CN105780023B - A kind of corrosion inhibiter and its synthetic method for pickling - Google Patents
A kind of corrosion inhibiter and its synthetic method for pickling Download PDFInfo
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- CN105780023B CN105780023B CN201610349380.9A CN201610349380A CN105780023B CN 105780023 B CN105780023 B CN 105780023B CN 201610349380 A CN201610349380 A CN 201610349380A CN 105780023 B CN105780023 B CN 105780023B
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- pickling
- corrosion inhibiter
- acrylate
- sulfonic acid
- allylthiourea
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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
- C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
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- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention discloses a kind of corrosion inhibiter and its synthetic method for pickling, the described corrosion inhibiter for pickling is to be using Allyl thiourea, AEO acrylate and the terpolymer prepared to styrene sulfonic acid as comonomer, the mass ratio of allylthiourea, AEO acrylate and p styrene sulfonic acid：1:0.2~1:0.5 ~ 1.5, the mean molecule quantity of terpolymer is 300 ~ 1500, and wherein AEO acrylate has structural formula, R is C in formula5‑18Alkyl, n are 6 ~ 20.The copolymer can reach more than 90% corrosion inhibition rate in industrial equipment acid cleaning process, and the grease soils attached on wall can be removed, the double effectses that pickling is washed with solvent are served simultaneously, are the high efficient restrainers that man-hour reduction expense is saved in a kind of industrial equipment cleaning process.
Description
Technical field
The invention belongs to water treatment agent field, and in particular to a kind of corrosion inhibiter and its synthetic method for pickling.
Background technology
Metal material equipment, pipe surface are carried out using the inorganic organic acid such as hydrochloric acid, sulfuric acid, citric acid to clean scale removal
Cleaning method, it is widely used in the industries such as intermetallic composite coating, machinery, metallurgy, electric power, chemical industry.Due to the corrosion of acidity, in pickling
During usually there is " cross lose " phenomenon, i.e. cleaning process not only removes corrosion and the dirt on surface, while also by Metal Substrate
Material erodes a part in the lump.Therefore, the loss of metal material and the waste of pickle in acid cleaning process are caused, while is produced again
Raw substantial amounts of pickle liquor, causes environmental pollution.
In order to avoid " cross and lose " phenomenon of metal base, it is a kind of directly effective side that corrosion inhibiter is added in pickle
Method.Thiourea process is generally practical in early forties as metal pickling corrosion inhibitor.In thiourea process
N, S there are unshared lone pair electrons, form coordinate bond with the empty d rail interactions of metal surface, be adsorbed in metal watch
Face forms one layer of adsorbed film and protects metal surfaces from corroding.
Qi Hong China et al. have studied corrosion inhibition of the allylthiourea in metal chlorohydric acid pickling, but water-soluble between pi-allyl
Property is undesirable to make it cumbersome in use, and for the metallic substrate surface corrosion mitigating effect with greasy dirt by very big
Influence.
Pickle is in some industrial equipments such as surface corrosion of reactor, air conditioner, oil plant cooling pipe etc., incrustation scale etc.
It can be fallen with pickling, and the cleaning to the greasy dirt on its surface does not have effect, it is therefore necessary to add solvent and wash or surfactant
The process washed, surfactant is added in pickle in order to which aspect shortening process also has, but corrosion inhibiter, acid and surface are lived sometimes
The compatibility of property agent is not fine and influences its treatment effect.
The content of the invention
The present invention proposes a kind of corrosion inhibiter and its synthetic method for pickling to solve the above problems, the inhibition
The corrosion inhibition for preventing hydrogen embrittlement is not only played in agent in acid cleaning process to metal surface, and can soak dissolving metal surface
Obstinate greasy dirt plays the cleaning action of oil removing.The copolymer adds 200mg/m in the acid cleaning process such as equipment pipe3, Neng Gouda
To more than 90% corrosion inhibition rate.
Specific technical scheme is as follows：
A kind of corrosion inhibiter for pickling, it is characterised in that the described corrosion inhibiter for pickling be with allylthiourea,
AEO acrylate and the terpolymer that p styrene sulfonic acid is comonomer preparation, allyl sulfide
The mass ratio of urea, AEO acrylate and p styrene sulfonic acid is：1:0.2~1:0.5 ~ 1.5, ternary polymerization
The mean molecule quantity of thing is 300 ~ 1500.
