CN107868043A - A kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and preparation method thereof - Google Patents
A kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and preparation method thereof Download PDFInfo
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- CN107868043A CN107868043A CN201711123440.6A CN201711123440A CN107868043A CN 107868043 A CN107868043 A CN 107868043A CN 201711123440 A CN201711123440 A CN 201711123440A CN 107868043 A CN107868043 A CN 107868043A
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- quinoline
- inner salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/10—Quaternary compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
- C22B3/362—Heterocyclic compounds of a single type
- C22B3/364—Quinoline
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacturing & Machinery (AREA)
- Geology (AREA)
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- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and preparation method thereof, it is used mol ratio as 1:1~3 quinoline and 1,3 dibromopropanes, 1,4 dibromobutanes, 1,5 dibromo pentanes or 1, a kind of quaternizing agent dissolving in 6 dibromo-hexanes is in organic solvent, 60 DEG C~140 DEG C and the 48~72h that flows back are warming up under the conditions of lucifuge to be prepared, product by washing, recrystallizing, dry after obtain；The quinoline quatemay ammonium inner salt type corrosion inhibiter need not compound other components and can be used as acidification corrosion inhibitor use; and the good corrosion inhibition shown; the corrosion to N80 metal sleeves can be greatly reduced to the pollution-free Low Damage of reservoir; environmental pollution is small; it is safe to use, completion fluid is protected in the permanent stability in underground and reservoir protection ability.
Description
Technical field
The present invention relates to corrosion inhibitor product technical field, more particularly to a kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and its preparation
Method.
Background technology
Acidifying is to inject acid solution to stratum by oil-water well, removes the tamper on stratum, as di-iron trioxide, vulcanization are sub-
Iron, clay etc., or the rock on dissolving stratum, reach volume increase, the well stimulation for recovering and improving stratum permeability.In order to improve acid
To change effect, many additives are added in general system, wherein corrosion inhibiter is essential that it is added on a small quantity, about 0.5~
2wt% is with regard to that can greatly reduce metal erosion；And the corrosion inhibiter of acid medium is needed in the acid solution of acidifying strata.
The corrosion inhibiter of acid medium is generally divided into two classes：Adsorbed film type corrosion inhibiter, if such as methenamine, alkylamine, fourth；
" interphase " type corrosion inhibiter, such as octyne alcohol, methylparafynol, this kind of corrosion inhibiter are to play inhibition by the formation of " interphase " to make
With.At present, this two classes acidifying is typically all compounding use with corrosion inhibiter, can not play the effect of anticipation sometimes；In addition, now
Also acidifying corrosion inhibiter is matched somebody with somebody through important intermediate reflexs such as conventional imidazoline and its derivative, aldehyde ketone amine condensation polymers, it is anti-sometimes
The performances such as high temperature, reduction inhibition speed do not reach requirement.Therefore, the new corrosion inhibiter suitable for acid system need to be studied.
The content of the invention
Metal sleeve corrosion rate is effectively reduced it is an object of the invention to provide a kind of and to the pollution-free Low Damage of reservoir
Quinoline quatemay ammonium inner salt type corrosion inhibiter.
It is a further object of the present invention to provide a kind of preparation method for preparing above-mentioned quinoline quatemay ammonium inner salt type corrosion inhibiter.
Therefore, technical solution of the present invention is as follows：
A kind of quinoline quatemay ammonium inner salt type corrosion inhibiter, the general structure of the quinoline quatemay ammonium inner salt are as follows：
Wherein, n=1~4.
A kind of preparation method of the quinoline quatemay ammonium inner salt type corrosion inhibiter with above-mentioned formula, step are as follows：It is by mol ratio
1:1~3 quinoline and quaternizing agent is dissolved in organic solvent A, and 60 DEG C~140 DEG C are warming up under the conditions of lucifuge and is flowed back
48~72h；Be subsequently cooled to room temperature, remove supernatant liquor and product is washed with organic solvent B, recrystallized, vacuum is done
It is dry, obtain white crystal.
