CN108486575A - A kind of water solubility bi-imidazoline derivative corrosion inhibiter and its preparation method and application - Google Patents
A kind of water solubility bi-imidazoline derivative corrosion inhibiter and its preparation method and application Download PDFInfo
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- CN108486575A CN108486575A CN201810471938.XA CN201810471938A CN108486575A CN 108486575 A CN108486575 A CN 108486575A CN 201810471938 A CN201810471938 A CN 201810471938A CN 108486575 A CN108486575 A CN 108486575A
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- corrosion inhibiter
- imidazoline
- water solubility
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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Abstract
A kind of water solubility bi-imidazoline derivative corrosion inhibiter, it is characterized in that：Its general structure is：
Description
Technical field
The invention belongs to oil gas field corrosion inhibiter organic compound technical fields more particularly to a kind of water-soluble bi-imidazoline to spread out
Biologic inhibitor and its preparation method and application.
Background technology
In global resources, today of energy shortage, also it is faced in oil and gas exploitation and transmission process increasingly tighter
The etching problem of weight.Corrosion is very frequent and serious to the injury of natural gas transportation pipeline.Faced with this situation, it needs every
The pipeline of corrosion is overhauled and replaced to year, this can not only bring very huge cost, while also have the safe structure to the public
At potential threat.The presence of carbon dioxide, hydrogen sulfide in oil well or pipeline can produce in the case of moistening with carbon steel surface
Raw electrochemical reaction, makes the etching problem of metal equipment become especially prominent.
Proper inhibition and aseptic technic are taken, can not only take precautions against the generation of disaster, but also can retrieve caused by corrosion
Loss, and bring huge economic benefit for petroleum industry.There is corrosion inhibiter high efficiency, low cost, simple operation and other advantages to make
It is had outstanding performance and is used widely in petrochemical industry.From in the 1950s, the heterocycle containing N organic imidazoline and its
Derivative corrosion inhibiter is succeeded in developing in the U.S., and CO is prevented for metal equipment in oil gas field production operation2Corrosion, and multiple
There is good corrosion mitigating effect in the application of oil gas field.
Invention content
In order to overcome the shortcomings of in background technology, the purpose of the present invention is a kind of water solubility of oil gas field gathering line is double
Imidazolidine derivatives corrosion inhibiter.
It is a further object of the present invention to provide the preparation methods of the water solubility bi-imidazoline derivative corrosion inhibiter.
Third object of the present invention is to provide the ghiourea group modified imidazolines as oil gas field gathering line equipment anticorrosion
The application of agent.
In order to realize that the goal of the invention, the present invention adopt the following technical scheme that：A kind of water solubility bi-imidazoline derivative
Corrosion inhibiter, general structure are：
Wherein n is 1,2,3 ....
A kind of preparation method of water solubility bi-imidazoline derivative corrosion inhibiter, preparation process are：S1, by half Guang of carboxymethyl
Bi-imidazoline intermediate is obtained by the reaction in propylhomoserin and polyamines, and chemical equation is as follows：
Bi-imidazoline intermediate obtained in S1 and quaternizing agent are obtained by the reaction the water solubility bi-imidazoline and derived by S2
Object corrosion inhibiter, chemical equation are as follows：
In order to be further improved technical solution, polyamines of the present invention is diethylenetriamine, triethylene tetramine or four ethylene
Five amine.
In order to be further improved technical solution, the mass ratio of Carbocisteine and polyamines of the present invention is 1：2
~1：2.5.
In order to be further improved technical solution, the concrete operation step of S1 of the present invention is：By Carbocisteine
With polyamines example 1 in mass ratio：2~1：2.5 are added to the container, and under the conditions of existing for azeotropic agent dimethylbenzene, take and gradually heat up
Method, first carry out amide reaction, then carry out annulation to get to imidazoline intermediate.
In order to be further improved technical solution, the quaternizing agent in step S2 of the present invention is benzyl chloride, will be in S1
Benzyl chloride is slowly added dropwise in the reaction solution of bi-imidazoline intermediate and benzyl chloride obtained, is stirred to react 2~4h, obtains water solubility
Bi-imidazoline derivative corrosion inhibiter.
