CN106283014B - A kind of chrome-free tanning agent and its preparation method and application - Google Patents
A kind of chrome-free tanning agent and its preparation method and application Download PDFInfo
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- CN106283014B CN106283014B CN201610894417.6A CN201610894417A CN106283014B CN 106283014 B CN106283014 B CN 106283014B CN 201610894417 A CN201610894417 A CN 201610894417A CN 106283014 B CN106283014 B CN 106283014B
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
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Abstract
The present invention relates to a kind of chrome-free tanning agent and its preparation method and application, the chrome-free tanning agent includes: straight chain fatty acid alkylolamides compound 45%~91.5% by percentage to the quality；Straight chain hydrophobic fatty acid 9.5%~55%.Preparation method are as follows: raw material is uniformly mixed to obtain finished product with taking by each component；Or the mixture of hydrophobic fat acid and fatty acid alcohol amide compound composition is first prepared by design component, it then adds reinforcing agent and obtains finished product.The chrome-free tanning agent is suitable for the surface passivating treatment containing manganese Metal.The chrome-free tanning agent developed of the present invention has the characteristics that good water solubility, nontoxic, pollution-free, manganese metal inactivating performance be good and film layer selfreparing, existing electrolytic manganese chromating technique can be preferably substituted, with more significant environmental benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of chrome-free tanning agents and its preparation method and application, belong to manganese field of metallurgy.
Background technique
Manganese and its compound are widely used in departments such as metallurgy, chemical industry, light industry, electronic material, agriculture and animal husbandries, especially in steel
In iron industry, the presence of manganese can significantly improve the mechanical performance of steel, often there is " no manganese not Cheng Gang " this saying.However, due to
The chemical potential of manganese metal is lower, and activity is very high, is in air easy to react and cause the corrosion of manganese metal with oxygen
Occur, the corrosion of manganese not only will be greatly reduced the mechanical performance of manganese, shorten the service life of manganese mechanical equipment, and can destroy gold
The electronics and optical characteristics for belonging to material, or even cause catastrophic accident and huge economic loss, therefore, it is necessary to its into
Row is passivated to improve the corrosion resistance of manganese.Traditional chromating technique has simple process and low cost, and tank liquor is stablized,
Gained passivating film color is uniform, and binding force is good, and corrosion resistance is high, and passivating film has the characteristics that good self-repairing capability, quilt
It is widely used in electrolytic manganese industrial production.However, Cr VI used in the technique is severe toxicity and carcinogen, to environment
And human health risk is serious, the use of limitation chromating technique has all been give stricted orders by many countries, therefore, develops novel environment friendly
Passivating agent products, the benign development of electrolytic manganese industry is had a very important significance.
Currently, the research of chrome-free tanning agent becomes the hot spot of lot of domestic and international scientific worker concern.For example, patent
CN200510086577.X disclose it is a kind of using 0.1~20% phosphate aqueous solution as electrolytic manganese passivating liquid, with alkali adjust pH be 3
~14, there is certain effect to the passivation of manganese metal.Patent CN201210439032.2 discloses one kind with phosphoric acid or phosphate
For main passivator, citric acid and acetic acid are cosolvent, and sodium tartrate is corrosion inhibiter, and zinc sulfate and calcium nitrate are the novel of brightener
Chrome-free tanning agent, the passivating solution treated manganese metal have good color and excellent passivation effect.However, due to phosphoric acid
Use, passivating solution can generate a large amount of waste liquid containing phosphor passivation, have certain harm to water body, while also be easy to causeing manganese metal
Phosphorus content is exceeded in product.Patent CN200610018760.0 discloses one kind with silicate, cosolvent, corrosion inhibiter, accelerator
For the electrolytic manganese chromate-free passivation agent of principal component.The product of product moisture-proof thermal energy power and potassium bichromate passivation after passivator passivation
It is close, but silicone content increases in product, can reduce the quality of Electrolytic Manganese Product to a certain degree.In conclusion existing nothing
Chromium passivating agent product, more or less exist phosphorus pollution, passivating solution is unstable, product quality is bad, does not have the drawbacks such as self-repairability,
Therefore, it is badly in need of the chrome-free tanning agent product of exploitation novel environment friendly.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of chrome-free tanning agents and its preparation method and application.
