CN104988519B - A kind of restrainer and the method that pickling is carried out with the restrainer - Google Patents
A kind of restrainer and the method that pickling is carried out with the restrainer Download PDFInfo
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Abstract
The present invention relates to corrosion inhibiter field, a kind of method for disclosing restrainer and pickling being carried out with the restrainer, the restrainer includes quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt, and phytic acid and/or tannic acid.The restrainer can be used in special steel grade as automobile structural steel, and dosage is few and has excellent corrosion inhibition, can obtain the preferable automobile structural steel hot rolling acid-cleaning plate of surface quality, and operating cost is low, good in economic efficiency.
Description
Technical field
The present invention relates to corrosion inhibiter field, and in particular, to a kind of restrainer, the preparation side of the restrainer
Method, and the method using the restrainer to automobile structural steel progress pickling.
Background technology
Expensive goods in the hot rolling acid-cleaning plate category acid-cleaning plate of the series automobiles structural steel such as P510, P510L, SAPH, mainly
For structure positions such as automobile chassis or internal hilar plates, it has a forming property and surface quality to compare favourably with cold-reduced sheet, and intensity
It is higher than cold-reduced sheet again.With the continuous development of automobile industry, requirement of the market to automobile using hot rolling acid-cleaning plate is continuously improved, and is protecting
Under the premise of card punch forming performance, it is also necessary to there is certain surface gloss, product painting and pretreatment meter are improved to reach
The target of face quality.
Corrosion inhibiter common at present mainly has heterocyclic, amine, carboxylic acids, Schiff bases, Thiourea, purines etc., example
As CN1844457A discloses a kind of carbon steel corrosion inhibitor, its main component is purine compound, including guanine, adenine,
Diaminopurine, monothio purine, two thio-purines etc..But the research for corrosion inhibiter at present is all generally directed to ordinary carbon steel
Carry out, and corrosion mitigating effect and unobvious for this kind of extraordinary steel grade of the series automobiles structural steel such as P510, P510L, SAPH.This
When the hot rolled plate of a little automobile structural steels carries out pickling using conventional corrosion inhibiter, surface usually occur the blackspot of full plate face, macula lutea,
Phosphorus occurs during the preceding processing application use in later stage in mass defect, the acid-cleaning plate of such defect such as bulk blackspot and obfuscation
Bad defect of changing that film layer is imperfect, phosphating coat grain size is uneven etc., influence last electrophoretic painting coating adhesion property and
The defects of corrosion resisting property.Therefore, the more preferable corrosion inhibiter of corrosion inhibition is developed, is especially still had to automobile structural steel excellent
The corrosion inhibiter of corrosion inhibition is very necessary.
The content of the invention
It is an object of the invention to overcome existing corrosion inhibiter surface matter usually occur when being used for the pickling of automobile structural steel
Measure the technical problem of defect, there is provided a kind of restrainer and the method that pickling is carried out using the restrainer, the pickling are delayed
Erosion agent can be used in special steel grade as automobile structural steel, and dosage is few and has excellent corrosion inhibition, can obtain surface
The preferable automobile structural steel hot rolling acid-cleaning plate of quality, and operating cost is low, good in economic efficiency.
The present inventor has found during carrying out hot rolling acid-cleaning to automobile structural steel using existing corrosion inhibiter, sour
Usually feel that steel plate does not wash clean after washing, it is often found that there is full plate during being dried during pickling or after pickling
The problems such as blackspot in face, macula lutea, bulk blackspot and obfuscation, and the very high quality loss of the corrosion rate of steel plate is more, not only influences
Surface quality, also brings subsequent treatment adverse effect, to this present inventor it is thought that due to automobile mechanism
Caused by containing higher chromium, content of vanadium in steel, and recognize that a kind of inhibition especially suitable for automobile structural steel should be developed
Agent.The existing usual comparison of ingredients of corrosion inhibitor product is single, generally comprises only the compound of one or two kinds of types, and of the invention
Inventor have been surprisingly found that in the course of the research, polytype compound phase interworking merga pass is adjusted into matching somebody with somebody between each component
Than that can obtain that corrosion mitigating effect is more preferable, and the corrosion inhibiter of automobile structural steel can be suitable for.
The present invention provides a kind of restrainer, which includes quaternary ammonium compound, thiocarbamide, hydroxyl second
Pitch diphosphonic acid and/or its salt, and phytic acid and/or tannic acid.