In order to be further improved technical solution, the process gradually to heat up in step S1 of the present invention is being stirred continuously
Under the conditions of, it is warming up to 210 DEG C~220 DEG C, temperature reaction 4h is to get to bi-imidazoline intermediate；Imidazoline in the step S2
Intermediate cooling temperature is 60 DEG C, and the quaternization reaction time is 2~4h.
In order to be further improved technical solution, Carbocisteine of the present invention：Polyamines：The mass ratio of benzyl chloride
It is 1：2：2.
A kind of water solubility bi-imidazoline derivative corrosion inhibiter, itself and thiocarbamide, KI or surfactant is compounded, later
As the application of oil gas field gathering line equipment corrosion inhibiter, addition is 100~500ppm.
By adopting the above-described technical solution, the present invention has the advantages that：The present invention prepares a kind of water solubility
Bi-imidazoline derivative achievees the purpose that the gathering line corrosion of oil resistant gas field, which is to make Carbocisteine and polyamines
(such as：Diethylenetriamine, triethylene tetramine, tetraethylenepentamine etc.) bi-imidazoline intermediate is obtained by the reaction, then with quaternized examination
Agent is (such as：Benzyl chloride) bi-imidazoline quaternary ammonium salt is obtained by the reaction, i.e., water-soluble bi-imidazoline derivative.After water dilutes with thiocarbamide,
KI, surfactant compound use, and actual use amount is 0.2~2.0%, and corrosion inhibiter is used for oil gas field gathering line, and existing
Oil gas field corrosion inhibiter compare, this kind water solubility bi-imidazoline derivative introduces cysteine, can be generated with metal surface more
Center is adsorbed, and is had better mobility, is enhanced corrosion inhibiter corrosion mitigating effect, and the N atoms in imidazoline are by quaternized, formation
One cation macromolecular has very strong covering effect, enhances film forming.This kind water solubility bi-imidazoline derivative belongs to
Environmentally friendly green corrosion inhibitor, and through overtesting, corrosion mitigating effect is good, and it is slow to efficiently solve traditional oil-soluble inhibitor
Lose the bad problem of effect.
In corrosion inhibiter provided by the invention, bi-imidazoline derivative is mainly by the five-ring heterocycles of two double bonds containing C=N, partly
Cystine and quaternary ammonium N+Composition.When inhibitor molecular is adsorbed with metal interface, the imidazoline ring Preferential adsorption on molecule,
One layer of hydrophobic membrane is formed, H in solution is hindered2O, H+, HCO3 -, HS-Equal corrosive mediums are migrated to metal surface.The half Guang ammonia introduced
Acid can be adsorbed on iron surface and inhibit corrosion, and the absorption of amino acid and metallic iron due to containing hetero atom in molecule
Along with the generation of chemical reaction, the complex of formation is more stable.By quaternized imidazolidine derivatives be easy for by
Metal surface active site of the surface with negative electrical charge is adsorbed, and has very big inhibiting effect to the electric discharge of oxonium ion, to inhibit cloudy
Pole is reacted, and enhances water solubility.When in use, the bi-imidazoline derivative and thiocarbamide, KI, surfactant compound, make tool
There is better mobility, multicenter chemisorption is generated when being contacted with metal, to improve corrosion mitigating effect.
Specific implementation mode
By the following examples can the detailed explanation present invention, the open purpose of the present invention is intended to protect model of the present invention
Enclose all interior technological improvements.
Embodiment one
The present embodiment provides a kind of preparation methods of water-soluble bi-imidazoline derivative corrosion inhibiter.The double imidazoles of this kind of water solubility
Quinoline derivant is bi-imidazoline intermediate to be obtained by the reaction in Carbocisteine and polyamines, then be obtained by the reaction with benzyl chloride.