Described AEO acrylate has structural formula
Wherein R is C6-18 alkyl, and n is 6 ~ 20.
Preferably, the quality of described allylthiourea, AEO acrylate and p styrene sulfonic acid
Than for：1:0.2~0.5:0.7~1.2.
Preferably, the mean molecule quantity of described terpolymer is 480 ~ 1500.
A kind of synthetic method of the above-mentioned corrosion inhibiter for pickling, its specific preparation process are：
（1）Allylthiourea, AEO acrylate and p styrene sulfonic acid are added in reactor,
Adding the solvent of polymerized monomer gross mass 30% ~ 120% makes its dissolving；
（2）Rate-determining steps（1）Reaction system be warming up to 50 ~ 70 DEG C, after into reaction system, dropwise addition is dissolved with solvent
Initiator, the addition of initiator are the 0.1 ~ 5% of polymerized monomer gross mass, and initiator time for adding was controlled at 0.5 ~ 2 hour；
（3）Temperature is improved after being added dropwise to 60 ~ 95 DEG C, reacts 2 ~ 10 hours, adds deionized water to dilute.
Step (1) and step（2）Described solvent is the one or more in methanol, ethanol, isopropanol and ethylene glycol.
Initiator described in step (2) is azodiisobutyronitrile, or benzoyl peroxide and sodium hydrogensulfite is mixed
Compound, benzoyl peroxide, the mol ratio of sodium hydrogensulfite are 2:1.
Preferably, step（1）Described allylthiourea, AEO acrylate and p styrene sulfonic acid
Mass ratio be：1:0.2~0.5:0.7~1.2；Step（1）Described solvent adding amount for polymerized monomer gross mass 30% ~
100%。
Preferably, step（2）Described temperature of reaction system is 50 ~ 60 DEG C；Step（2）The addition of described initiator
For the 0.5 ~ 3% of polymerized monomer gross mass；Step（3）Described temperature is 85 ~ 90 DEG C；Step（3）The described reaction time be 3 ~
7 hours.
For in the acid cleaning process of industrial equipment, the addition of described corrosion inhibiter to be 30 ~ 500ppm.
Target product terpolymer of the present invention has the side chain of aliphatic alcohol polyether, has to the obstinate grease of substrate surface
Good emulsifying effectiveness, and pendent sulfonic acid has good dispersing and dissolving performance to the grease of emulsification, therefore in the process of pickling
In be not only able to protect surface not to be corroded and also there is emulsion dispersion effect to obstinate oil foulant.
The beneficial effects of the invention are as follows：Can have simultaneously to cleaning during industrial equipment cleans using the present invention
Metal base inhibition and the effect of oil removing, the double action that pickling is washed with solvent is served, realizes one multiple-effect；Set in industry
More than 90% corrosion inhibition rate can be reached in standby acid cleaning process；Product of the present invention is without phosphorus, it is nontoxic be a kind of water process of safety and environmental protection
Agent product.
Embodiment
Embodiment 1
A kind of corrosion inhibiter for pickling of the invention is by allylthiourea, AEO acrylate, right
The terpolymer that styrene sulfonic acid copolymerization forms, wherein AEO acrylate have structural formulaMiddle R is C12H21-, n 9.
The copolymer synthesis process is as follows：
(1) by allylthiourea, AEO acrylate and p styrene sulfonic acid according to mass ratio 1:
0.5:1 ratio is added in reactor, adds the methanol of total monomer quality 100%, and stirring and dissolving；
(2) open and be heated to 55 DEG C, the initiator azodiisobutyronitrile for weighing total monomer quality 0.5% is dissolved with methanol, control
System is added dropwise for 1 hour；
(3) it is added dropwise and improves temperature to 85 DEG C, continue reaction 6 hours, obtains the ternary polymerization that mean molecule quantity is 865
Thing, deionized water is added to be diluted to 40% solid content.
