CN104988519A - Acid pickling corrosion inhibitor and pickling method by using the same - Google Patents
Acid pickling corrosion inhibitor and pickling method by using the same Download PDFInfo
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- CN104988519A CN104988519A CN201510456723.7A CN201510456723A CN104988519A CN 104988519 A CN104988519 A CN 104988519A CN 201510456723 A CN201510456723 A CN 201510456723A CN 104988519 A CN104988519 A CN 104988519A
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Abstract
The present invention relates to the field of corrosion inhibitor, and discloses an acid pickling corrosion inhibitor and a pickling method by using the same. The acid pickling corrosion inhibitor includes a quaternary ammonium compound, thiourea, HEDP and / or its salts, and phytic acid and / or tannic acid. The acid pickling corrosion inhibitor can be used for special steel such automobile structural steel, and has less usage amount and excellent corrosion performance; automotive structural steel hot rolled pickling plate with good surface quality can be obtained; and the method has low operation costs and good economic benefit.
Description
Technical field
The present invention relates to inhibiter field, particularly, relate to a kind of restrainer, the preparation method of this restrainer, and use this restrainer to carry out the method for pickling to automobile structural steel.
Background technology
The hot rolling acid-cleaning plate of the series automobiles structure iron such as P510, P510L, SAPH belongs to the expensive goods in acid-cleaning plate, be mainly used in the structure position such as automobile chassis or internal hilar plate, it has the forming property and surface quality that compare favourably with cold-reduced sheet, and intensity is higher than cold-reduced sheet.Along with the development of automobile industry, the requirement of market to automobile hot rolling acid-cleaning plate improves constantly, and under guarantee impact briquetting performance prerequisite, also needs to have certain surface gloss, reaches the target improving product painting and pre-treatment surface quality.
Inhibiter common at present mainly contains heterocyclic, amine, carboxylic-acid, Schiff bases, Thiourea, purines etc., such as CN1844457A discloses a kind of carbon steel corrosion inhibitor, its main component is purine compound, comprises guanine, VITAMIN B4, diaminopurine, monothio purine, dithio purine etc.But carry out for plain carbon stool for the research of inhibiter is all general at present, and not obvious for corrosion mitigating effect this kind of extraordinary steel grade of the series automobiles structure iron such as P510, P510L, SAPH.When the hot-rolled sheet of these automobile structural steels uses conventional inhibiter to carry out pickling, usually there is the mass defects such as the blackspot in full plate face, macula lutea, bulk blackspot and obfuscation in surface, the acid-cleaning plate of such defect there will be the bad defects such as phosphorization membrane is imperfect, phosphatize phosphate coat grain size is uneven in the pre-treatment application use procedure in later stage, affects the defects such as last electrophoretic painting coating adhesion property and corrosion resisting property.Therefore, the better inhibiter of exploitation corrosion inhibition, the inhibiter especially automobile structural steel still to the corrosion inhibition of excellence is very necessary.
Summary of the invention
The technical problem of surface quality defect is usually there is when the object of the invention is to overcome the pickling of existing inhibiter for automobile structural steel, a kind of restrainer is provided and uses this restrainer to carry out the method for pickling, this restrainer can be used in the so special steel grade of automobile structural steel, consumption is few and have excellent corrosion inhibition, can obtain the good automobile structural steel hot rolling acid-cleaning plate of surface quality, and running cost is low, good in economic efficiency.
The present inventor uses existing inhibiter to carry out finding in the process of hot rolling acid-cleaning to automobile structural steel, usually feel after pickling that steel plate does not wash clean, usually find to have occurred the blackspot in full plate face in the process of pickling or in the process of pickling post-drying, macula lutea, the problems such as bulk blackspot and obfuscation, and very high quality loss is more for the corrosion rate of steel plate, not only have impact on surface quality, also disadvantageous effect is brought to subsequent disposal, this the present inventor is thised is presumably because in automobile mechanism steel containing higher chromium, caused by content of vanadium, and recognize and should develop a kind of inhibiter being specially adapted to automobile structural steel.The usual comparison of ingredients of existing corrosion inhibitor product is single, the general compound only containing one or both types, and the present inventor is in the favorite outer discovery of research process, polytype Compound Phase interworking merga pass is regulated the proportioning between each composition, corrosion mitigating effect can be obtained better, and the inhibiter of automobile structural steel can be applicable to.
The invention provides a kind of restrainer, this restrainer comprises quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt, and phytic acid and/or Weibull.
