CN104988518B - A kind of hot rolling acid-cleaning corrosion inhibiter and the method for carrying out pickling with the hot rolling acid-cleaning corrosion inhibiter - Google Patents
A kind of hot rolling acid-cleaning corrosion inhibiter and the method for carrying out pickling with the hot rolling acid-cleaning corrosion inhibiter Download PDFInfo
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Abstract
The present invention relates to corrosion inhibiter field, disclose a kind of hot rolling acid-cleaning corrosion inhibiter and the method for carrying out pickling with the hot rolling acid-cleaning corrosion inhibiter, the hot rolling acid-cleaning corrosion inhibiter includes quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt, and hydroxyacetic acid.The hot rolling acid-cleaning corrosion inhibiter can be used in special steel grade as automobile structural steel, and consumption is few and with 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, in particular it relates to a kind of hot rolling acid-cleaning corrosion inhibiter, the hot rolling acid-cleaning corrosion inhibiter
Preparation method, and the method that pickling is carried out to automobile structural steel using the hot rolling acid-cleaning corrosion inhibiter.
Background technology
The hot rolling acid-cleaning plate of the series automobiles structural steel such as P510, P510L, SAPH belongs to the expensive goods in acid-cleaning plate, mainly
For structure positions such as automobile chassis or internal hilar plates, it has a forming property and surface quality compared favourably with cold-reduced sheet, and intensity
It is higher than again cold-reduced sheet.With continuing to develop for automobile industry, requirement of the market to automobile hot rolling acid-cleaning plate is improved constantly, and is being protected
Under the premise of card punch forming performance, in addition it is also necessary to raising product painting and pretreatment meter are reached with certain surface gloss
The target of face quality.
Corrosion inhibiter common at present mainly has heterocyclic, amine, carboxylic acids, Schiff bases, Thiourea, purines etc., example
A kind of carbon steel corrosion inhibitor is disclosed such as CN1844457A, its main component is purine compound, including guanine, adenine,
Diaminopurine, monothio purine, two thio-purines etc..But the research for corrosion inhibiter is all generally directed to ordinary carbon steel at present
Carry out, and corrosion mitigating effect is not obvious 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,
The mass defect such as bulk blackspot and obfuscation, the acid-cleaning plate of such defect occurs phosphorus during the preceding treatment application use in later stage
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 such as 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
Usually there is surface matter when being used for the pickling of automobile structural steel it is an object of the invention to overcome existing corrosion inhibiter
Measure the technical problem of defect, there is provided a kind of hot rolling acid-cleaning corrosion inhibiter and the method for carrying out pickling using the hot rolling acid-cleaning corrosion inhibiter,
The hot rolling acid-cleaning corrosion inhibiter can be used in special steel grade as automobile structural steel, and consumption is few and with excellent corrosion inhibition,
The preferable automobile structural steel hot rolling acid-cleaning plate of surface quality can be obtained, and operating cost is low, good in economic efficiency.
The present inventor has found during hot rolling acid-cleaning is carried out to automobile structural steel using existing corrosion inhibiter, sour
Usually feel that steel plate is not washed clean after washing, it is often found that occurring in that 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 corrosion rate very high-quality loss of steel plate is more, not only influences
Surface quality, also brings adverse effect, to this present inventor it is thought that due to automobile mechanism to subsequent treatment
Containing caused by chromium higher, content of vanadium in steel, and recognize that a kind of inhibition for being particularly well-suited to automobile structural steel should be developed
Agent.The existing usual comparison of ingredients of corrosion inhibitor product is single, typically comprises only the compound of one or two types, and of the invention
Inventor had been surprisingly found that in research process, polytype compound phase interworking merga pass is adjusted into matching somebody with somebody between each composition
Than corrosion mitigating effect can be obtained more preferably, and can be applied to the corrosion inhibiter of automobile structural steel.
The invention provides a kind of hot rolling acid-cleaning corrosion inhibiter, the hot rolling acid-cleaning corrosion inhibiter includes quaternary ammonium compound, sulphur
Urea, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt, and hydroxyacetic acid.
Acid washing method is carried out to automobile structural steel present invention also offers a kind of, the method includes：With pickle to automobile
Structural steel carries out pickling, and the pickle contains hot rolling acid-cleaning corrosion inhibiter of the invention.
