CN117512599B - Preparation method and application of high-temperature-resistant and corrosion-inhibition water-soluble corrosion inhibitor - Google Patents
Preparation method and application of high-temperature-resistant and corrosion-inhibition water-soluble corrosion inhibitor Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 142
- 230000007797 corrosion Effects 0.000 title claims abstract description 141
- 239000003112 inhibitor Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- JEUPWQVILXWUFD-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)ethanol Chemical compound OCCC1=NC=CN1 JEUPWQVILXWUFD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 7
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- CMAMPIMEOWYCDC-UHFFFAOYSA-N 2,4,5-triethyl-1h-imidazole Chemical compound CCC1=NC(CC)=C(CC)N1 CMAMPIMEOWYCDC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- -1 beta-chlorobutyryl ketone Chemical compound 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 32
- 229910000831 Steel Inorganic materials 0.000 abstract description 29
- 239000010959 steel Substances 0.000 abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 230000004888 barrier function Effects 0.000 abstract description 4
- 238000005536 corrosion prevention Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000002585 base Substances 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000010992 reflux Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- KWHROBAOVAZOEH-UHFFFAOYSA-N 3,7-dichlorononan-5-one Chemical compound CCC(Cl)CC(=O)CC(Cl)CC KWHROBAOVAZOEH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005292 vacuum distillation 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
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of metal corrosion inhibition, and discloses a preparation method and application of a high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor. The corrosion inhibitor contains hydrophilic quaternary ammonium salt and carboxyl group, and has good solubility in water. The corrosion inhibitor contains Mannich base quaternary ammonium salt and imidazole as chelating ligand, contains polar nitrogen atom, and has lone pair electron forming coordination bond with iron atom on the steel surface; the corrosion inhibitor is tightly adsorbed on the surface of steel metal, so that a stable barrier layer with a space network structure is formed by self-assembly between a hydrochloric acid corrosion medium and the steel; preventing H in etching medium + And water contacts with the surface of steel, so that the corrosion reaction rate is reduced, and a good corrosion prevention and inhibition effect is achieved.
Description
Technical Field
The invention relates to the technical field of metal corrosion inhibition, in particular to a preparation method and application of a high-temperature-resistant and corrosion-inhibition water-soluble corrosion inhibitor.
Background
Under the chemical or electrochemical action of mediums such as acid and alkali, the metal can generate chemical corrosion and electrochemical corrosion phenomena, the corrosion phenomena are widely existing in facilities and equipment such as petroleum exploitation, petroleum refining and the like, for example, oil refining equipment mainly comprises an atmospheric and vacuum distillation device, a catalytic cracking device, a continuous reforming device and the like, and a large amount of corrosion mediums such as hydrochloric acid, hydrogen sulfide, ammonia and the like exist in the production process of the devices, so that the damage to the equipment is great, the production operation is influenced, and potential safety hazards are caused; the current corrosion prevention method for the mechanical equipment mainly comprises an alkaline neutralizer, a corrosion inhibitor and the like. The development of a novel corrosion inhibitor is a research hotspot, for example, the patent with publication number of CN101921233B discloses that ethylenediamine, methyl acrylate, fatty acid and the like are used as reaction raw materials to prepare a tree-like imidazoline quaternary ammonium salt corrosion inhibitor containing a plurality of imidazoline rings, and the tree-like imidazoline quaternary ammonium salt corrosion inhibitor has the advantage of high corrosion inhibition rate; the traditional corrosion inhibitor has poor water solubility and cannot resist high temperature, and has poor corrosion resistance and corrosion inhibition performance in high-temperature severe environments such as petroleum exploitation, petroleum refining and the like, so that the temperature resistance, the water solubility and the corrosion resistance of the corrosion inhibitor are required to be improved.
Disclosure of Invention
The technical problems to be solved are as follows: the water-soluble corrosion inhibitor with the three-dimensional branched network structure is prepared with high temperature resistance and high corrosion inhibition performance.
The technical scheme is as follows:
the preparation method of the high-temperature-resistant and corrosion-inhibition water-soluble corrosion inhibitor comprises the following steps:
step (1), adding a reaction solvent, a hydroxyethyl imidazole Mannich base intermediate and 2-bromoethanol into a flask, reacting for 36-48h at the temperature of 80-90 ℃, rotary evaporating, and recrystallizing to obtain the quaternary ammonium salt intermediate of the triethyl imidazole Mannich base, wherein the structural formula is shown in the specification
And (2) adding a solvent, pyromellitic anhydride and a quaternary ammonium salt intermediate of the tris (hydroxyethyl) mannich base into the flask, introducing nitrogen, reacting for 5-10 hours at 15-30 ℃, pouring the solution into methanol to separate out precipitate, carrying out suction filtration, washing, and drying for 2-5 hours at 40-80 ℃ to obtain the high-temperature and corrosion-resistant water-soluble corrosion inhibitor.