Present invention also offers one and carry out acid washing method to automobile structural steel, the method comprises: carry out pickling with pickle solution to automobile structural steel, and described pickle solution contains restrainer of the present invention.
Compared with prior art, the main advantage of restrainer of the present invention is:
(1) restrainer of the present invention has excellent corrosion inhibition, time in for the hot rolling acid-cleaning process of automobile structural steel, the surface gloss of the hot rolling acid-cleaning plate obtained can reach more than 3 (yellow chromaticity b value≤1.0), brightness value can reach more than 40, overcome the surface imperfection that conventional inhibiter brings, improve the outward appearance of product;
(2) restrainer consumption of the present invention is few, and the consumption of the acid that pickling is used is low, steel plate corrosion rate low (metal loss amount is low), thus decreases running cost, and can bring economic benefit;
(3) restrainer blending process of the present invention is simple to operation, can " namely join in production scene and namely use ", and its stable in properties, can place after being configured to the aqueous solution reach more than 120 days and do not occur precipitating, the phenomenon of layering.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of restrainer, this restrainer comprises quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt, and phytic acid and/or Weibull.
The present inventor finds, although existing research has been found that polytype compound can be used as inhibiter, but prior art only adopts the compound of one or both types wherein to prepare corrosion inhibitor product usually, these corrosion inhibitor product have good corrosion mitigating effect for ordinary steels such as carbon steels, but for the automobile structural steel containing higher chromium and/or vanadium corrosion mitigating effect not obviously and usually occur surface quality problems.For this reason, the present inventor has carried out a large amount of creative researches and unexpected discovery, optionally polytype corrosion inhibitor compound can be carried out with the use of, the restrainer obtained has the beyond thought corrosion mitigating effect that one-component cannot realize, especially to automobile structural steel, there is excellent corrosion mitigating effect, with the automobile structural steel after such restrainer pickling, there is good surface gloss and brightness.
In the present invention, there is no particular limitation for the component content of each component in described restrainer, the difference of appearance two and the above order of magnitude is not had between the content of each composition, preferably, the weight ratio of described quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull can be 1:0.3-2.5:0.3-2.5:0.2-1.2, is more preferably 1:0.5-2:0.5-2:0.3-1; The present inventor finds, can reach good fiting effect when the content of quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt is roughly equal and phytic acid and/or Weibull content is lower slightly, such as, can be 1:0.8-1.2:0.8-1.2:0.6-0.8.In addition, in the composition of described " 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its 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, only can there is wherein a kind of material, also can mix with arbitrary proportion by two kinds of materials, the salt of described 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is preferably 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium.In the composition of described " phytic acid and/or Weibull ", there is no particular limitation for the proportioning of phytic acid and Weibull, only can there is wherein a kind of material, also can mix with arbitrary proportion by two kinds of materials, preferably there is phytic acid and the content of phytic acid is greater than the content of Weibull.
In the present invention, there is no particular limitation for the kind of described quaternary ammonium compound, this area is used to be conventionally used as the quaternary ammonium compound of inhibiter, preferably, described quaternary ammonium compound be selected from imidazoline quaternary ammonium salt, bi-imidazoline quaternary ammonium salt, have formula (I) structure Hydrin quaternary ammonium salt and have in the quaternary ammonium salt of formula (II) structure one or more
Wherein R
1, R
2, R
3and R
4be selected from alkyl (such as, methyl, butyl, dodecyl, tetradecyl etc.) and the benzyl of C1-C14 independently of one another, X
1and X
2be selected from halogen (such as, chlorine, bromine, iodine) independently of one another, m is the integer of 2-8, is preferably the integer of 3-5; Wherein, the quaternary ammonium salt described in formula (II) structure be preferably selected from tetrabutylammonium iodide, tetradecyl benzyl chloride and two dodecyl dimethyl ammonium chloride further one or more.
In the present invention, described restrainer is considered from the convenient angle stored and sell, and can make the form of solid, also can exist in form of an aqueous solutions in addition, and the preferred form described restrainer being mixed with the aqueous solution before the use; At the total content (i.e. the total content of quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull) of the aqueous acid medium pickling inhibitor of this restrainer, there is no particular limitation, according to the total content during routine configuration corrosion inhibitor solution of this area, such as, in the aqueous solution of this restrainer, the total content of quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull is 10-50 % by weight, be preferably 18-35 % by weight, be more preferably 20-30 % by weight.
