CN114921790A - CO 2 Corrosion inhibitor and application thereof - Google Patents
CO 2 Corrosion inhibitor and application thereof Download PDFInfo
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- CN114921790A CN114921790A CN202210612533.XA CN202210612533A CN114921790A CN 114921790 A CN114921790 A CN 114921790A CN 202210612533 A CN202210612533 A CN 202210612533A CN 114921790 A CN114921790 A CN 114921790A
- Authority
- CN
- China
- Prior art keywords
- parts
- corrosion inhibitor
- polyquinoline
- quaternary ammonium
- ammonium salt
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- 238000005260 corrosion Methods 0.000 title claims abstract description 175
- 230000007797 corrosion Effects 0.000 title claims abstract description 175
- 239000003112 inhibitor Substances 0.000 title claims abstract description 117
- -1 imidazoline quaternary ammonium salt Chemical class 0.000 claims abstract description 97
- 229920000292 Polyquinoline Chemical class 0.000 claims abstract description 92
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- 239000002904 solvent Chemical class 0.000 claims abstract description 19
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 38
- 239000002455 scale inhibitor Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 125000001153 fluoro group Chemical group F* 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 11
- 239000003208 petroleum Substances 0.000 abstract description 10
- 230000036961 partial effect Effects 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 230000009919 sequestration Effects 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 238000012360 testing method Methods 0.000 description 25
- 239000000126 substance Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002462 imidazolines Chemical class 0.000 description 3
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
- C23F15/00—Other methods of preventing corrosion or incrustation
- C23F15/005—Inhibiting incrustation
-
- 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
- Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
- Y02P90/70—Combining sequestration of CO2 and exploitation of hydrocarbons by injecting CO2 or carbonated water in oil wells
Landscapes
- 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)
Abstract
The invention provides a CO 2 Corrosion inhibitors and their use. The CO is 2 The corrosion inhibitor comprises: a hydrocarbyl-substituted imidazoline quaternary ammonium salt, polyquinoline and a solvent; the hydrocarbyl-substituted imidazoline quaternary ammonium salt has a cation with a structure shown in a formula (I); the anion of the hydrocarbyl-substituted imidazoline quaternary ammonium salt is selected from SO 4 2‑ Or Cl ‑ (ii) a The polymerization degree of the polyquinoline is 10-80. The hydrocarbyl-substituted imidazoline quaternary ammonium salt with a specific structure and the polyquinoline with a specific polymerization degree are used simultaneously, so that the synergistic effect of the hydrocarbyl-substituted imidazoline quaternary ammonium salt and the polyquinoline can be exerted, the stability of a corrosion inhibitor film is favorably improved, the corrosion inhibition effect of the corrosion inhibitor is improved, and the petroleum pipeline is favorably protected from being corroded. The method is applied to high temperature (60-180 ℃) and high CO 2 Content (CO) 2 Partial pressure of 1-5 MPa) can achieve excellent corrosion inhibition performance under the working condition, and further the service life of oilfield equipment can be remarkably prolonged. Is particularly suitable for the project of carbon dioxide complement, utilization and sequestration (CCUS-EOR).
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, in particular to CO 2 A corrosion inhibitor and application thereof.
Background
CO 2 Is common corrosive accompanying gas, CO, in the process of oil and gas exploitation 2 The application of the oil displacement technology can lead to CO in the oil exploitation process 2 Content sharply increased, CO 2 Dissolved in water to produce carbonic acid, causing electrochemical corrosion. Thus, oil casings and surface pipelines are exposed to high levels of CO during oil and gas production, particularly in the carbon dioxide sequestration, utilization and sequestration (CCUS-EOR) project 2 The test of the water-containing strong corrosive environment.
The corrosion inhibitor is added to inhibit CO in oil and gas fields at present 2 One of the important routes for corrosion. Common CO 2 The corrosion inhibitor mainly takes imidazoline and derivatives thereof as main materials, but the highest application temperature of the imidazoline is 60 ℃, and when the temperature is higher than 60 ℃, the corrosion inhibition performance of the imidazoline and the derivatives thereof is sharply reduced. In addition, the oil well is in a severe corrosive environment, the environmental temperature is usually higher than 100 ℃, and the working conditions of high salinity, high flow rate and the like of EOR engineering are met. To solve the problem of poor tolerance of imidazoline compoundsTemperature, researchers often employ quinoline as a corrosion inhibitor. In order to improve the temperature resistance of quinoline, the high-polymerization quinoline polymerized at the temperature of more than 130 ℃ can enhance the temperature resistance of quinoline, but the solubility and stability of the high-polymerization polyquinoline are poor, so that the inhibition of CO in oil fields is limited 2 Application in the field of corrosion.
Therefore, in view of the above problems, there is a need to develop and research a novel CO 2 Corrosion inhibitors to inhibit high temperature and high CO 2 Content of CO 2 The corrosion to the petroleum pipeline is of great significance for protecting the petroleum pipeline from being corroded.
Disclosure of Invention
The invention mainly aims at providing CO 2 Corrosion inhibitor and its application for solving the problem of CO existing in the prior art 2 The corrosion inhibitor is used at high temperature (60-180 ℃) and high CO 2 Content (CO) 2 Partial pressure of 1-5 MPa) under the working condition.
