CN108977812B - Cold rolling pickling corrosion inhibitor and preparation method thereof - Google Patents

Cold rolling pickling corrosion inhibitor and preparation method thereof Download PDF

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CN108977812B
CN108977812B CN201810995415.5A CN201810995415A CN108977812B CN 108977812 B CN108977812 B CN 108977812B CN 201810995415 A CN201810995415 A CN 201810995415A CN 108977812 B CN108977812 B CN 108977812B
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corrosion inhibitor
organic amine
pickling
cold rolling
alcohol solvent
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CN108977812A (en
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程鹏
黄先球
庞涛
郎丰军
彭浩
马颖
李江文
宋建红
何嘉
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Wuhan Iron and Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/063—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel

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Abstract

The invention discloses a cold-rolling pickling corrosion inhibitor which is prepared by sequentially carrying out condensation reaction, normal-temperature stirring reaction and distillation to remove a solvent on vitamin B3 and organic amine according to a molar ratio of 1.5: 1-1: 1.5; wherein the carbon number of the organic amine is 8-16. The invention provides a novel corrosion inhibitor synthesized by the reaction of vitamin B3 and organic amine for the first time, and the corrosion inhibitor is applied to the processes of cold rolling, pickling and the like, can show the advantages of small using amount, high corrosion inhibition efficiency and the like, can effectively improve the surface quality of a steel plate after pickling, has no quality defects of black spots, darkening and the like, and can improve a brand new means for a high-efficiency clear process; the related preparation method is simple and low in cost, and has important popularization and application values.