Compared with prior art, the main advantage of hot rolling acid-cleaning corrosion inhibiter of the invention is：
(1) hot rolling acid-cleaning corrosion inhibiter of the invention has excellent corrosion inhibition, when used for the hot rolling acid of automobile structural steel
When during washing, the surface gloss of the hot rolling acid-cleaning plate for obtaining can reach more than 3 (yellow chromaticity b value≤1.0), and brightness value can reach
To more than 40, the surface defect that conventional corrosion inhibiter brings is overcome, improve the outward appearance of product；
(2) hot rolling acid-cleaning inhibiter consumption of the invention is few, and the sour consumption used by pickling is low, and steel plate corrosion rate is low
(metal loss amount is low), so as to reduce operating cost, and can bring economic benefit；
(3) hot rolling acid-cleaning corrosion inhibiter preparing process of the invention is simple to operation, can production scene " i.e. with i.e. use ",
And its is stable in properties, the phenomenon for precipitation being occurred without up to more than 120 days, being layered can be placed after being configured to the aqueous solution.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of hot rolling acid-cleaning corrosion inhibiter, the hot rolling acid-cleaning corrosion inhibiter includes quaternary ammonium compound, sulphur
Urea, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt, and hydroxyacetic acid.
Although it was found by the inventors of the present invention that existing research has been found that polytype compound can be used as delaying
Erosion agent, but prior art generally prepares corrosion inhibitor product only with the compound of one or two types therein, these delay
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.Therefore, the present inventor carried out it is substantial amounts of
Creative research simultaneously has been surprisingly found that, optionally can be used cooperatively polytype corrosion inhibitor compound, resulting
Hot rolling acid-cleaning corrosion inhibiter there is the unexpected corrosion mitigating effect that one-component cannot realize, especially have to automobile structural steel
There is excellent corrosion mitigating effect, there is preferable surface gloss with the automobile structural steel after such hot rolling acid-cleaning corrosion inhibiter pickling
And brightness.
In the present invention, there is no particular limitation for the component content of each component in the hot rolling acid-cleaning corrosion inhibiter, respectively into
There is no the difference for two and the above order of magnitude occur between the content being divided to, it is preferable that the quaternary ammonium compound, sulphur
The weight ratio of urea, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt and hydroxyacetic 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 working as quaternary ammonium compound, thiocarbamide, hydroxyl
The content of ethylidene diphosphonic acid and/or its salt is roughly equal and can reach during the lower slightly content of hydroxyacetic acid and preferably coordinate effect
Really, for example 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 salt " into
In point, 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 wherein one
Plant material, it is also possible to which two kinds of materials are mixed with arbitrary proportion, the salt of the 1-hydroxy ethylidene-1,1-diphosphonic acid is preferably the phosphorus of hydroxy ethylidene two
Sour potassium.
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 many in quaternary ammonium salt, the Hydrin quaternary ammonium salt with formula (I) structure and the quaternary ammonium salt with formula (II) structure
Kind,
Formula (I),
Formula (II),
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, 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 hot rolling acid-cleaning corrosion inhibiter can make solid from from the point of view of convenient storage and selling
Form, can also exist in form of an aqueous solutions in addition, and before the use preferably match somebody with somebody the hot rolling acid-cleaning corrosion inhibiter
It is made the form of the aqueous solution；Total content (the i.e. quaternary ammonium salt of hot rolling acid-cleaning corrosion inhibiter in the aqueous solution of the hot rolling acid-cleaning corrosion inhibiter
Class compound, thiocarbamide, the total content of 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt and hydroxyacetic acid) there is no particular limitation, according to
This area routinely configures total content during corrosion inhibitor solution, for example, in the aqueous solution of the hot rolling acid-cleaning corrosion inhibiter, quaternary ammonium
Salt compounds, thiocarbamide, the total content of 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt and hydroxyacetic acid are 10-50 weight %, preferably
It is 18-35 weight %, more preferably 20-30 weight %.
In the present invention, the hot rolling acid-cleaning corrosion inhibiter can be obtained by existing various methods, for example can be by shape
Raw material into the corrosion inhibiter composition is well mixed and is obtained according to aforementioned ratio, therefore the present invention is to the step of the mixing
Rapid and condition is without particular/special requirement.When the hot rolling acid-cleaning corrosion inhibiter is the aqueous solution, its compound method can also be using routine
Compound method, for example can be under conditions of stirring, by quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its
Salt, and hydroxyacetic acid mixes and dissolves in water；Wherein by quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or
There is no particular limitation for its salt and the mode of hydroxyacetic acid dissolving, preferably by quaternary ammonium compound, thiocarbamide, hydroxy ethylidene
Diphosphonic acid and/or its salt and hydroxyacetic acid are dissolved in the water successively, i.e., add again after the range estimation of former composition is completely dissolved
Enter a kind of lower composition；There is no particular limitation for the condition of the stirring, can be completely dissolved each composition.