In order to achieve the above object, one aspect of the present invention provides a CO 2 Corrosion inhibitor of the CO 2 The corrosion inhibitor comprises: a hydrocarbyl-substituted imidazoline quaternary ammonium salt, polyquinoline and a solvent; the hydrocarbyl-substituted imidazoline quaternary ammonium salt has a cation with a structure shown in a formula (I):
wherein R is 1 Is selected from C 10 ～C 18 Alkyl of (C) 10 ～C 18 Alkenyl of (a), fluoro-substituted C 10 ～C 18 Alkyl of (2), or fluorine substituted C 10 ～C 18 Alkenyl of R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen atom, fluorine substituted or unsubstituted C 1 ～C 5 Alkyl, fluoro substituted or unsubstituted C 2 ～C 5 And R is alkenyl of 2 、R 3 、R 4 And R 5 Contains at least one fluorine atom; the anion of the hydrocarbyl-substituted imidazoline quaternary ammonium salt is selected from SO 4 2- Or Cl - (ii) a The polymerization degree of the polyquinoline is 10-80.
Further, by weight, CO 2 The corrosion inhibitor comprises 15-20 parts of alkyl substituted imidazoline quaternary ammonium salt, 10-15 parts of polyquinoline and 30-60 parts of solvent.
Further, when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 4, the polymerization degree of the polyquinoline is 10-20; when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 3, the polymerization degree of the polyquinoline is 20-40; when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 2, the polymerization degree of the polyquinoline is 40-60; when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 1, the polymerization degree of the polyquinoline is 60 to 80.
Furthermore, the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline is (15-20) to (10-15).
Further, CO 2 The corrosion inhibitor also comprises a surfactant; by weight, CO 2 The corrosion inhibitor comprises 8-12 parts of surfactant; preferably, the surfactant is selected from perfluoroalkyl sulfonates, more preferably n-CF 3 (CF 2 ) 8 SO 3 Na and/or n-CF 3 (CF 2 ) 10 SO 3 Na。
Further, CO 2 The corrosion inhibitor also comprises a scale inhibitor; by weight, CO 2 The corrosion inhibitor comprises 5-10 parts of scale inhibitor.
Further, the scale inhibitor is a mixture formed by one or more of 2-acrylamide-2-methylpropanesulfonic acid, sodium dodecyl sulfate and polyepoxysuccinic acid; preferably, the scale inhibitor comprises, by weight, 25-35 parts of 2-acrylamido-2-methylpropanesulfonic acid, 25-35 parts of sodium dodecyl sulfate and 35-45 parts of polyepoxysuccinic acid.
Further, the solvent is a mixture of chloroform and alcohol; the solvent comprises 20-30 parts by weight of chloroform and 10-30 parts by weight of alcohol; preferably, the alcohol is selected from ethanol and/or propanol.
Further, by weight, CO 2 The corrosion inhibitor comprises 15-20 parts of alkyl substituted imidazoline quaternary ammonium salt, 10-15 parts of polyquinoline, 8-12 parts of surfactant, 5-10 parts of scale inhibitor, 20-30 parts of chloroform and 10-30 parts of alcohol.
In order to achieve the above object, another aspect of the present invention also provides a CO as described above 2 The application of the corrosion inhibitor in the field of oil and gas field exploitation.
By applying the technical scheme of the invention, the quaternary ammonium salt of the imidazoline substituted by the fluorocarbon group contains the hydrocarbon branched chain R 1 The group, the nitrogen-containing group, the heterocycle and the like have charge structures, and the polyquinoline structure contains N atoms, so that the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline have strong nucleophilicity. When the inhibitor and the metal matrix are applied to the field of oil and gas field exploitation, the nitrogen-containing group and the N atom can form a coordinate bond with the Fe atom, so that the metal matrix (such as the surface of a petroleum pipeline) is tightly combined, the corrosion inhibitor is adsorbed on the surface of the metal matrix to form a corrosion inhibitor film, the corrosion rate of an anode is reduced, and a good corrosion inhibition effect is achieved. And hydrocarbon branched chain R in alkyl substituted imidazoline quaternary ammonium salt 1 The groups can form a hydrophobic layer, and further inhibit a corrosive medium from diffusing and migrating to the surface of the metal matrix.
F atoms or fluorine-containing groups are introduced into the structure of the alkyl-substituted imidazoline quaternary ammonium salt to improve the high-temperature resistance of the imidazoline quaternary ammonium salt; meanwhile, the polymerization degree of the polyquinoline is limited within a specific range, so that the solubility and the thermal stability of the polyquinoline can be improved, the adsorption stability of the corrosion inhibitor film on the surface of the metal matrix can be improved, and a good corrosion inhibition effect can be still exerted under a high-temperature condition.
The hydrocarbyl-substituted imidazoline quaternary ammonium salt with a specific structure and the polyquinoline with a specific polymerization degree are used simultaneously, so that the synergistic effect of the hydrocarbyl-substituted imidazoline quaternary ammonium salt and the polyquinoline can be exerted, the stability of a corrosion inhibitor film is favorably improved, the corrosion inhibition effect of the corrosion inhibitor is improved, and the petroleum pipeline is favorably protected from being corroded. In a word, the high-temperature carbon dioxide is applied to high temperature (60-180 ℃) and high CO 2 Content (CO) 2 Partial pressure of 1-5 MPa) can achieve excellent corrosion inhibition performance under the working condition, and further oilfield equipment can be remarkably improvedThe service life of (2). The above CO provided by the present application 2 The corrosion inhibitor is particularly suitable for the project of carbon dioxide complement, utilization and sealing (CCUS-EOR).