Embodiment 2
A kind of corrosion inhibiter for pickling of the invention is by allylthiourea, AEO acrylate, right
The terpolymer that styrene sulfonic acid copolymerization forms, wherein AEO acrylate have structural formulaMiddle R is C8H17-, n 6.
The copolymer synthesis process is as follows：
(1) by allylthiourea, AEO acrylate and p styrene sulfonic acid according to mass ratio 1:
0.3:0.7 ratio is added in reactor, adds the ethanol of total monomer quality 30%, and stirring and dissolving；
(2) open and be heated to 60 DEG C, weigh benzoyl peroxide/sodium hydrogensulfite of total monomer quality 1%（Mol ratio 2:
1）Dissolved with ethanol, control is added dropwise for 0.5 hour；
(3) it is added dropwise and improves temperature to 90 DEG C, continue reaction 3 hours, obtains the ternary polymerization that mean molecule quantity is 480
Thing, deionized water is added to be diluted to 40% solid content.
Embodiment 3
A kind of corrosion inhibiter for pickling of the invention is by allylthiourea, AEO acrylate, right
The terpolymer that styrene sulfonic acid copolymerization forms, wherein AEO acrylate have structural formulaMiddle R is C6H13-, n 10.
The copolymer synthesis process is as follows：
(1) by allylthiourea, AEO acrylate and p styrene sulfonic acid according to mass ratio 1:
0.2:1.2 ratio is added in reactor, adds the isopropanol of total monomer quality 80%, and stirring and dissolving；
(2) open and be heated to 60 DEG C, weigh benzoyl peroxide/sodium hydrogensulfite of total monomer quality 3%（Mol ratio 2:
1）Dissolved with isopropanol, control is added dropwise for 1.5 hours；
(3) it is added dropwise and improves temperature to 90 DEG C, continue reaction 5 hours, obtains the ternary polymerization that mean molecule quantity is 1000
Thing, deionized water is added to be diluted to 40% solid content.
Embodiment 4
A kind of corrosion inhibiter for pickling of the invention is by allylthiourea, AEO acrylate, right
The terpolymer that styrene sulfonic acid copolymerization forms, wherein AEO acrylate have structural formulaMiddle R is C18H35-, n 20.
The copolymer synthesis process is as follows：
(1) by allylthiourea, AEO acrylate and p styrene sulfonic acid according to mass ratio 1:
0.2:1.2 ratio is added in reactor, adds the ethylene glycol of total monomer quality 50%, and stirring and dissolving；
(2) open and be heated to 50 DEG C, it is molten to weigh the azodiisobutyronitrile solvent dissolving isopropanol of total monomer quality 0.8%
Solution, control are added dropwise for 2 hours；
(3) it is added dropwise and improves temperature to 90 DEG C, continue reaction 7 hours, obtains the ternary polymerization that mean molecule quantity is 1500
Thing, deionized water is added to be diluted to 40% solid content.
Present copolymer monomer is safe and non-toxic without phosphorus monomer, and polymer solvent is lower aliphatic alcohols, polymerization initiation
It is for without phosphorus system, whole course of reaction and reaction product are nontoxic, also phosphorous " eutrophy " will not be caused to endanger to environment, be
The water treatment agent product of a kind of safety and environmental protection.
Application example
Measure rotating suspension by the technique products obtained therefrom of embodiment 1 ~ 4 according to GB/T18175-2000 water treatment agent corrosion inhibitions
Piece method carries out corrosion inhibition test.Experimental liquid is the pickle that concentration of hydrochloric acid is 13%, and lacing film is A3 carbon steels, experimental temperature 45
DEG C, rotary speed 90r/min, it is as follows to obtain the product corrosion mitigating effect of the embodiment of the present invention 1 ~ 4：
Claims (10)
1. a kind of corrosion inhibiter for pickling, it is characterised in that the described corrosion inhibiter for pickling is with allylthiourea, fat
Fat alcohol APEO acrylate and the terpolymer that p styrene sulfonic acid is comonomer preparation, allylthiourea, fat
The mass ratio of fat alcohol APEO acrylate and p styrene sulfonic acid is：1:0.2~1:0.5 ~ 1.5, terpolymer
Mean molecule quantity is 300 ~ 1500.
