CN109055942B - Environment-friendly high-temperature acidizing corrosion inhibitor and preparation method thereof - Google Patents
Environment-friendly high-temperature acidizing corrosion inhibitor and preparation method thereof Download PDFInfo
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Abstract
The invention provides an environment-friendly high-temperature acidizing corrosion inhibitor and a preparation method thereof, wherein the environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 10-50 parts of a corrosion inhibitor main agent, 1-10 parts of a synergist, 0.5-1.5 parts of a surfactant, 40-60 parts of a solvent and 5-10 parts of mercapto acid; the corrosion inhibitor main agent comprises 5-15 parts of quinoline quaternary ammonium salt, 5-10 parts of imidazole quaternary ammonium salt and 10-25 parts of Mannich base; the synergist comprises 1-5 parts of organic alkynol and 1-10 parts of plant extract; wherein the plant extract comprises one or more of radix Stephaniae Tetrandrae extract, rhizoma corydalis extract, flos Sophorae Immaturus extract, and fructus Rosae Normalis extract. The environment-friendly high-temperature resistant acidizing corrosion inhibitor has the excellent performances of environmental protection, high temperature resistance, low damage and the like.
Description
Technical Field
The invention relates to the technical field of corrosion inhibitors, in particular to an environment-friendly high-temperature acidizing corrosion inhibitor and a preparation method thereof.
Background
With the continuous deepening of oil field development, newly-invested development blocks are increasingly well-opened, and acidification operation is used as an important means for improving the recovery ratio and is widely applied to yield increasing measures of low-permeability and ultra-low permeability oil fields. As well depth increases, the formation temperature increases. When high-concentration acid liquor is injected into a shaft, the wall of an oil well pipe in a high-temperature state can be contacted with the acid liquor, so that severe acid liquor corrosion is caused, and therefore, a corrosion inhibitor for acidification is added into an acid liquor injection system. The organic corrosion inhibitor is widely applied to acidized liquid systems due to the characteristics of high efficiency and economy, and has the defects of strong toxicity and no high temperature resistance.
In addition, the high-temperature resistant acidizing corrosion inhibitor commonly used in China at present has the defects of easy coking, delamination, unstable dissolution and dispersion and the like at high temperature, and not only can the oil well pipe and underground metal equipment not be protected, but also the formation can be damaged.
Therefore, with the increasing awareness of safety and environmental protection of people and the increasingly complex underground environment working conditions, the development of an environment-friendly high-temperature resistant acidizing corrosion inhibitor is urgently needed.
Disclosure of Invention
Aiming at the problems, the invention aims to provide an environment-friendly high-temperature acidizing corrosion inhibitor and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 10-50 parts of a corrosion inhibitor main agent, 1-10 parts of a synergist, 0.5-1.5 parts of a surfactant, 40-60 parts of a solvent and 5-10 parts of mercapto acid; the corrosion inhibitor main agent comprises, by weight, 5-15 parts of quinoline quaternary ammonium salt, 5-10 parts of imidazole quaternary ammonium salt and 10-25 parts of Mannich base; the synergist comprises 1-5 parts by weight of organic alkynol and 1-10 parts by weight of plant extract.
In a further improvement of the invention, the surfactant is sodium laurate; the solvent is one of isopropanol, propanol and ethanol; the mercaptoacid is thioglycolic acid.
In a further improvement of the invention, the quaternary ammonium salt of quinoline is prepared by the following process: adding quinoline and benzyl chloride into a reactor, stirring and heating to 70-90 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 150-170 ℃, adding ethanol, carrying out heat preservation reaction for 2-4 h, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt.
The invention has the further improvement that the mol ratio of the quinoline, the benzyl chloride, the polyoxyethylene fatty alcohol ether and the ethanol is 1: (1.05-1.3): (0.05-0.2): (1-1.3).
In a further improvement of the invention, the imidazole-type quaternary ammonium salt is prepared by the following process:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, after dropwise adding, heating to 130-150 ℃, carrying out heat preservation reaction for 1-3 h, then heating to 170-190 ℃, carrying out heat preservation reaction for 5-7 h, and concentrating dry xylene under reduced pressure after reaction;
(2) adding dimethyl carbonate into the product obtained in the step (1), heating to 75-95 ℃, carrying out heat preservation reaction for 4-6 h, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 4-6 h, cooling to room temperature after the reaction is finished, adding acetone, heating to 50-70 ℃, carrying out heat preservation for 0.5-2 h, cooling to 0-5 ℃, carrying out heat preservation for 0.5-2 h, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt.
The invention is further improved in that the weight ratio of the benzoic acid, the dimethylbenzene and the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: (1.05-1.3): (1-1.2): (0.5 to 0.6); the weight ratio of dimethyl carbonate to acetone is 1: 8.
in a further development of the invention, the mannich bases are prepared by the following process: adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 2-3, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 110-130 ℃ under stirring, carrying out reflux reaction for 22-25 h, and cooling to room temperature after the reaction is finished to obtain the Mannich base.