Further, the ratio of the reaction solvent, the hydroxyethyl imidazole Mannich base intermediate and the 2-bromoethanol in the step (1) is (2-4) L to 1mol (2.2-2.6) mol.
Further, the reaction solvent comprises ethanol and isopropanol.
Further, in the step (1), the proportion of the solvent, pyromellitic anhydride and the quaternary ammonium salt intermediate of the trimethylol Mannich base is (2.5-4) L to 1mol (0.6-0.7) mol.
Further, the solvent includes N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide.
Further, the hydroxyethyl imidazole mannich base intermediate is prepared according to the following method:
step (3), acetonitrile solvent, imidazole, beta-chlorobutanone and potassium carbonate are added into a flask to react for 6-18 hours at the temperature of 40-60 ℃, rotary evaporation and extraction are carried out, and a butanone-based imidazole intermediate is obtained;
step (4), adding an ethanol solvent, a butanone-based imidazole intermediate, N-methyl-2-hydroxy ethylamine and a formaldehyde aqueous solution into a flask, dropwise adding a hydrochloric acid solution, reacting for 4-10 hours at the temperature of 50-65 ℃, cooling, adding sodium hydroxide for neutralization, rotary evaporating, and extracting to obtain a hydroxyethyl imidazole mannich base intermediate;
further, the ratio of acetonitrile, imidazole, beta-chlorobutylketone and potassium carbonate in the step (3) is (4-6) L1 mol (1-1.4) mol (1.3-1.7) mol.
Further, in the step (4), the ratio of ethanol, butanone-based imidazole intermediate, N-methyl-2-hydroxy ethylamine and formaldehyde is (1.5-2.5) L to 1mol (1.2-1.5) mol (1.4-1.8).
Further, in the step (4), the hydrochloric acid solution is dropwise added to control the pH of the reaction solution to 3-4, and the concentration of the hydrochloric acid solution is 25-37%.
The invention has the technical effects that: the intermediate of the quaternary ammonium salt of the trimethylol Mannich base contains three hydroxyl groups, and the intermediate and pyromellitic anhydride are subjected to polymerization reaction to obtain the high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor with a branched network structure. The corrosion inhibitor contains hydrophilic quaternary ammonium salt and carboxyl group, and has good solubility in water.
The high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor comprises Mannich base quaternary ammonium salt, imidazole and carboxyl functional groups, wherein the Mannich base quaternary ammonium salt and the imidazole are used as chelating ligands, contain polar nitrogen atoms, and have lone pair electrons which can enter a hybridization empty orbit of iron atoms on the surface of steel to form coordination bonds; meanwhile, the carboxyl can form coordination with the steel metal surface to form a stable chemical bond, so that the water-soluble corrosion inhibitor is tightly adsorbed on the steel metal surface, has a three-dimensional branched network structure, has more adsorption centers in molecules and high adsorption strength with the steel metal surface, and is self-assembled between a hydrochloric acid corrosion medium and steel to form a stable barrier layer with a space network structure; preventing H in etching medium + And water contacts with the surface of steel, so that the corrosion reaction rate is reduced, and a good corrosion prevention and inhibition effect is achieved.
The high-temperature-resistant and corrosion-inhibiting water-soluble corrosion inhibitor is a branched network polymer containing aromatic ring structural units, and compared with a small molecular corrosion inhibitor, the polymer has the advantages of large molecular weight, good structural stability, high heat resistance and difficult decomposition at high temperature, so that the high corrosion inhibition rate is maintained at high temperature, and the high temperature-resistant performance is shown. The corrosion and corrosion inhibition agent has wide application prospect in facilities and equipment such as petroleum exploitation, petroleum refining and the like.
Drawings
FIG. 1 is a reaction scheme for a quaternary ammonium salt intermediate of a triethylenemannich base.
FIG. 2 is a reaction mechanism diagram of a high corrosion resistant water-soluble corrosion inhibitor.
FIG. 3 is an infrared spectrum of a high corrosion resistant water soluble corrosion inhibitor.