A kind of 2. corrosion inhibiter for pickling according to claim 1, it is characterised in that described aliphatic alcohol polyethenoxy
Ether acrylate has structural formula
Wherein R is C6-18 alkyl, and n is 6 ~ 20.
3. a kind of corrosion inhibiter for pickling according to claim 1, it is characterised in that described allylthiourea, fat
The mass ratio of fat alcohol APEO acrylate and p styrene sulfonic acid is：1:0.2~0.5:0.7~1.2.
4. a kind of corrosion inhibiter for pickling according to claim 1, it is characterised in that described terpolymer is put down
Average molecular weight is 480 ~ 1500.
A kind of 5. corrosion inhibiter for pickling according to claim 1, it is characterised in that the pickling for industrial equipment
During, the addition of described corrosion inhibiter is 30 ~ 500ppm.
A kind of 6. synthetic method of the corrosion inhibiter as claimed in claim 1 for pickling, it is characterised in that its specific preparation
Step is：（1）Allylthiourea, AEO acrylate and p styrene sulfonic acid are added in reactor,
Adding the solvent of polymer monomer gross mass 30% ~ 120% makes its dissolving；（2）Rate-determining steps（1）Reaction system be warming up to 50
~ 70 DEG C, the initiator after dropwise addition is dissolved with solvent into reaction system, the addition of initiator is polymer monomer gross mass
0.1 ~ 5%, initiator time for adding control at 0.5 ~ 2 hour；（3）Temperature is improved after being added dropwise to 60 ~ 95 DEG C, reaction 2 ~
10 hours, deionized water is added to dilute.
A kind of 7. synthetic method of corrosion inhibiter for pickling according to claim 6, it is characterised in that step (1) and
Step（2）Described solvent is the one or more in methanol, ethanol, isopropanol and ethylene glycol.
A kind of 8. synthetic method of corrosion inhibiter for pickling according to claim 6, it is characterised in that step (2) institute
The initiator stated is azodiisobutyronitrile, or the mixture of benzoyl peroxide and sodium hydrogensulfite, benzoyl peroxide,
The mol ratio of sodium hydrogensulfite is 2:1.
A kind of 9. synthetic method of corrosion inhibiter for pickling according to claim 6, it is characterised in that step（1）Institute
The mass ratio of allylthiourea, AEO acrylate and the p styrene sulfonic acid stated is：1:0.2~0.5:
0.7~1.2；Step（1）Described solvent adding amount is the 30% ~ 100% of polymer monomer gross mass.
A kind of 10. synthetic method of corrosion inhibiter for pickling according to claim 6, it is characterised in that step（2）
Described temperature of reaction system is 50 ~ 60 DEG C；Step（2）The addition of described initiator for polymerized monomer gross mass 0.5 ~
3%；Step（3）Described temperature is 85 ~ 90 DEG C；Step（3）The described reaction time is 3 ~ 7 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914775A (en) * | 2010-06-29 | 2010-12-15 | 青岛大学 | Water-soluble anthranilic acid polymer carbon steel acid cleaning inhibitor and application thereof |
| CN103771596A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water |
| CN103804593A (en) * | 2012-11-13 | 2014-05-21 | 谭勇 | Synthesis technology of maleic anhydride-crylic acid-methyl acrylate copolymer |
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2016
- 2016-05-24 CN CN201610349380.9A patent/CN105780023B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914775A (en) * | 2010-06-29 | 2010-12-15 | 青岛大学 | Water-soluble anthranilic acid polymer carbon steel acid cleaning inhibitor and application thereof |
| CN103771596A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water |
| CN103804593A (en) * | 2012-11-13 | 2014-05-21 | 谭勇 | Synthesis technology of maleic anhydride-crylic acid-methyl acrylate copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 聚合物缓蚀剂的研究现状与展望;李小敏;《腐蚀与防护》;20120731;第33卷;第210-214页 * |
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Address after: 277100 Jinan Quancheng Patent and Trademark Office, Zaozhuang City, Shandong Province Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: 277000 Shandong Taihe Water Treatment Technology Co., Ltd., No. 10, Guangming East Road, Shizhong District, Zaozhuang City, Shandong Province Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |