CN118166358A - Ethoxylation modified multi-hydrophobic-group corrosion inhibitor and preparation method thereof - Google Patents
Ethoxylation modified multi-hydrophobic-group corrosion inhibitor and preparation method thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 60
- 230000007797 corrosion Effects 0.000 title claims abstract description 60
- 239000003112 inhibitor Substances 0.000 title claims abstract description 50
- 238000007046 ethoxylation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 sulfonate compound Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 9
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229940046307 sodium thioglycolate Drugs 0.000 claims abstract description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940126062 Compound A Drugs 0.000 claims abstract description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 6
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical class [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 claims description 10
- PFBBCIYIKJWDIN-BUHFOSPRSA-N 2-[(e)-tetradec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O PFBBCIYIKJWDIN-BUHFOSPRSA-N 0.000 claims description 8
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical group CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 2
- 229950004394 ditiocarb Drugs 0.000 claims description 2
- TUFJPPAQOXUHRI-KTKRTIGZSA-N n'-[(z)-octadec-9-enyl]propane-1,3-diamine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCN TUFJPPAQOXUHRI-KTKRTIGZSA-N 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Chemical group 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing 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
- C23F11/12—Oxygen-containing compounds
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 discloses an ethoxylation modified multi-hydrophobic-group corrosion inhibitor and a preparation method thereof. The method comprises the following steps: the mass ratio of the alkylamine to the long-chain alkenyl acid is 1: mixing the components in the proportion of (1-3), and reacting to obtain a multi-hydrophobe compound A; the mass ratio of the double bond sulfonate compound to the multi-hydrophobic group compound A is 1: mixing the components in the proportion of (1-3), and reacting to obtain a polymer B; adding a catalyst into the polymer B, heating to 140 ℃, vacuumizing, and introducing ethylene oxide, wherein the mass ratio of the ethylene oxide to the polymer B is (10-20): 1, reacting to obtain an ethoxylation modified multi-hydrophobic group compound C; mixing an ethoxylation modified multi-hydrophobic group compound C with DTC salt, sodium thioglycolate solution, mercaptoethanol and water according to the mass ratio of 20:20:5:3:52, and uniformly stirring to obtain the corrosion inhibitor. The corrosion inhibitor has the characteristics of low corrosion rate control, stable property, good compatibility and the like.
Description
Technical Field
The invention relates to the technical field of oil-gas-water treatment corrosion and protection, in particular to an ethoxylation modified multi-hydrophobic-group corrosion inhibitor and a preparation method thereof.
Background
Along with the continuous proceeding of oil field exploitation, the water content of the produced liquid is increased increasingly, so that the corrosion of metal in an environment medium is effectively prevented, the service life of the metal is prolonged, and the addition of a corrosion inhibitor becomes an indispensable chemical means. The corrosion inhibitor is added to enter various positions of a production system along with the flowing of water to protect metal materials, through the adsorption groups such as nitrogen, oxygen, sulfur, phosphorus and the like on the corrosion inhibitor, lone pair electrons are provided to form coordination bonds with empty d orbits on the metal surface, polar groups are preferentially adsorbed on the metal surface due to stronger charge transfer effect, and nonpolar alkyl long chains deviate from the metal surface to form a hydrophobic film with a close-packed structure.
The corrosion inhibitor of offshore oil fields at present takes imidazoline, imidazoline quaternary ammonium salt and the like as main application agents. These corrosion inhibitors generally have the problems of high solubility in oil and low solubility in water. The high solubility of the corrosion inhibitor in the oil can reduce the corrosion inhibition efficiency of the corrosion inhibitor, and the consumption and the application cost of the corrosion inhibitor are increased; meanwhile, the imidazoline and the imidazoline quaternary ammonium salt have poor compatibility, can react with agents such as a water scavenger, an antiscaling agent and the like, so that problems such as precipitation and precipitation are generated during large-dose mixing, and corrosion inhibition effect is reduced, corrosion inhibition failure is caused during on-site dosing concentration.
Disclosure of Invention
The invention provides an ethoxylation modified multi-hydrophobic-base corrosion inhibitor and a preparation method thereof, which aim to solve the problems of low water solubility and poor compatibility of the existing corrosion inhibitor. The method changes and adjusts the molecular structure of the corrosion inhibitor through ethoxylation and cooperates with synergists such as micromolecules containing nitrogen and sulfur, so that the corrosion inhibitor has higher water solubility, compatibility and salt tolerance in the offshore oilfield corrosion environment, and corrosion inhibition efficiency.
In a first aspect, the invention provides a preparation method of an ethoxylation modified multi-hydrophobic-group corrosion inhibitor, which is realized by adopting the following technical scheme.