The source of each component does not require particularly in hot rolling acid-cleaning corrosion inhibiter of the invention, and can be prepared with oneself can also
It is commercially available, use the product of commercially available technical grade.In addition, hot rolling acid-cleaning corrosion inhibiter of the invention can also add a small amount of ability
The conventional additive in domain.
In the present invention, although each composition in hot rolling acid-cleaning corrosion inhibiter can cooperate unexpected so as to realize
Superior technique effect, but studied through the present inventor and speculated, comparatively, wherein each composition played it is main
Effect also slightly stresses, for example, the quaternary ammonium compound mainly plays inhibition and polishing, the thiocarbamide mainly rises
(after steel plate is dried through pickling) corrosion-resistant is acted on, and the 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt mainly play sustained release and makes Surface Oxygen
Change the effect of film layer fixation, hydroxyacetic acid mainly serves with Fe ion complexations so that steel plate is anti-corrosion；It is emphasized that
Can not be given play to when these composition individualisms, or can not well give play to and similar given play in the present invention
Effect, the present invention can realize has the technical effect that these compositions cooperate result.
Hot rolling acid-cleaning corrosion inhibiter of the invention can be applied to various materials, such as carbon steel, stainless steel, copper and its alloy,
Aluminium and its alloy etc., and can show preferable corrosion mitigating effect；Especially, hot rolling acid-cleaning corrosion inhibiter of the invention can
Suitable for the existing corrosion inhibiter automobile structural steel containing higher chromium and/or vanadium to be applicable, and can show non-
The corrosion mitigating effect of Chang Youyi, 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, the method is included with pickle to automobile knot
Structure steel carries out pickling, and the pickle contains hot rolling acid-cleaning corrosion inhibiter of the invention.
In the present invention, the automobile structural steel refers to being generally used for vehicle structure position containing chromium and/or vanadium
The series automobiles structural steel such as special 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 is after the hot rolled plate to automobile structural steel carries out pickling
Can sell can also carry out the technique such as cold rolling, and the hot rolled plate of the automobile structural steel after preferred pair pickling carries out Cold-roller
Skill.
Because hot rolling acid-cleaning corrosion inhibiter of the invention has unique property, therefore pickling is being carried out to automobile structural steel
During the consumption of hot rolling acid-cleaning corrosion inhibiter that is added can well below this area pickling when conventional consumption (generally 1-
5 weight %), the phenomenon of deficient pickling occurs (such as when reaching 1 weight %) when the content of hot rolling acid-cleaning corrosion inhibiter is excessive, this
Because corrosion inhibiter of the invention plays the role of to make hot rolling plate surface passivation film occur, if using excessive, can reduce acid solution and
The reaction speed of surface of steel plate；Therefore in the present invention, on the basis of the gross weight of pickle, the hot rolling acid-cleaning corrosion inhibiter
Content can show preferable corrosion mitigating effect when being 0.05-0.5 weight %, the further preferred hot rolling acid-cleaning corrosion inhibiter
Content is 0.15-0.36 weight %.
In the present invention, the content to acid in the pickle is not required particularly, and those skilled in the art can be with pin
Model to different automobile structural steels is selected the content of acid, for example, content of the acid in the pickle in terms of HCl
Can be 150-250g/L.In the present invention, the acid can be suitable to the inorganic acid of pickling and/or organic acid for various；The nothing
Machine acid is preferably selected from least one in 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 in base phosphonic acids, 2- phosphinylidyne butane -1,2,4- tricarboxylic acids and ethylenediamine tetramethylene phosphonic acid；Highly preferred
In implementation method, the acid in the pickle is hydrochloric acid.
In the present invention, the condition and mode of operation of pickling can be carried out according to the conventional method in this area, for example, sour
The temperature washed can be 60-90 DEG C, and preferably 70-80 DEG C, the speed of pickling can be 60-240m/min, preferably 100-
150m/min。
The method of the present invention also includes the vehicle structure steel hot-rolled sheet after pickling is cleaned and dried, the cleaning and baking
There is no particular limitation for dry mode, according to the mode of cleaning and drying after the conventional pickling in this area, it is preferable that drying
Temperature be 60-100 DEG C, the time is 30-120s.Or drying can also be replaced with placing naturally, such as in room temperature (10-30
DEG C) under place 10-30 hours.