The specific synthesis step for present embodiments providing above-mentioned modified imidazoline, is as follows：
By Carbocisteine and diethylenetriamine according toMolar ratio puts into reactor, and azeotropic agent dimethylbenzene exists
In the case of be gradually warming up to 220 DEG C under constant stirring, the temperature reaction time is 4 hours, obtains bi-imidazoline intermediate；It is cold
But to after 60 DEG C according to molar ratioBenzyl chloride is slowly added dropwise, while reacting 3h under agitation, double imidazoles are obtained after cooling
Quinoline derivant a, through testing the favorable solubility in water, ethyl alcohol, isopropanol.
Embodiment two
The present embodiment provides a kind of preparation methods of water-soluble bi-imidazoline derivative corrosion inhibiter.The double imidazoles of this kind of water solubility
Quinoline derivant is bi-imidazoline intermediate to be obtained by the reaction in Carbocisteine and polyamines, then be obtained by the reaction with benzyl chloride.
By Carbocisteine and triethylene tetramine according toMolar ratio puts into reactor, and azeotropic agent dimethylbenzene exists
In the case of be gradually warming up to 210 DEG C under constant stirring, the temperature reaction time is 4 hours, obtains bi-imidazoline intermediate；It is cold
But to after 60 DEG C according to molar ratioBenzyl chloride is slowly added dropwise, while reacting 3h under agitation, double imidazoles are obtained after cooling
Quinoline derivant b, through testing the favorable solubility in water, ethyl alcohol, isopropanol.
Embodiment three
The present embodiment provides a kind of preparation methods of water-soluble bi-imidazoline derivative corrosion inhibiter.The double imidazoles of this kind of water solubility
Quinoline derivant is bi-imidazoline intermediate to be obtained by the reaction in Carbocisteine and polyamines, then be obtained by the reaction with benzyl chloride.
By Carbocisteine and tetraethylenepentamine according toMolar ratio puts into reactor, and azeotropic agent dimethylbenzene exists
In the case of be gradually warming up to 220 DEG C under constant stirring, the temperature reaction time is 4 hours, obtains bi-imidazoline intermediate；It is cold
But to after 60 DEG C according to molar ratioBenzyl chloride is slowly added dropwise, while reacting 3h under agitation, double imidazoles are obtained after cooling
Quinoline derivant c, through testing the favorable solubility in water, ethyl alcohol, isopropanol.
By water-soluble bi-imidazoline derivative a, b, c difference of gained in above-described embodiment one, embodiment two, embodiment three
It is interpreted into 20% solution with isopropanol floride, increases the mobility of corrosion inhibiter by diluting, reduces the condensation point of corrosion inhibiter, make it can
To be used when temperature is relatively low.
By by the dilution and thiocarbamide, potassium iodide (KI), dodecane of a, b, c water solubility bi-imidazoline derivative corrosion inhibiter
Base sodium sulphate (SDS) is compounded, and optimum compound proportion example see the table below 1 with inhibition efficiency：
Table 1 is the rate of corrosion and inhibition rate of the dilution of the water-soluble bi-imidazoline derivative corrosion inhibiter of embodiment one~tri-
In conclusion bi-imidazoline derivative is a kind of excellent corrosion inhibiter, it can be with thiocarbamide, potassium iodide (KI), dodecyl
Sodium sulphate (SDS) etc. is used in compounding.It prepares, is easy to implement, and inhibition efficiency is high.The present invention can be used for oil gas field collector and delivery pipe
Road anti-corrosion.
The above is only presently preferred embodiments of the present invention, is appointed to the limitation of other forms of implementation of the invention
What those skilled in the art is slightly made an amendment possibly also with above-mentioned technology contents to imitate case study on implementation, as long as cannot take off
Content from technical scheme of the present invention makes any simple modification to above example according to the technical essence of the invention,
Equivalent variations etc. still belong to the protection domain of technical solution of the present invention.
Part not in the detailed description of the invention is the prior art.
Claims (9)
1. a kind of water solubility bi-imidazoline derivative corrosion inhibiter, it is characterized in that：Its general structure is：
Wherein n is 1,2,3 ....