Wherein, the quaternizing agent is 1,3- dibromopropanes, Isosorbide-5-Nitrae-dibromobutane, 1,5 dibromo pentanes or 1,6- dibromo
Hexane.
The organic solvent A is acetone, dichloromethane or dimethylbenzene.It is preferred that the dosage of the organic solvent A be quinoline with
3~10 times of quaternizing agent gross mass.
The organic solvent B is one or both of absolute ethyl alcohol, absolute methanol, absolute ether, ethyl acetate.
It is preferred that from 1,3- dibromopropanes as quaternizing agent when, the synthesis step of corresponding propyl quinoline quaternary ammonium bromide
It is rapid as follows：By mol ratio 1:1~3 quinoline and 1,3- dibromopropane are dissolved in organic solvent A, in lucifuge and 56~60 DEG C of temperature
Flowed back 48~72h under the conditions of degree, is cooled to indoor temperature, filters, and filter cake is recrystallized with organic solvent B, obtains white crystal.Its
In, organic solvent A is acetone；Organic solvent B is absolute methanol.
The structural formula of the propyl quinoline quaternary ammonium bromide of gained is prepared as shown in following formula I：
It is preferred that from Isosorbide-5-Nitrae-dibromobutane as quaternizing agent when, the synthesis side of corresponding butane group quinoline quaternary ammonium bromide
Method, step are as follows：By mol ratio 1:1~3 quinoline and Isosorbide-5-Nitrae-dibromobutane are dissolved in organic solvent A, lucifuge and 58~
Flowed back 48~72h under 60 DEG C of temperature conditionss, is cooled to indoor temperature, filters, and filter cake is recrystallized with organic solvent B, obtains white
Crystal.Wherein, organic solvent A is acetone；Organic solvent B is absolute ether.
The structural formula of the butane group quinoline quaternary ammonium bromide of gained is prepared as shown in Formula Il：
It is preferred that from 1,5 dibromo pentane as quaternizing agent when, the synthesis side of corresponding pentyl quinoline quaternary ammonium bromide
Method, step are as follows：By mol ratio 1:1~3 quinoline and 1,5 dibromo pentanes are dissolved in organic solvent A, in lucifuge and 56~60
Flowed back 48~72h under DEG C temperature conditionss, is cooled to indoor temperature, filters, and filter cake is recrystallized with organic solvent B, obtains white crystalline substance
Body.Wherein, organic solvent A is acetone；Organic solvent B is methanol.
Shown in the following formula III of structural formula for preparing the pentyl quinoline quaternary ammonium bromide of gained：
It is preferred that from 1,6- dibromo-hexanes as quaternizing agent when, the synthesis side of corresponding hexyl quinoline quaternary ammonium bromide
Method, step are as follows：By mol ratio 1:1~3 quinoline and 1,6- dibromo-hexane are dissolved in organic solvent A, lucifuge and 100~
Flowed back 48~72h under 140 DEG C of temperature conditionss, is cooled to indoor temperature, filters, and filter cake is recrystallized with organic solvent B, obtains white
Crystal.Wherein, organic solvent A is dimethylbenzene；Organic solvent B is that volume ratio is 1:1~3 ethyl acetate and absolute ethyl alcohol it is mixed
Bonding solvent.
Shown in the following formula IV of structural formula for preparing the hexyl quinoline quaternary ammonium bromide of gained：
In the building-up process of above-mentioned each alkyl quinoline quaternary ammonium bromide, the molar ratio of quinoline and quaternizing agent is preferably
1:1.5。
In use, the quinoline quatemay ammonium inner salt type corrosion inhibiter need not compound other components and can be directly added to hydrochloric acid, mud acid
Etc. in system, its dosage is 1wt.%~4wt.%.