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
S1, mixing alkylamine and long-chain alkenyl acid according to the mass ratio of 1: mixing and stirring the components in proportion in the step (1-3), and reacting for 4-5 hours at the temperature of 140-160 ℃ to obtain the multi-hydrophobe compound A;
S2, mixing the double bond sulfonate compound with the multi-hydrophobic group compound A obtained in the step S1 according to the mass ratio of 1: uniformly mixing the components in the proportion of (1-3), and reacting for 4-5 hours at the temperature of 120-140 ℃ to obtain a polymer B;
s3, adding a catalyst into the polymer B obtained in the step S2, heating to 130-150 ℃, vacuumizing for deoxidization, and slowly introducing ethylene oxide, wherein the mass ratio of the ethylene oxide to the polymer B is (10-20): 1, reacting for 4-6h to obtain an ethoxylation modified multi-hydrophobic group compound C;
S4, mixing the ethoxylation modified multi-hydrophobic group compound C obtained in the step S3 with DTC salt (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 10-20:5-20:1-5:1-3:52-83, and uniformly stirring to obtain the corrosion inhibitor.
In step S1, the alkylamine is one of octadecylamine, N-oleyl-1, 3-propanediamine, and N-oleyl dipropylene triamine.
In step S1, the long-chain alkenyl acid is tetradecenyl succinic acid.
In step S2, the double bond sulfonate compound is selected from sodium 2-acrylamide-2-methylpropanesulfonate or sodium allylsulfonate.
In step S3, the catalyst is potassium hydroxide or sodium formate.
Further, in the step S3, the addition amount of the catalyst is 0.2% -0.5% of the mass of the polymer B.
Further, in step S4, the DTC salt is sodium diethyldithiocarbamate.
In a second aspect, the invention provides an ethoxylation modified multi-hydrophobic-group corrosion inhibitor, which is realized by adopting the following technical scheme.
The ethoxylation modified multi-hydrophobic-group corrosion inhibitor prepared by the preparation method.
The application has the following beneficial effects.
The ethoxylation modified multi-hydrophobic corrosion inhibitor has the characteristics of multi-hydrophobic and stronger surface activity, can isolate corrosion of water quality to metal by utilizing the characteristics of the multi-hydrophobic, can improve the water solubility of the corrosion inhibitor and increase the effective concentration in water by utilizing the stronger surface activity of the corrosion inhibitor, and has the characteristics of water solubility, good compatibility (especially, the performance is not affected with the anti-scaling agent and the bactericide).
Detailed Description
The present application is further illustrated below with reference to examples.
The experimental methods used in the following preparation examples and examples are conventional methods unless otherwise specified; materials, reagents and the like used in the following preparation examples and examples are commercially available unless otherwise specified.
Example 1
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
(1) 53.5g of octadecylamine and 29.4g of tetradecenyl succinic acid are mixed, the temperature is raised to 60 ℃, stirring is started, and the mixture reacts for 4 hours at 140 ℃ to obtain a multi-hydrophobe compound A1;
(2) Uniformly mixing the multi-hydrophobic group compound A1 obtained in the step (1) with 41.4g of 2-acrylamide-2-methylpropanesulfonic acid sodium salt, and reacting for 4 hours at 120 ℃ to obtain a polymer B1;
(3) Adding 0.25g of catalyst potassium hydroxide into the polymer B1, heating to 130 ℃, vacuumizing to remove oxygen, slowly introducing 88g of ethylene oxide, and reacting for 4 hours to obtain an ethoxylated modified multi-hydrophobe compound C1;
(4) The ethoxylation modified multi-hydrophobic group compound C1 obtained by the reaction is mixed with diethyl sodium dithiocarbamate (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 20:20:5:3:52, mixing and stirring uniformly to obtain the corrosion inhibitor.
Example 2
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
(1) Mixing 65.2g of N-oil-based-1, 3-propylene diamine and 29.4g of tetradecenyl succinic acid, heating to 60 ℃, starting stirring, and reacting for 5 hours at 150 ℃ to obtain a multi-hydrophobe compound A2;
(2) Uniformly mixing the multi-hydrophobic group compound A2 obtained in the step (1) with 41.4g of 2-acrylamide-2-methylpropanesulfonic acid sodium salt, and reacting for 5 hours at 130 ℃ to obtain a polymer B2;
(3) Adding 0.3g of catalyst potassium hydroxide into the polymer B2, heating to 150 ℃, vacuumizing to remove oxygen, slowly introducing 88g of ethylene oxide, and reacting for 6 hours to obtain an ethoxylated modified multi-hydrophobe compound C2;
(4) The ethoxylation modified multi-hydrophobic group compound C2 obtained by the reaction is mixed with diethyl sodium dithiocarbamate (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 20:10:5:3:62, mixing and stirring uniformly to obtain the corrosion inhibitor.