A kind of chrome-free tanning agent of the present invention, it is characterised in that by percentage to the quality include following components:
Straight chain fatty acid alkylolamides compound 45%~91.5%；
Straight chain hydrophobic fatty acid 9.5%~55%.
As more excellent scheme, a kind of chrome-free tanning agent of the present invention, includes following components by percentage to the quality:
Straight chain fatty acid alkylolamides compound 45%~90%, preferably 70%~89%, further preferably 75%~
85%；
Straight chain hydrophobic fatty acid 9.5~50%, preferably 9.5~28%, further preferably 13.5~23.3%；
Reinforcing agent 0.5~5%, preferably 1.5~2%, further preferably 1.5~1.7%.
Chrome-free tanning agent in the present invention, the sum of each component gross mass percentage are 100%.
The carbon atom number of chrome-free tanning agent in the present invention, the hydrophobic fat acid is more than or equal to 6.Preferably 6~
26.The hydrophobic fat acid is more preferably C6~C26At least one of straight chain unitary hydrophobic carboxylic acid.Further
Preferably lauric acid (C12), myristic acid (C14), palmitinic acid (C16), stearic acid (C18), oleic acid (C18 unsaturated fatty acid)
At least one.
Chrome-free tanning agent in the present invention, the reinforcing agent are ethylenediamine tetra-acetic acid, citric acid, ascorbic acid, diethanol
Amine, triethanolamine, any one or two kinds in triisopropanolamine etc. are with mixture made of arbitrarily matching.
Chrome-free tanning agent in the present invention, the fatty acid alcohol amide compound are one glycollic amide of fatty acid or diethyl
Alkylolamides class compound.
Preferably, the fatty acid alcohol amide compound is by C6~C26Straight chain unitary hydrophobic carboxylic acid and diethanol amine or one
Ethanol amine occurs amidation process and is prepared.
Scheme as a further preference, the fatty acid alcohol amide compound are selected from lauric acid diethyl amide, Pork and beans
Cool acid diglycollic amide, palmitinic acid diglycollic amide, Stearic acid diethanolamine salt, oleic acid diethyl amide, one ethyl alcohol of lauric acid
Amide, one glycollic amide of myristic acid, one glycollic amide of palmitinic acid, one glycollic amide of stearic acid, in one glycollic amide of oleic acid
It is at least one.
The chrome-free tanning agent of the described electrolytic manganese metal surface treatment, product can according to component and content requirement, with
Excess fatty acids be raw material and diethanol amine or monoethanolamine etc. react to obtain fatty acid and fatty acid alcohol amide mixture (see
Technology path 1), it then adds a certain amount of reinforcing agent and obtains passivating agent products；
It can also be simply mixed and be prepared (see technical solution 2) by each component, technology path is as follows:
Technology path 1:
The technology path 1 includes following two step:
Step 1
Diethanol amine and/or monoethanolamine are added in excessive straight chain hydrophobic fatty acid, is reacted, fatty acid is generated
With the mixture of fatty acid alcohol amide；
Step 2
By design component, with taking reinforcing agent, and reinforcing agent is added in mixture obtained by step 1, is uniformly mixed, obtains
The chrome-free tanning agent.
Technology path 2: by be designed to distribution cut-off chain fatty acid alkylolamides class compound, hydrophobic fat acid, reinforcing agent,
After mixing, the passivator will be obtained with each component taken.
As preferred method, in step 1, a certain amount of C is first chosen6~C26Straight chain unitary hydrophobic carboxylic acid, in molar ratio rouge
Fat acid: hydramine=1:0.30~0.50 addition alcohol amine compound reacts 3~6h under the conditions of 100~150 DEG C, then add
The hydramine and basic catalyst of 0.15~0.40 times of fatty acid dosage (mole), 60~90 DEG C of progress ammonolysis reactions 2~
4h generates the mixture of fatty acid and fatty acid alcohol amide；The hydramine is diethanol amine and/or monoethanolamine, the alkalinity
Catalyst be KOH or or NaOH, the dosage of the basic catalyst be hydrophobic fat acid and hydramine gross mass 0.5%~
1%.