Compared with prior art, the quinoline quatemay ammonium inner salt type corrosion inhibiter single use need not compound other components and can be used as
Acidification corrosion inhibitor uses, and the good corrosion inhibition shown, can greatly reduce the corrosion to N80 metal sleeves to reservoir without dirt
Low Damage is contaminated, environmental pollution is small, safe to use, protects completion fluid in the permanent stability in underground and reservoir protection ability.
In addition, the quinoline quatemay ammonium inner salt type corrosion inhibiter preparation method is simple and feasible, raw materials used wide material sources, suitable for industrialized production and
Popularization.
Embodiment
With reference to specific embodiment, the present invention is described further, but following embodiments absolutely not to the present invention have appoint
What is limited.
Embodiment 1
The synthesis of propyl quinoline quaternary ammonium bromide：
25mL quinoline and 45.6g 1,3- dibromopropanes are dissolved in 400mL acetone, lucifuge, 60 DEG C of return stirrings are anti-
48h is answered, is cooled to room temperature, is filtered, filter cake recrystallizing methanol 1~2 time, 23 grams of white crystal is obtained after vacuum dried, is produced
Product yield >=40%.
Embodiment 2
The synthesis of butane group quinoline quaternary ammonium bromide：
2.5mL quinoline and 5.13g Isosorbide-5-Nitrae-dibromobutane are dissolved in 30mL acetone, lucifuge, 60 DEG C of return stirrings
60h is reacted, is cooled to room temperature；Filter, filter cake is recrystallized 1~2 time with absolute ether, and white crystal is obtained after vacuum dried
3.7 grams, product yield >=57.6%.
Embodiment 3
The synthesis of pentyl quinoline quaternary ammonium bromide：
2.5mL quinoline and 5.45g 1,5 dibromo pentanes are dissolved in 40mL acetone, lucifuge, 58 DEG C of return stirrings are anti-
72h is answered, is cooled to room temperature, is filtered, filter cake absolute ethyl alcohol and re-crystallizing in ethyl acetate 1~2 time, is obtained after vacuum dried white
3.45 grams of color crystal, product yield >=47.8%.
Embodiment 4
The synthesis of hexyl quinoline quaternary ammonium bromide：
25mL quinoline and 58.5g 1,6- dibromo-hexanes are dissolved in 100mL dimethylbenzene, lucifuge, 135 DEG C of back flow reactions
60h, room temperature is cooled to, removes supernatant liquor, the dark oil thing of lower floor is sufficiently washed with ethyl acetate, then uses volume ratio
For 1:2 ethyl acetate and the mixed solvent of ethanol are recrystallized 2~3 times again, and white crystal 32g is obtained after vacuum dried, production
Product yield >=50%.
Performance test：
(2) inhibition is tested：
Respectively to added with quinoline quatemay ammonium inner salt type under 90 DEG C, 120 DEG C, 140 DEG C, 160 DEG C and 180 DEG C of temperature conditionss
The inhibition speed of Hydrochloric Acidizing Fluid system and soil acid acidizing liquid system to N80 steel after corrosion inhibiter is tested.Specific test
Method referring to《Corrosion inhibiter method for testing performance and evaluation index are used in SY-T 5405-1996 acidifyings》.Test structure see the table below 1.
Wherein, in corrosion inhibition test, Hydrochloric Acidizing Fluid system uses 20wt.% hydrochloric acid solutions；Acidizing Fluid on Mud Acid
System uses 12wt.%HCl and 3wt.%HF mixed solution.
Test condition：CO2Partial pressure 1MPa, flow velocity 1M/s, 500ppm
Table 1：
The quinoline quatemay ammonium inner salt type corrosion inhibiter of the preparation of embodiment 1~5 is can be seen that 90~180 from the test result of table 1
It is rotten using embodying fabulous anticorrosion effect in Hydrochloric Acidizing Fluid system and soil acid acidizing liquid system under DEG C temperature conditionss
Erosion speed is far below first class index as defined in evaluation criterion, has significant corrosion mitigating effect.
