CN108977812A - A kind of cold-rolling pickling corrosion inhibiter and preparation method thereof - Google Patents

A kind of cold-rolling pickling corrosion inhibiter and preparation method thereof Download PDF

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Publication number
CN108977812A
CN108977812A CN201810995415.5A CN201810995415A CN108977812A CN 108977812 A CN108977812 A CN 108977812A CN 201810995415 A CN201810995415 A CN 201810995415A CN 108977812 A CN108977812 A CN 108977812A
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cold
corrosion inhibiter
rolling pickling
organic amine
pickling corrosion
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CN201810995415.5A
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CN108977812B (en
Inventor
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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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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The invention discloses a kind of cold-rolling pickling corrosion inhibiter, it is pressed the molar ratio of 1.5:1~1:1.5 by vitamin B3 and organic amine, successively carry out condensation reaction, stirring at normal temperature reaction, and redistillation removal solvent forms；Wherein the carbon number of organic amine is 8~16.This law invention, which is put forward for the first time, synthesizes a kind of novel corrosion inhibitor for vitamin B3 and organic amine reaction, it is applied to the techniques such as cold-rolling pickling, it can express the advantages that dosage is few, inhibition efficiency is high, and it can effectively promote the surface quality of steel plate after pickling, the mass defects such as no blackspot and obfuscation can improve the completely new means of kind for efficiently clear technique；And the preparation method being related to is simple, at low cost, has important application value.