In industrial applications, when the alcohol amine compound is diethanol amine and/or monoethanolamine, described in step 1
Mixture is the mixture of hydrophobic fat acid and two/mono- glycollic amide of hydrophobic fat acid composition.
In industrial applications, the passivator is added in 70~90 DEG C, preferably 80 DEG C of water, is uniformly mixed, is obtained
The passivating solution that passivator mass percentage concentration is 0.5~5%.The passivating solution can be used directly.
The application of one of present invention chrome-free tanning agent, including it is used for processing product containing manganese Metal.
Preferred embodiment as application comprising following step:
Chrome-free tanning agent and water are hybridly prepared into passivating solution to be placed in deactivation slot, manganese Metal product will be contained is immersed in and match
It is passivated 1~5 minute in the chromium-free passivation liquid made, is cleaned after taking-up, it is dry, obtain finished product.
The mass percentage concentration of chrome-free tanning agent is 0.5~5% in the passivating solution.
The product containing manganese Metal is preferably manganese metal product.Further preferably electrolysis gained manganese metal product, i.e., it is electric
Solve the manganese metal product on cathode plate.
After the completion of passivation, it is rinsed with water clean.The drying is preferably dried.
The beneficial effects of the present invention are:
(1) straight-chain monobasic carboxylic acid has preferable hydrophobicity, is used for being capable of forming performance when Treatment of Metal Surface good
Good hydrophobic film, but solvent need to be generally made of organic solvents such as dehydrated alcohols, acquired solution is volatile, it is difficult to directly apply to
The open system at scene；Fatty acid alcohol amides compound can also form certain passivation effect in metal surface, but be passivated effect
Fruit is not ideal enough.In the present invention, based on the emulsifiability of fatty acid alcohol amides compound, hydrophobic fat acid is realized in water
In preferable dispersion, and then realize the collaboration of hydrophobic fat acid and fatty acid alcohol amides compound to the surface containing manganese Metal
Passivation, makes inactivating performance that (see comparative example 1 and embodiment 1,2, corrosion current reduces 1 order of magnitude or more) be substantially improved.
(2) present invention can prepare the mixture of fatty acid and fatty acid alcohol amide under the conditions of compared with low temperature, compared to tradition
The preparation of fatty acid alcohol amide, reaction process side reaction is few, and obtained mix product complies fully with the master of passivator of the present invention
Component requirements.
(3) fatty acid and fatty acid alcohol amides compound used in the present invention have hydrophobic carbochain and carboxylic acid group or
The functional groups such as amide groups, in water solution system, it is higher that each component can be self-assembly of compactness in the collaboration of manganese metal surface
Passivation layer；On the other hand, the bases such as multiple hydroxyls, the carboxyl that the compounds such as ethylenediamine tetra-acetic acid, citric acid, ascorbic acid have
Group, synergistic effect strengthen passivation film on manganese metal surface.Further, since on reinforcing agent and fatty acid alcohol amides compound
All there are multiple functional groups, in film forming there are also functional group's active site of deposit, when film layer is destroyed, which can
To act on exposed fresh manganese metal, the self-regeneration of passivation film is realized.
Chrome-free tanning agent prepared by the present invention has many advantages, such as easy to operate, at low cost, environmentally friendly, self-repairability, for
Electrolytic manganese industrial expansion has a very important significance.
Detailed description of the invention
Attached drawing 1 is the electrochemistry for the manganese metal being passivated prepared by the manganese metal not being passivated and embodiment 1 and comparative example 2
Energy-polarization curve result figure.
Attached drawing 2 is the surface electron microscope for the manganese metal being passivated prepared by the manganese metal not being passivated and embodiment 1.