2. a kind of preparation method of water-soluble bi-imidazoline derivative corrosion inhibiter as described in claim 1, it is characterized in that：It is made
It is for step：Bi-imidazoline intermediate is obtained by the reaction in Carbocisteine and polyamines by S1, and chemical equation is as follows：
Bi-imidazoline intermediate obtained in S1 is obtained by the reaction the water solubility bi-imidazoline derivative with quaternizing agent and delayed by S2
Agent is lost, chemical equation is as follows：
3. the preparation method of water solubility bi-imidazoline derivative corrosion inhibiter as claimed in claim 2, it is characterized in that：The polyamines
For diethylenetriamine, triethylene tetramine or tetraethylenepentamine.
4. the preparation method of water solubility bi-imidazoline derivative corrosion inhibiter as claimed in claim 2, it is characterized in that：The carboxylic first
The mass ratio of base cysteine and polyamines is 1：2~1：2.5.
5. the preparation method of water solubility bi-imidazoline derivative corrosion inhibiter as claimed in claim 2, it is characterized in that：The S1's
Concrete operation step is：By Carbocisteine and polyamines example 1 in mass ratio：2~1：2.5 are added to the container, in azeotropic agent
Under the conditions of dimethylbenzene is existing, the method gradually to heat up is taken, first carries out amide reaction, then carries out annulation to get to miaow
Oxazoline intermediate.
6. the preparation method of water solubility bi-imidazoline derivative corrosion inhibiter as claimed in claim 2, it is characterized in that：The step
Quaternizing agent in S2 is benzyl chloride, will be slowly added dropwise in the reaction solution of bi-imidazoline intermediate obtained and benzyl chloride in S1
Benzyl chloride is stirred to react 2~4h, obtains water-soluble bi-imidazoline derivative corrosion inhibiter.
7. the preparation method of water solubility bi-imidazoline derivative corrosion inhibiter as claimed in claim 2, it is characterized in that：The step
The process gradually to heat up in S1 is to be warming up to 210 DEG C~220 DEG C under conditions of being stirred continuously, and temperature reaction 4h is to get to double
Imidazoline intermediate；Imidazoline intermediate cooling temperature is 60 DEG C in the step S2, and the quaternization reaction time is 2~4h.
8. the preparation method of water solubility bi-imidazoline derivative corrosion inhibiter as claimed in claim 2, it is characterized in that：The carboxylic first
Base cysteine：Polyamines：The mass ratio of benzyl chloride is 1：2：2.
9. a kind of water-soluble bi-imidazoline derivative corrosion inhibiter as described in claim 1, it is characterized in that：By itself and thiocarbamide, KI
Or surfactant is compounded, the application as oil gas field gathering line equipment corrosion inhibiter later.
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Cited By (3)
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|---|---|---|---|---|
| CN110760853A (en) * | 2019-11-29 | 2020-02-07 | 陕西科技大学 | Water-soluble gemini polyether imidazoline corrosion inhibitor and preparation method thereof |
| CN110863204A (en) * | 2019-11-29 | 2020-03-06 | 陕西科技大学 | Water-soluble bis-imidazoline corrosion inhibitor and preparation method thereof |
| CN111020596A (en) * | 2019-12-23 | 2020-04-17 | 西安三维科技发展有限责任公司 | Water-soluble corrosion inhibitor for gas well and preparation method thereof |
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| CN110760853A (en) * | 2019-11-29 | 2020-02-07 | 陕西科技大学 | Water-soluble gemini polyether imidazoline corrosion inhibitor and preparation method thereof |
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| CN111020596A (en) * | 2019-12-23 | 2020-04-17 | 西安三维科技发展有限责任公司 | Water-soluble corrosion inhibitor for gas well and preparation method thereof |
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Effective date of registration: 20210114 Address after: 471000 No. 111, Huanghe Road, Huayang Industrial Cluster, Baihe Town, Mengjin County, Luoyang City, Henan Province Patentee after: Luoyang hualite building materials Co.,Ltd. Address before: 471000 No. 90, Wangcheng Avenue, Luolong District, Luoyang City, Henan Province Patentee before: LUOYANG INSTITUTE OF SCIENCE AND TECHNOLOGY |
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