In addition, the quinoline quatemay ammonium inner salt type corrosion inhibiter can be applied equally in completion brine system, it is complete in salt solution
Good corrosion mitigating effect is respectively provided with well liquid system, and embodies good compatibility.The quinoline quatemay ammonium inner salt type corrosion inhibiter exists
Dosage in completion brine system is 1~2wt.%.
In addition, the quinoline quatemay ammonium inner salt type corrosion inhibiter no matter is applied in liquid system is acidified or completion brine system
In, its with the mixed process of corresponding system, corrosion inhibiter itself is non-foaming, it is seen that using the corrosion inhibiter without subsequently considering
Defoaming problem to corrosion inhibiter.
Claims (4)
1. a kind of quinoline quatemay ammonium inner salt type corrosion inhibiter, it is characterised in that the general structure of the quinoline quatemay ammonium inner salt is as follows：
Wherein, n=1~4.
2. a kind of preparation method of quinoline quatemay ammonium inner salt type corrosion inhibiter, it is characterised in that step is as follows：It is 1 by mol ratio:1~3
Quinoline and quaternizing agent be dissolved in organic solvent A, be warming up under the conditions of lucifuge 60 DEG C~140 DEG C and flow back 48~
72h；It is subsequently cooled to room temperature；If product is solidliquid mixture, product is washed, recrystallized, be dried in vacuo after
To white crystal；If product is layering liquid phase mixture, product is washed with organic solvent B after removing supernatant liquor
Wash, recrystallize, be dried in vacuo, obtain white crystal；Wherein, the quaternizing agent is 1,3- dibromopropanes, Isosorbide-5-Nitrae-dibromo fourth
Alkane, 1,5 dibromo pentanes or 1,6- dibromo-hexanes；The organic solvent A is acetone, dichloromethane or dimethylbenzene；It is described organic molten
Agent B is one or both of absolute ethyl alcohol, methanol, absolute ether, ethyl acetate.
3. quinoline quatemay ammonium inner salt type corrosion inhibiter according to claim 2, it is characterised in that the quinoline and quaternizing agent
Molar ratio be 1:1.5.
4. quinoline quatemay ammonium inner salt type corrosion inhibiter according to claim 1, it is characterised in that the dosage of the organic solvent A
3~10 times for quinoline with quaternizing agent gross mass.
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| CN201711123440.6A CN107868043A (en) | 2017-11-14 | 2017-11-14 | A kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and preparation method thereof |
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| CN201711123440.6A CN107868043A (en) | 2017-11-14 | 2017-11-14 | A kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306489A (en) * | 2018-11-14 | 2019-02-05 | 上海应用技术大学 | Functionalization quinolines liquid corrosion inhibitor, preparation method and application |
Citations (1)
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|---|---|---|---|---|
| CN106146396A (en) * | 2015-04-27 | 2016-11-23 | 中国石油化工股份有限公司 | Quinoline type derivant and corrosion inhibiting and descaling agent and application thereof and oil-field flooding pit shaft corrosion protection method of scale inhibition |
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2017
- 2017-11-14 CN CN201711123440.6A patent/CN107868043A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146396A (en) * | 2015-04-27 | 2016-11-23 | 中国石油化工股份有限公司 | Quinoline type derivant and corrosion inhibiting and descaling agent and application thereof and oil-field flooding pit shaft corrosion protection method of scale inhibition |
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| CRETU STELIANA ET AL.: "Corrosion inhibition effects of quaternary ammonium salt derivatives of pyridine and quinoline. Part I", 《REVISTADE CHIMIE》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109306489A (en) * | 2018-11-14 | 2019-02-05 | 上海应用技术大学 | Functionalization quinolines liquid corrosion inhibitor, preparation method and application |
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