In Fig. 1: No. 1 curve is the chemical property-polarization curve for the manganese metal not being passivated；No. 2 curves are embodiment 1
Chemical property-polarization curve of the prepared manganese metal being passivated, No. 3 curves are the gold being passivated prepared by comparative example 2
Belong to chemical property-polarization curve of manganese.
In Fig. 2: a is that the surface electron microscope for the manganese metal not being passivated is completed in rigid electrolysis, b is to place the gold not being passivated after a week
Belong to manganese surface electron microscope, c passivation after one week manganese metal of placement surface electron microscope.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, but the scope of the present invention is not by the limit of these embodiments
System.
In embodiment unless otherwise specified all percentages refer both to mass percent.
Embodiment 1
Electrolytic manganese is prepared in diaphram tank with electrolysis method first: using stainless steel for cathode plate, and lead four alloy sheets of silver are sun
Pole plate.Electrolytic condition: ammonium sulfate 120g/L, manganese sulfate 36.91g/L, the catholyte of selenium dioxide 0.05g/L, catholyte pH is about
It is 6.8~7.0, current density 350A/m2, 38 DEG C of electrolysis temperature, electrolysis time 1.5h, prepared electrolysis manganese product is used for
Subsequent Inactivation experiment and it is passivated a layer performance evaluation.
Weight percent shared by passivator each component are as follows: stearic acid 16.4%, Stearic acid diethanolamine salt 81.9% are anti-bad
Hematic acid 1.7%.By stearic acid, Stearic acid diethanolamine salt and water, first heating stirring dissolves under the conditions of 80 DEG C, is then added anti-
Bad hematic acid stirring and dissolving obtains the chromium-free passivation liquid (concentration 3%) being surface-treated for electrolytic manganese metal.
Chromium-free passivation liquid is placed in deactivation slot, and the cathode plate surface for completing electrolysis is rinsed with clear water, is then placed in deactivation slot
In, so that chromium-free passivation liquid is submerged cathode plate surface, is taken out after passivation 2 minutes and use distilled water flushing, drying, the gold after being passivated
Belong to manganese product.Electrochemical property test, polarization curve result such as Fig. 1 are carried out to the manganese metal not being passivated and the manganese metal being passivated
And shown in table 1.
The non-passive metal manganese of table 1 and passive metal manganese polarization curve result
| Ecorr(V) | Corrosion current icorr(Acm-2) | R(ohm) | Corrosion rate (mil/year) | |
| It is not passivated | -1.178 | 9.01E-05 | 377 | 4.75E+02 |
| After passivation | -0.95 | 4.626E-07 | 27100 | 2.442E+0 |
By attached drawing 1 and 1 polarization curve result of table it is found that sample corrosion potential increases after manganese metal passivation, self-corrosion electricity
A possibility that position size reflects a possibility that corroding size, and corrosion potential is more negative, corrodes is bigger, passivated
Afterwards, since the presence of passivating film, corrosion potential become just, a possibility that manganese metal corrodes, polarization resistance are greatly reduced
It sharply increases, corrosion current reduces two orders of magnitude, and the corrosion rate of manganese metal is also reduced accordingly, the results showed that, it should
Passivator (stearic acid 16.4%, Stearic acid diethanolamine salt 81.9%, ascorbic acid 1.7%) can effectively improve electrolyzing gold
Belong to the Corrosion Protection of manganese.In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 85s, and is not passivated
Simple substance manganese Coloring Time is 6s.
(a is the electron microscopic picture that just non-passive metal manganese is completed in electrolysis, b to sample passivation front and back Electronic Speculum result as shown in Fig. 2
Electron microscopic picture after a week is placed for non-passive metal manganese, c is chrome-free tanning agent (stearic acid 16.4%, stearic acid diethanol acyl
Amine 81.9%, ascorbic acid 1.7%) electron microscopic picture of manganese metal after a week is placed after passivation).As shown in Figure 2, just electrolysis comes out
Manganese metal have irregular taper, taper plane of crystal is smooth, above the electrolyte do not rinsed well of attachment portion, place one
Zhou Hou, plane of crystal generates the villiform oxidation product of white and surface color is obviously dimmed, and manganese metal is obviously oxidized, and blunt
Manganese metal surface after change is still bright smooth, and apparent defect does not occur in surface, it can be seen that, the passivator is to metal
The passivation of manganese has good effect.