When the method according to the invention carries out pickling using hot rolling acid-cleaning corrosion inhibiter of the invention, acid in the pickle
The consumption of acid when consumption can carry out pickling well below this area, for example, when the vehicle structure steel dimensions that treat pickling are
During 1000m long × 1850m wide × thickness 4mm, the consumption of acid is generally in terms of HCl during using hot rolling acid-cleaning corrosion inhibiter of the invention
2-4kg, using prior art corrosion inhibiter when acid consumption be generally 3-6kg in terms of HCl, it can be seen that using this
The hot rolling acid-cleaning corrosion inhibiter of invention can substantially reduce the consumption of acid, reduce operating cost.
When the method according to the invention carries out pickling using hot rolling acid-cleaning corrosion inhibiter of the invention, the corrosion rate of steel plate is (i.e.
The loss amount of metal) can be well below corrosion rate when carrying out pickling using existing corrosion inhibiter, for example, when the vapour that treat pickling
When bassinet structure steel dimensions are 1000m long × 1850m wide × thickness 4mm, steel plate is molten during using hot rolling acid-cleaning corrosion inhibiter of the invention
Erosion rate is generally 0.15%-0.25%, preferably 0.16-0.18%, using prior art corrosion inhibiter when steel plate corrosion rate
Generally 0.20%-0.33%, it can be seen that the corrosion of steel plate can be substantially reduced using hot rolling acid-cleaning corrosion inhibiter of the invention
Rate, reduces operating cost.
The method of the present invention, can by the use for reducing corrosion inhibiter, the consumption for reducing acid and the corrosion rate for reducing 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 corrosion inhibiter of the invention can be had very
Excellent surface quality, such as its surface gloss can be reached 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 the problems such as blackspot, macula lutea, bulk blackspot and obfuscation.
Below will the present invention will be described in detail by embodiment.The corrosion inhibiter in embodiment is subsequently used for convenience
Prepare in form of an aqueous solutions, this is not construed as limiting the invention, can also match somebody with somebody for the ease of sale in industrial production
It is made solid form.
In the following Examples and Comparative Examples, hydrochloric acid used and sulfuric acid 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, 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, hydroxyl
Acetic acid is purchased from the calm and peaceful water process Co., Ltd in Shandong, 17 alkenyl amine ethyl imidazol(e) hyamines and amphoteric gemini imidazoline quaternary ammonium
, purchased from Qinhuangdao triumph Chemical Co., Ltd., the outsourcing corrosion inhibiter IBITNH-D trades mark used by comparative example 3 are purchased from morning sun chemistry for salt
Company.
Embodiment 1-6 and comparative example 1-3 be used for illustrate corrosion inhibiter composition and preparation method thereof,
Embodiment 1
To in container add 70kg water, under conditions of stirring to water in sequentially add 5kg Hydrin base three
Ammonio methacrylate (formula (I) structure, X1=Cl, m=4), 10kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 5kg hydroxyl second
Acid simultaneously makes them dissolve successively, finally gives the aqueous solution I1 of hot rolling acid-cleaning corrosion inhibiter.
Embodiment 2
To in container add 65kg water, under conditions of stirring to water in sequentially add 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 hydroxyacetic acids simultaneously make it
Dissolve successively, finally give the aqueous solution I2 of hot rolling acid-cleaning corrosion inhibiter.
Embodiment 3
To in container add 82kg water, under conditions of stirring to water in sequentially add 5kg myristyl benzyl diformazans
Ammonium chloride, 5kg thiocarbamides, 5kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 3kg hydroxyacetic acids simultaneously make them dissolve successively, finally give
The aqueous solution I3 of hot rolling acid-cleaning corrosion inhibiter.
Embodiment 4
To the water that 76kg is added in container, under conditions of stirring to water in sequentially add the double dodecyl dimethyls of 10kg
Ammonium chloride, 5kg thiocarbamides, 5kg 1-hydroxy ethylidene-1,1-diphosphonic acids and 4kg hydroxyacetic acids simultaneously make them dissolve successively, finally give hot rolling
The aqueous solution I4 of restrainer.
Embodiment 5
To in container add 70kg water, under conditions of stirring to water in sequentially add the alkenyl amine ethyl miaows of 10kg 17
Oxazoline quaternary ammonium salt, 5kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 5kg hydroxyacetic acids simultaneously make them dissolve successively, final
To the aqueous solution I5 of hot rolling acid-cleaning corrosion inhibiter.