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background of the invention, existing CO 2 The corrosion inhibitor is used at high temperature (60-180 ℃) and high CO 2 Content (CO) 2 Partial pressure of 1-5 MPa) under the working condition. In order to solve the above technical problems, the present application provides a CO 2 Corrosion inhibitor of the CO 2 The corrosion inhibitor comprises: a hydrocarbyl-substituted imidazoline quaternary ammonium salt, polyquinoline and a solvent; the hydrocarbyl-substituted imidazoline quaternary ammonium salt has a cation with a structure shown in a formula (I):
wherein R is 1 The radicals being selected from C 10 ～C 18 Alkyl of (C) 10 ～C 18 Alkenyl of (a), fluoro-substituted C 10 ～C 18 Alkyl of (2), or fluorine substituted C 10 ～C 18 Alkenyl of R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen atom, fluorine substituted or unsubstituted C 1 ～C 5 Alkyl, fluoro substituted or unsubstituted C 2 ～C 5 And R is alkenyl of 2 、R 3 、R 4 And R 5 Contains at least one fluorine atom; anions of hydrocarbyl-substituted imidazoline quaternary ammonium salts include, but are not limited to, SO 4 2- Or Cl - (ii) a The polymerization degree of the polyquinoline is 10-80.
The alkyl-substituted imidazoline quaternary ammonium salt contains hydrocarbon branched chain R 1 The group, the nitrogen-containing group, the heterocycle and the like have charge structures, and the polyquinoline structure contains N atoms, so that the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline have stronger nucleophilic propertyAnd (4) sex. When the inhibitor and the metal matrix are applied to the field of oil and gas field exploitation, the nitrogen-containing group and the N atom can form a coordinate bond with the Fe atom, so that the metal matrix (such as the surface of a petroleum pipeline) is tightly combined, the corrosion inhibitor is adsorbed on the surface of the metal matrix to form a corrosion inhibitor film, the corrosion rate of an anode is reduced, and a good corrosion inhibition effect is achieved. And hydrocarbon branched chain R in alkyl substituted imidazoline quaternary ammonium salt 1 The groups can form a hydrophobic layer, and further inhibit the corrosive medium from diffusing and migrating to the surface of the metal matrix.
F atoms or fluorine-containing groups are introduced into the structure of the alkyl-substituted imidazoline quaternary ammonium salt to improve the high-temperature resistance; meanwhile, the polymerization degree of the polyquinoline is limited within a specific range, so that the solubility and the thermal stability of the polyquinoline can be improved, the adsorption stability of the corrosion inhibitor film on the surface of the metal matrix can be improved, and a good corrosion inhibition effect can be still exerted under a high-temperature condition.
The hydrocarbyl-substituted imidazoline quaternary ammonium salt with a specific structure and the polyquinoline with a specific polymerization degree are used simultaneously, so that the synergistic effect of the hydrocarbyl-substituted imidazoline quaternary ammonium salt and the polyquinoline can be exerted, the stability of a corrosion inhibitor film is favorably improved, the corrosion inhibition effect of the corrosion inhibitor is improved, and the petroleum pipeline is favorably protected from being corroded. In a word, the high-temperature-resistant and high-CO-content carbon dioxide is applied to high temperature (60-180 ℃), and high CO content 2 Content (CO) 2 Partial pressure of 1-5 MPa) can achieve excellent corrosion inhibition performance under the working condition, and further the service life of oilfield equipment can be remarkably prolonged. The above CO provided by the present application 2 The corrosion inhibitor is particularly suitable for projects of carbon dioxide collection, utilization and sequestration (CCUS-EOR).
In a preferred embodiment, the CO is present in parts by weight 2 The corrosion inhibitor comprises 15-20 parts of alkyl-substituted imidazoline quaternary ammonium salt, 10-15 parts of polyquinoline and 30-60 parts of solvent. The dosage of the alkyl-substituted imidazoline quaternary ammonium salt, the polyquinoline and the solvent includes but is not limited to the range, and the limitation of the dosage in the range is favorable for further playing the synergistic effect of the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline, and is favorable for further improving the stability of the corrosion inhibitor film, so that the corrosion inhibition effect of the corrosion inhibitor is further improved.
In a preferred embodimentIn the formula, when R 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 4, the polymerization degree of the polyquinoline is 10-20; when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 3, the polymerization degree of the polyquinoline is 20-40; when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 2, the polymerization degree of the polyquinoline is 40-60; when R is 2 、R 3 、R 4 And R 5 When the total number of fluorine atoms is 1, the polymerization degree of the polyquinoline is 60 to 80. The preferable types are adopted for matching, so that the compatibility of the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline can be further improved, and the synergistic effect of the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline can be further exerted.
In a preferred embodiment, the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline is (15-20): 10-15). The weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline includes but is not limited to the range, and the limitation of the weight ratio to the range is favorable for further playing the synergistic effect of the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline, and further improving the stability of the corrosion inhibitor film, thereby further improving the corrosion inhibition effect of the corrosion inhibitor.
An essential feature of oil and gas field development processes is localized corrosion due to CO 2 Dissolved in water to produce carbonic acid, causing electrochemical corrosion as follows. (1) Iron in CO 2 The anode reaction in the aqueous solution is an anodic oxidation process of iron, and the anode reaction is as follows: fe + OH - →FeOH+e；FeO→FeOH + +e；FeOH + →Fe 2+ +OH - (ii) a (2) The substance of the cathode reaction is CO 2 HCO formed in solution in water 3 - Ionize to give H + So that the total corrosion reaction is CO 2 +H 2 O+Fe→FeCO 3 +H 2 . In the presence of CO 2 In the medium, FeCO being a corrosion product 3 、CaCO 3 The scale or other product film has different coverage in different areas of the steel surface, and corrosion couple or blocking battery with strong autocatalysis is formed between the different covered areas to form CO 2 Local corrosion of。
In a preferred embodiment, CO 2 The corrosion inhibitor also includes a surfactant. Because the corrosion inhibitor provided by the application contains a plurality of components, the addition of the surfactant is beneficial to avoiding the layering phenomenon caused by uneven mixing of the components; meanwhile, the introduction of the surfactant is favorable for improving the film forming property of the corrosion inhibitor film and inhibiting CO 2 Local corrosion of (2).