Acid washing method is carried out to automobile structural steel present invention also offers a kind of, this method includes：With pickle to automobile
Structural steel carries out pickling, and the pickle contains the restrainer of the present invention.
Compared with prior art, the main advantage of restrainer of the invention is：
(1) restrainer of the invention has excellent corrosion inhibition, when the hot rolling acid-cleaning mistake for automobile structural steel
When in journey, the surface gloss of obtained hot rolling acid-cleaning plate can reach more than 3 (yellow chromaticity b value≤1.0), and brightness value can reach 40
More than, the surface defect that conventional corrosion inhibiter is brought is overcome, improves the appearance of product；
(2) restrainer dosage of the invention is few, and the sour consumption used in pickling is low, the low (metal of steel plate corrosion rate
Loss amount is low), so as to reduce operating cost, and economic benefit can be brought；
(3) restrainer preparing process of the invention is simple to operation, " can match somebody with somebody and use " in production scene, and
Its property is stablized, and can place up to more than 120 days after being configured to aqueous solution and occur without precipitation, the phenomenon of layering.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of restrainer, which includes quaternary ammonium compound, thiocarbamide, hydroxyl second
Pitch diphosphonic acid and/or its salt, and phytic acid and/or tannic acid.
It was found by the inventors of the present invention that although existing research has been found that polytype compound can be used as delaying
Agent is lost, but the prior art usually prepares corrosion inhibitor product only with the compound of one or two kinds of types therein, these are slow
Erosion agent product has preferable corrosion mitigating effect for ordinary steels such as carbon steels, but for the vehicle structure containing higher chromium and/or vanadium
The corrosion mitigating effect of steel is not obvious enough and surface quality problems usually occurs.For this reason, the present inventor has carried out largely
Creative research simultaneously has been surprisingly found that, optionally can be used cooperatively polytype corrosion inhibitor compound, resulting
Restrainer there is the unexpected corrosion mitigating effect that can not realize of one-component, especially have to automobile structural steel excellent
Different corrosion mitigating effect, has preferable surface gloss and brightness with the automobile structural steel after such restrainer pickling.
In the present invention, there is no particular limitation for the component content of each component in the restrainer, each component
There is no the difference for two and the above order of magnitude occur between content, it is preferable that the quaternary ammonium compound, thiocarbamide, hydroxyl
Base ethylidene diphosphonic acid and/or its salt and the weight ratio of phytic acid and/or tannic acid can be 1：0.3-2.5：0.3-2.5：0.2-
1.2 more preferably 1：0.5-2：0.5-2：0.3-1；It was found by the inventors of the present invention that when quaternary ammonium compound, thiocarbamide, hydroxyl
The content of ethylidene diphosphonic acid and/or its salt is roughly equal and when content of phytic acid and/or tannic acid is lower slightly can reach preferable
Fiting effect, such as can be 1：0.8-1.2：0.8-1.2：0.6-0.8.In addition, described " 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its
In the component of salt ", there is no particular limitation for the proportioning of the salt of 1-hydroxy ethylidene-1,1-diphosphonic acid and 1-hydroxy ethylidene-1,1-diphosphonic acid, can only exist
One of which material, can also two kinds of materials mixed with arbitrary proportion, the salt of the 1-hydroxy ethylidene-1,1-diphosphonic acid is preferably hydroxyl second
Pitch diphosphonic acid potassium.In the component of " phytic acid and/or the tannic acid ", there is no particular limitation for the proportioning of phytic acid and tannic acid, can
To only exist one of which material, can also two kinds of materials mixed with arbitrary proportion, the preferred content there are phytic acid and phytic acid
More than the content of tannic acid.
In the present invention, there is no particular limitation for the species of the quaternary ammonium compound, is conventionally used as using this area
The quaternary ammonium compound of corrosion inhibiter, it is preferable that the quaternary ammonium compound is selected from imidazoline quaternary ammonium salt, bi-imidazoline
One kind or more in quaternary ammonium salt, the Hydrin quaternary ammonium salt with formula (I) structure and the quaternary ammonium salt with formula (II) structure
Kind,
Wherein R1、R2、R3And R4The alkyl of C1-C14 is each independently selected from (for example, methyl, butyl, dodecyl, ten
Tetraalkyl etc.) and benzyl, X1And X2Halogen (for example, chlorine, bromine, iodine) is each independently selected from, m is the integer of 2-8, is preferably 3-5
Integer；Wherein, the quaternary ammonium salt with formula (II) structure is further preferably selected from tetrabutylammonium iodide, myristyl benzyl
One or more in alkyl dimethyl ammonium chloride and double dodecyl dimethyl ammonium chlorides.