Comparative example 1
The preparation of electrolytic manganese metal is the same as embodiment 1.
Weight percent shared by passivator each component are as follows: stearic acid 16.4%, Stearic acid diethanolamine salt 83.6%.It will be hard
Resin acid, Stearic acid diethanolamine salt and water are first heated at 80 DEG C, and magnetic agitation makes stearic acid dissolution, are obtained for electrolytic manganese metal
The chromium-free passivation liquid (concentration 3%) of surface treatment.
Chrome-free tanning agent is placed in deactivation slot, is rinsed electrolysis cathode plate surface with clear water, is then placed in deactivation slot, makes nothing
Chromium passivating agent submerges electrolysis cathode plate surface, takes out after passivation 2 minutes and uses distilled water flushing, drying, the metal after being passivated
Manganese product.Electrochemical property test is carried out to the manganese metal being passivated, shown in polarization curve result table 2.
Table 2 is not passivated and passive metal manganese polarization curve result
In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 72s.
Comparative example 2
The preparation of electrolytic manganese metal is the same as embodiment 1.
Stearic acid diethanolamine salt and water are first dissolved in 80 DEG C of heating stirrings, 3% Stearic acid diethanolamine salt is configured
Solution, is passivated electrolytic manganese using the passivating solution and electrochemical property test, and the results are shown in Table 3 for polarization curve.
3 manganese metal polarization curve result of table
In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 36s.
It can be seen that the present invention in the presence of having reinforcing agent by embodiment 1 and comparative example 1, comparative example 2,
Its effect is better than the effect that comparative example 1 and comparative example 2 are taken；This has also turned out the present invention and there was only each component synergistic effect,
It can be only achieved optimal effectiveness.
Comparative example 3
The preparation of electrolytic manganese metal is the same as embodiment 1.
Weight percent shared by passivator each component are as follows: oleic acid diethyl amide 98.1%, ethylenediamine tetra-acetic acid 1.9%.
Oleic acid diethyl amide and water are first dissolved in 80 DEG C of heating stirrings, ethylenediamine tetra-acetic acid is then added, obtains for electrolyzing gold
Belong to the chromium-free passivation liquid (concentration 3%) of manganese surface treatment.Electrolytic manganese is passivated using the passivating solution and chemical property
Test, the results are shown in Table 4 for polarization curve.
Table 4 is passivated polarization curve result
In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 38s.
Comparative example 4
The preparation of electrolytic manganese metal is the same as embodiment 1.
Weight percent shared by passivator each component are as follows: lauric acid 57%, oleic acid diethyl amide 41.4%, triethanolamine
1.6%.By lauric acid, oleic acid diethyl amide and water are first dissolved in 80 DEG C of heating stirrings, and triethanolamine is then added, is used
In the chromium-free passivation liquid (concentration 3%) of electrolytic manganese metal surface treatment.The experimental results showed that when potassium permanganate point dropping liquid changes colour
Between be 47s.But there is floccule appearance in solution, solution is unstable, is not suitable for being passivated, therefore fatty acid proportion in passivator
It should not be too high.
Embodiment 2
The preparation of electrolytic manganese metal is the same as embodiment 1.
Weight percent shared by passivator each component are as follows: lauric acid 16%, oleic acid diethyl amide 82.4%, ethylenediamine tetraacetic
Acetic acid 1.6%.By lauric acid, oleic acid diethyl amide and water are first dissolved in 80 DEG C of heating stirrings, and ethylenediamine tetrem is then added
Acid obtains the chromium-free passivation liquid (concentration 3%) being surface-treated for electrolytic manganese metal.Electrolytic manganese is carried out using the passivator
Passivation and electrochemical property test, the results are shown in Table 5 for polarization curve.