Detailed Description
The technical scheme of the invention is further described in detail below through the specific embodiments and the attached drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
30mL of acetonitrile solvent, 5mmol of imidazole, 7mmol of beta-chlorobutanone and 8.5mmol of potassium carbonate are added into a flask for reflux reaction for 18h at the temperature of 40 ℃, the solvent is removed by rotary evaporation, water and ethyl acetate are added, an upper organic phase is separated after shaking extraction, rotary evaporation is carried out by a rotary evaporation evaporator, and the solvent is removed, so as to obtain the butanone-based imidazole intermediate.
20mL of ethanol solvent, 10mmol of butanone-based imidazole intermediate, 13mmol of N-methyl-2-hydroxy ethylamine and an aqueous solution containing 16mmol of formaldehyde are added into a flask, a hydrochloric acid solution with the concentration of 37% is dropwise added to control the pH of the reaction solution to 3, reflux is carried out for 4 hours at the temperature of 60 ℃, cooling is carried out, sodium hydroxide is added for neutralization, rotary evaporation is carried out to remove the solvent, water and ethyl acetate are added, an upper organic phase is separated after shaking extraction, and the solvent is removed by rotary evaporation, thus obtaining the hydroxyethyl imidazole mannich base intermediate.
48mL of isopropanol reaction solvent, 12mmol of hydroxyethyl imidazole Mannich base intermediate and 31.2mmol of 2-bromoethanol are added into a flask, reflux is carried out for 48 hours at the temperature of 80 ℃, the solvent is removed by rotary evaporation, and ethanol is recrystallized to obtain the triethyl imidazole Mannich base quaternary ammonium salt intermediate. The reaction formula is shown in figure 1 of the specification.
30mL of N, N-dimethylformamide, 12mmol of pyromellitic anhydride and 7.2mmol of the quaternary ammonium salt intermediate of the trimethylol Mannich base are added into a flask, nitrogen is introduced into the flask, the mixture is reacted for 10 hours at 15 ℃, the solution is poured into methanol to separate out precipitate, the filter cake is washed by ethanol after suction filtration, and the mixture is dried for 5 hours at 40 ℃ to obtain the high-temperature and corrosion-resistant water-soluble corrosion inhibitor with a branched network structure. The reaction mechanism is shown in figure 2 of the specification.
The infrared spectrum of the high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor shown in the specification in figure 3 shows that 1746cm < -1 > is the absorption peak of C=O in carboxyl; 1648cm-1 is the absorption peak of c=o in the ester group; 1329cm-1 is the C-N stretching peak vibration in imidazole; 932cm-1 is the absorption peak of the quaternary ammonium salt N-C.
Example 2
To the flask, 20mL of acetonitrile solvent, 5mmol of imidazole, 5mmol of beta-chlorobutanone and 6.5mmol of potassium carbonate were added, the mixture was refluxed at 60℃for 12 hours, rotary evaporation was performed, water and ethyl acetate were added, the upper organic phase was separated after shaking extraction, and rotary evaporation was performed, to obtain a butanone-based imidazole intermediate.
15mL of ethanol solvent, 10mmol of butanone-based imidazole intermediate, 12mmol of N-methyl-2-hydroxy ethylamine and an aqueous solution containing 14mmol of formaldehyde are added into a flask, 25% hydrochloric acid solution is dropwise added to control the pH of the reaction solution to 4, reflux is carried out for 10 hours at 50 ℃, cooling is carried out, sodium hydroxide is added for neutralization, rotary evaporation is carried out, water and ethyl acetate are added, the upper organic phase is separated after shaking extraction, and rotary evaporation is carried out, thus obtaining the hydroxyethyl imidazole mannich base intermediate.
To the flask were added 24mL of isopropanol reaction solvent, 12mmol of hydroxyethylimidazole Mannich base intermediate, 26.4mmol of 2-bromoethanol, reflux at 85℃for 36h, rotary evaporation, ethanol recrystallization, and the triethylenemannich base quaternary ammonium salt intermediate was obtained.
40mL of N, N-dimethylacetamide solvent, 12mmol of pyromellitic anhydride and 7.8mmol of the quaternary ammonium salt intermediate of the trimethylol Mannich base are added into a flask, nitrogen is introduced into the flask, the mixture is reacted for 6 hours at the temperature of 25 ℃, the solution is poured into methanol to separate out precipitate, the filter cake is washed by ethanol after suction filtration, and the mixture is dried for 5 hours at the temperature of 80 ℃ to obtain the high-temperature and corrosion-resistant water-soluble corrosion inhibitor with a branched network structure.