In the present invention, the restrainer can make the shape of solid from the point of view of convenient storage and selling
Formula, in addition can also exist in form of an aqueous solutions, and before the use preferably be configured to the restrainer water-soluble
The form of liquid；In total content (i.e. quaternary ammonium compound, thiocarbamide, the hydroxyl of the aqueous acid medium pickling inhibitor of the restrainer
Base ethylidene diphosphonic acid and/or its salt and the total content of phytic acid and/or tannic acid) there is no particular limitation, and it is normal according to this area
Total content during rule configuration corrosion inhibitor solution, for example, in the aqueous solution of the restrainer, quaternary ammonium compound,
Thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt and the total content of phytic acid and/or tannic acid are 10-50 weight %, are preferably
18-35 weight %, more preferably 20-30 weight %.
In the present invention, the restrainer can be obtained by existing various methods, such as can be by being formed
Corrosion inhibiter is stated to be uniformly mixed and be made according to aforementioned ratio with the raw material of composition, thus the present invention to the mixing the step of and
Condition is without particular/special requirement.When the restrainer is aqueous solution, its preparation method can also use conventional preparation method,
Such as can be under conditions of stirring, by quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt, Yi Jizhi
Acid and/or tannic acid are mixed and dissolved in water；Wherein by quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its
There is no particular limitation for salt and the mode of phytic acid and/or tannic acid dissolving, preferably by quaternary ammonium compound, thiocarbamide, hydroxyl
Base ethylidene diphosphonic acid and/or its salt and phytic acid and/or tannic acid are dissolved in the water successively, i.e., when the range estimation of former component is complete
A kind of lower component is added after dissolving；There is no particular limitation for the condition of the stirring, can be completely dissolved each component.
The source of each component does not require particularly in the restrainer of the present invention, oneself can prepare can also business
Purchase, uses the product of commercially available technical grade.In addition, the restrainer of the present invention can also add it is a small amount of commonly used in the art
Additive.
In the present invention, although each component in restrainer can cooperate so as to fulfill unexpected more preferable
Technique effect, but study and speculate through the present inventor, comparatively, wherein the main function that each component is played
Also slightly stress, for example, the quaternary ammonium compound mainly plays inhibition and polishing, the thiocarbamide mainly plays (steel plate
After pickling is dried) corrosion-resistant effect, the 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt mainly play sustained release and make surface oxidation film
The effect of fixation, phytic acid and/or tannic acid mainly play (after steel plate acid-washing) corrosion-resistant；It is emphasized that when these into
It can not have been given play to when dividing individualism, or the similar effect given play in the present invention cannot have been given play to well,
What the present invention can realize has the technical effect that the result that these components cooperate.
The restrainer of the present invention can be suitable for various materials, for example, carbon steel, stainless steel, copper and its alloy, aluminium and
Its alloy etc., and can show preferable corrosion mitigating effect；Especially, restrainer of the invention can be suitable for existing
The automobile structural steel containing higher chromium and/or vanadium that some corrosion inhibiter cannot be applicable in, and can show very excellent
Corrosion mitigating effect, the automobile structural steel after pickling can have good surface quality.
Acid washing method is carried out to automobile structural steel present invention also offers a kind of, this method is included with pickle to automobile knot
Structure steel carries out pickling, and the pickle contains the restrainer of the present invention.
In the present invention, the automobile structural steel refer to containing chromium and/or vanadium commonly used in vehicle structure position
Special steel, such as the series automobiles structural steel such as P510, P510L, SAPH.Also, the automobile structural steel of pickling is treated in the present invention
The hot rolled plate of automobile structural steel is referred in the preferred case；The present invention to the hot rolled plate of automobile structural steel after pickling is carried out
Can sell can also carry out the techniques such as cold rolling, preferably carry out cold-rolling process to the hot rolled plate of the automobile structural steel after pickling.
