CN107541199A - One kind has water soluble polymer corrosion inhibiter of viscosity reduction effect and preparation method thereof concurrently - Google Patents
One kind has water soluble polymer corrosion inhibiter of viscosity reduction effect and preparation method thereof concurrently Download PDFInfo
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- CN107541199A CN107541199A CN201710905293.1A CN201710905293A CN107541199A CN 107541199 A CN107541199 A CN 107541199A CN 201710905293 A CN201710905293 A CN 201710905293A CN 107541199 A CN107541199 A CN 107541199A
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Abstract
The present invention relates to the water soluble polymer corrosion inhibiter, imidazoline polyacrylic acid and preparation method thereof that one kind has viscosity reduction effect concurrently.Its preparation method is that molecular weight ranges synthesize imidazoline polyacrylic acid with organic polyamine for 3000~5000 polyacrylic acid through amidatioon and cyclization.The polymer is water miscible, there is viscosity reduction effect, it may have good anticorrosion ability.Its preparation method concise in technology, it is simple to operate, it is adapted to industrialized production.Upgrading of the popularization and application to macromolecule oil dope as corrosion inhibiter and thinner has facilitation, has good social effect and economic implications.
Description
Technical field
Polymeric corrosion inhibitor of viscosity reduction effect and preparation method thereof is had concurrently the present invention relates to one kind, specifically by polyacrylic acid
With organic polyamine be dehydrated imidazoline polyacrylic acid preparation method, and the imidazoline polyacrylic acid as having concurrently
The use of the water soluble polymer oil dope of inhibition and viscosity reduction effect.
Background technology
Crude oil is strategic resource, and the economic and social safety national to one has very important meaning.With
The rapid development of World Economics, the demand of the energy are also growing day by day.During oil extraction, one side corrosion phenomenon is universal
In the presence of and it is more serious, on the other hand because viscosity of crude is big, exploitation is difficult, not only can bring massive losses in economic aspect,
And the catastrophic effects such as safety issue and environmental pollution can be triggered.
Crude oil production, conveying and refining are necessarily carried out around inhibition, viscosity reduction, pour point depression modification or modifying process.
Addition corrosion inhibiter, thinner have the advantages that technique is simple, and expense is relatively low, so as to as the corrosion of solution crude oil and drop
The conventional method of viscous problem.
High molecular polymer with side chain can change the crystal habit of wax, make wax be not easy to form space networks at normal temperatures
Shape structure, there is viscosity reduction, improves the effect of low temperature flow, wherein polyacrylate thinner is with its low cost, easily preparation, drop
The features such as viscous significant effect and as the focus studied both at home and abroad.Kuzmic AE in 2008 etc. are using carrying single polar group
The polymer of acrylate long-chain ester crude oil fluidity is improved as thinner.Mutually bright brightness in 2010 etc. is with acrylic acid ten
Octaester, styrene and maleic anhydride are that, by the modified thinner of octadecyl alcolol, the viscosity break ratio to crude oil is after monomer polymerize
40% or so.
Polymer has the advantages that efficient, lasting, environmentally friendly as corrosion inhibiter for low molecule corrosion inhibiter.Wherein
Polyacrylic acid (PAA) can prevent iron in the acid medium such as hydrochloric acid or sulfuric acid because side chain carboxyl group and metal have chelation
Corrosion, and due to polyacrylic acid good water solubility, nontoxic, preparation method is simple, is relatively early gathering as metal inhibitor application
Compound.Wang Lirong have studied the polyacrylic acid of different molecular weight in corrosive medium to the inhibition efficiency of Q235 steel, the results showed that
Polyacrylic acid corrosion inhibition rate in the case where addition is few is relatively low.
Existing method, thinner and corrosion inhibiter add respectively as two oil dopes.Exploitation have concurrently viscosity reduction,
The multifunctional crude oil such as inhibition, pour point depression additive replaces the thinner of existing simple function, or corrosion inhibiter, simplifies crude oil addition
The preparation of agent and adding technology, running cost is reduced, be the developing direction of oil dope, turn into following Crude Additive development
Direction.
For inventor in patent CN201610522907.3, CN201610567250.2 reports the polymerization of acrylic acid imidazoline
Thing, acrylic acid imidazoline are two kinds of polymeric corrosion inhibitors for having viscosity reduction effect concurrently with acrylate binary polymer, but both
All it is oil-soluble additive, it is not handy in aqueous solution systems.Popularization and application are to macromolecule as corrosion inhibiter and thinner
The upgrading of oil dope has facilitation.