5 lauric acid of table etc. is passivated polarization curve result
| Ecorr(V) | icorr(Acm-2) | R(ohm) | Corrosion rate (mil/year) | |
| It is not passivated | -1.178 | 9.01E-05 | 377 | 4.75E+02 |
| After passivation | -0.950 | 7.475E-07 | 20116 | 3.946E+00 |
In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 87s.
Embodiment 3
The preparation of electrolytic manganese metal is the same as embodiment 1.
Weight percent shared by passivator each component are as follows: palmitinic acid 16%, Stearic acid diethanolamine salt 82.4%, three ethyl alcohol
Amine 1.6%.By palmitinic acid, Stearic acid diethanolamine salt and water are first dissolved in 80 DEG C of heating stirrings, and triethanolamine is then added, obtains
To the chromium-free passivation liquid (concentration 3%) being surface-treated for electrolytic manganese metal.Electrolytic manganese is passivated using the passivating solution
And electrochemical property test, the results are shown in Table 6 for polarization curve.
Table 6 is passivated polarization curve result
| Ecorr(V) | icorr(Acm-2) | R(ohm) | Corrosion rate (mil/year) | |
| Simple substance manganese | -1.178 | 9.01E-05 | 377 | 4.75E+02 |
| After passivation | -0.95 | 5.628E-06 | 3218 | 2.971E+01 |
In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 79s.
Embodiment 4
The preparation of electrolytic manganese metal is the same as embodiment 1.
Stearic acid in molar ratio: diethanol amine=1:0.35 adds alcohol amine compound, reacts 6h under the conditions of 130 DEG C, so
The diethanol amine and 1wt%KOH for adding 0.25 times of fatty acid dosage (mole) afterwards, in 80 DEG C of progress ammonolysis reaction 4h,
Generate the mixture of fatty acid and fatty acid hydramine；It is 18% through stearic acid content in detection mixture, stearic acid diethanol acyl
Amine 78%, diethanol amine content 4%.It is configured to the passivating solution that concentration is 3%, electrolytic manganese is passivated using the passivating solution
And electrochemical property test, the results are shown in Table 7 for polarization curve.
Table 7 is passivated polarization curve result
| Ecorr(V) | icorr(Acm-2) | R(ohm) | Corrosion rate (mil/year) | |
| Simple substance manganese | -1.178 | 9.01E-05 | 377 | 4.75E+02 |
| After passivation | -0.923 | 4.109E-07 | 29104 | 2.169E+00 |
In the experiment of potassium permanganate nitric acid drop, potassium permanganate point dropping liquid Coloring Time is 88s.
Claims (6)
1. a kind of chrome-free tanning agent, it is characterised in that by percentage to the quality include following components:
Straight chain fatty acid alkylolamides compound 45%~90%；
Straight chain hydrophobic fatty acid 9.5%~50%；
Reinforcing agent 0.5%~5%；
The preparation of the chrome-free tanning agent includes following two schemes:
Scheme one
The scheme one includes following two step:
Step 1
Diethanol amine and/or monoethanolamine are added in excessive straight chain hydrophobic fatty acid, is reacted, fatty acid and rouge are generated
The mixture of fat acid alcohol amine；
Step 2
By design component, with taking reinforcing agent, and reinforcing agent is added in the resulting mixture of step 1, is uniformly mixed, obtains institute
State chrome-free tanning agent；
Scheme two
Fatty acid alcohol amides compound, hydrophobic fat acid, reinforcing agent are taken by being designed to distribute, will be mixed with each component taken
After uniformly, the passivator is obtained；
The straight chain fatty acid alkylolamides compound is one glycollic amide of fatty acid and/or fatty acid diglycollic amide class
Close object；
The carbon atom number of the straight chain hydrophobic fatty acid molecule is more than or equal to 6；
The reinforcing agent is ethylenediamine tetra-acetic acid, citric acid, ascorbic acid, diethanol amine, triethanolamine, in triisopropanolamine etc.
Any one or two kinds with mixture made of arbitrarily matching；
The carbon atom number of the hydrophobic fat acid molecule is 6~26.
2. a kind of chrome-free tanning agent according to claim 1；It is characterized by:
The hydrophobic fat acid is C6~C26At least one of straight chain unitary hydrophobic carboxylic acid；
The hydrophobic fat acid is selected from least one of lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid.
3. a kind of chrome-free tanning agent according to claim 1；It is characterized by: the fatty acid alcohol amide compound
By C6~C26Straight chain unitary hydrophobic carboxylic acid occurs amidation process with diethanol amine and/or monoethanolamine and is prepared.
4. a kind of chrome-free tanning agent according to claim 1；It is characterized by: the fatty acid alcohol amide compound is selected from
Lauric acid diethyl amide, myristic acid diglycollic amide, palmitinic acid diglycollic amide, Stearic acid diethanolamine salt, oleic acid two
Glycollic amide, one glycollic amide of lauric acid, one glycollic amide of myristic acid, one glycollic amide of palmitinic acid, one glycollyl of stearic acid
At least one of amine, one glycollic amide of oleic acid.
5. a kind of application of the chrome-free tanning agent as described in claim 1-4 any one；It is characterized by: the application includes
It is used for processing product containing manganese Metal.
6. a kind of application of chrome-free tanning agent according to claim 5；Match it is characterized by: chrome-free tanning agent is mixed with water
Passivating solution is made to be placed in deactivation slot, manganese Metal product will be contained and be immersed in 1~5 point of passivation in prepared chromium-free passivation liquid
Clock cleans after taking-up, dry, obtains finished product；The mass percentage concentration of chrome-free tanning agent is 0.5%~5% in the passivating solution.
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| CN110760835A (en) * | 2019-09-27 | 2020-02-07 | 江阴达克罗金属制品有限公司 | Conductivity-enhanced aqueous passivator and preparation method thereof |
| CN113969401B (en) * | 2020-07-24 | 2022-09-06 | 中南大学 | Active metal chromium-free passivation method |
| CN115161628B (en) * | 2021-04-07 | 2023-10-13 | 中南大学 | Passivation agent and passivation method for electrolytic manganese |
| CN115323365B (en) * | 2021-05-10 | 2023-10-13 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
| CN113957424A (en) * | 2021-10-18 | 2022-01-21 | 烟台万华聚氨酯合成材料有限公司 | Passivation cleaning agent and preparation method and application thereof |
| CN114990539A (en) * | 2022-06-14 | 2022-09-02 | 无锡伊佩克科技有限公司 | Hot galvanizing chromium-free passivator and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618357A (en) * | 2012-02-13 | 2012-08-01 | 中国人民解放军空军油料研究所 | Sealing and antirust oil composition |
| CN104130849A (en) * | 2014-07-30 | 2014-11-05 | 梧州市旺捷机械制造有限公司 | Antirust emulsified liquid for cast iron and production method thereof |
| CN105463472A (en) * | 2015-12-08 | 2016-04-06 | 彭国泉 | Water-soluble antirust agent |
-
2016
- 2016-10-13 CN CN201610894417.6A patent/CN106283014B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618357A (en) * | 2012-02-13 | 2012-08-01 | 中国人民解放军空军油料研究所 | Sealing and antirust oil composition |
| CN104130849A (en) * | 2014-07-30 | 2014-11-05 | 梧州市旺捷机械制造有限公司 | Antirust emulsified liquid for cast iron and production method thereof |
| CN105463472A (en) * | 2015-12-08 | 2016-04-06 | 彭国泉 | Water-soluble antirust agent |
Non-Patent Citations (3)
| Title |
|---|
| 两步法合成硬脂酸二乙醇酰胺;卿宁等;《华东理工大学学报》;20001225;第26卷(第6期);第650-653页 |
| 工业洗涤剂的剖析研究;荀合;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120615;B018-34 |
| 硬脂酸乙醇胺系列表面活性剂的合成与表征;赵小平;《精细与专用化学品》;20130121;第21卷(第1期);第32-36页 |
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