Since the restrainer of the present invention has unique property, the process of pickling is being carried out to automobile structural steel
Conventional dosage (generally 1-5 weights when the dosage of middle added restrainer can be well below this area pickling
Measure %), when the content of restrainer is excessive, the phenomenon of deficient pickling occurs in (such as when reaching 1 weight %), this is because sheet
The corrosion inhibiter of invention plays the role of making hot rolling plate surface passivation film occur, if using excessively, can reduce acid solution and surface of steel plate
Reaction speed；Therefore in the present invention, on the basis of the gross weight of pickle, the content of the restrainer is 0.05-0.5 weights
Preferable corrosion mitigating effect can be shown when measuring %, the content of the further preferred restrainer is 0.15-0.36 weight %.
In the present invention, content sour in the pickle is not required particularly, and those skilled in the art can be with pin
The model of different automobile structural steels makes choice the content of acid, for example, content of the acid in terms of HCl in the pickle
Can be 150-250g/L.In the present invention, the acid can be various inorganic acids and/or organic acid suitable for pickling；The nothing
Machine acid is preferably selected from least one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and phosphoric acid；The organic acid is preferably selected from amino sulphur
Acid, citric acid, hydroxyacetic acid, formic acid, ethylenediamine tetra-acetic acid, oxalic acid, tartaric acid, hydroxy ethylene diphosphonic acid, amino trimethylene first
At least one of base phosphonic acids, 2- phosphinylidyne butane -1,2,4- tricarboxylic acids and ethylenediamine tetramethylene phosphonic acid；Highly preferred
In embodiment, the acid in the pickle is hydrochloric acid.
In the present invention, the condition of pickling and mode of operation can be carried out according to the method for this area routine, for example, sour
The temperature washed can be 60-90 DEG C, be preferably 70-80 DEG C, and the speed of pickling can be 60-240m/min, be preferably 100-
150m/min。
The method of the present invention, which is further included, is cleaned and is dried to the vehicle structure steel hot-rolled sheet after pickling, the cleaning and baking
There is no particular limitation for dry mode, in the way of cleaning and drying after the pickling of this area routine, it is preferable that drying
Temperature be 60-100 DEG C, time 30-120s.Or drying can also be replaced with placing naturally, such as in room temperature (10-30
DEG C) under place 10-30 it is small when.
When the method according to the invention carries out pickling using the restrainer of the present invention, sour consumption in the pickle
Amount can carry out the consumption of acid during pickling well below this area, for example, when the vehicle structure steel dimensions for treating pickling are length
During 1000m × wide 1850m × thickness 4mm, 2- of the consumption of acid during restrainer of the invention generally in terms of HCl is used
4kg, using the prior art corrosion inhibiter when acid consumption be generally 3-6kg in terms of HCl, it can be seen that use the present invention
Restrainer can substantially reduce acid consumption, reduce operating cost.
When the method according to the invention carries out pickling using the restrainer of the present invention, corrosion rate (the i.e. metal of steel plate
Loss amount) can be well below corrosion rate when carrying out pickling using existing corrosion inhibiter, for example, when treating the automobile knot of pickling
When structure steel dimensions are long 1000m × wide 1850m × thickness 4mm, the corrosion rate using steel plate during restrainer of the invention is general
Be preferably 0.16-0.18% for 0.15%-0.25%, using the prior art corrosion inhibiter when steel plate corrosion rate be generally
0.20%-0.33%, it can be seen that the corrosion rate of steel plate can be substantially reduced using the restrainer of the present invention, is reduced
Operating cost.
The method of the present invention, can by reducing the use of corrosion inhibiter, reducing sour consumption and reducing the corrosion rate of steel plate
Operating cost is substantially reduced, or even significant economic benefit can be brought.
The method according to the invention carries out the automobile mechanism steel after pickling using the corrosion inhibiter of the present invention can have very
Excellent surface quality, such as its surface gloss can reach on more than 3 (yellow chromaticity b values are less than or equal to 1.0), and brightness value can reach
To more than 40, and occur without blackspot, macula lutea, bulk blackspot and obfuscation the problems such as.
The present invention will be described in detail by way of examples below.The follow-up corrosion inhibiter used in embodiment for convenience
Prepare in form of an aqueous solutions, this is not construed as limiting the invention, and can also match somebody with somebody for the ease of selling in industrial production
Solid form is made.