The invention has the further improvement that the mol ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: (1-1.3): (0.9-1.1): (1-1.3): (0.01 to 0.1); and regulating the pH value to 2-3 by adopting hydrochloric acid with the mass fraction of 20%.
The invention further improves that the organic alkynol is one or more of propiolic alcohol, 1, 4-butynediol and methanesulfonic acid-2-propiolic-1-alcohol; the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: (0.1-0.5): (0.2-0.5): (0.1-0.4).
A preparation method of an environment-friendly high-temperature acidizing corrosion inhibitor comprises the steps of adding a corrosion inhibitor main agent, a synergist, a surfactant, a solvent and mercapto acid into a reactor according to parts by weight, and uniformly stirring to obtain the environment-friendly high-temperature acidizing corrosion inhibitor.
Compared with the prior art, the invention has the following beneficial effects: the quinoline quaternary ammonium salt can be completely dissociated into positively charged quaternary ammonium cations and positively charged anion Cl in hydrochloric acid-Wherein, the quaternary ammonium salt cation acts on the cathode area of the surface of the metallic iron to generate electrostatic adsorption with the negatively charged metal surface, and the reduction reaction of cathode hydrogen ions is inhibited; meanwhile, the quinoline quaternary ammonium salt contains a condensed ring structure, and due to the fact that larger total electron delocalization energy is arranged on the condensed ring, the ability of unshared electrons to coordinate and combine with N atoms on the metal surface is enhanced, a chemical adsorption layer with a stable structure gradually appears, activation energy of anode reaction in a corrosion process is improved, and therefore corrosion rate of an anode is reduced. The cation of the quaternary ammonium salt in the imidazole quaternary ammonium salt acts on the cathode area of the surface of the metallic iron to generate electrostatic adsorption with the negatively charged metallic surface, so that the reduction reaction of cathode hydrogen ions is inhibited; the hydrophobic nonpolar group is arranged far away from the metal surface in an oriented way, thereby effectively blocking Fe3+Diffusing into the solution while also allowing H in the solution+The migration to the process of the corrosion reaction of the metal is slowed down. The Mannich base corrosion inhibitor molecule contains a plurality of nitrogen atoms or oxygen atoms with lone-pair electrons, 2 or 3 non-coordinating atoms are arranged between nitrogen, nitrogen or oxygen and nitrogen, wherein polar groups in the molecule can be adsorbed on the surface layer of metal, and the non-polar groups in the molecule are arranged upwards on the surface layer of metal, so that the structure of a metal double electric layer can be changed, and a layer of hydrophobic protective film is formed on the surface layer of metal to prevent corrosion reaction. The environment-friendly high-temperature resistant acidizing corrosion inhibitor has the excellent performances of environmental protection, high temperature resistance, low damage and the like.
Furthermore, the tetrandra root extract in the plant extract contains alkaloid components, is a relatively complex nitrogen-containing organic compound, is mostly a heterocyclic compound, and has nitrogen atoms in benzene rings; the radix stephaniae tetrandrae extract, the rhizoma corydalis extract, the sophora flower bud extract and the rosa roxburghii extract have obvious corrosion inhibition synergistic effect, and a film layer formed by molecular adsorption in the plant extract covers the metal surface, so that corrosion reaction can only be carried out on the uncovered metal surface, the area of the corroded metal surface is greatly reduced, and the corrosion of the metal is slowed down.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The invention provides an environment-friendly high-temperature acidizing corrosion inhibitor which comprises, by weight, 10-50 parts of a corrosion inhibitor main agent, 1-10 parts of a synergist, 0.5-1.5 parts of a surfactant, 40-60 parts of a solvent and 5-10 parts of mercapto acid; the corrosion inhibitor main agent comprises 5-15 parts of quinoline quaternary ammonium salt, 5-10 parts of imidazole quaternary ammonium salt and 10-25 parts of Mannich base; the synergist comprises 1-5 parts of organic alkynol and 1-10 parts of plant extract;
preferably, the environment-friendly high-temperature acidification corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base in parts by weight; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract in parts by weight.
In one embodiment, the raw materials for preparing the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol.
In one embodiment, the molar ratio of the quinoline, the benzyl chloride, the polyoxyethylene fatty alcohol ether and the ethanol in the preparation raw material of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent is 1: (1.05-1.3): (0.05-0.2): (1-1.3); preferably, the molar ratio of said quinoline, said benzyl chloride, said polyoxyethylene fatty alcohol ether and said ethanol is 1: 1.2: 0.1: 1.1.
the preparation method of the quinoline quaternary ammonium salt comprises the following steps:
adding quinoline and benzyl chloride into a reactor, stirring and heating to 80 ℃, then slowly dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 160 ℃, adding ethanol, keeping the temperature for reaction for 3 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt.