The content of the invention
1. it is an object of the invention to provide the water soluble polymer corrosion inhibiter that one kind has viscosity reduction effect concurrently, the family macromolecule
Corrosion inhibiter is the polyacrylic acid of the imidazoline formed by polyacrylic acid and organic polyamine class compound condensation.
The molecular weight ranges of the polyacrylic acid are 3000~5000, and organic polyamine class compound is diethylenetriamine, three
One kind in ethene tetramine, TEPA and AEEA.
2. the water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently of the present invention can be used for the viscosity reduction of oil product, oil field water with delaying
Erosion.
3. the present invention also provide it is a kind of such have concurrently viscosity reduction effect water soluble polymer corrosion inhibiter preparation method, including
Following steps：
Step (1)：The raw material polyacrylic acid aqueous solution and organic polyamine carry out dehydration of amide reaction life in the presence of azeotropic agent
Into polyacrylic acid amide product；
Step (2)：The polyacrylic acid amide product of step (1) generation continues to carry out cyclodehydration in the presence of azeotropic agent
Reaction obtains imidazoline polyacrylic acid；
Step (3)：Water, solvent and the unreacted raw material of elimination reaction generation.
Step (1) is preferably carried out with step (2) reaction in same reactor, may be carried out simultaneously, can also step (2)
Carried out after step (1) reaction.
In above-mentioned preparation process, the mass ratio of raw material polyacrylic acid and organic polyamine is 5 in the step (1):1~1:
1；Preferably, the mass ratio of raw material polyacrylic acid and organic polyamine is 4 in the step (1):1~2:1.
In above-mentioned preparation process, step (1) the dehydration of amide reaction temperature is 100 DEG C~150 DEG C, and the reaction time is
0.5~3 hour；Cyclization in the step (2), reaction temperature are 120 DEG C~230 DEG C, and the reaction time is 3~8 hours.
Preferably, step (1) the dehydration of amide reaction temperature is 110 DEG C~130 DEG C, and the reaction time is 1.0~1.5 small
When；Cyclisation dehydration temperature is 150 DEG C~190 DEG C in the step (2), and the reaction time is 3~5 hours.
Solvent and azeotropic agent can be added in the step (1), (2), take the water that generates in reaction out of, promotion react into
OK, azeotropic agent is dimethylbenzene, toluene and benzene.
Preferably, the step (1), (2) azeotropic agent are dimethylbenzene.
Beneficial effect：The present invention provides a kind of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently and preparation method thereof.
The additive can be used for oil product, the viscosity reduction of oil field water and inhibition.The present invention has concise in technology, and easily realizes industrial metaplasia
The characteristics of production.Popularization and application can promote the upgrading of macromolecule oil dope corrosion inhibiter and thinner.
Brief description of the drawings
Fig. 1 is the infrared spectrum spectrogram of polyacrylic acid；
Fig. 2 is the infrared spectrum spectrogram of imidazoline polyacrylic acid.
Specific implementation method
It is illustrative to the application and further understand below in conjunction with specific embodiment, but embodiment is only used as example
Son provides, and is not intended as whole technical schemes of the present invention, is not limited overall technical solution.It is all have it is identical or
Similar technique feature, simple change or replacement, belong to the scope of the present invention.
Embodiment 1
Add in the 250mL four-hole boiling flasks equipped with thermometer, reflux condensing tube, mechanical agitator and logical nitrogen protection tracheae
Enter the polyacrylic acid aqueous solution (34.4g) that content is 30%, dimethylbenzene (100.0mL), diethylenetriamine (10.32g), acid amide matter
Amount is than being 1:1,120 DEG C are heated to, is reacted 1 hour, then 190 DEG C are warming up to, add fraction water device water-dividing to react 4 hours, divide water
3.5mL, after desolventizing polyacrylic acid imidazoline.
Prepare two parts of 500mL 1M H2SO4Etchant solution, polyacrylic acid imidazoline (100.0mg) is dissolved in a copy of it corruption
Lose in solution, at 30 DEG C, under the conditions of rotating speed is 100r/min, the N80 metals of two groups of 50 × 25 × 2mm specifications after pre-treatment
Steel disc rotary hanging plate 6 hours, survey two groups of steel discs and front and rear quality is soaked in etchant solution.
According to formulaIt is 71.33% to calculate corrosion inhibition rate, wherein m0
For the average original quality of steel disc being put into blank etchant solution, m0' for corrosion after steel disc average quality；m1For be put into added with
The average original quality of steel disc in polyacrylic acid imidazoline etchant solution, m1Steel disc average quality after ' corrosion.