In the following Examples and Comparative Examples, hydrochloric acid and sulfuric acid used are pure, the Hydrin base trimethyl chlorine of analysis
Change ammonium (formula (I) structure, X1=Cl, m=4) purchased from Korean and Japanese chemical company, tetrabutylammonium iodide is purchased from the permanent female chemical industry in Yancheng, and 14
Alkyl benzyl dimethyl ammonium chloride and double dodecyl dimethyl ammonium chlorides are purchased from Shandong Pai Ni Chemical Co., Ltd.s, and thiocarbamide is purchased from
Sichuan section dragon reagent, 1-hydroxy ethylidene-1,1-diphosphonic acid potassium and 1-hydroxy ethylidene-1,1-diphosphonic acid are purchased from the calm and peaceful water process Co., Ltd in Shandong, phytic acid
Purchased from Chengdu east enterprise-like corporation, tannic acid is purchased from one hundred moral Chemical Co., Ltd. of Suzhou, 17 alkenyl amine ethyl imidazol(e) quinoline quaternary ammoniums
Salt and amphoteric gemini imidazoline quaternary ammonium salt are purchased from Qinhuangdao triumph Chemical Co., Ltd., the outsourcing corrosion inhibiter used in comparative example 3
The IBITNH-D trades mark are purchased from Korean and Japanese chemical company.
Embodiment 1-6 and comparative example 1-3 is used for illustrating corrosion inhibiter composition and preparation method thereof,
Embodiment 1
The water of 70kg is added into container, sequentially adds 5kg Hydrin base three into water under conditions of stirring
Ammonio methacrylate (formula (I) structure, X1=Cl, m=4), 10kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 5kg phytic acid simultaneously
Them is dissolved successively, finally obtain the aqueous solution I1 of restrainer.
Embodiment 2
The water of 65kg is added into container, sequentially added under conditions of stirring into water 10kg tetrabutylammonium iodides,
10kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids and 1-hydroxy ethylidene-1,1-diphosphonic acid potassium 1:1 mixture and 5kg phytic acid and make they according to
Secondary dissolving, finally obtains the aqueous solution I2 of restrainer.
Embodiment 3
The water of 82kg is added into container, sequentially adds 5kg myristyl benzyl diformazans into water under conditions of stirring
Ammonium chloride, 5kg thiocarbamides, 5kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 3kg phytic acid and tannic acid 1:1 mixture and make they according to
Secondary dissolving, finally obtains the aqueous solution I3 of restrainer.
Embodiment 4
The water of 76kg is added into container, sequentially adds the double dodecyl dimethyls of 10kg into water under conditions of stirring
Ammonium chloride, 5kg thiocarbamides, 5kg 1-hydroxy ethylidene-1,1-diphosphonic acids and 4kg phytic acid simultaneously make them dissolve successively, finally obtain pickling inhibition
The aqueous solution I4 of agent.
Embodiment 5
The water of 70kg is added into container, sequentially adds 17 alkenyl amine ethyl miaows of 10kg into water under conditions of stirring
Oxazoline quaternary ammonium salt, 5kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 5kg tannic acid simultaneously make them dissolve successively, finally obtain
The aqueous solution I5 of restrainer.
Embodiment 6
The water of 72kg is added into container, sequentially adds 8kg amphoteric gemini imidazoline seasons into water under conditions of stirring
Ammonium salt, 8kg thiocarbamides, 8kg 1-hydroxy ethylidene-1,1-diphosphonic acids and 1-hydroxy ethylidene-1,1-diphosphonic acid potassium 1:2 mixture and 4kg phytic acid and tannin
Acid 2:1 mixture simultaneously makes them dissolve successively, finally obtains the aqueous solution I6 of restrainer.
Comparative example 1
The water of 70kg is added into container, 10kg Hydrin bases trimethyl ammonium chloride is added into water, and (formula (I) is tied
Structure, X1=Cl, m=4), 10kg thiocarbamides and 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and stirring and dissolving, obtain corrosion inhibiter aqueous solution D1.
Comparative example 2
The water of 70kg is added into container, 10kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 10kg are added into water and is planted
Acid and stirring and dissolving, obtain corrosion inhibiter aqueous solution D2.