To further increase CO 2 Compatibility of the components of the corrosion inhibitor while further improving film-forming properties, in a preferred embodiment, CO is present in parts by weight 2 The corrosion inhibitor comprises 8-12 parts of surfactant.
To further increase CO 2 The compatibility of each component in the corrosion inhibitor can be further improved, and the film forming property and the stability of the surfactant under high-temperature conditions can be further improved, preferably, the surfactant comprises but is not limited to perfluoroalkyl sulfonate compounds, and more preferably n-CF 3 (CF 2 ) 8 SO 3 Na and/or n-CF 3 (CF 2 ) 10 SO 3 Na。
Under the working condition of high mineralization degree, a large number of cations such as calcium, magnesium, barium and strontium ions and carbonate ions, bicarbonate ions, sulfate radicals and the like in the solution react with anions to generate calcium carbonate, magnesium carbonate, barium sulfate and strontium sulfate scale precipitates, so that the blockage of an aquifer and a water conveying well pipe is caused. Meanwhile, the scale substances can accelerate corrosion of the petroleum pipeline, and corrosion products and the scale substances are accompanied at the same time, so that the blockage of the petroleum pipeline is accelerated. In a preferred embodiment, for the preparation of anti-CO 2 The corrosion inhibitor composition of the corrosion inhibitor also includes a scale inhibitor. In order to improve the removal rate of easy-scaling substances such as calcium ions, magnesium ions and the like and inhibit the blockage of the easy-scaling substances on a water conveying well pipe, the method is used for preparing CO in parts by weight 2 The corrosion inhibitor composition comprises 5-10 parts of a high-temperature scale inhibitor.
In a preferred embodiment, the scale inhibitor is a mixture of one or more of 2-acrylamido-2-methylpropanesulfonic acid, sodium lauryl sulfate, and polyepoxysuccinic acid. The introduction of 2-acrylamide-2-methylpropanesulfonic acid is favorable for combining with barium and strontium cations, so that the generation of scaling substances such as barium sulfate, strontium sulfate and the like is inhibited; polyepoxysuccinic acid is a nitrogen-free and non-phosphorus organic matter which can be combined with calcium and magnesium cations in a solution by chelation, so that the generation of scaling substances such as calcium carbonate and magnesium carbonate is inhibited; the sodium dodecyl sulfate serving as an anionic surfactant can change the scaling appearance of calcium carbonate, and can simultaneously play a synergistic interaction role with other scale inhibitor components to further inhibit the generation of calcium carbonate scale.
In order to further exert the synergistic effect among the components in the scale inhibitor, thereby further inhibiting the generation of scale and improving the removal rate of scale-forming substances, the scale inhibitor preferably comprises, by weight, 25-35 parts of 2-acrylamido-2-methylpropanesulfonic acid, 25-35 parts of sodium dodecyl sulfate and 35-45 parts of polyepoxysuccinic acid.
In a preferred embodiment, the solvent is a mixture of chloroform and an alcohol. The mixed solvent formed by chloroform and alcohol is favorable for improving CO 2 Solubility and homogeneity of the components in the corrosion inhibitor.
In a preferred embodiment, the solvent includes 20 to 30 parts by weight of chloroform and 10 to 30 parts by weight of alcohol. The ratio of chloroform to alcohol used includes, but is not limited to, the above range, and it is preferable to limit the ratio to the above range to further improve the solubility and uniformity of each component in the corrosion inhibitor. The alcohol solvent employed may be a solvent commonly used in the art, preferably, the alcohol includes, but is not limited to, ethanol and/or propanol.
In a preferred embodiment, the CO is present in parts by weight 2 The corrosion inhibitor comprises 15-20 parts of alkyl substituted imidazoline quaternary ammonium salt, 10-15 parts of polyquinoline, 8-12 parts of surfactant, 5-10 parts of scale inhibitor, 20-30 parts of chloroform and 10-30 parts of alcohol. CO in the above dosage range 2 The corrosion inhibitor is not only beneficial to further improving the stability of the corrosion inhibitor film, but also beneficial to further improving the removal rate of the scaling substances, thereby further improving the corrosion inhibition effect.
The second aspect of the present application further provides a synthesis method of a preferred alkyl-substituted imidazoline quaternary ammonium salt, wherein the synthesis route is as follows:
S1，
S2，
S3，
the synthesis method of the alkyl-substituted imidazoline quaternary ammonium salt comprises the following steps: s1, adding the raw material 1 and diethylenetriamine into a round-bottom flask in a mass ratio of 1:1, and performing amidation reaction at 140-160 ℃ for 3-5 h to obtain an intermediate 1, wherein the raw material 1 has the following structure:
intermediate 1 has the following structure:
r is as defined above 1 Have the same definitions as previously described; s2, vacuumizing at 220-240 ℃ to perform dehydration cyclization reaction for 6 hours to obtain an intermediate 2, wherein the intermediate 2 has the following structure:
s3, mixing the intermediate 3 with sulfuric acid and tetrafluoroethylene, and reacting for 5-6 h at 150-160 ℃ to obtain the alkyl-substituted imidazoline quaternary ammonium salt, wherein R in the alkyl-substituted imidazoline quaternary ammonium salt 2 、R 3 、R 4 And R 5 All are F atoms, and the pH of the reaction system in S3 is 1-2.