Embodiment 6
To in container add 72kg water, under conditions of stirring to water in sequentially add 8kg amphoteric gemini imidazoline seasons
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 hydroxyacetic acids is simultaneously
Them is dissolved successively, finally give the aqueous solution I6 of hot rolling acid-cleaning corrosion inhibiter.
Comparative example 1
To the water that 70kg is added in container, to 10kg Hydrin bases trimethyl ammonium chloride is added in water, (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
To the water that 70kg is added in container, to addition 10kg thiocarbamides, 10kg 1-hydroxy ethylidene-1,1-diphosphonic acids potassium and 10kg hydroxyls in water
Guanidine-acetic acid and stirring and dissolving, obtain corrosion inhibiter aqueous solution D2.
Comparative example 3
To the water that 70kg is added in container, to addition 10kg tetrabutylammonium iodides, 10kg thiocarbamides and 10kg hydroxyl second in water
Acid and stirring and dissolving, obtain corrosion inhibiter aqueous solution D3.
Comparative example 4
To the water that 70kg is added in container, to the double dodecyl dimethyl ammonium chlorides of addition 10kg, 10kg hydroxyl second in water
Fork diphosphonic acid and 10kg hydroxyacetic acids and stirring and dissolving, obtain corrosion inhibiter aqueous solution D4.
Comparative example 5
To the water that 70kg is added in container, to being added in water, the 30kg outsourcing corrosion inhibiter IBITNH-D trades mark are chemical purchased from morning sun
Company's (main component organic quaternary ammonium salt contains the weight % of active principle about 30) and stirring and dissolving, obtain corrosion inhibiter aqueous solution D5.
Embodiment 7-12 and comparative example 6-11 is used for illustrating acid washing method of the invention and technique effect
Respectively pickle II1-II6 and D ' 1-D ' are prepared using above-described embodiment and comparative example gained hot rolling acid-cleaning corrosion inhibiter
6, and use gained pickle carries out pickling to the vehicle structure steel hot-rolled sheet of 1000m long × 1850m wide × thickness 4mm respectively, acid
The parameter such as speed of the species and content of hot rolling acid-cleaning corrosion inhibiter, the species of acid and content, the temperature of pickling and pickling in washing lotion
As shown in table 1.
Table 1
The reduction of acid concentration is detected in acid cleaning process and the consumption of acid is calculated, pickling terminate after by the automobile knot after pickling
Structure steel hot-rolled sheet is placed 24 hours at 20 DEG C respectively, then tests its surface brightness and glossiness, and is weighed and calculated automobile
Structure steel hot-rolled sheet weight-loss ratio (reflection corrosion rate) after pickling, the results are shown in Table shown in 2, and 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 BYK group companies of Germany；
(3) weight × 100% before weight-loss ratio=(weight after weight-pickling before pickling)/pickling.
Table 2
Contrast is carried out as can be seen that using hot rolling acid-cleaning corrosion inhibiter of the invention and basis by by embodiment and comparative example
When acid washing method of the invention carries out pickling to automobile structural steel, the consumption of hot rolling acid-cleaning corrosion inhibiter used is significantly lower, acid
Consumption and steel plate weight-loss ratio (corrosion rate) it is significantly lower, and automobile structural steel after pickling has significantly higher table
Face brightness and glossiness.Also, when corrosion inhibiter of the invention is excessively used (comparative example 11), occur in that the phenomenon of not pickling.
In addition, being carried out to automobile structural steel using hot rolling acid-cleaning corrosion inhibiter of the invention and acid washing method of the invention
Pickling can also bring economic benefit, and computational methods are as follows：
Rule of thumb do hypothesis below with actual conditions first：
The price of the outsourcing corrosion inhibiter IBITNH-D trades mark (used by comparative example 3) is 7000 yuan/t, hot rolling acid-cleaning of the invention
The price of corrosion inhibiter I (embodiment 1 prepares gained) is 30,000 yuan/t, and pickling line every batch presses 5000t tissue productions, and acid discharge amount is pressed
200m3Calculate, coil of strip price is calculated by 5000 yuan/t；
Method according to embodiment 1 prepares hot rolling acid-cleaning corrosion inhibiter I1 and carries out pickling (pickling according to the method for embodiment 7
The content of corrosion inhibiter is 0.15 weight % in liquid), the method according to comparative example 5 prepares outsourcing corrosion inhibitor solution and according to comparative example
10 method carries out pickling (content of corrosion inhibiter is 1.00 weight % in pickle)；It is known that embodiment 7 from table 2
The weight-loss ratio of steel plate is 0.1741%, and the weight-loss ratio of the steel plate of comparative example 10 is 0.2078%；In addition, inventor's experiment is measured,
When any corrosion inhibiter is added without, the weight-loss ratio of steel plate is 0.3864%.