Comparative example 3
The water of 70kg is added into container, 10kg tetrabutylammonium iodides, 10kg thiocarbamides and 10kg phytic acid are added simultaneously into water
Stirring and dissolving, obtains corrosion inhibiter aqueous solution D3.
Comparative example 4
The water of 70kg is added into container, the double dodecyl dimethyl ammonium chlorides of 10kg, 10kg hydroxyl second are added into water
Diphosphonic acid and 10kg phytic acid and stirring and dissolving are pitched, obtains corrosion inhibiter aqueous solution D4.
Comparative example 5
The water of 70kg is added into container, the 30kg outsourcing corrosion inhibiter IBITNH-D trades mark are added into water purchased from morning sun chemistry
Company's (main component organic quaternary ammonium salt, contains about 30 weight % of active principle) and stirring and dissolving, obtain corrosion inhibiter aqueous solution D5.
Embodiment 7-12 and comparative example 6-11 is used for the acid washing method and technique effect for illustrating the present invention
Pickle II1-II6 and D ' 1-D ' 6 is prepared using restrainer obtained by above-described embodiment and comparative example respectively, and
Pickle obtained by use carries out pickling, pickle to the vehicle structure steel hot-rolled sheet of long 1000m × wide 1850m × thickness 4mm respectively
The parameters such as the speed of the species and content of middle restrainer, the species of acid and content, the temperature of pickling and pickling are as shown in table 1.
Table 1
The reduction of acid concentration is detected in acid cleaning process and calculates the consumption of acid, by the automobile knot after pickling after pickling
Structure steel hot-rolled sheet respectively at 20 DEG C place 24 it is small when, then test its surface brightness and glossiness, and weigh and calculate automobile
The weight-loss ratio (reflection corrosion rate) of structure steel hot-rolled sheet after pickling, the results are shown in Table shown in 2, specific test mode is as follows：
(1) sour consumption=(concentration after concentration-pickling before pickling) × acid solution volume × density；
(2) surface brightness and glossiness are measured by the glossiness tester of German BYK group companies；
(3) weight × 100% before weight-loss ratio=(weight after weight-pickling before pickling)/pickling.
Table 2
By the way that embodiment and comparative example are carried out contrast as can be seen that using restrainer of the invention and according to this hair
When bright acid washing method carries out pickling to automobile structural steel, the dosage of restrainer used is significantly lower, sour consumption
It is significantly lower with the weight-loss ratio (corrosion rate) of steel plate, and the automobile structural steel after pickling have significantly higher surface brightness and
Glossiness.Also, when the corrosion inhibiter of the present invention is excessively used (comparative example 11), there is the phenomenon of not pickling.
In addition, pickling is carried out to automobile structural steel using the restrainer and acid washing method according to the present invention of the present invention
Economic benefit can also be brought, computational methods are as follows：
First rule of thumb hypothesis below is done with actual conditions：
The price of the outsourcing corrosion inhibiter IBITNH-D trades mark (used in comparative example 3) is 7000 yuan/t, pickling inhibition of the invention
The price of agent I (embodiment 1 prepares gained) is 30,000 yuan/t, and pickling line every batch of presses 200m by 5000t tissue productions, acid discharge amount3Meter
Calculate, coil of strip price is calculated by 5000 yuan/t；
Restrainer I1 is prepared according to the method for embodiment 1 and pickling is carried out (in pickle according to the method for embodiment 7
The content of corrosion inhibiter is 0.15 weight %), outsourcing corrosion inhibitor solution is prepared and according to comparative example 10 according to the method for comparative example 5
Method carries out pickling (content of corrosion inhibiter is 1.00 weight % in pickle)；It is known that the steel plate of embodiment 7 from table 2
Weight-loss ratio be 0.1748%, the weight-loss ratio of the steel plate of comparative example 10 is 0.2078%；In addition, inventor's experiment measures, when not
The weight-loss ratio of steel plate is 0.3864% when adding any corrosion inhibiter.
It is calculated as below on the premise of above-mentioned hypothesis and experimental data：
(1) outsourcing corrosion inhibiter metal loss is reduced and brought benefits
Metal loss is reduced：5000t × (0.3864%-0.2078%) × 5000 yuan/t=44650 members
Corrosion inhibiter increases expense newly：200m3×1t/m3× 1% × 7000 yuan/t=14000 members
Annual output is based on 120,000 t, then year wound is imitated：
Ten thousand yuan of the ÷ 5000=73.56 of (44650 yuan -14000 yuan) × 120000.