Description

Cold rolling pickling corrosion inhibitor and preparation method thereof
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a cold rolling pickling corrosion inhibitor and a preparation method thereof.
Background
The general large-scale steel group cold rolling production line adopts a hydrochloric acid shallow slot continuous pickling technology to remove iron scales on the surface of cold-rolled strip steel, adjust the coil weight and provide qualified blanks for a rolling mill so as to ensure that a cold rolling machine can smoothly produce qualified strip steel products. The acid solution used in the acid washing technology is generally about 15 percent, and the use temperature is 80 +/-5 ℃. And when the pickling is carried out according to the conventional pickling process in the pickling process, the surface of the steel plate has quality defects of black spots, darkening and the like.
The addition of corrosion inhibitors to the acid is an effective means to avoid excessive consumption of metal or acid during pickling and to prevent detrimental corrosion. The corrosion inhibitor is a chemical substance which is added in a small amount in a corrosion medium and can greatly reduce the corrosion rate of metal. However, the traditional corrosion inhibitor generally has the defects of large addition amount, acid mist, high cost, toxicity, harm, low corrosion efficiency under the condition of high temperature and strong acid and the like, so that the development of a cold-rolling pickling corrosion inhibitor with small addition amount, high corrosion inhibition efficiency and environmental friendliness is urgently needed.
Disclosure of Invention
The invention mainly aims to provide a cold-rolling pickling inhibitor aiming at the defects in the prior art, which has the advantages of low addition amount, high corrosion inhibition efficiency, low cost and the like, and can effectively prevent the cold-rolling strip steel and products thereof from unnecessary corrosion in the pickling process; and the related preparation method is simple, low in cost and suitable for popularization and application.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
mixing vitamin B3 and organic amine in an alcohol solvent according to the molar ratio of 1.5: 1-1: 1.5, sequentially carrying out condensation reaction and normal-temperature stirring reaction, and removing the alcohol solvent to prepare the vitamin B water-soluble organic solvent; wherein the carbon number of the organic amine is 8-16.
Preferably, the organic amine can be dodecylamine, myristylamine, octylamine, or the like.
In the above scheme, the condensation reaction step comprises: adding vitamin B3 and organic amine into an alcohol solvent, uniformly mixing, adding a catalyst, and reacting at the temperature of 70-80 ℃ for 3-4 hours.
In the scheme, the catalyst can be selected from thionyl chloride, phosphorus trichloride, DMF (N, N-dimethylformamide), triethylamine and the like.
In the scheme, the alcohol solvent can be ethanol or isopropanol and the like.
In the scheme, the normal-temperature stirring reaction time is 2-4 h.
The preparation method of the cold rolling pickling corrosion inhibitor specifically comprises the following steps:
1) adding vitamin B3 and organic amine into an alcohol solvent according to the molar ratio of 1.5: 1-1: 1.5, and uniformly mixing to obtain a reaction solution;
2) adding a catalyst into the obtained reaction solution, heating to 70-80 ℃, reacting for 3-4 hours, then stirring for 2-4 hours at normal temperature, and distilling to remove the alcohol solvent, thus obtaining the cold rolling pickling inhibitor.
The cold-rolling pickling corrosion inhibitor obtained by the scheme is applied to treatment of cold-rolling strip steel, a hydrochloric acid solution (35-150 g/L) is usually used in a cold-rolling pickling line, the pickling temperature is 70-80 ℃, and the pickling speed is 70-75 m/min; the addition amount of the corrosion inhibitor is 50-500 mg/L.
Preferably, the corrosion inhibition efficiency and the pickling cost are comprehensively considered, and the addition amount of the corrosion inhibitor is 50-100 mg/L.
The principle of the invention is as follows:
the vitamin B3 molecule is a compound with heterocyclic ring, nitrogen atom on pyridine ring in the structure forms nitrogen positive ion active group in acid liquor, and then the nitrogen positive ion active group is adsorbed with metal surface with negative charge to play a role in inhibiting corrosion; the pyridine ring of the corrosion inhibitor is provided with an electron-withdrawing amide substituent, the carbonyl of the amide substituent can produce an electron-withdrawing effect on the pyridine ring at a meta position of a nitrogen atom, according to the characteristics of a benzene ring, the electron cloud density of the group is increased, the electron cloud density of C adjacent to the group is reduced, and the nitrogen atom of the corrosion inhibitor is exactly at the meta position of the carbon atom bonded with the substituent, so that the electron cloud density of the corrosion inhibitor is reduced, and the corrosion inhibitor is easier to generate electrostatic force with the surface of a cathode so as to be adsorbed to the surface of metal and has better corrosion inhibition rate.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly proposes that vitamin B3 reacts with organic amine to synthesize a novel corrosion inhibitor; the vitamin B3 which is one of the main components has wide sources and low cost, and has remarkable economic benefit.
2) The corrosion inhibitor obtained by the invention has low usage amount, excellent corrosion inhibition effect, corrosion inhibition rate of more than 95 percent, effective reduction of acid mist, improvement of surface quality of the steel plate after acid cleaning, no quality defects of black spots, darkening and the like, and has important popularization and application value.
3) The synthetic method of the corrosion inhibitor is simple, the reaction condition is mild, and the corrosion inhibitor is suitable for popularization and application.
Drawings
FIG. 1 is a graph of the corrosion inhibition efficiency of the cold rolling pickling corrosion inhibitor obtained in example 1 under different concentration conditions.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A cold rolling pickling corrosion inhibitor comprises the following steps:
1) adding vitamin B3 and organic amine (myristylamine) into ethanol at a molar ratio of 1:1, and mixing;
2) and adding thionyl chloride into the obtained reaction solution, heating to 70 ℃ for reaction for 4 hours, then stirring at normal temperature for 3.5 hours, and distilling to remove the alcohol solvent to obtain the cold-rolling pickling corrosion inhibitor.
Example 2
A cold rolling pickling corrosion inhibitor comprises the following steps:
1) adding vitamin B3 and organic amine (myristylamine) into ethanol at a molar ratio of 1:1.5, and mixing;
2) and adding thionyl chloride into the obtained reaction solution, heating to 70 ℃ for reaction for 4 hours, then stirring at normal temperature for 3.5 hours, and distilling to remove the alcohol solvent to obtain the cold-rolling pickling corrosion inhibitor.
Example 3
A cold rolling pickling corrosion inhibitor comprises the following steps:
1) adding vitamin B3 and organic amine (myristylamine) into ethanol at a molar ratio of 1.5:1, and mixing;
2) and adding thionyl chloride into the obtained reaction solution, heating to 70 ℃ for reaction for 4 hours, then stirring at normal temperature for 3.5 hours, and distilling to remove the alcohol solvent to obtain the cold-rolling pickling corrosion inhibitor.
Example 4
A cold rolling pickling corrosion inhibitor comprises the following steps:
1) adding vitamin B3 and organic amine (myristylamine) into ethanol at a molar ratio of 1.5:1, and mixing;
2) and adding thionyl chloride into the obtained reaction solution, heating to 80 ℃, reacting for 4 hours, then stirring for 2.5 hours at normal temperature, and distilling to remove the alcohol solvent to obtain the cold-rolling pickling corrosion inhibitor.
Example 5
A cold rolling pickling corrosion inhibitor comprises the following steps:
1) adding vitamin B3 and organic amine (myristylamine) into ethanol at a molar ratio of 1:1, and mixing;
2) and adding thionyl chloride into the obtained reaction solution, heating to 80 ℃, reacting for 4 hours, then stirring for 3.5 hours at normal temperature, and distilling to remove the alcohol solvent to obtain the cold-rolling pickling corrosion inhibitor.
The corrosion inhibition performance of the cold rolling pickling corrosion inhibitor obtained by each embodiment of the invention is evaluated by adopting a weight loss method: carrying out static hanging experiment according to a performance test method and evaluation index of the corrosion inhibitor for acidification (SY/T5405-1996); the test steel sheet is a Q235 steel sheet, the corrosion medium is 6mol/L HCl solution, the test temperature is 70 ℃, 80 ℃, the test time is 4 hours, and the corrosion weightlessness of the sample in the corrosion medium without the corrosion inhibitor and after the corrosion inhibitor is added is respectively measured, so that the corrosion rate is determined, and the corrosion inhibition rate is calculated; the test results are shown in Table 1.
The corrosion rate calculation formula is:
Figure BDA0001781743240000031
in the formula: v is the corrosion rate, g/(m)2h)；W0And WtThe mass g before and after the sample weight loss respectively; s is the area of the test piece, m2(ii) a t is the corrosion time of the test piece, h.
Figure BDA0001781743240000032
Wherein η is corrosion inhibition efficiency of corrosion inhibitor, V0The corrosion rate of the test piece without adding the corrosion inhibitor is g/(m)2h)；VtThe corrosion rate of the test piece is g/(m) when the corrosion inhibitor is added2h)
Table 1 results of testing corrosion inhibition performance of the cold rolling pickling corrosion inhibitor obtained in examples 1 to 5
Figure BDA0001781743240000041
FIG. 1 is a graph of the corrosion inhibition efficiency of the cold-rolling acid pickling corrosion inhibitor obtained in the embodiment under different concentrations (the test steel sheet is Q235 steel sheet, the corrosion medium is 6mol/L HCl solution, the test temperature is 70 ℃, and the test time is 4 hours), and the results show that the corrosion inhibition efficiency can reach more than 90% when the concentration of the adopted corrosion inhibitor is 100 mg/L; when the addition amount of the corrosion inhibitor is more than 200mg/L, the corrosion inhibition rate is more than 97.5 percent.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (8)