Claim one glass of crude oil (105.31g), it is 1585mPas to measure viscosity at 50 DEG C with rotary viscosity, by polyacrylic acid miaow
Oxazoline (0.10g) is added in crude oil, is stirred, then viscosimetric is 282mPas at 70 DEG C.Calculating viscosity break ratio is
82.21%.
Embodiment 2
Take the polyacrylic acid aqueous solution 103.17g and diethylenetriamine 10.32g (about 0.1mol) that content is 30%, acid amide
Mass ratio is 3:1, add in the four-hole boiling flask that the 250mL equipped with thermometer, reflux condensing tube, mechanical agitator is dried, open
Stirring and heater, add 100.0mL dimethylbenzene and make solvent and azeotropic agent, isothermal reaction is worked as in water knockout drum and delayed for 1.5 hours
During slow water outlet, then be warming up to 190 DEG C of isothermal reactions, treat in water knockout drum that water reaches constant and no longer increase, release abjection water and
Stop reaction after solvent, pour out while hot, drying obtains polyacrylic acid imidazoline corrosion inhibiter.
Prepare two parts of 500mL 1M H2SO4Etchant solution, polyacrylic acid imidazoline (100.0mg) is dissolved in a copy of it corruption
Lose in solution.At 30 DEG C, under the conditions of rotating speed is 100r/min, the N80 metals of two groups of 50 × 25 × 2mm specifications after pre-treatment
Steel disc rotary hanging plate 6 hours, survey two groups of steel discs and front and rear quality is soaked in etchant solution.
According to formulaCorrosion inhibition rate is calculated as 80.65%.Wherein m0
For the average original quality of steel disc being put into blank etchant solution, m0' for corrosion after steel disc average quality；m1For be put into added with
The average original quality of steel disc in polyacrylic acid imidazoline etchant solution, m1Steel disc average quality after ' corrosion.
Claim one glass of crude oil (108.01g), it is 1583mPas to measure viscosity at 70 DEG C with rotary viscosity, by polyacrylic acid miaow
Oxazoline (0.11g) is added in crude oil, is stirred, then viscosimetric is 289mPas at 70 DEG C.Calculating viscosity break ratio is
81.70%.
Embodiment 3
Prepare two parts of 500mL 1M H2SO4Etchant solution, polyacrylic acid (100.0mg) is dissolved in a copy of it etchant solution
In, at 30 DEG C, under the conditions of rotating speed is 100r/min, the N80 metal steel disc rotating suspensions of two groups of 50 × 25 × 2mm specifications after polishing
Piece 6 hours, survey two groups of steel discs and front and rear quality is soaked in etchant solution.
According to formulaCorrosion inhibition rate is calculated as 49.67%.Wherein m0
For the average original quality of steel disc being put into blank etchant solution, m0' for corrosion after steel disc average quality；m1For be put into added with
The average original quality of steel disc in polyacrylic acid imidazoline etchant solution, m1Steel disc average quality after ' corrosion.
Claim one glass of crude oil (105.41g), it is 1580mPas to measure viscosity at 70 DEG C with rotary viscosity, by polyacrylic acid miaow
Oxazoline (0.13g) is added in crude oil, is stirred, then viscosimetric is 1221mPas at 70 DEG C.Calculate viscosity break ratio
22.72%.
Claims (9)
1. one kind have concurrently viscosity reduction effect water soluble polymer corrosion inhibiter, such polymeric corrosion inhibitor be by polyacrylic acid with it is organic
The polyacrylic acid for the imidazoline that polyamine compounds condensation forms.
2. one kind according to claim 1 has the water soluble polymer corrosion inhibiter of viscosity reduction effect concurrently, it is characterized in that：It is described poly-
The molecular weight ranges of acrylic acid are 3000~5000, and the organic polyamine class compound is diethylenetriamine, triethylene tetramine, four
One kind in the amine of ethene five and AEEA.
3. one kind according to claim 1 has the water soluble polymer corrosion inhibiter of viscosity reduction effect, its preparation method feature concurrently
It is to include following preparation process：
Step (1)：It is poly- to carry out dehydration of amide reaction generation in the presence of azeotropic agent for the raw material polyacrylic acid aqueous solution and organic polyamine
Acrylic acid amide product；
Step (2)：The polyacrylic acid amide product of step (1) generation continues to carry out cyclodehydration reaction in the presence of azeotropic agent
Obtain imidazoline polyacrylic acid；
Step (3)：Water, solvent and the unreacted raw material of elimination reaction generation.