The third aspect of the present application also provides the above CO provided by the present application 2 The application of the corrosion inhibitor in the field of oil and gas field exploitation.
The above CO provided by the present application 2 The corrosion inhibitor has excellent slow release effect, and can be applied to high temperature (60-180 ℃) and high CO 2 Content (CO) 2 Partial pressure of 1-5 MPa) can achieve excellent corrosion inhibition performance.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
It should be noted that the corrosion rate of the corrosion inhibitor in all the examples and comparative examples in this application is determined as follows:
(1) preparing simulated water: 100000mg/L NaCl +5000mg/L MgCl 2 ·6H 2 O+3000mg/L Na 2 SO 4 +5000mg/L CaCl 2 +500mg/L NaHCO 3 。
(2) The test conditions were as follows: firstly, polishing and brightening the steel (number N80) for the oil pipe, then cleaning and drying the steel by petroleum ether and ethanol, weighing the steel, and putting the weighed steel sheet into an autoclave. The prepared simulated water is sealed and deoxidized for 2 hours, the deoxidized simulated water is introduced, and 300ppm of CO in the examples or the comparative examples of the application is added 2 Corrosion inhibitor, stirring and heating to 180 deg.C, introducing high-purity CO 2 And maintain CO 2 The partial pressure is 5MPa, and high-purity N is introduced 2 And maintain N 2 And (3) taking out the sample after the pressure is 20MPa (total pressure is 20MPa) and the sample is stabilized for 96 hours under the condition, removing a corrosion product film on the surface of the sample, weighing after drying and calculating the corrosion rate.
Example 1
The corrosion inhibitor comprises 15 parts by weight of alkyl-substituted imidazoline quaternary ammonium salt, 15 parts by weight of polyquinoline and 10 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 8 SO 3 Na, 10 parts of scale inhibitor, 30 parts of chloroform and 20 parts of ethanol (the total weight parts are 100 parts). Wherein the chemical structural formula of the alkyl-substituted imidazoline quaternary ammonium salt is shown as the formula (II):
The synthetic route of the alkyl-substituted imidazoline quaternary ammonium salt in the embodiment is as follows:
a method for synthesizing alkyl-substituted imidazoline quaternary ammonium salt comprises the following steps:
s1, adding oleic acid and diethylenetriamine into a 100mL round-bottom flask according to the mass ratio of 1:1, and reacting for 5 hours at 140 ℃ to obtain an intermediate 1 a; s2, carrying out vacuum-pumping dehydration for 6 hours at 220 ℃ to obtain an intermediate 2 a; s3, mixing the intermediate 3 with sulfuric acid and tetrafluoroethylene, and reacting for 6h at 150 ℃ to obtain the alkyl-substituted imidazoline quaternary ammonium salt shown in the formula (II).
The adopted polyquinoline is self-made, the polymerization reaction condition is that the polyquinoline reacts for 4 hours at 90 ℃, and the polymerization degree of the obtained polyquinoline is 14.
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0969 mm/a.
Example 2
The corrosion inhibitor comprises 20 parts by weight of alkyl substituted imidazoline quaternary ammonium salt, 10 parts by weight of polyquinoline and 12 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 8 SO 3 Na, 5 parts of scale inhibitor, 25 parts of chloroform and 28 parts of ethanol (the total weight parts are 100 parts). Wherein the quaternary ammonium salt of alkyl-substituted imidazoline and the antisludging agent are respectively the same as the embodiment 1.
A method for synthesizing alkyl-substituted imidazoline quaternary ammonium salt comprises the following steps:
s1, adding oleic acid and diethylenetriamine into a 100mL round-bottom flask according to the mass ratio of 1:1, and reacting for 4 hours at 150 ℃ to obtain an intermediate 1 a; s2, carrying out vacuum-pumping dehydration for 6 hours at 230 ℃ to obtain an intermediate 2 a; s3, mixing the intermediate 3 with sulfuric acid and tetrafluoroethylene, and reacting for 5h at 160 ℃ to obtain the hydrocarbyl-substituted imidazoline quaternary ammonium salt shown in the formula (II).
The adopted polyquinoline is self-made, the polymerization reaction condition is that the polyquinoline reacts for 4 hours at 90 ℃, and the polymerization degree of the obtained polyquinoline is 14.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0925 mm/a.
Example 3
The corrosion inhibitor comprises 18 parts by weight of alkyl substituted imidazoline quaternary ammonium salt, 15 parts by weight of polyquinoline and 9 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 8 SO 3 Na, 8 parts of scale inhibitor, 20 parts of chloroform and 30 parts of ethanol (the total weight parts are 100 parts). Wherein the quaternary ammonium salt of alkyl-substituted imidazoline and the antisludging agent are respectively the same as the embodiment 1.
A method for synthesizing alkyl-substituted imidazoline quaternary ammonium salt comprises the following steps:
s1, adding oleic acid and diethylenetriamine into a 100mL round-bottom flask according to the mass ratio of 1:1, and reacting for 3 hours at 160 ℃ to obtain an intermediate 1 a; s2, performing vacuum-pumping dehydration for 6 hours at the temperature of 240 ℃ to obtain an intermediate 2 a; s3, mixing the intermediate 3 with sulfuric acid and tetrafluoroethylene, and reacting at 155 ℃ for 5h to obtain the hydrocarbyl-substituted imidazoline quaternary ammonium salt shown in the formula (II).
The polyquinoline used was prepared by itself, and the polymerization conditions were the same as in example 1, and the polymerization degree of the obtained polyquinoline was 14.
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0745 mm/a.