Example 3
To the flask, 30mL of acetonitrile solvent, 5mmol of imidazole, 6mmol of beta-chlorobutanone and 7.5mmol of potassium carbonate were added, and the mixture was refluxed at 60℃for 6 hours, rotary evaporated, water and ethyl acetate were added, and after shaking extraction, the upper organic phase was separated, and rotary evaporated to obtain a butanone-based imidazole intermediate.
To the flask were added 25mL of ethanol solvent, 10mmol of butanone-based imidazole intermediate, 15mmol of N-methyl-2-hydroxyethylamine and an aqueous solution containing 18mmol of formaldehyde, dropwise adding a 37% hydrochloric acid solution to control the pH of the reaction solution to 3, refluxing at 65℃for 4 hours, cooling, adding sodium hydroxide for neutralization, rotary evaporation, adding water and ethyl acetate, shaking extraction, separating an upper organic phase, and rotary evaporation to obtain a hydroxyethyl imidazole mannich base intermediate.
40mL of ethanol reaction solvent, 12mmol of hydroxyethyl imidazole Mannich base intermediate and 30.2mmol of 2-bromoethanol are added into a flask, reflux is carried out for 36h at the temperature of 90 ℃, rotary evaporation and ethanol recrystallization are carried out, and the triethyl imidazole Mannich base quaternary ammonium salt intermediate is obtained.
48mL of N-methylpyrrolidone, 12mmol of pyromellitic anhydride and 8.4mmol of the quaternary ammonium salt intermediate of the trimethylol Mannich base are added into a flask, nitrogen is introduced into the flask to react for 5 hours at the temperature of 30 ℃, the solution is poured into methanol to precipitate, the filter cake is washed by ethanol after suction filtration, and the filter cake is dried for 2 hours at the temperature of 80 ℃ to obtain the high-temperature and corrosion-resistant water-soluble corrosion inhibitor with a branched network structure.
Solubility test of high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor:
weighing the high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor, adding the high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor into water, preparing a solution with the concentration of 20-50g/L, uniformly stirring at 25 ℃, standing for 48h, and observing the state of the solution.
TABLE 1 dissolution test of high temperature and Corrosion resistant Water-soluble Corrosion inhibitor
The high-temperature-resistant corrosion-inhibition water-soluble corrosion inhibitor prepared in each embodiment contains hydrophilic quaternary ammonium salt and carboxyl groups, and has good solubility when the concentration of the high-temperature-resistant corrosion-inhibition water-soluble corrosion inhibitor in water is 20-35 g/L.
And (3) testing the corrosion inhibition and corrosion resistance of the high-temperature-resistant and corrosion-inhibition water-soluble corrosion inhibitor:
comparative example 1 a hydroxyethyl imidazolmannich base intermediate was used as a corrosion inhibitor; the preparation method is the same as in example 1.
Comparative example 2 a quaternary ammonium salt of a triethylenemannich base intermediate as a corrosion inhibitor; the preparation method is the same as in example 1.
Comparative example 3
30mL of N, N-dimethylformamide, 12mmol of pyromellitic anhydride and 7.2mmol of hydroxyethyl imidazole Mannich base intermediate (the preparation method is the same as that of the example 1) are added into a flask, nitrogen is introduced into the flask, the mixture is reacted for 10 hours at 15 ℃, the solution is poured into methanol to separate out precipitate, the filter cake is washed by ethanol after suction filtration, and the solution is dried for 5 hours at 40 ℃ to obtain the corrosion inhibitor.
Washing and degreasing the surface of the N-80 steel sheet, polishing and brightening, and weighing;
adding a hydrochloric acid solution with the concentration of 1mol/L into a flask, adding a corrosion inhibitor, stirring uniformly, and controlling the concentration of the corrosion inhibitor in the solution to be 30mg/L to serve as an experimental group; no corrosion inhibitor is added as a control group; n-80 steel sheet (60 mm. Times.60 mm. Times.0.5 mm) was suspended in the solution and immersed at 25℃for 24 hours; and taking out the steel sheet, washing with water, fully drying, weighing, and calculating the weight loss and corrosion inhibition rate (%).
Corrosion inhibition = (W) 0 -W)/W 0 ×100％。W 0 Is the weight loss of the N-80 steel sheet of the control group. W is the weight loss of the test group N-80 steel sheet.
