratio of 68wt% nitric acid and 50wt% hydrofluoric acid in control degreasing fluid and between 1.5~2.5, thoroughly eliminates degreasing tank production
The risk of raw precipitation.
Further, the Con trolling index of chromaking liquid is：Chromic anhydride CrO32.5~3.5g/L, 50wt% hydrofluoric acid 0.4~
5~7g/L of 0.8g/L, 68wt% nitric acid, pH 1.8~2.2.By the additive amount for controlling chromic anhydride so that film layer has enough
Thickness has enough compactness extents.By the control to chromaking liquid pH value, control film forming speed in the reasonable scope, improves
Film quality.
Further, medicament is added in chromaking liquid During Process of Long-term Operation as nitric acid and the solution of hydrofluoric acid, chromaking liquid adds
Adding medicine 68wt% nitric acid ÷ 50wt% hydrofluoric acid=8~12.The ratio between two acid of selection chromaking slot additive meticulously.Pass through control
Between 8~12, thorough eliminationization slot generates the weight ratio of 68wt% nitric acid and 50wt% hydrofluoric acid in additive in chromaking liquid
The risk of precipitation.
Below by way of specific embodiment, the present invention is further explained.
Each component is as shown in the table in degreasing fluid and chromaking liquid in Examples 1 to 5.
In Examples 1 to 5, the acidity value of degreasing fluid in the range of 1.0~1.5, the pH value of chromaking liquid 1.8~
In the range of 2.2.During degreasing tank longtime running, the weight ratio of 68wt% nitric acid and 50wt% hydrofluoric acid in the addition medicament of degreasing fluid
Between 1.5~2.5；During chromaking liquid longtime running, 68wt% nitric acid and 50wt% hydrofluoric acid in the addition medicament of chromaking liquid
Weight ratio is between 8~12.
Aluminium processing procedure is in Examples 1 to 5：Aluminium oil removing 3 minutes in the degreasing fluid of degreasing tank, through two water
The twice flowing washing in each 30 seconds of washing trough, the chromaking 3 minutes in the chromaking liquid of chromaking slot, then the twice each 30 through two rinsing bowls
Second flowing washing.Aluminium is dried, is detected.The appearance color after aluminium chromaking is observed, then dusts, cure, then carry out
Boiling, cupping, impulse detection detect chromaking film adhesive force, the results showed that every Testing index is all qualified.
In Examples 1 to 5, degreasing tank and chromaking slot run 45 days without precipitated crystal.
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 explanation herein, the technology of this field
Personnel would not require any inventive effort the other specific embodiments that can associate the present invention, these modes are fallen within
Within protection scope of the present invention.
Claims (6)
1. a kind of Aluminum subtracts the oil removing of slag and chromaking medicament is stablized and compatible method, which is characterized in that including degreasing tank and chromium
Change slot, the degreasing tank is interior to have degreasing fluid, has chromaking liquid in the chromaking slot, and the degreasing fluid is nitric acid and hydrofluoric acid
Solution, the chromaking liquid are the solution of chromic anhydride, hydrofluoric acid and nitric acid, and the degreasing fluid and chromaking liquid are compatible, the oil removing
Slot and chromaking slot generate in During Process of Long-term Operation without precipitation.
2. Aluminum according to claim 1 subtracts the oil removing of slag and chromaking medicament is stablized and compatible method, which is characterized in that
The Con trolling index of the degreasing fluid is：40~60g/L of 68wt% nitric acid, 5~15g/L of 50wt% hydrofluoric acid, acid concentration 1.0~
1.5 equivalent.
3. Aluminum according to claim 2 subtracts the oil removing of slag and chromaking medicament is stablized and compatible method, which is characterized in that
Medicament is added in the degreasing tank During Process of Long-term Operation as nitric acid and the solution of hydrofluoric acid, in the addition medicament of the degreasing tank
68wt% nitric acid ÷ 50wt% hydrofluoric acid=1.5~2.5.
4. Aluminum according to claim 1 subtracts the oil removing of slag and chromaking medicament is stablized and compatible method, which is characterized in that
The Con trolling index of the chromaking liquid is：Chromic anhydride CrO32.5~3.5g/L, 0.4~0.8g/L of 50wt% hydrofluoric acid, 68wt% nitric acid
5~7g/L, pH 1.8~2.2.
5. Aluminum according to claim 4 subtracts the oil removing of slag and chromaking medicament is stablized and compatible method, which is characterized in that
Medicament is added in the chromaking liquid During Process of Long-term Operation as nitric acid and the solution of hydrofluoric acid, the addition medicament of the chromaking slot
68wt% nitric acid ÷ 50wt% hydrofluoric acid=8~12.
6. Aluminum according to claim 1 subtracts the oil removing of slag and chromaking medicament is stablized and compatible method, which is characterized in that
The degreasing fluid with chromaking liquid is compatible refers to：
When the part degreasing fluid in the degreasing tank is brought into chromaking slot, chromaking slot is run without influence, to the chromium of chromaking liquid
Change ability is without influence；
When the part chromaking liquid in the chromaking slot is brought into degreasing tank, degreasing tank is run without influence, degreasing fluid is removed
Oily ability is without influence.
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| CN109518173A (en) * | 2018-12-17 | 2019-03-26 | 熊映明 | The Al alloy powder spraying pretreatment water-saving configuration of chromaking line ejected wash water differential concatenation |
| CN109554698A (en) * | 2018-12-17 | 2019-04-02 | 熊映明 | Al alloy powder sprays degreasing tank to the compatible formula design of chromaking slot medicament |
| CN109778170A (en) * | 2019-01-30 | 2019-05-21 | 北方民族大学 | The treatment fluid and film layer preparation method of Mg alloy surface iron cyanide chemical composition coating |
| CN114324740A (en) * | 2021-12-30 | 2022-04-12 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Method for analyzing mixed acid solution of three-acid deoxidation |
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| CN105821402A (en) * | 2016-03-28 | 2016-08-03 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Aluminium alloy chromate-free overall agent compatibility treatment and wastewater zero discharge system |
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| CN105274545A (en) * | 2015-11-25 | 2016-01-27 | 天津航空机电有限公司 | Electroplating or chemical-plating pretreatment method of aluminum alloy and application of electroplating or chemical-plating pretreatment method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109518173A (en) * | 2018-12-17 | 2019-03-26 | 熊映明 | The Al alloy powder spraying pretreatment water-saving configuration of chromaking line ejected wash water differential concatenation |
| CN109554698A (en) * | 2018-12-17 | 2019-04-02 | 熊映明 | Al alloy powder sprays degreasing tank to the compatible formula design of chromaking slot medicament |
| CN109778170A (en) * | 2019-01-30 | 2019-05-21 | 北方民族大学 | The treatment fluid and film layer preparation method of Mg alloy surface iron cyanide chemical composition coating |
| CN114324740A (en) * | 2021-12-30 | 2022-04-12 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Method for analyzing mixed acid solution of three-acid deoxidation |
| CN114324740B (en) * | 2021-12-30 | 2024-01-30 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Method for analyzing mixed acid solution of tri-acid deoxidization |
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