Example 4
The corrosion inhibitor comprises 15 parts by weight of alkyl substituted imidazoline quaternary ammonium salt, 15 parts by weight of polyquinoline and 10 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 10 SO 3 Na, 10 parts of scale inhibitor, 30 parts of chloroform and 20 parts of propanol (the total parts are 100 parts). Wherein the alkyl substituted imidazoline quaternary ammonium salt and the scale inhibitor are respectively the same as the embodiment 1.
In this example, the method for synthesizing the hydrocarbyl-substituted imidazoline quaternary ammonium salt was exactly the same as in example 1, and the hydrocarbyl-substituted imidazoline quaternary ammonium salt represented by formula (II) was obtained.
The polyquinoline used was prepared by itself, and the polymerization conditions were the same as in example 1, and the polymerization degree of the obtained polyquinoline was 14.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0953 mm/a.
Example 5
The corrosion inhibitor comprises 20 parts by weight of alkyl-substituted imidazoline quaternary ammonium salt, 10 parts by weight of polyquinoline and 10 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 10 SO 3 Na, 5 parts of scale inhibitor, 25 parts of chloroform and 30 parts of propanol (the total parts by weight is 100 parts). Wherein the quaternary ammonium salt of alkyl-substituted imidazoline and the antisludging agent are respectively the same as the embodiment 1.
A method for synthesizing alkyl-substituted imidazoline quaternary ammonium salt comprises the following steps:
s1, adding oleic acid and diethylenetriamine into a 100mL round-bottom flask according to the mass ratio of 1:1, and reacting for 4 hours at 150 ℃ to obtain an intermediate 1 a; s2, carrying out vacuum-pumping dehydration for 6 hours at 230 ℃ to obtain an intermediate 2 a; s3, mixing the intermediate 3 with sulfuric acid and tetrafluoroethylene, and reacting for 5h at 160 ℃ to obtain the hydrocarbyl-substituted imidazoline quaternary ammonium salt shown in the formula (II).
The adopted polyquinoline is prepared by self, the polymerization reaction condition is that the reaction is carried out for 4 hours at 90 ℃, and the polymerization degree of the obtained polyquinoline is 14.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0906 mm/a.
Example 6
The corrosion inhibitor comprises 18 parts by weight of alkyl substituted imidazoline quaternary ammonium salt, 15 parts by weight of polyquinoline and 8 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 10 SO 3 Na, 9 parts of scale inhibitor, 20 parts of chloroform and 30 parts of propanol (the total parts are 100 parts). Wherein the alkyl substituted imidazoline quaternary ammonium salt and the scale inhibitor are respectively the same as the embodiment 1.
A method for synthesizing alkyl-substituted imidazoline quaternary ammonium salt comprises the following steps:
s1, adding oleic acid and diethylenetriamine into a 100mL round-bottom flask according to the mass ratio of 1:1, and reacting for 3 hours at 160 ℃ to obtain an intermediate 1 a; s2, performing vacuum-pumping dehydration for 6 hours at the temperature of 240 ℃ to obtain an intermediate 2 a; s3, mixing the intermediate 3 with sulfuric acid and tetrafluoroethylene, and reacting for 5h at 155 ℃ to obtain the hydrocarbyl-substituted imidazoline quaternary ammonium salt shown in the formula (II).
The adopted polyquinoline is self-made, the polymerization reaction condition is that the polyquinoline reacts for 4 hours at 90 ℃, and the polymerization degree of the obtained polyquinoline is 14.
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0732 mm/a.
Example 7
The difference from example 1 is that: the corrosion inhibitor comprises 10 parts of alkyl-substituted imidazoline quaternary ammonium salt, 20 parts of polyquinoline and 65 parts of solvent (chloroform and ethanol), the using ratio of the other components is the same as that of the embodiment 1, and the total weight part is 100 parts.
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.1040 mm/a.
Example 8
The difference from example 1 is that: the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline is 15: 10.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0856 mm/a.
Example 9
The difference from example 1 is that: the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline is 20: 15.
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0732 mm/a.
Example 10
The difference from example 1 is that: the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline is 10: 10.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.1050 mm/a.
Example 11
The difference from example 1 is that: the scale inhibitor comprises 25 parts by weight of the 2-acrylamide-2-methylpropanesulfonic acid, 35 parts by weight of sodium dodecyl sulfate and 40 parts by weight of polyepoxysuccinic acid.
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0921 mm/a.
Example 12
The difference from example 1 is that: the scale inhibitor comprises 35 parts by weight of the 2-acrylamide-2-methylpropanesulfonic acid, 25 parts by weight of sodium dodecyl sulfate and 40 parts by weight of polyepoxysuccinic acid.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0906 mm/a.
Example 13
The difference from example 1 is that: the scale inhibitor comprises 30 parts by weight of the 2-acrylamide-2-methylpropanesulfonic acid, 35 parts by weight of sodium dodecyl sulfate and 35 parts by weight of polyepoxysuccinic acid.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0895 mm/a.
Example 14
The difference from example 1 is that: the scale inhibitor comprises 30 parts by weight of the 2-acrylamide-2-methylpropanesulfonic acid, 25 parts by weight of sodium dodecyl sulfate and 45 parts by weight of polyepoxysuccinic acid.
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0908 mm/a.
Example 15
The difference from example 1 is that: the chemical structure of the alkyl-substituted imidazoline quaternary ammonium salt is shown as the formula (III):
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0856 mm/a.
Example 16
The difference from example 1 is that: the chemical structure of the alkyl-substituted imidazoline quaternary ammonium salt is shown as (III):
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0907 mm/a.
Example 17
The difference from example 1 is that: the chemical structure of the alkyl-substituted imidazoline quaternary ammonium salt is shown as (IV):
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0947 mm/a.