In one embodiment, the imidazole type quaternary ammonium salt in the main agent of the corrosion inhibitor is prepared from diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane.
In one embodiment, the molar ratio of the diethylenetriamine, the benzoic acid, the dimethyl carbonate and the 1, 4-dibromobutane in the preparation raw material of the imidazole type quaternary ammonium salt in the corrosion inhibitor main agent is 1: (1.05-1.3): (1-1.2): (0.5 to 0.6); preferably, the molar ratio of the diethylenetriamine, the benzoic acid, the dimethyl carbonate and the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54.
the preparation method of the imidazole type quaternary ammonium salt comprises the following steps:
(1) adding benzoic acid, xylene and a zinc particle catalyst into a reactor, stirring uniformly, slowly dropwise adding diethylenetriamine, after dropwise adding, heating to 140 ℃, carrying out heat preservation reaction for 2 hours, then heating to 180 ℃, carrying out heat preservation reaction for 6 hours, and concentrating dry xylene under reduced pressure after the reaction is finished; the weight ratio of the benzoic acid to the dimethylbenzene to the zinc particles is 1: 8: 0.002;
(2) adding dimethyl carbonate into the product obtained in the step (1), heating to 85 ℃, carrying out heat preservation reaction for 5 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 5 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 60 ℃, carrying out heat preservation for 1 hour, cooling to 0-5 ℃, carrying out heat preservation for 1 hour, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt; the weight ratio of the dimethyl carbonate to the acetone is 1: 8.
in one embodiment, the mannich base in the corrosion inhibitor main agent is prepared from benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10.
In one embodiment, the mol ratio of the benzotriazole, the absolute ethyl alcohol, the benzaldehyde, the piperazine and the octyl phenol polyoxyethylene ether-10 in the raw materials for preparing the mannich base in the corrosion inhibitor main agent is 1: (1-1.3): (0.9-1.1): (1-1.3): (0.01 to 0.1); preferably, the molar ratio of the benzotriazole, the absolute ethyl alcohol, the benzaldehyde, the piperazine and the octyl phenol polyoxyethylene ether-10 is 1: 1.2: 1: 1.2: 0.05.
the preparation method of the Mannich base comprises the following steps:
adding benzotriazole and absolute ethyl alcohol into a reactor, dropwise adding hydrochloric acid with the mass fraction of 20% to neutralize the mixed solution until the pH value is 2-3, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, stirring the solution, heating to 120 ℃, carrying out reflux reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain the Mannich base.
In one embodiment, the surfactant is sodium laurate; the solvent comprises one of isopropanol, propanol and ethanol; the mercaptoacid is thioglycolic acid; the organic alkynol comprises one or more of propiolic alcohol, 1, 4-butynediol and methanesulfonic acid-2-propiolic-1-alcohol;
preferably, the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol.
In one embodiment, the plant extract is a mixture of stephania tetrandra extract, corydalis tuber extract, sophora flower bud extract and rosa roxburghii extract; the weight ratio of the tetrandra root extract to the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract in the plant extracts is 1: (0.1-0.5): (0.2-0.5): (0.1 to 0.4); preferably, the weight ratio of the radix stephaniae tetrandrae extract to the rhizoma corydalis extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.3: 0.3: 0.2.
the radix stephaniae tetrandrae extract is purchased from Hengchu biotechnology limited of Hunan; corydalis yanhusuo extract was purchased from Shaanxi forest Freund Natural products, Inc.; the flos Sophorae Immaturus extract is available from Sienna Dewei Biotech limited; rosa roxburghii extract is available from Shaanxi Sengfer Natural products, Inc.
The invention also provides a preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor, which at least comprises the following steps:
adding a main agent of the corrosion inhibitor, a synergist, a surfactant, a solvent and mercapto acid into a reactor according to parts by weight, mixing and uniformly stirring to obtain the environment-friendly high-temperature acidizing corrosion inhibitor.
The quinoline quaternary ammonium salt can be completely dissociated into positively charged quaternary ammonium cations and positively charged anion Cl in hydrochloric acid-Wherein, the quaternary ammonium salt cation acts on the cathode area of the surface of the metallic iron to generate electrostatic adsorption with the negatively charged metal surface, and the reduction reaction of cathode hydrogen ions is inhibited; meanwhile, the quinoline quaternary ammonium salt contains a condensed ring structure, and due to the fact that larger total electron delocalization energy is arranged on the condensed ring, the ability of unshared electrons to coordinate and combine with N atoms on the metal surface is enhanced, a chemical adsorption layer with a stable structure gradually appears, activation energy of anode reaction in a corrosion process is improved, and therefore corrosion rate of an anode is reduced.
The cation of the quaternary ammonium salt in the imidazole quaternary ammonium salt acts on the cathode area of the surface of the metallic iron to generate electrostatic adsorption with the negatively charged metallic surface, so that the reduction reaction of cathode hydrogen ions is inhibited; the hydrophobic nonpolar group is arranged far away from the metal surface in an oriented way, thereby effectively blocking Fe3+Diffusing into the solution while also allowing H in the solution+The migration to the process of the corrosion reaction of the metal is slowed down.