Table 2 corrosion inhibition and corrosion resistance test table for corrosion inhibitors
The high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor prepared in each embodiment contains Mannich base quaternary ammonium salt, imidazole and carboxyl functional groups, wherein the Mannich base quaternary ammonium salt and the imidazole are used as chelating ligands, contain polar nitrogen atoms, and have lone pair electrons which can enter a hybridization empty orbit of iron atoms on the surface of steel to form coordination bonds; at the same time, the carboxyl can form coordination with the surface of steel metal to form stable chemical bond, so thatThe corrosion inhibitor is tightly adsorbed on the surface of steel metal, and has a three-dimensional branched network structure, more adsorption centers in molecules and high adsorption strength with the surface of steel metal, so that a stable barrier layer with a space network structure is formed by self-assembly between a hydrochloric acid corrosion medium and steel; preventing H in etching medium + And water contacts with the surface of steel, so that the corrosion reaction rate is reduced, and a good corrosion prevention and inhibition effect is achieved. The corrosion inhibition rate of the soluble corrosion inhibitor prepared in each embodiment reaches 81.1-88.6%.
Comparative example 1 a hydroxyethyl imidazolmannich base intermediate was used as a corrosion inhibitor; the quaternary ammonium salt of the Mannich base and the carboxyl structure are not contained.
Comparative example 2 a quaternary ammonium salt of a triethylenemannich base intermediate as a corrosion inhibitor; does not contain carboxyl structure.
Comparative example 3 the polymerization of pyromellitic anhydride and hydroxyethyl imidazole mannich base intermediate was carried out, and the corrosion inhibitor obtained did not contain a mannich base quaternary ammonium salt structure.
The coordination performance between comparative examples 1-3 and the steel surface is poor, a barrier layer is difficult to form by self-assembly between a hydrochloric acid corrosion medium and the steel, the corrosion inhibition rate is low, and the corrosion inhibition performance is poor.
Adding a hydrochloric acid solution with the concentration of 1mol/L into the flask, adding a corrosion inhibitor, uniformly stirring, and controlling the concentration of the corrosion inhibitor in the solution to be 30-60mg/L to serve as an experimental group; no corrosion inhibitor is added as an experimental group; n-80 steel sheet (60 mm. Times.60 mm. Times.0.5 mm) was suspended in the solution, immersed at 25℃for 24 hours, and mounted with a reflux condenser; and taking out the steel sheet, washing with water, fully drying, weighing, and calculating the weight loss and the high-temperature corrosion inhibition rate (%). Corrosion inhibition = (W) 0 -W)/W 0 ×100％。
TABLE 3 Corrosion inhibition Performance test Table of Corrosion inhibitors at different concentrations
When the mass fraction of the corrosion inhibitor in the hydrochloric acid solution of the corrosive medium is 50-60mg/L, the corrosion inhibition rate of each embodiment is best and reaches 97.4% at most.
Adding a hydrochloric acid solution with the concentration of 1-3mol/L into the flask, adding a corrosion inhibitor, uniformly stirring, and controlling the concentration of the corrosion inhibitor in the solution to be 50mg/L to serve as an experimental group; no corrosion inhibitor is added as an experimental group; n-80 steel sheet (60 mm. Times.60 mm. Times.0.5 mm) was suspended in the solution, immersed at 25℃for 24 hours, and mounted with a reflux condenser; and taking out the steel sheet, washing with water, fully drying, weighing, and calculating the weight loss and corrosion inhibition rate (%). Corrosion inhibition = (W) 0 -W)/W 0 ×100％。
TABLE 4 Corrosion inhibition Performance test Table of Corrosion inhibitors of different hydrochloric acid concentrations
The high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor prepared in each embodiment still has good corrosion inhibition rate in a high-concentration hydrochloric acid corrosion medium (1-3 mol/L), and the maximum corrosion inhibition rate is 88.9%.