Example 3
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
(1) Mixing 76.2g of N-oil-based-dipropylenetriamine and 29.4g of tetradecenyl succinic acid, heating to 60 ℃, starting stirring, and reacting for 5 hours at 150 ℃ to obtain a multi-hydrophobe compound A3;
(2) Uniformly mixing the multi-hydrophobic group compound A3 obtained in the step (1) with 41.4g of 2-acrylamide-2-methylpropanesulfonic acid sodium salt, and reacting for 5 hours at the temperature of 140 ℃ to obtain a polymer B3;
(3) Adding 0.35g of catalyst potassium hydroxide into the polymer B3, heating to 150 ℃, vacuumizing to remove oxygen, slowly introducing 88g of ethylene oxide, and reacting for 6 hours to obtain an ethoxylated modified multi-hydrophobe compound C3;
(4) The ethoxylation modified multi-hydrophobic group compound C3 obtained by the reaction is mixed with diethyl sodium dithiocarbamate (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 20:20:5:3:52, mixing and stirring uniformly to obtain the corrosion inhibitor.
Example 4
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
(1) 53.8g of octadecylamine and 29.4g of tetradecenyl succinic acid are mixed, the temperature is raised to 60 ℃, stirring is started, and the mixture reacts for 4 hours at 140 ℃ to obtain a multi-hydrophobe compound A4;
(2) Uniformly mixing the multi-hydrophobic group compound A4 obtained in the step (1) with 28.8g of sodium allylsulfonate, and reacting for 4 hours at 120 ℃ to obtain a polymer B4;
(3) Adding 0.25g of catalyst potassium hydroxide into the polymer B4, heating to 130 ℃, vacuumizing to remove oxygen, slowly introducing 88g of ethylene oxide, and reacting for 4 hours to obtain an ethoxylated modified multi-hydrophobe compound C4;
(4) The ethoxylation modified multi-hydrophobic group compound C4 obtained by the reaction is mixed with diethyl sodium dithiocarbamate (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 20:15:5:2:58, mixing and stirring uniformly to obtain the corrosion inhibitor.
Example 5
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
(1) Mixing 65.2g of N-oil-based-1, 3-propylene diamine and 29.4g of tetradecenyl succinic acid, heating to 60 ℃, starting stirring, and reacting for 5 hours at 160 ℃ to obtain a multi-hydrophobe compound A5;
(2) Uniformly mixing the multi-hydrophobic group compound A5 obtained in the step (1) with 28.8g of sodium allylsulfonate, and reacting for 5 hours at 140 ℃ to obtain a polymer B5;
(3) Adding 0.3g of catalyst potassium hydroxide into the polymer B5, heating to 130 ℃, vacuumizing to remove oxygen, slowly introducing 88g of ethylene oxide, and reacting for 5 hours to obtain an ethoxylated modified multi-hydrophobe compound C5;
(4) The ethoxylation modified multi-hydrophobic group compound C5 obtained by the reaction is mixed with diethyl sodium dithiocarbamate (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 20:15:5:3:58, mixing and stirring uniformly to obtain the corrosion inhibitor.
Example 6
The preparation method of the ethoxylation modified multi-hydrophobic-base corrosion inhibitor comprises the following steps:
(1) Mixing 76.2g of N-oil-based-dipropylenetriamine and 29.4g of tetradecenyl succinic acid, heating to 60 ℃, starting stirring, and reacting for 5 hours at 160 ℃ to obtain a multi-hydrophobe compound A6;
(2) Uniformly mixing the multi-hydrophobe compound A6 obtained in the step (1) with 28.8g of allylsulfonic acid, and reacting for 5 hours at 140 ℃ to obtain a polymer B6;
(3) Adding 0.35g of catalyst potassium hydroxide into the polymer B6, heating to 150 ℃, vacuumizing to remove oxygen, slowly introducing 88g of ethylene oxide, and reacting for 6 hours to obtain an ethoxylated modified multi-hydrophobe compound C6;
(4) The ethoxylation modified multi-hydrophobic group compound C6 obtained by the reaction is mixed with diethyl sodium dithiocarbamate (99%), sodium thioglycolate solution (20%), mercaptoethanol (99%) and water according to the mass ratio of 20:10:5:3:62, mixing and stirring uniformly to obtain the corrosion inhibitor.