The Mannich base corrosion inhibitor molecule contains a plurality of nitrogen atoms or oxygen atoms with lone-pair electrons, 2 or 3 non-coordinating atoms are arranged between nitrogen, nitrogen or oxygen and nitrogen, wherein polar groups in the molecule can be adsorbed on the surface layer of metal, and the non-polar groups in the molecule are arranged upwards on the surface layer of metal, so that the structure of a metal double electric layer can be changed, and a layer of hydrophobic protective film is formed on the surface layer of metal to prevent corrosion reaction.
The tetrandra root extract in the plant extract contains alkaloid components, is a relatively complex nitrogen-containing organic compound, and is mostly a heterocyclic compound with nitrogen atoms in benzene rings; the radix stephaniae tetrandrae extract, the rhizoma corydalis extract, the sophora flower bud extract and the rosa roxburghii extract have obvious corrosion inhibition synergistic effect, and a film layer formed by molecular adsorption in the plant extract covers the metal surface, so that corrosion reaction can only be carried out on the uncovered metal surface, the area of the corroded metal surface is greatly reduced, and the corrosion of the metal is slowed down.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.
Example 1
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; the weight ratio of the radix stephaniae tetrandrae extract, the rhizoma corydalis extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.3: 0.3: 0.2;
the preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor at least comprises the following steps:
adding a main agent of the corrosion inhibitor, a synergist, a surfactant, a solvent and mercapto acid into a reactor according to the weight parts, and uniformly mixing and stirring to obtain the environment-friendly high-temperature acidizing corrosion inhibitor.
The preparation method of the quinoline quaternary ammonium salt comprises the following steps:
adding quinoline and benzyl chloride into a reactor, stirring and heating to 80 ℃, then slowly dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 160 ℃, adding ethanol, keeping the temperature for reaction for 3 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt.
The molar ratio of the quinoline, the benzyl chloride, the polyoxyethylene fatty alcohol ether and the ethanol is 1: 1.2: 0.1: 1.1;
the preparation method of the imidazole type quaternary ammonium salt comprises the following steps:
(1) adding benzoic acid, xylene and a zinc particle catalyst into a reactor, stirring uniformly, slowly dropwise adding diethylenetriamine, after dropwise adding, slowly heating to 140 ℃, reacting for 2 hours in a heat preservation manner, then heating to 180 ℃, reacting for 6 hours in a heat preservation manner, and concentrating dry xylene under reduced pressure after the reaction is finished; the weight ratio of the benzoic acid to the xylene to the zinc particles is 1: 8: 0.002;
(2) adding dimethyl carbonate into the step (1), heating to 85 ℃, carrying out heat preservation reaction for 5 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 5 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 60 ℃, carrying out heat preservation for 1 hour, cooling to 0-5 ℃, carrying out heat preservation for 1 hour, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt; the weight ratio of the dimethyl carbonate to the acetone is 1: 8.
the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the weight ratio of dimethyl carbonate to acetone is 1: 8.
the preparation method of the Mannich base comprises the following steps:
adding benzotriazole and absolute ethyl alcohol into a reactor, dropwise adding hydrochloric acid with the mass fraction of 20% to neutralize the mixed solution until the pH value is 2-3, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, stirring the solution, heating to 120 ℃, carrying out reflux reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain the Mannich base.
The mol ratio of the benzotriazole, the absolute ethyl alcohol, the benzaldehyde, the piperazine and the octyl phenol polyoxyethylene ether-10 is 1: 1.2: 1: 1.2: 0.05.
example 2
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1;
the preparation raw materials of the imidazole type quaternary ammonium salt comprise diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane, wherein the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; the weight ratio of the radix stephaniae tetrandrae extract to the rhizoma corydalis extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.1: 0.2: 0.1;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt, the preparation method of the imidazole quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1.
Comparative example 1
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1; the preparation raw materials of the imidazole type quaternary ammonium salt comprise diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane, wherein the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is a radix stephaniae tetrandrae extract;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt, the preparation method of the imidazole quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1.
Comparative example 2
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1; the preparation raw materials of the imidazole type quaternary ammonium salt comprise diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane, wherein the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is corydalis tuber extract;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt, the preparation method of the imidazole quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1.
Comparative example 3
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1; the preparation raw materials of the imidazole type quaternary ammonium salt comprise diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane, wherein the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is a sophora flower bud extract;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt, the preparation method of the imidazole quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1.
Comparative example 4
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1; the preparation raw materials of the imidazole type quaternary ammonium salt comprise diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane, wherein the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is a roxburgh rose extract;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt, the preparation method of the imidazole quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1.