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 units
Corrosion inhibiter increases expense newly：200m3×1t/m3× 1% × 7000 yuan/t=14000 units
Based on 120,000 t, then year wound is imitated for annual production：
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%-0.1741%) × 5000 yuan/t=53075 units
Corrosion inhibiter increases expense newly：200m3×1t/m3× 0.15% × 30000 yuan/t=9000 units
Based on 120,000 t, then year wound is imitated for annual production：
Ten thousand yuan of the ÷ 5000=105.78 of (52925 yuan -9000 yuan) × 120000.
Calculate also residual including spent acid treating capacity reduction (iron concentration reduction) after addition corrosion inhibiter and regenerated acid above
Corrosion inhibiter is stayed to recycle reduced expense.
Be can be seen that using hot rolling acid-cleaning corrosion inhibiter of the invention and acid washing method of the invention by above-mentioned calculating
Carrying out pickling to automobile structural steel can bring considerable economic benefit.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.Additionally, can also enter between a variety of implementation methods of the invention
Row any combination, as long as it is without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of hot rolling acid-cleaning corrosion inhibiter, the hot rolling acid-cleaning corrosion inhibiter includes quaternary ammonium compound, thiocarbamide, the phosphorus of hydroxy ethylidene two
Acid and/or its salt, and hydroxyacetic acid；The quaternary ammonium compound is selected from the Hydrin season with formula (I) structure
Ammonium salt and/or the quaternary ammonium salt with formula (II) structure,
Wherein X1Selected from halogen, m is the integer of 2-8；The quaternary ammonium salt with formula (II) structure is selected from tetrabutylammonium iodide, ten
One or more in tetraalkyl benzyl chloride and double dodecyl dimethyl ammonium chlorides.
2. hot rolling acid-cleaning corrosion inhibiter according to claim 1, wherein, the quaternary ammonium compound, thiocarbamide, hydroxy ethylidene
The weight ratio of diphosphonic acid and/or its salt and hydroxyacetic acid is 1：0.3-2.5：0.3-2.5：0.2-1.2.
3. hot rolling acid-cleaning corrosion inhibiter according to claim 2, wherein, the quaternary ammonium compound, thiocarbamide, hydroxy ethylidene
The weight ratio of diphosphonic acid and/or its salt and hydroxyacetic acid is 1：0.5-2：0.5-2：0.3-1.
4. hot rolling acid-cleaning corrosion inhibiter according to claim 1, wherein, the hot rolling acid-cleaning corrosion inhibiter is deposited in form of an aqueous solutions
, and in the aqueous solution of the hot rolling acid-cleaning corrosion inhibiter, quaternary ammonium compound, thiocarbamide, 1-hydroxy ethylidene-1,1-diphosphonic acid and/or its salt
And the total content of hydroxyacetic acid is 18-35 weight %.
5. a kind of to carry out acid washing method to automobile structural steel, the method includes：Pickling is carried out to automobile structural steel with pickle, its
It is characterised by, the pickle contains the hot rolling acid-cleaning corrosion inhibiter described in any one in claim 1-4.
6. method according to claim 5, wherein, on the basis of the gross weight of pickle, the hot rolling acid-cleaning corrosion inhibiter
Content be 0.05-0.5 weight %.
7. method according to claim 6, wherein, on the basis of the gross weight of pickle, the hot rolling acid-cleaning corrosion inhibiter
Content be 0.15-0.36 weight %.
8. the method according to any one in claim 5-7, wherein, the content of acid in the pickle in terms of HCl
It is 150-250g/L.
9. method according to claim 5, wherein, the temperature of pickling is 60-90 DEG C, and the speed of pickling is 60-240m/
min。
10. method according to claim 5, wherein, the automobile structural steel contains chromium and/or vanadium.
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| CN103114289A (en) * | 2013-03-07 | 2013-05-22 | 天津亿利科能源科技发展股份有限公司 | Composite corrosion inhibitor for offshore high-chlorine high-carbon-dioxide oilfield gathering and transferring system and preparation method thereof |
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