1. A cold rolling pickling corrosion inhibitor is prepared by mixing vitamin B3 and organic amine in an alcohol solvent according to a molar ratio of 1.5: 1-1: 1.5, sequentially carrying out condensation reaction and normal-temperature stirring reaction, and removing the alcohol solvent; wherein the carbon number of the organic amine is 8-16;
the organic amine is myristylamine;
the preparation method comprises the following steps:
1) adding vitamin B3 and organic amine into an alcohol solvent according to the molar ratio of 1.5: 1-1: 1.5, and uniformly mixing to obtain a reaction solution;
2) adding a catalyst into the obtained reaction solution, heating to 70-80 ℃, reacting for 3-4 hours, then stirring for 2-4 hours at normal temperature, and distilling to remove the alcohol solvent, thus obtaining the cold rolling pickling inhibitor.
2. The cold rolling restrainer of claim 1, wherein the condensation reaction step comprises: adding vitamin B3 and organic amine into an alcohol solvent, uniformly mixing, adding a catalyst, and reacting for 3-4 hours at the temperature of 70-80 ℃.
3. The cold rolling restrainer of claim 2, wherein the catalyst is thionyl chloride or triethylamine.
4. The cold-rolling restrainer of claim 2, wherein the alcohol solvent is ethanol or isopropanol.
5. The cold-rolling pickling corrosion inhibitor according to claim 1, wherein the normal-temperature stirring reaction time is 2-4 h.
6. The preparation method of the cold rolling pickling corrosion inhibitor of any one of claims 1 to 5 is characterized by comprising the following steps:
1) adding vitamin B3 and organic amine into an alcohol solvent according to the molar ratio of 1.5: 1-1: 1.5, and uniformly mixing to obtain a reaction solution;
2) adding a catalyst into the obtained reaction solution, heating to 70-80 ℃, reacting for 3-4 hours, then stirring for 2-4 hours at normal temperature, and distilling to remove the alcohol solvent, thus obtaining the cold rolling pickling inhibitor.
7. The application of the cold rolling pickling corrosion inhibitor of any one of claims 1 to 5, wherein the pickling temperature is 70-80 ℃, and the addition amount of the corrosion inhibitor is 50-500 mg/L.
8. The use according to claim 7, wherein the corrosion inhibitor is added in an amount of 50 to 100 mg/L.
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Publication number Priority date Publication date Assignee Title
DE2532532A1 (en) * 1974-08-06 1976-02-26 Lonza Ag HOUSEHOLD SUPPLIES IN TABLET FORM
CN104726883A (en) * 2015-03-30 2015-06-24 江苏理工学院 Stainless steel surface scale removal method and pickling solution adopted by same
CN106520412A (en) * 2016-10-28 2017-03-22 广西鑫雅皇庭园林工程有限责任公司 Electronic screen cleaning agent

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
DE2532532A1 (en) * 1974-08-06 1976-02-26 Lonza Ag HOUSEHOLD SUPPLIES IN TABLET FORM
CN104726883A (en) * 2015-03-30 2015-06-24 江苏理工学院 Stainless steel surface scale removal method and pickling solution adopted by same
CN106520412A (en) * 2016-10-28 2017-03-22 广西鑫雅皇庭园林工程有限责任公司 Electronic screen cleaning agent

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