Comparative example 5
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 8 parts of quinoline quaternary ammonium salt, 7 parts of imidazole quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1; the preparation raw materials of the imidazole type quaternary ammonium salt comprise diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane, wherein the molar ratio of the diethylenetriamine to the benzoic acid to the dimethyl carbonate to the 1, 4-dibromobutane is 1: 1.15: 1.05: 0.54; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt, the preparation method of the imidazole quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1 (the difference from example 1 is that no plant extract exists).
Comparative example 6
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 31 parts of a corrosion inhibitor main agent, 8 parts of a synergist, 0.8 part of a surfactant, 45 parts of a solvent and 6 parts of mercapto acid; the corrosion inhibitor main agent comprises 15 parts of quinoline quaternary ammonium salt and 16 parts of Mannich base; the synergist comprises 3 parts of organic alkynol and 5 parts of plant extract;
the preparation raw materials of the quinoline quaternary ammonium salt in the corrosion inhibitor main agent comprise quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether and ethanol, wherein the molar ratio of the quinoline to the benzyl chloride to the polyoxyethylene fatty alcohol ether to the ethanol is 1: 1.2: 0.1: 1.1; the surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid; the organic alkynol is propiolic alcohol; the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; the weight ratio of the radix stephaniae tetrandrae extract to the rhizoma corydalis extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.3: 0.3: 0.2;
the preparation method of the environment-friendly high-temperature acidification corrosion inhibitor, the preparation method of the quinoline quaternary ammonium salt and the preparation method of the Mannich base are the same as those in example 1.
And (3) performance testing:
1. corrosion inhibition performance test
And evaluating the corrosion inhibition effect at the temperature of more than 120 ℃, and evaluating according to a high-temperature high-pressure dynamic corrosion rate measuring method in the petroleum and natural gas industry standard SY/T5405-1996 corrosion inhibitor for acidification performance test method and evaluation index of the people's republic of China. Pouring the prepared sample (the adding amount of the corrosion inhibitor is 2%) into a high-temperature high-pressure kettle, then putting the treated test piece into the kettle, starting timing when the temperature reaches the specified temperature, taking out the test piece after reacting for 4 hours for treatment, and calculating the average corrosion rate.
Table 1 results of performance testing
From the data, the environment-friendly high-temperature resistant acidizing corrosion inhibitor provided by the invention has the excellent performances of environmental protection, high temperature resistance, low damage and the like.
Example 3
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 10 parts of a corrosion inhibitor main agent, 1 part of a synergist, 0.5 part of a surfactant, 40 parts of a solvent and 5 parts of mercapto acid; the corrosion inhibitor main agent comprises 15 parts of quinoline quaternary ammonium salt, 10 parts of imidazole quaternary ammonium salt and 20 parts of Mannich base in parts by weight; the synergist comprises 1 part of organic alkynol and 10 parts of plant extract in parts by weight.
The surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid.
The quinoline quaternary ammonium salt is prepared by the following steps: and adding quinoline and benzyl chloride into the reactor, stirring, heating to 90 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 170 ℃, adding ethanol, carrying out heat preservation reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt. Wherein the mol ratio of quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether to ethanol is 1: 1.05: 0.05: 1.
the azole-type quaternary ammonium salt is prepared by the following steps:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, heating to 130 ℃ after dropwise adding, carrying out heat preservation reaction for 3 hours, heating to 190 ℃, carrying out heat preservation reaction for 5 hours, and concentrating dry xylene under reduced pressure after reaction;
(2) and (2) adding dimethyl carbonate into the product obtained in the step (1), heating to 75 ℃, carrying out heat preservation reaction for 6 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 4 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 50 ℃, carrying out heat preservation for 2 hours, cooling to 0 ℃, carrying out heat preservation for 0.5 hour, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt. Wherein the weight ratio of the benzoic acid to the xylene to the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: 1.05: 1: 0.5; the weight ratio of dimethyl carbonate to acetone is 1: 8.
mannich bases are prepared by the following procedure:
adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 2 by adopting hydrochloric acid with the mass fraction of 20%, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 120 ℃ under stirring, carrying out reflux reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain the Mannich base. Wherein the mol ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: 1.1: 0.9: 1: 0.01;
the organic alkynol is propiolic alcohol;
the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.5: 0.2: 0.1.
according to the preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor, the corrosion inhibitor main agent, the synergist, the surfactant, the solvent and the mercapto acid are added into a reactor according to the parts by weight, and the mixture is uniformly stirred, so that the environment-friendly high-temperature acidizing corrosion inhibitor is obtained.
Example 4
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 20 parts of a corrosion inhibitor main agent, 3 parts of a synergist, 0.7 part of a surfactant, 60 parts of a solvent and 8 parts of mercapto acid; the corrosion inhibitor main agent comprises, by weight, 10 parts of quinoline quaternary ammonium salt, 8 parts of imidazole quaternary ammonium salt and 25 parts of Mannich base; the synergist comprises 2 parts of organic alkynol and 7 parts of plant extract in parts by weight.