Example 18
The difference from example 1 is that: the chemical structure of the alkyl-substituted imidazoline quaternary ammonium salt is shown as (IV):
The corrosion inhibitor of the formulation has good water solubility in the test medium (simulated water), and the corrosion rate is measured to be 0.0934 mm/a.
Example 19
The difference from example 1 is that: the chemical structure of the alkyl-substituted imidazoline quaternary ammonium salt is shown as (V):
The corrosion inhibitor of this formulation has good water solubility in the test medium (simulated water) and the measured corrosion rate is 0.0886 mm/a.
Example 20
The difference from example 1 is that: the chemical structure of the hydrocarbyl-substituted imidazoline quaternary ammonium salt is shown as (VI):
The corrosion inhibitor of the formula has good water solubility in a test medium (simulated water), and the measured corrosion rate is 0.0827 mm/a.
Comparative example 1
The corrosion inhibitor in the comparative example 1 comprises 33 parts by weight of alkyl substituted imidazoline quaternary ammonium salt and 8 parts by weight of perfluorononane sodium sulfonate n-CF 3 (CF 2 ) 10 SO 3 Na, 9 parts of scale inhibitor, 20 parts of chloroform and 30 parts of propanol. Wherein the hydrocarbyl-substituted imidazoline quaternary ammonium salt is prepared by the synthesis method in the embodiment 6. The scale inhibitor was the same as in example 1.
The corrosion inhibitor of the formula has good water solubility in a test medium, and the corrosion rate is 0.1132 mm/a.
Comparative example 2
The difference from example 1 is that: the polymerization degree of polyquinoline is higher and is 120.
The corrosion inhibitor of this formulation was poorly soluble in the test medium and the corrosion rate was 0.1356 mm/a.
CO in examples 1 to 6 and comparative example 1 of the present application 2 The composition of the corrosion inhibitors is summarized in table 1, and the results of the corrosion rate tests of all the examples and comparative examples described above in the present application are summarized in table 2.
TABLE 1
TABLE 2
| Corrosion Rate (mm/a) | |
| Example 1 | 0.0969 |
| Example 2 | 0.0925 |
| Example 3 | 0.0745 |
| Example 4 | 0.0953 |
| Example 5 | 0.0906 |
| Example 6 | 0.0732 |
| Example 7 | 0.1040 |
| Example 8 | 0.0856 |
| Example 9 | 0.0732 |
| Example 10 | 0.1050 |
| Example 11 | 0.0921 |
| Example 12 | 0.0906 |
| Example 13 | 0.0895 |
| Example 14 | 0.0908 |
| Example 15 | 0.0856 |
| Example 16 | 0.0907 |
| Example 17 | 0.0947 |
| Example 18 | 0.0934 |
| Example 19 | 0.0886 |
| Example 20 | 0.0827 |
| Comparative example 1 | 0.1132 |
| Comparative example 2 | 0.1356 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
comparing examples 1 to 6 with comparative example 1, it can be seen that the corrosion inhibitor provided by the present application is applied to high temperature (60-180 ℃) and high CO 2 Content (CO) 2 Partial pressure of 1-5 MPa) can achieve excellent corrosion inhibition performance.
Comparing example 1 with comparative example 2, it can be seen that the polyquinoline having a high polymerization degree has a lower solubility and stability and a faster corrosion rate. The polyquinoline with the preferable polymerization degree range has good solubility and high stability, and the corrosion inhibition effect of the corrosion inhibitor can be improved by applying the polyquinoline in the corrosion inhibitor.
Comparing examples 1 and 7, it can be seen that the amounts of the hydrocarbyl-substituted imidazoline quaternary ammonium salt, the polyquinoline, and the solvent include, but are not limited to, the preferred ranges of the present application, and the limitation of the amounts of the hydrocarbyl-substituted imidazoline quaternary ammonium salt, the polyquinoline, and the solvent within the preferred ranges of the present application is beneficial to further exerting the synergistic effect of the hydrocarbyl-substituted imidazoline quaternary ammonium salt and the polyquinoline, and further improving the stability of the corrosion inhibitor film, so as to further improve the corrosion inhibition effect of the corrosion inhibitor.
Comparing examples 1, 8 to 10, it is clear that the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline includes, but is not limited to, the preferable range of the present application, and limiting the weight ratio to the preferable range of the present application is beneficial to further exerting the synergistic effect of the alkyl-substituted imidazoline quaternary ammonium salt and the polyquinoline, and further improving the stability of the corrosion inhibitor film, thereby further improving the corrosion inhibition effect of the corrosion inhibitor.
As can be seen from comparison of examples 1 and 11 to 14, the scale inhibitor containing the preferred components and the preferred amount range of the present invention is advantageous in further exhibiting the synergistic effect between the components in the scale inhibitor, thereby further suppressing the formation of scale and improving the removal rate of scale-forming substances.
It can be seen from comparison of examples 1 and 15 to 18 that the compatibility of the hydrocarbyl-substituted imidazoline quaternary ammonium salt and the polyquinoline can be further improved by adopting the preferred species of the present application, which is beneficial to further exerting the synergistic effect of the hydrocarbyl-substituted imidazoline quaternary ammonium salt and the polyquinoline.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. CO (carbon monoxide) 2 Corrosion inhibitor, characterized in that the CO 2 The corrosion inhibitor comprises: a hydrocarbyl-substituted imidazoline quaternary ammonium salt, polyquinoline and a solvent; the alkyl-substituted imidazoline quaternary ammonium salt has a cation with a structure shown in a formula (I):
wherein R is 1 Is selected from C 10 ～C 18 Alkyl of (C) 10 ～C 18 Alkenyl of (a), fluoro-substituted C 10 ～C 18 Alkyl of (2), or fluorine substituted C 10 ～C 18 Alkenyl of (a), R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen atom, fluorine substituted or unsubstituted C 1 ～C 5 Alkyl, fluoro substituted or unsubstituted C 2 ～C 5 And said R is 2 The R is 3 R said 4 And said R 5 Contains at least one fluorine atom;
the anion of the alkyl-substituted imidazoline quaternary ammonium salt is selected from SO 4 2- Or Cl - ；
The polymerization degree of the polyquinoline is 10-80.