(2) corrosion inhibiter metal loss of the present invention is reduced and brought benefits
Metal loss is reduced：5000t × (0.3864%-0.1748%) × 5000 yuan/t=52900 members
Corrosion inhibiter increases expense newly：200m3×1t/m3× 0.15% × 30000 yuan/t=9000 members
Annual output is based on 120,000 t, then year wound is imitated：
Ten thousand yuan of the ÷ 5000=105.36 of (52900 yuan -9000 yuan) × 120000.
Calculate above also residual including spent acid treating capacity reduction (iron concentration reduction) after addition corrosion inhibiter and regenerated acid
Stay corrosion inhibiter recycle reduction expense.
Restrainer and acid washing method according to the present invention using the present invention can be seen that to vapour by above-mentioned calculating
Bassinet structure steel, which carries out pickling, can bring considerable economic benefit.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.In addition, can also be between a variety of embodiments of the present invention
Row any combination, as long as it without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of restrainer, the restrainer by quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its
Salt, and phytic acid and/or tannic acid composition, wherein, the quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its
The weight ratio of salt and phytic acid and/or tannic acid is 1：0.3-2.5：0.3-2.5：0.2-1.2, the quaternary ammonium compound choosing
From imidazoline quaternary ammonium salt, bi-imidazoline quaternary ammonium salt, the Hydrin quaternary ammonium salt with formula (I) structure and with formula (II) tie
One or more in the quaternary ammonium salt of structure,
Wherein R1、R2、R3And R4It is each independently selected from the alkyl and benzyl of C1-C14, X1And X2It is each independently selected from halogen, m
For the integer of 2-8.
2. restrainer according to claim 1, wherein, the quaternary ammonium compound, thiocarbamide, two phosphorus of hydroxy ethylidene
Acid and/or its salt and the weight ratio of phytic acid and/or tannic acid are 1：0.5-2：0.5-2：0.3-1.
3. restrainer according to claim 1, wherein, which exists in form of an aqueous solutions, and
In the aqueous solution of the restrainer, quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt and phytic acid and/
Or the total content of tannic acid is 18-35 weight %.
4. restrainer according to claim 1, wherein, the quaternary ammonium salt with formula (II) structure is selected from the tetrabutyl
One or more in ammonium iodide, myristyl benzyl chloride and double dodecyl dimethyl ammonium chlorides.
5. a kind of carry out acid washing method to automobile structural steel, this method includes：Pickling is carried out to automobile structural steel with pickle, its
It is characterized in that, the pickle contains the restrainer described in any one in claim 1-4.
6. according to the method described in claim 5, wherein, on the basis of the gross weight of pickle, the restrainer contains
Measure as 0.05-0.5 weight %.
7. according to the method described in claim 6, wherein, on the basis of the gross weight of pickle, the restrainer contains
Measure as 0.15-0.36 weight %.
8. according to the method described in any one in claim 5-7, wherein, content of the acid in terms of HCl in the pickle
For 150-250g/L.
9. according to the method described in claim 5, wherein, the temperature of pickling is 60-90 DEG C, and the speed of pickling is 60-240m/
min。
10. according to the method described in claim 5, wherein, the automobile structural steel contains chromium and/or vanadium.
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| CN101538718A (en) * | 2009-04-30 | 2009-09-23 | 西北工业大学 | Carbon steel restrainer and use method thereof |
| KR101116557B1 (en) * | 2008-06-17 | 2012-02-28 | 판강 그룹 리서치 인스티투트 컴퍼니 리미티드 | A composition containing silica sol, its preparation method, and galvanized self-lubricating metal material using the composition |
| CN104131304A (en) * | 2014-08-25 | 2014-11-05 | 钱宏彬 | High-efficiency multifunctional batch hot galvanizing acid wash additive and preparation method thereof |
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| KR101116557B1 (en) * | 2008-06-17 | 2012-02-28 | 판강 그룹 리서치 인스티투트 컴퍼니 리미티드 | A composition containing silica sol, its preparation method, and galvanized self-lubricating metal material using the composition |
| CN101538718A (en) * | 2009-04-30 | 2009-09-23 | 西北工业大学 | Carbon steel restrainer and use method thereof |
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