The surfactant is sodium laurate; the solvent is propanol; the mercaptoacid is thioglycolic acid.
The quinoline quaternary ammonium salt is prepared by the following steps: and adding quinoline and benzyl chloride into the reactor, stirring, heating to 70 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 155 ℃, adding ethanol, carrying out heat preservation reaction for 3 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt. Wherein the mol ratio of quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether to ethanol is 1: 1.3: 0.15: 1.2.
the azole-type quaternary ammonium salt is prepared by the following steps:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, heating to 140 ℃ after dropwise adding, carrying out heat preservation reaction for 2.5 hours, heating to 170 ℃, carrying out heat preservation reaction for 7 hours, and concentrating dry xylene under reduced pressure after the reaction is finished;
(2) and (2) adding dimethyl carbonate into the product obtained in the step (1), heating to 85 ℃, carrying out heat preservation reaction for 5 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 5 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 60 ℃, carrying out heat preservation for 1.5 hours, cooling to 2 ℃, carrying out heat preservation for 1 hour, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt. Wherein the weight ratio of the benzoic acid to the xylene to the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: 1.3: 1.1: 0.6; the weight ratio of dimethyl carbonate to acetone is 1: 8.
mannich bases are prepared by the following procedure:
adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 3 by adopting hydrochloric acid with the mass fraction of 20%, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 110 ℃ under stirring, carrying out reflux reaction for 25h, and cooling to room temperature after the reaction is finished to obtain the Mannich base. Wherein the mol ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: 1.2: 1.1: 1.2: 0.1;
the organic alkynol is 1, 4-butynediol;
the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.2: 0.5: 0.3.
according to the preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor, the corrosion inhibitor main agent, the synergist, the surfactant, the solvent and the mercapto acid are added into a reactor according to the parts by weight, and the mixture is uniformly stirred, so that the environment-friendly high-temperature acidizing corrosion inhibitor is obtained.
Example 5
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 50 parts of a corrosion inhibitor main agent, 5 parts of a synergist, 1 part of a surfactant, 50 parts of a solvent and 7 parts of mercapto acid; the corrosion inhibitor main agent comprises 12 parts of quinoline quaternary ammonium salt, 6 parts of imidazole quaternary ammonium salt and 23 parts of Mannich base in parts by weight; the synergist comprises 3 parts of organic alkynol and 1 part of plant extract in parts by weight.
The surfactant is sodium laurate; the solvent is ethanol; the mercaptoacid is thioglycolic acid.
The quinoline quaternary ammonium salt is prepared by the following steps: and adding quinoline and benzyl chloride into the reactor, stirring, heating to 75 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 150 ℃, adding ethanol, carrying out heat preservation reaction for 3 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt. Wherein the mol ratio of quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether to ethanol is 1: 1.1: 0.2: 1.3.
the azole-type quaternary ammonium salt is prepared by the following steps:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, heating to 150 ℃ after dropwise adding, carrying out heat preservation reaction for 1h, heating to 180 ℃, carrying out heat preservation reaction for 6h, and concentrating dry xylene under reduced pressure after the reaction is finished;
(2) and (2) adding dimethyl carbonate into the product obtained in the step (1), heating to 90 ℃, carrying out heat preservation reaction for 4 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 6 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 70 ℃, carrying out heat preservation for 0.5 hour, cooling to 3 ℃, carrying out heat preservation for 2 hours, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt. Wherein the weight ratio of the benzoic acid to the xylene to the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: 1.2: 1.2: 0.52; the weight ratio of dimethyl carbonate to acetone is 1: 8.
mannich bases are prepared by the following procedure:
adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 2 by adopting hydrochloric acid with the mass fraction of 20%, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 130 ℃ under stirring, carrying out reflux reaction for 22h, and cooling to room temperature after the reaction is finished to obtain the Mannich base. Wherein the mol ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: 1.3: 0.95: 1.3: 0.03;
the organic alkynol is a mixture of propargyl alcohol, 1, 4-butynediol and methanesulfonic acid-2-propyn-1-ol;
the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.4: 0.4: 0.4.
according to the preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor, the corrosion inhibitor main agent, the synergist, the surfactant, the solvent and the mercapto acid are added into a reactor according to the parts by weight, and the mixture is uniformly stirred, so that the environment-friendly high-temperature acidizing corrosion inhibitor is obtained.
Example 6
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 40 parts of a corrosion inhibitor main agent, 10 parts of a synergist, 1.5 parts of a surfactant, 55 parts of a solvent and 9 parts of mercapto acid; the corrosion inhibitor main agent comprises, by weight, 5 parts of quinoline quaternary ammonium salt, 5 parts of imidazole quaternary ammonium salt and 10 parts of Mannich base; the synergist comprises 4 parts of organic alkynol and 3 parts of plant extract in parts by weight.