Adding a hydrochloric acid solution with the concentration of 1mol/L into the flask, adding a corrosion inhibitor, stirring uniformly, and controlling the concentration of the corrosion inhibitor in the solution to be 50mg/L to serve as an experimental group; no corrosion inhibitor is added as an experimental group; suspending N-80 steel sheet (60 mm×60mm×0.5 mm) in the solution, soaking at 25-80deg.C for 24 hr, and mounting reflux condenser on the flask; and taking out the steel sheet, washing with water, fully drying, weighing, and calculating the weight loss and the high-temperature corrosion inhibition rate (%). High temperature corrosion inhibition = (W) 0 -W)/W 0 ×100％。
TABLE 5 Corrosion inhibition Performance test Table of Corrosion inhibitors at different temperatures
The high-temperature-resistant and corrosion-inhibiting water-soluble corrosion inhibitor prepared in each embodiment still has high corrosion inhibition rate and corrosion inhibition performance at a high temperature of 80 ℃, because the corrosion inhibitor contains branched network polymers of aromatic ring structural units, compared with the small molecular corrosion inhibitors prepared in comparative examples 1-3, the polymer has large molecular weight, good structural stability and high heat resistance, is not easy to decompose at a high temperature, and therefore, the corrosion inhibition rate still remains high at a high temperature.
Claims (8)
1. The preparation method of the high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor is characterized by comprising the following steps of:
step (1), adding a reaction solvent, a hydroxyethyl imidazole Mannich base intermediate and 2-bromoethanol into a flask, reacting for 36-48h at the temperature of 80-90 ℃, rotary evaporating, and recrystallizing to obtain the quaternary ammonium salt intermediate of the triethyl imidazole Mannich base, wherein the structural formula is shown in the specification；
Step (2), adding a solvent, pyromellitic anhydride and a quaternary ammonium salt intermediate of the tris (hydroxyethyl) mannich base into a flask, introducing nitrogen, reacting for 5-10 hours at 15-30 ℃, pouring the solution into methanol to separate out precipitate, carrying out suction filtration, washing, and drying for 2-5 hours at 40-80 ℃ to obtain the high-temperature and corrosion-resistant water-soluble corrosion inhibitor;
the proportion of the solvent, pyromellitic anhydride and the quaternary ammonium salt intermediate of the tris (hydroxyethyl) mannich base in the step (2) is (2.5-4) L, 1mol (0.6-0.7) mol.
2. The method for preparing the high-temperature and high-corrosion-resistance water-soluble corrosion inhibitor according to claim 1, wherein the proportion of the reaction solvent, the hydroxyethyl imidazole mannich base intermediate and the 2-bromoethanol in the step (1) is (2-4) L, and (2.2-2.6) L.
3. The method for preparing the high-temperature and corrosion-resistant water-soluble corrosion inhibitor according to claim 2, wherein the reaction solvent comprises ethanol and isopropanol.
4. The method for preparing the high-temperature and high-corrosion-resistance water-soluble corrosion inhibitor according to claim 1, wherein the solvent in the step (2) comprises N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
5. The method for preparing the high-temperature-resistant and corrosion-resistant water-soluble corrosion inhibitor according to claim 1, wherein the hydroxyethyl imidazole mannich base intermediate is prepared according to the following method:
step (3), acetonitrile solvent, imidazole, beta-chlorobutanone and potassium carbonate are added into a flask to react for 6-18 hours at the temperature of 40-60 ℃, rotary evaporation and extraction are carried out, and a butanone-based imidazole intermediate is obtained;
and (4) adding an ethanol solvent, a butanone-based imidazole intermediate, N-methyl-2-hydroxy ethylamine and a formaldehyde aqueous solution into a flask, dropwise adding a hydrochloric acid solution, reacting for 4-10 hours at the temperature of 50-65 ℃, cooling, adding sodium hydroxide for neutralization, rotary evaporating, and extracting to obtain a hydroxyethyl imidazole Mannich base intermediate.
6. The method for preparing the high-temperature and high-corrosion-resistance water-soluble corrosion inhibitor according to claim 5, wherein the proportion of acetonitrile, imidazole, beta-chlorobutyryl ketone and potassium carbonate in the step (3) is (4-6) L, 1mol (1-1.4) mol (1.3-1.7) mol.
7. The method for preparing the high-temperature and high-corrosion-resistance water-soluble corrosion inhibitor according to claim 5, wherein the proportion of ethanol, butanone-based imidazole intermediate, N-methyl-2-hydroxy ethylamine and formaldehyde in the step (4) is (1.5-2.5) L, 1mol (1.2-1.5) mol (1.4-1.8) mol.
8. The method for preparing the high-temperature and high-corrosion-resistant water-soluble corrosion inhibitor according to claim 5, wherein the hydrochloric acid solution is dropwise added in the step (4) to control the pH of the reaction solution to 3-4, and the concentration of the hydrochloric acid solution is 25-37%.
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