Description

A kind of cold-rolling pickling corrosion inhibiter and preparation method thereof
Technical field
The invention belongs to field of metal surface treatment technology, and in particular to a kind of cold-rolling pickling corrosion inhibiter and its preparation side Method.
Background technique
General large size steel enterprise rolling mill production line removes Cold-strip Steel Surface using hydrochloric acid shallow slot continuous acid-washing technology Iron scale, adjustment volume weight gives milling train to provide qualified blank, to guarantee that cold rolling function successfully produces qualified strip Product.The acid strength used in this pickling technology is generally 15% or so, the use of temperature is 80 ± 5 DEG C.And in pickling When routinely acid cleaning process carries out pickling in the process, surface will appear the mass defects such as blackspot and obfuscation.
In order to avoid the generation for consuming and preventing unwanted corrosion excessively of metal in acid cleaning process or acid, it is added in acid Corrosion inhibiter is effective means.Corrosion inhibiter be one kind in corrosive medium additional amount it is considerably less and can substantially reduce metal erosion speed The chemical substance of rate.But the generally existing additional amount of traditional corrosion inhibiter is big, has acid mist, is at high cost, is poisonous and harmful, high-temperature strong acid Under the conditions of the disadvantages such as corrosion efficiency is low, therefore there is an urgent need to develop that a kind of additive amount is few, inhibition efficiency is high and environmental-friendly cold Roll restrainer.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, provide a kind of cold-rolling pickling corrosion inhibiter, it Have many advantages, such as that additive amount is low, inhibition efficiency is high, it is at low cost, can effectively prevent cold-strip steel and its product in acid cleaning process not Necessary corrosion；And the preparation method being related to is simple, at low cost, is suitble to promote and apply.
To realize above scheme, the technical solution adopted by the present invention are as follows:
It is mixed in alcoholic solvent by the molar ratio of 1.5:1~1:1.5 by vitamin B3 and organic amine, is successively condensed Reaction, stirring at normal temperature reaction, and remove alcoholic solvent and be made；Wherein, the carbon number of organic amine is 8~16.
Preferably, lauryl amine, myristyl amine or octylame etc. can be selected in the organic amine.
In above scheme, the step of condensation includes: that vitamin B3, organic amine are added in alcoholic solvent, uniformly mixed It closes, after catalyst is added, the reaction response 3~4 hours under the conditions of 70~80 DEG C of temperature.
In above scheme, the catalyst can be selected thionyl chloride, phosphorus trichloride, DMF (n,N-Dimethylformamide) or Triethylamine etc..
In above scheme, ethyl alcohol or isopropanol etc. is can be selected in the alcoholic solvent.
In above scheme, the stirring at normal temperature reaction time is 2~4h.
A kind of preparation method of above-mentioned cold-rolling pickling corrosion inhibiter, specifically comprises the following steps:
1) vitamin B3, organic amine are added in alcoholic solvent by the molar ratio of 1.5:1~1:1.5, are uniformly mixed, must react Solution；
2) catalyst is added into gained reaction solution, is heated to 70~80 DEG C of reactions 3~4 hours, then stirring at normal temperature 2 ~4h, distillation removal alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
Cold-rolling pickling corrosion inhibiter obtained by above scheme is applied to processing cold-strip steel, cold-rolling pickling line often uses hydrochloric acid solution (35~150g/L), pickling temperature are 70-80 DEG C, and pickling speed is 70~75m/min；The additive amount of required corrosion inhibiter be 50~ 500mg/L。
Preferably, comprehensively consider inhibition efficiency and pickling cost, the additive amount of required corrosion inhibiter is 50-100mg/L.
The principle of the present invention are as follows:
Vitamin B3 molecule is the compound with heterocycle, and the nitrogen-atoms in structure on pyridine ring forms nitrogen in acid solution Then cation active group adsorbs again with negatively charged metal surface, plays inhibition of corrosion；The pyrrole of corrosion inhibiter There are an electrophilic amide substituents in phenazine ring, and in nitrogen-atoms meta position, the carbonyl of amide substituents can generate pyridine ring Sucting electronic effect, according to the characteristic of phenyl ring, which increases, and C cloud density adjacent thereto is reduced, this is slow Lose the nitrogen-atoms of agent exactly in the carbon atom meta position with substituent group bonding, lead to the reduction of its cloud density, thus be easier with Electrostatic force occurs for cathode surface to be adsorbed onto metal surface, has better corrosion inhibition rate.
Compared with prior art, the invention has the benefit that
1) present invention firstly provides by vitamin B3 and organic amine reaction, a kind of novel corrosion inhibitor is synthesized；Its main component One of vitamin B3 it is from a wealth of sources, cost is relatively low, have significant economic benefit.
2) present invention gained corrosion inhibiter usage amount is low, corrosion mitigating effect is excellent, corrosion inhibition rate, and can be effective up to 95% or more Acid mist is reduced, plate surface quality improves after pickling, and the mass defects such as no blackspot and obfuscation have important popularization and application valence Value.
3) synthetic method that corrosion inhibiter of the present invention is related to is simple, and reaction condition is mild, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is the inhibition efficiency figure under the conditions of 1 gained cold-rolling pickling corrosion inhibiter various concentration of embodiment.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention Content is not limited solely to the following examples.
Embodiment 1
A kind of cold-rolling pickling corrosion inhibiter, preparation method include the following steps:
1) vitamin B3, organic amine (myristyl amine) are added in ethyl alcohol by the molar ratio of 1:1, are uniformly mixed；
2) thionyl chloride is added into gained reaction solution, is heated to 70 DEG C of reaction 4h, then stirring at normal temperature 3.5h, then steam It evaporates except alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
Embodiment 2
A kind of cold-rolling pickling corrosion inhibiter, preparation method include the following steps:
1) vitamin B3, organic amine (myristyl amine) are added in ethyl alcohol by the molar ratio of 1:1.5, are uniformly mixed；
2) thionyl chloride is added into gained reaction solution, is heated to 70 DEG C of reaction 4h, then stirring at normal temperature 3.5h, then steam It evaporates except alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
Embodiment 3
A kind of cold-rolling pickling corrosion inhibiter, preparation method include the following steps:
1) vitamin B3, organic amine (myristyl amine) are added in ethyl alcohol by the molar ratio of 1.5:1, are uniformly mixed；
2) thionyl chloride is added into gained reaction solution, is heated to 70 DEG C of reaction 4h, then stirring at normal temperature 3.5h, then steam It evaporates except alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
Embodiment 4
A kind of cold-rolling pickling corrosion inhibiter, preparation method include the following steps:
1) vitamin B3, organic amine (myristyl amine) are added in ethyl alcohol by the molar ratio of 1.5:1, are uniformly mixed；
2) thionyl chloride is added into gained reaction solution, is heated to 80 DEG C of reaction 4h, then stirring at normal temperature 2.5h, then steam It evaporates except alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
Embodiment 5
A kind of cold-rolling pickling corrosion inhibiter, preparation method include the following steps:
1) vitamin B3, organic amine (myristyl amine) are added in ethyl alcohol by the molar ratio of 1:1, are uniformly mixed；
2) thionyl chloride is added into gained reaction solution, is heated to 80 DEG C of reaction 4h, then stirring at normal temperature 3.5h, then steam It evaporates except alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
It is evaluated using corrosion inhibition of the weight-loss method to cold-rolling pickling corrosion inhibiter obtained by various embodiments of the present invention: according to " being acidified with corrosion inhibiter method for testing performance and evaluation index " (SY/T5405-1996) carries out static steel experiment；Test steel disc For Q235 steel disc, corrosive medium is the HCl solution of 6mol/L, and test temperature is 70 DEG C, 80 DEG C, test period 4 hours, is surveyed respectively Determine corrosion weight loss of the sample in the corrosive medium after being not added with corrosion inhibiter and adding corrosion inhibiter, so that it is determined that its corrosion rate, And calculate corrosion inhibition rate；Test result is shown in Table 1.
Corrosion rate calculates formula are as follows:
In formula: V is corrosion rate, g/ (m2h)；W0And WtThe respectively quality of the weightless front and back of sample, g；S is test piece area, m2；T is test piece etching time, h.
In formula: η is the inhibition efficiency of corrosion inhibiter；V0The corrosion rate of test piece, g/ (m when not add corrosion inhibiter2h)；VtTo add The corrosion rate of test piece when adding corrosion inhibiter, g/ (m2h)
The corrosion inhibition testing result of cold-rolling pickling corrosion inhibiter obtained by 1 Examples 1 to 5 of table
Fig. 1 is that (test steel disc is Q235 to inhibition efficiency of the cold-rolling pickling corrosion inhibiter obtained by the present embodiment under various concentration Steel disc, corrosive medium are the HCl solution of 6mol/L, and test temperature is 70 DEG C, test period 4 hours) figure, the results showed that, when adopting When the concentration of corrosion inhibiter is 100mg/L, corrosion inhibition rate can reach 90% or more；When corrosion inhibiter additive amount is greater than 200mg/L When, corrosion inhibition rate is greater than 97.5%.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified It moves within still in the protection scope of the invention.