In the present invention, described restrainer can be obtained by existing various method, such as can mix being formed the raw material of described inhibiter composition according to aforementioned ratio and obtain, therefore the present invention to the step of described mixing and condition without particular requirement.When described restrainer is the aqueous solution, its compound method also can adopt conventional compound method, can be such as under the condition stirred, by quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt, and phytic acid and/or Weibull mix and dissolve in water; There is no particular limitation for the mode of wherein quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull being dissolved, preferably quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull are dissolved in the water successively, namely current a kind of composition range estimation adds lower a kind of composition after dissolving completely again; There is no particular limitation for the condition of described stirring, each composition can be dissolved completely.
In restrainer of the present invention, the not special requirement in the source of each component, also can be purchased, use the product of the technical grade be purchased in oneself preparation.In addition, restrainer of the present invention also can add the conventional additive in a small amount of this area.
In the present invention, although each composition in restrainer can cooperatively interact thus realize beyond thought better technique effect, but study through the present inventor and infer, comparatively speaking, the Main Function that wherein each composition plays also slightly stresses, such as, described quaternary ammonium compound mainly plays inhibition and polishing, rot-resistant effect that described thiocarbamide mainly plays (steel plate is after pickling is dried), described 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt mainly play slowly-releasing and make surface oxidation film fixation, phytic acid and/or Weibull mainly play the effect of (after steel plate acid-washing) rot-resistant, it is emphasized that and can not to have given play to when these composition Individual existences, or can not give play to similar effect given play in the present invention well, the technique effect that the present invention can realize is the result that these compositions cooperatively interact.
Restrainer of the present invention can be applicable to various material, such as carbon steel, stainless steel, copper and alloy, Aluminum-aluminum alloy etc., and all can show good corrosion mitigating effect; Especially, restrainer of the present invention can be applicable to the automobile structural steel containing higher chromium and/or vanadium that existing inhibiter can not be suitable for, and can show very excellent corrosion mitigating effect, the automobile structural steel after pickling can have good surface quality.
Present invention also offers one and carry out acid washing method to automobile structural steel, the method comprises carries out pickling with pickle solution to automobile structural steel, and described pickle solution contains restrainer of the present invention.
In the present invention, described automobile structural steel refers to the special steel being generally used for vehicle structure position containing chromium and/or vanadium, the series automobiles structure iron such as such as P510, P510L, SAPH.Further, treat that the automobile structural steel of pickling refers to the hot-rolled sheet of automobile structural steel in the preferred case in the present invention; The present invention can sell after carrying out pickling to the hot-rolled sheet of automobile structural steel also can carry out the techniques such as cold rolling, preferably carries out cold-rolling process to the hot-rolled sheet of the automobile structural steel after pickling.
Because restrainer of the present invention has unique character, therefore can well below the consumption of routine during the pickling of this area (being generally 1-5 % by weight) at the consumption of the restrainer carrying out adding in the process of pickling to automobile structural steel, when the content of restrainer is excessive, (when such as reaching 1 % by weight) there will be the phenomenon of deficient pickling, this is because inhibiter of the present invention has the effect making hot-rolled sheet surface occur passivation film, if use too much, the speed of response of acid solution and surface of steel plate can be reduced; Therefore in the present invention, with the gross weight of pickle solution for benchmark, can show good corrosion mitigating effect when the content of described restrainer is 0.05-0.5 % by weight, the content of further preferred described restrainer is 0.15-0.36 % by weight.
In the present invention, to the not special requirement of the content of acid in described pickle solution, and those skilled in the art can select for the content of the model of different automobile structural steels to acid, such as, the acid in described pickle solution can for 150-250g/L in the content of HCl.In the present invention, described acid can be various mineral acid and/or the organic acid being suitable for pickling; Described mineral acid is preferably selected from least one in hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and phosphoric acid; Described organic acid is preferably selected from thionamic acid, citric acid, oxyacetic acid, formic acid, ethylenediamine tetraacetic acid (EDTA), oxalic acid, tartrate, hydroxy ethylene diphosphonic acid, Amino Trimethylene Phosphonic Acid, 2-phosphinylidyne butane-1, at least one in 2,4-tricarboxylic acid and ethylenediamine tetramethylene phosphonic acid; In highly preferred embodiment, the acid in described pickle solution is hydrochloric acid.
In the present invention, the condition of pickling and operating method all can be carried out according to the method for this area routine, and such as, the temperature of pickling can be 60-90 DEG C, and be preferably 70-80 DEG C, the speed of pickling can be 60-240m/min, are preferably 100-150m/min.