4. a kind of preparation method of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently according to claim 3, it is special
Sign is：The mass ratio of raw material polyacrylic acid and organic polyamine is 5 in the step (1):1~1:1.
5. a kind of preparation method of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently according to claim 4, it is special
Sign is：The mass ratio of step (1) polyacrylic acid and organic polyamine is 4:1~2:1.
6. a kind of preparation method of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently according to claim 3, it is special
Sign is：Step (1) the dehydration of amide reaction temperature is 100 DEG C~150 DEG C, and the reaction time is 0.5~3 hour；The step
(2) cyclization in, reaction temperature are 120 DEG C~230 DEG C, and the reaction time is 3~8 hours.
7. a kind of preparation method of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently according to claim 6, it is special
Sign is：110 DEG C~130 DEG C of step (1) the dehydration of amide reaction temperature, reaction time are 1~1.5 hour；The step (2)
Middle cyclisation dehydration temperature is 150 DEG C~190 DEG C, and the reaction time is 3~5 hours.
8. a kind of preparation method of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently according to claim 3, it is special
Sign is：The step (1), the azeotropic agent of (2) are one kind in dimethylbenzene, toluene and benzene, or several mixtures.
9. a kind of preparation method of water soluble polymer corrosion inhibiter for having viscosity reduction effect concurrently according to claim 8, it is special
Sign is：The step (1), the azeotropic agent of (2) are dimethylbenzene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527550A (en) * | 2021-05-24 | 2021-10-22 | 中国石油化工集团有限公司 | Plugging film-forming polyamine for drilling fluid, preparation method of plugging film-forming polyamine and drilling fluid |
| CN115613036A (en) * | 2022-10-11 | 2023-01-17 | 常州大学 | Corrosion inhibitor with flocculation function and preparation method thereof |
| CN115746183A (en) * | 2022-11-23 | 2023-03-07 | 广州天润新材料科技有限公司 | Amide polymer and preparation method and application thereof |
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| CN103469211A (en) * | 2013-08-19 | 2013-12-25 | 四川仁智石化科技有限责任公司 | Polymeric imidazoline corrosion inhibitor and preparation method thereof |
| CN104370819A (en) * | 2014-10-22 | 2015-02-25 | 金浦新材料股份有限公司 | Preparation method and application of water-soluble imidazoline amide corrosion inhibitor |
| CN106008789A (en) * | 2016-07-05 | 2016-10-12 | 常州大学 | Preparation method of high-molecule viscosity reducer with corrosion inhibition effect |
| CN106188362A (en) * | 2016-07-18 | 2016-12-07 | 常州大学 | One class has inhibition polymer with viscosity reduction effect and preparation method thereof concurrently |
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2017
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Patent Citations (4)
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| CN103469211A (en) * | 2013-08-19 | 2013-12-25 | 四川仁智石化科技有限责任公司 | Polymeric imidazoline corrosion inhibitor and preparation method thereof |
| CN104370819A (en) * | 2014-10-22 | 2015-02-25 | 金浦新材料股份有限公司 | Preparation method and application of water-soluble imidazoline amide corrosion inhibitor |
| CN106008789A (en) * | 2016-07-05 | 2016-10-12 | 常州大学 | Preparation method of high-molecule viscosity reducer with corrosion inhibition effect |
| CN106188362A (en) * | 2016-07-18 | 2016-12-07 | 常州大学 | One class has inhibition polymer with viscosity reduction effect and preparation method thereof concurrently |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527550A (en) * | 2021-05-24 | 2021-10-22 | 中国石油化工集团有限公司 | Plugging film-forming polyamine for drilling fluid, preparation method of plugging film-forming polyamine and drilling fluid |
| CN115613036A (en) * | 2022-10-11 | 2023-01-17 | 常州大学 | Corrosion inhibitor with flocculation function and preparation method thereof |
| CN115613036B (en) * | 2022-10-11 | 2024-05-03 | 常州大学 | Corrosion inhibitor with flocculation effect and preparation method thereof |
| CN115746183A (en) * | 2022-11-23 | 2023-03-07 | 广州天润新材料科技有限公司 | Amide polymer and preparation method and application thereof |
| CN115746183B (en) * | 2022-11-23 | 2023-09-29 | 广州天润新材料科技有限公司 | Amide polymer and preparation method and application thereof |
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Application publication date: 20180105 |