The surfactant is sodium laurate; the solvent is isopropanol; the mercaptoacid is thioglycolic acid.
The quinoline quaternary ammonium salt is prepared by the following steps: and adding quinoline and benzyl chloride into the reactor, stirring, heating to 80 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 165 ℃, adding ethanol, carrying out heat preservation reaction for 2.5 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt. Wherein the mol ratio of quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether to ethanol is 1: 1.2: 0.08: 1.1.
the azole-type quaternary ammonium salt is prepared by the following steps:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, heating to 135 ℃ after dropwise adding, carrying out heat preservation reaction for 1.5h, heating to 175 ℃, carrying out heat preservation reaction for 7h, and concentrating dry xylene under reduced pressure after the reaction is finished;
(2) and (2) adding dimethyl carbonate into the product obtained in the step (1), heating to 95 ℃, carrying out heat preservation reaction for 4 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 4 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 55 ℃, carrying out heat preservation for 1.5 hours, cooling to 4 ℃, carrying out heat preservation for 1.5 hours, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt. Wherein the weight ratio of the benzoic acid to the xylene to the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: 1.1: 115: 0.57; the weight ratio of dimethyl carbonate to acetone is 1: 8.
mannich bases are prepared by the following procedure:
adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 3 by adopting hydrochloric acid with the mass fraction of 20%, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 115 ℃ under stirring, carrying out reflux reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain the Mannich base. Wherein the mol ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: 1: 1.05: 1.1: 0.07;
the organic alkynol is a mixture of propargyl alcohol and 1, 4-butynediol;
the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.15: 0.25: 0.25.
according to the preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor, the corrosion inhibitor main agent, the synergist, the surfactant, the solvent and the mercapto acid are added into a reactor according to the parts by weight, and the mixture is uniformly stirred, so that the environment-friendly high-temperature acidizing corrosion inhibitor is obtained.
Example 7
An environment-friendly high-temperature acidizing corrosion inhibitor comprises, by weight, 45 parts of a corrosion inhibitor main agent, 6 parts of a synergist, 1.2 parts of a surfactant, 60 parts of a solvent and 10 parts of mercapto acid; the corrosion inhibitor main agent comprises 6 parts of quinoline quaternary ammonium salt, 9 parts of imidazole quaternary ammonium salt and 13 parts of Mannich base in parts by weight; the synergist comprises 5 parts of organic alkynol and 4 parts of plant extract in parts by weight.
The surfactant is sodium laurate; the solvent is propanol; the mercaptoacid is thioglycolic acid.
The quinoline quaternary ammonium salt is prepared by the following steps: and adding quinoline and benzyl chloride into the reactor, stirring, heating to 90 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 160 ℃, adding ethanol, carrying out heat preservation reaction for 3 hours, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt. Wherein the mol ratio of quinoline, benzyl chloride, polyoxyethylene fatty alcohol ether to ethanol is 1: 1.15: 0.17: 1.2.
the azole-type quaternary ammonium salt is prepared by the following steps:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, heating to 145 ℃ after dropwise adding, carrying out heat preservation reaction for 2 hours, heating to 185 ℃, carrying out heat preservation reaction for 6 hours, and concentrating dry xylene under reduced pressure after the reaction is finished;
(2) and (2) adding dimethyl carbonate into the product obtained in the step (1), heating to 80 ℃, carrying out heat preservation reaction for 5 hours, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 5 hours, cooling to room temperature after the reaction is finished, adding acetone, heating to 65 ℃, carrying out heat preservation for 1 hour, cooling to 5 ℃, carrying out heat preservation for 1 hour, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt. Wherein the weight ratio of the benzoic acid to the xylene to the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: 1.25: 1.1: 0.58; the weight ratio of dimethyl carbonate to acetone is 1: 8.
mannich bases are prepared by the following procedure:
adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 2.5 by adopting hydrochloric acid with the mass fraction of 20%, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 125 ℃ under stirring, carrying out reflux reaction for 23h, and cooling to room temperature after the reaction is finished to obtain the Mannich base. Wherein the mol ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: 1.05: 1.1: 1.05: 0.08;
the organic alkynol is methanesulfonic acid-2-propyne-1-ol;
the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: 0.25: 0.35: 0.3.
according to the preparation method of the environment-friendly high-temperature acidizing corrosion inhibitor, the corrosion inhibitor main agent, the synergist, the surfactant, the solvent and the mercapto acid are added into a reactor according to the parts by weight, and the mixture is uniformly stirred, so that the environment-friendly high-temperature acidizing corrosion inhibitor is obtained.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. An environment-friendly high-temperature acidizing corrosion inhibitor is characterized by comprising, by weight, 10-50 parts of a corrosion inhibitor main agent, 1-10 parts of a synergist, 0.5-1.5 parts of a surfactant, 40-60 parts of a solvent and 5-10 parts of mercapto acid; the corrosion inhibitor main agent comprises, by weight, 5-15 parts of quinoline quaternary ammonium salt, 5-10 parts of imidazole quaternary ammonium salt and 10-25 parts of Mannich base; the synergist comprises 1-5 parts by weight of organic alkynol and 1-10 parts by weight of plant extract;
the plant extract is a mixture of a tetrandra root extract, a corydalis tuber extract, a sophora flower bud extract and a rosa roxburghii tratt extract; and the weight ratio of the radix stephaniae tetrandrae extract, the corydalis tuber extract, the sophora flower bud extract and the rosa roxburghii tratt extract is 1: (0.1-0.5): (0.2-0.5): (0.1-0.4).