Method of the present invention also comprises the vehicle structure steel hot-rolled sheet after to pickling and cleans and dry, there is no particular limitation for the mode of this cleaning and oven dry, according to the mode of cleaning and oven dry after the pickling of this area routine, preferably, the temperature of drying is 60-100 DEG C, and the time is 30-120s.Or also can replace drying with naturally placing, such as, under room temperature (10-30 DEG C), place 10-30 hour.
When method according to the present invention uses restrainer of the present invention to carry out pickling, the consumption of acid when the consumption of acid can carry out pickling in described pickle solution well below this area, such as, when being of a size of long 1000m × wide 1850m × thick 4mm until the automobile structural steel of pickling, the consumption of acid during restrainer of the present invention is used to be generally 2-4kg in HCl, the consumption of acid during the inhibiter of prior art is used to be generally 3-6kg in HCl, can find out, use restrainer of the present invention greatly can reduce the consumption of acid, reduce running cost.
When method according to the present invention uses restrainer of the present invention to carry out pickling, corrosion rate when the corrosion rate (i.e. the loss amount of metal) of steel plate can carry out pickling well below using existing inhibiter, such as, when being of a size of long 1000m × wide 1850m × thick 4mm until the automobile structural steel of pickling, the corrosion rate of steel plate during restrainer of the present invention is used to be generally 0.15%-0.25%, be preferably 0.16-0.18%, the corrosion rate of steel plate during the inhibiter of prior art is used to be generally 0.20%-0.33%, can find out, use restrainer of the present invention greatly can reduce the corrosion rate of steel plate, reduce running cost.
Method of the present invention, by reducing the use of inhibiter, reducing the corrosion rate of sour consumption and reduction steel plate, greatly can reduce running cost, even can bring significant economic benefit.
Automobile mechanism steel after method according to the present invention uses inhibiter of the present invention to carry out pickling can have very excellent surface quality, such as its surface gloss can reach on more than 3 (yellow chromaticity b value is less than or equal to 1.0), brightness value can reach more than 40, and does not occur the problems such as blackspot, macula lutea, bulk blackspot and obfuscation.
Below will be described the present invention by embodiment.Inhibiter conveniently in follow-up use embodiment is prepared all in form of an aqueous solutions, and this is not construed as limiting the invention, and also can be mixed with solid form in industrial production for the ease of selling.
In the following Examples and Comparative Examples, hydrochloric acid used and sulfuric acid are analytical pure, Hydrin base trimethyl ammonium chloride (formula (I) structure, X
1=Cl, m=4) purchased from Korean and Japanese chemical company, tetrabutylammonium iodide is purchased from the permanent female chemical industry in Yancheng, tetradecyl benzyl chloride and two dodecyl dimethyl ammonium chloride are purchased from Shandong Pai Ni Chemical Co., Ltd., 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 treatment company limited in Shandong, phytic acid is purchased from east, Chengdu enterprise-like corporation, Weibull is purchased from Suzhou one hundred moral Chemical Co., Ltd., 17 alkenyl amine ethyl imidazol(e) hyamines and amphoteric gemini imidazoline quaternary ammonium salt are purchased from Qinhuangdao triumph Chemical Co., Ltd., the comparative example 3 outsourcing inhibiter IBITNH-D trade mark used is purchased from Korean and Japanese chemical company.
Embodiment 1-6 and comparative example 1-3 is used for inhibiter composition and method of making the same is described,
Embodiment 1
In container, add the water of 70kg, under the condition stirred, in water, add 5kg Hydrin base trimethyl ammonium chloride (formula (I) structure, X successively
1=Cl, m=4), 10kg thiocarbamide, 10kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium and 5kg phytic acid make them dissolve successively, finally obtain the aqueous solution I1 of restrainer.
Embodiment 2
The water of 65kg is added in container, under the condition stirred, in water, add the mixture of 10kg tetrabutylammonium iodide, 10kg thiocarbamide, 10kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium 1:1 and 5kg phytic acid successively and make them dissolve successively, finally obtaining the aqueous solution I2 of restrainer.
Embodiment 3
The water of 82kg is added in container, add successively in water under the condition stirred 5kg tetradecyl benzyl chloride, 5kg thiocarbamide, 5kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium and 3kg phytic acid and Weibull 1:1 mixture and make them dissolve successively, finally obtain the aqueous solution I3 of restrainer.