2. CO according to claim 1 2 Corrosion inhibitor, characterized in that, by weight, the CO is 2 The corrosion inhibitor comprises 15-20 parts of alkyl-substituted imidazoline quaternary ammonium salt, 10-15 parts of polyquinoline and 30-60 parts of solvent.
3. CO according to claim 1 or 2 2 A corrosion inhibitor, characterized in that when R is 2 The R is 3 The R is 4 And said R 5 When the total number of fluorine atoms is 4, the polymerization degree of the polyquinoline is 10-20;
when said R is 2 The R is 3 R said 4 And said R 5 When the total number of fluorine atoms is 3, the polymerization degree of the polyquinoline is 20-40;
when said R is 2 R said 3 The R is 4 And said R 5 When the total number of fluorine atoms is 2, the polymerization degree of the polyquinoline is 40-60;
when said R is 2 The R is 3 The R is 4 And said R 5 When the total number of fluorine atoms is 1, the polymerization degree of the polyquinoline is 60-80.
4. CO according to any one of claims 1 to 3 2 The corrosion inhibitor is characterized in that the weight ratio of the alkyl-substituted imidazoline quaternary ammonium salt to the polyquinoline is (15-20) to (10-15).
5. CO according to claim 4 2 Corrosion inhibitor, characterized in that the CO 2 The corrosion inhibitor also comprises a surfactant;
by weight, the CO is 2 The corrosion inhibitor comprises 8-12 parts of the surfactant;
preferably, the surfactant is selected from perfluoroalkylsulfonates, more preferably n-CF 3 (CF 2 ) 8 SO 3 Na and/or n-CF 3 (CF 2 ) 10 SO 3 Na。
6. CO according to claim 5 2 Corrosion inhibitor, characterized in that the CO 2 The corrosion inhibitor also comprises a scale inhibitor;
by weight, the CO is 2 The corrosion inhibitor comprises 5-10 parts of the scale inhibitor.
7. CO according to claim 6 2 The corrosion inhibitor is characterized in that the scale inhibitor is a mixture formed by one or more of 2-acrylamide-2-methylpropanesulfonic acid, sodium dodecyl sulfate and polyepoxysuccinic acid;
preferably, the scale inhibitor comprises 25-35 parts by weight of the 2-acrylamido-2-methylpropanesulfonic acid, 25-35 parts by weight of sodium dodecyl sulfate and 35-45 parts by weight of polyepoxysuccinic acid.
8. CO according to any of claims 5 to 7 2 The corrosion inhibitor is characterized in that the solvent is a mixture of chloroform and alcohol;
the solvent comprises 20-30 parts by weight of chloroform and 10-30 parts by weight of alcohol;
preferably, the alcohol is selected from ethanol and/or propanol.
9. CO according to claim 8 2 Corrosion inhibitor, characterized in that, by weight, the CO is 2 The corrosion inhibitor comprises 15-20 parts of alkyl substituted imidazoline quaternary ammonium salt, 10-15 parts of polyquinoline, 8-12 parts of surfactant, 5-10 parts of scale inhibitor, 20-30 parts of chloroform and 10-30 parts of alcohol.
10. A CO according to any one of claims 1 to 9 2 The corrosion inhibitor is applied to the field of oil and gas field exploitation.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210612533.XA CN114921790B (en) | 2022-05-31 | 2022-05-31 | CO 2 Corrosion inhibitor and application thereof |
| PCT/CN2022/138990 WO2023231365A1 (en) | 2022-05-31 | 2022-12-14 | Composition capable of reducing co2 corrosion, and co2 corrosion inhibitor and preparation method therefor and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210612533.XA CN114921790B (en) | 2022-05-31 | 2022-05-31 | CO 2 Corrosion inhibitor and application thereof |
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| CN114921790B CN114921790B (en) | 2023-11-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023231365A1 (en) * | 2022-05-31 | 2023-12-07 | 中国石油天然气集团有限公司 | Composition capable of reducing co2 corrosion, and co2 corrosion inhibitor and preparation method therefor and use thereof |
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| CN114921790B (en) * | 2022-05-31 | 2023-11-07 | 中国石油天然气集团有限公司 | CO 2 Corrosion inhibitor and application thereof |
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- 2022-12-14 WO PCT/CN2022/138990 patent/WO2023231365A1/en unknown
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| US20090181867A1 (en) * | 2008-01-10 | 2009-07-16 | Baker Hughes Incorporated | Corrosion inhibitors for oilfield applications |
| CN102021583A (en) * | 2011-01-07 | 2011-04-20 | 陕西省石油化工研究设计院 | Corrosion inhibitor for oil well and preparation method thereof |
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| WO2023231365A1 (en) * | 2022-05-31 | 2023-12-07 | 中国石油天然气集团有限公司 | Composition capable of reducing co2 corrosion, and co2 corrosion inhibitor and preparation method therefor and use thereof |
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| CN114921790B (en) | 2023-11-07 |
| WO2023231365A1 (en) | 2023-12-07 |
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