Comparative example 1
Commercial 20% oleic acid diethylenetriamine imidazoline +5% thiourea +3% acetic acid +72% tap water.
Comparative example 2
Commercial 20% triethylenetetramine oleate imidazoline +5% thiourea +3% acetic acid +72% tap water.
Performance detection
Corrosion inhibition performance comparison was made between examples 1-6 and comparative examples 1-2.
Experimental medium: offshore oil field simulation water quality (mineralization degree 50000 mg/L)
Experimental temperature: 68 DEG C
Concentration of the agent: 30mg/L
Hanging piece material: 20# carbon steel
Evaluation criteria: SY/T5273 method for evaluating performance of oilfield produced water corrosion inhibitor
The evaluation method comprises the following steps:
the steel test piece was immersed in absolute ethanol for about 5 minutes, the test piece was taken out, wiped dry with filter paper, wrapped with cold air, dried in a desiccator for 30 minutes, and weighed (accurate to 0.0001 g).
Pouring 2L of water sample into an autoclave, adding corrosion inhibitor with the experimental specified concentration, fixing three test pieces into a polytetrafluoroethylene groove of an autoclave hanging piece system, installing the autoclave, sequentially introducing nitrogen, vacuumizing to remove oxygen in the autoclave, and injecting carbon dioxide and nitrogen with the experimental specified pressure into the autoclave. And controlling the temperature to the experimental temperature, setting the rotating speed to 451rpm, and dynamically hanging the sheet for 72h. After heating to the specified temperature and running for 72 hours, water color and steel sheet appearance (brightness, film forming characteristics and local spots) were observed, and after treatment with standard pickling solution and absolute ethyl alcohol, weighing, recording and calculating were carried out. The results are shown in Table 1.
TABLE 1 Corrosion inhibitor Performance evaluation Table for simulated water samples of offshore oil fields
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (8)
1. A preparation method of an ethoxylation modified multi-hydrophobic-group corrosion inhibitor is characterized by comprising the following steps: the method comprises the following steps:
S1, mixing alkylamine and long-chain alkenyl acid according to the mass ratio of 1: mixing and stirring the components in proportion in the step (1-3), and reacting for 4-5 hours at the temperature of 140-160 ℃ to obtain the multi-hydrophobe compound A;
S2, mixing the double bond sulfonate compound with the multi-hydrophobic group compound A obtained in the step S1 according to the mass ratio of 1: uniformly mixing the components in the proportion of (1-3), and reacting for 4-5 hours at the temperature of 120-140 ℃ to obtain a polymer B;
s3, adding a catalyst into the polymer B obtained in the step S2, heating to 130-150 ℃, vacuumizing for deoxidization, and slowly introducing ethylene oxide, wherein the mass ratio of the ethylene oxide to the polymer B is (10-20): 1, reacting for 4-6h to obtain an ethoxylation modified multi-hydrophobic group compound C;
S4, mixing the ethoxylation modified multi-hydrophobic group compound C obtained in the step S3 with DTC salt, sodium thioglycolate solution, mercaptoethanol and water according to the mass ratio of 10-20:5-20:1-5:1-3:52-83, and uniformly stirring to obtain the corrosion inhibitor.
2. The method for preparing the ethoxylation modified multi-hydrophobic-base corrosion inhibitor according to claim 1, which is characterized in that: in the step S1, the alkylamine is one of octadecylamine, N-oleyl-1, 3-propylene diamine and N-oleyl dipropylene triamine.
3. The method for preparing the ethoxylation modified multi-hydrophobic-base corrosion inhibitor according to claim 1, which is characterized in that: in the step S1, the long-chain alkenyl acid is tetradecenyl succinic acid.
4. The method for preparing the ethoxylation modified multi-hydrophobic-base corrosion inhibitor according to claim 1, which is characterized in that: in the step S2, the double bond sulfonate compound is selected from 2-acrylamide-2-methylpropanesulfonate or sodium allylsulfonate.
5. The method for preparing the ethoxylation modified multi-hydrophobic-base corrosion inhibitor according to claim 1, which is characterized in that: in the step S3, the catalyst is potassium hydroxide or sodium formate.
6. The method for preparing the ethoxylation modified multi-hydrophobic-base corrosion inhibitor according to claim 1, which is characterized in that: in the step S3, the addition amount of the catalyst is 0.2-0.5% of the mass of the polymer B.
7. The method for preparing the ethoxylation modified multi-hydrophobic-base corrosion inhibitor according to claim 1, which is characterized in that: in step S4, the DTC salt is sodium diethyldithiocarbamate.
8. An ethoxylated modified multi-hydrophobe corrosion inhibitor prepared by the method of any one of claims 1-7.
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