Embodiment 4
The water of 76kg is added in container, under the condition stirred, in water, add 10kg two dodecyl dimethyl ammonium chloride, 5kg thiocarbamide, 5kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and 4kg phytic acid successively and make them dissolve successively, finally obtaining the aqueous solution I4 of restrainer.
Embodiment 5
The water of 70kg is added in container, under the condition stirred, in water, add 10kg 17 alkenyl amine ethyl imidazol(e) hyamine, 5kg thiocarbamide, 10kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium and 5kg Weibull successively and make them dissolve successively, finally obtaining the aqueous solution I5 of restrainer.
Embodiment 6
The water of 72kg is added in container, under the condition stirred, in water, add 8kg amphoteric gemini imidazoline quaternary ammonium salt, 8kg thiocarbamide, 8kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and the mixture of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium 1:2 and the mixture of 4kg phytic acid and Weibull 2:1 successively and make them dissolve successively, finally obtaining the aqueous solution I6 of restrainer.
Comparative example 1
In container, add the water of 70kg, Xiang Shuizhong adds 10kg Hydrin base trimethyl ammonium chloride (formula (I) structure, X
1=Cl, m=4), 10kg thiocarbamide and 10kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium stirring and dissolving, obtain inhibiter aqueous solution D1.
Comparative example 2
In container, add the water of 70kg, Xiang Shuizhong adds 10kg thiocarbamide, 10kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium and 10kg phytic acid and stirring and dissolving, obtains inhibiter aqueous solution D2.
Comparative example 3
In container, add the water of 70kg, Xiang Shuizhong adds 10kg tetrabutylammonium iodide, 10kg thiocarbamide and 10kg phytic acid and stirring and dissolving, obtains inhibiter aqueous solution D3.
Comparative example 4
In container, add the water of 70kg, Xiang Shuizhong adds 10kg two dodecyl dimethyl ammonium chloride, 10kg 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and 10kg phytic acid and stirring and dissolving, obtains inhibiter aqueous solution D4.
Comparative example 5
In container, add the water of 70kg, Xiang Shuizhong adds the 30kg outsourcing inhibiter IBITNH-D trade mark purchased from Korean and Japanese chemical company (main component organic quaternary ammonium salt, containing active substance about 30 % by weight) and stirring and dissolving, obtains inhibiter aqueous solution D5.
Embodiment 7-12 and comparative example 6-11 is used for acid washing method of the present invention and technique effect are described
Use above-described embodiment and comparative example gained restrainer preparating acid washing lotion II1-II6 and D ' 1-D ' 6 respectively, and using the vehicle structure steel hot-rolled sheet of gained pickle solution to long 1000m × wide 1850m × thick 4mm to carry out pickling respectively, the parameters such as the contamination of the contamination of restrainer, acid in pickle solution, the temperature of pickling and the speed of pickling are as shown in table 1.
Table 1
Detect the reduction of acid concentration in acid cleaning process and calculate sour consumption, after pickling terminates, the vehicle structure steel hot-rolled sheet after pickling is placed 24 hours respectively at 20 DEG C, then its surface brightness and glossiness is tested, and weigh and calculate vehicle structure steel hot-rolled sheet rate of weight loss after pickling (reflection corrosion rate), the results are shown in Table shown in 2, concrete test mode is as follows:
(1) consumption=(before pickling after concentration-pickling concentration) × acid solution volume × density of acid;
(2) surface brightness and glossiness are recorded by the glossiness tester of German BYK group company;
(3) weight × 100% before rate of weight loss=(before pickling after weight-pickling weight)/pickling.
Table 2
Can find out by embodiment and comparative example are carried out contrast, use restrainer of the present invention and acid washing method according to the present invention carries out pickling to automobile structural steel time, the consumption of restrainer used is significantly lower, the consumption of acid and the rate of weight loss (corrosion rate) of steel plate significantly lower, and the automobile structural steel after pickling has significantly higher surface brightness and glossiness.Further, when excessive use inhibiter of the present invention (comparative example 11), there is the phenomenon of not pickling.