Claims (9)

1. a kind of cold-rolling pickling corrosion inhibiter, it is pressed the molar ratio of 1.5:1~1:1.5 by vitamin B3 and organic amine in alcoholic solvent Mixing successively carries out condensation reaction, stirring at normal temperature reaction, and removes alcoholic solvent and be made；Wherein the carbon number of organic amine is 8~16.
2. cold-rolling pickling corrosion inhibiter according to claim 1, which is characterized in that the organic amine is lauryl amine, nutmeg Base amine or octylame.
3. cold-rolling pickling corrosion inhibiter according to claim 1, which is characterized in that the step of condensation includes: that will tie up Raw element B3, organic amine are added in alcoholic solvent, uniformly mix, after catalyst is added, under the conditions of 70~80 DEG C of temperature reaction 3~ 4 hours.
4. cold-rolling pickling corrosion inhibiter according to claim 3, which is characterized in that the catalyst is thionyl chloride, trichlorine Change phosphorus, DMF (N,N-dimethylformamide) or triethylamine.
5. cold-rolling pickling corrosion inhibiter according to claim 3, which is characterized in that the alcoholic solvent is ethyl alcohol or isopropanol.
6. cold-rolling pickling corrosion inhibiter according to claim 1, which is characterized in that the stirring at normal temperature reaction time be 2~ 4h。
7. the preparation method of any one of the claim 1~6 cold-rolling pickling corrosion inhibiter, which is characterized in that specifically include as follows Step:
1) vitamin B3, organic amine are added in alcoholic solvent by the molar ratio of 1.5:1~1:1.5, are uniformly mixed, must react molten Liquid；
2) catalyst is added into gained reaction solution, is heated to 70~80 DEG C of reactions 3~4, then 2~4h of stirring at normal temperature, steams It evaporates except alcoholic solvent is to get cold-rolling pickling corrosion inhibiter.
8. the application of any one of the claim 1~6 cold-rolling pickling corrosion inhibiter, which is characterized in that the pickling temperature used for 70-80 DEG C, the additive amount of corrosion inhibiter is 50~500mg/L.
9. application according to claim 8, which is characterized in that the additive amount of corrosion inhibiter is 50~100mg/L.
CN201810995415.5A 2018-08-29 2018-08-29 Cold rolling pickling corrosion inhibitor and preparation method thereof Active CN108977812B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110592598A (en) * 2019-09-30 2019-12-20 武汉钢铁有限公司 Novel cold-rolled strip steel pickling corrosion inhibitor and preparation method thereof

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

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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Title
丁文成等: ""合成烟酸衍生物对Q235钢在盐酸介质中的缓蚀性能"", 《材料保护》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110592598A (en) * 2019-09-30 2019-12-20 武汉钢铁有限公司 Novel cold-rolled strip steel pickling corrosion inhibitor and preparation method thereof
CN110592598B (en) * 2019-09-30 2022-03-18 武汉钢铁有限公司 Novel cold-rolled strip steel pickling corrosion inhibitor and preparation method thereof

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