In addition, use restrainer of the present invention and acid washing method according to the present invention carries out pickling to automobile structural steel can also bring economic benefit, method of calculation are as follows:
First rule of thumb following hypothesis is done with practical situation:
The price of the outsourcing inhibiter IBITNH-D trade mark (comparative example 3 is used) is 7000 yuan/t, the price of restrainer I of the present invention (embodiment 1 prepares gained) is 30,000 yuan/t, pickling line is often criticized and is produced by 5000t tissue, and acid discharge amount presses 200m
3calculate, coil of strip price calculates by 5000 yuan/t;
Prepare restrainer I1 according to the method for embodiment 1 and carry out pickling (in pickle solution, the content of inhibiter is 0.15 % by weight) according to the method for embodiment 7, prepare outsourcing corrosion inhibitor solution according to the method for comparative example 5 and carry out pickling (in pickle solution, the content of inhibiter is 1.00 % by weight) according to the method for comparative example 10; Can learn from table 2, the rate of weight loss of the steel plate of embodiment 7 is 0.1748%, and the rate of weight loss of the steel plate of comparative example 10 is 0.2078%; In addition, contriver's test records, and when not adding any inhibiter, the rate of weight loss of steel plate is 0.3864%.
Calculate as follows under the prerequisite of above-mentioned hypothesis and experimental data:
(1) minimizing of outsourcing inhibiter metal loss brings benefits
Metal loss reduces: 5000t × (0.3864%-0.2078%) × 5000 yuan/t=44650 unit
Inhibiter increases expense newly: 200m
3× 1t/m
3× 1% × 7000 yuan/t=14000 unit
Annual production is by 120,000 t, then year creates effect:
(44650 yuan-14000 yuan) × 120000 ÷ 5000=73.56 ten thousand yuan.
(2) inhibiter metal loss minimizing of the present invention brings benefits
Metal loss reduces: 5000t × (0.3864%-0.1748%) × 5000 yuan/t=52900 unit
Inhibiter increases expense newly: 200m
3× 1t/m
3× 0.15% × 30000 yuan/t=9000 unit
Annual production is by 120,000 t, then year creates effect:
(52900 yuan-9000 yuan) × 120000 ÷ 5000=105.36 ten thousand yuan.
More than calculate also not comprise and add spent acid treatment capacity after inhibiter and reduce (iron concentration reduction) and regenerating acid and remain inhibiter and recycle reduced expense.
Can be found out by above-mentioned calculating, use restrainer of the present invention and acid washing method according to the present invention carries out pickling to automobile structural steel can bring considerable economic benefit.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a restrainer, this restrainer comprises quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt, and phytic acid and/or Weibull.
2. restrainer according to claim 1, wherein, the weight ratio of described quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull is 1:0.3-2.5:0.3-2.5:0.2-1.2, is preferably 1:0.5-2:0.5-2:0.3-1.
3. restrainer according to claim 1, wherein, this restrainer exists in form of an aqueous solutions, and in the aqueous solution of this restrainer, the total content of quaternary ammonium compound, thiocarbamide, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and/or its salt and phytic acid and/or Weibull is 18-35 % by weight.
4. the restrainer according to claim 1 or 3, wherein, described quaternary ammonium compound be selected from imidazoline quaternary ammonium salt, bi-imidazoline quaternary ammonium salt, have formula (I) structure Hydrin quaternary ammonium salt and have in the quaternary ammonium salt of formula (II) structure one or more
Wherein R
1, R
2, R
3and R
4be selected from alkyl and the benzyl of C1-C14 independently of one another, X
1and X
2be selected from halogen independently of one another, m is the integer of 2-8.
5. restrainer according to claim 4, wherein, described in there is formula (II) structure quaternary ammonium salt be selected from tetrabutylammonium iodide, tetradecyl benzyl chloride and two dodecyl dimethyl ammonium chloride one or more.
6. carry out an acid washing method to automobile structural steel, the method comprises: carry out pickling with pickle solution to automobile structural steel, it is characterized in that, described pickle solution contains the restrainer in claim 1-5 described in any one.
7. method according to claim 6, wherein, with the gross weight of pickle solution for benchmark, the content of described restrainer is 0.05-0.5 % by weight, is preferably 0.15-0.36 % by weight.
8. the method according to claim 6 or 7, wherein, the acid in described pickle solution in the content of HCl for 150-250g/L.
9. method according to claim 6, wherein, the temperature of pickling is 60-90 DEG C, and the speed of pickling is 60-240m/min.
10. method according to claim 6, wherein, described automobile structural steel contains chromium and/or vanadium.
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| KR102201059B1 (en) * | 2019-09-05 | 2021-01-08 | 아사히 가가쿠 고교 가부시키가이샤 | Smut remover, manufacturing method thereof, and smut removal method using the same |
| CN113652695A (en) * | 2021-08-18 | 2021-11-16 | 马鞍山钢铁股份有限公司 | Production method for improving surface corrosion resistance of hot-rolled pickled steel plate |
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