2. The environment-friendly high-temperature acidizing corrosion inhibitor according to the claim 1, wherein the surfactant is sodium laurate; the solvent is one of isopropanol, propanol and ethanol; the mercaptoacid is thioglycolic acid.
3. The environment-friendly high-temperature acidizing corrosion inhibitor according to the claim 1, wherein the quaternary ammonium salt of quinoline is prepared by the following processes: adding quinoline and benzyl chloride into a reactor, stirring and heating to 70-90 ℃, then dropwise adding polyoxyethylene fatty alcohol ether, continuously heating to 150-170 ℃, adding ethanol, carrying out heat preservation reaction for 2-4 h, and cooling to room temperature after the reaction is finished to obtain the quinoline quaternary ammonium salt.
4. The environment-friendly high-temperature acidizing corrosion inhibitor according to claim 3, wherein the molar ratio of the quinoline, the benzyl chloride, the polyoxyethylene fatty alcohol ether and the ethanol is 1: (1.05-1.3): (0.05-0.2): (1-1.3).
5. The environment-friendly high-temperature acidizing corrosion inhibitor according to the claim 1, wherein the imidazole type quaternary ammonium salt is prepared by the following processes:
(1) adding benzoic acid, xylene and zinc particles into a reactor, uniformly stirring, dropwise adding diethylenetriamine, after dropwise adding, heating to 130-150 ℃, carrying out heat preservation reaction for 1-3 h, then heating to 170-190 ℃, carrying out heat preservation reaction for 5-7 h, and concentrating dry xylene under reduced pressure after reaction;
(2) adding dimethyl carbonate into the product obtained in the step (1), heating to 75-95 ℃, carrying out heat preservation reaction for 4-6 h, then adding 1, 4-dibromobutane, carrying out heat preservation reaction for 4-6 h, cooling to room temperature after the reaction is finished, adding acetone, heating to 50-70 ℃, carrying out heat preservation for 0.5-2 h, cooling to 0-5 ℃, carrying out heat preservation for 0.5-2 h, filtering, and drying under reduced pressure to obtain the imidazole type quaternary ammonium salt.
6. The environment-friendly high-temperature acidizing corrosion inhibitor according to claim 5, wherein the weight ratio of the benzoic acid, the xylene and the zinc particles is 1: 8: 0.002; the molar ratio of diethylenetriamine, benzoic acid, dimethyl carbonate and 1, 4-dibromobutane is 1: (1.05-1.3): (1-1.2): (0.5 to 0.6); the weight ratio of dimethyl carbonate to acetone is 1: 8.
7. the environment-friendly high-temperature acidizing corrosion inhibitor according to the claim 1, wherein the mannich base is prepared by the following processes: adding benzotriazole and absolute ethyl alcohol into a reactor, adjusting the pH value to 2-3, then adding benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10, heating to 110-130 ℃ under stirring, carrying out reflux reaction for 22-25 h, and cooling to room temperature after the reaction is finished to obtain the Mannich base.
8. The environment-friendly high-temperature acidizing corrosion inhibitor according to claim 7, wherein the molar ratio of benzotriazole, absolute ethyl alcohol, benzaldehyde, piperazine and octyl phenol polyoxyethylene ether-10 is 1: (1-1.3): (0.9-1.1): (1-1.3): (0.01 to 0.1); and regulating the pH value to 2-3 by adopting hydrochloric acid with the mass fraction of 20%.
9. The environmentally friendly high temperature acidizing corrosion inhibitor according to claim 1, wherein said organic alkynol is one or more of propiolic alcohol, 1, 4-butynediol, methanesulfonic acid-2-propiolic-1-ol.
10. A method for preparing the environment-friendly high-temperature acidizing corrosion inhibitor according to any one of the claims 1 to 9, which is characterized in that a corrosion inhibitor main agent, a synergist, a surfactant, a solvent and mercapto acid are added into a reactor according to parts by weight and are uniformly stirred to obtain the environment-friendly high-temperature acidizing corrosion inhibitor.
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| CN103450866B (en) * | 2013-09-06 | 2015-11-25 | 中国海洋石油总公司 | A kind of High-temperature carbon dioxide corrosion inhibitor |
| CN107418549B (en) * | 2017-08-29 | 2020-03-24 | 中国石油集团渤海钻探工程有限公司 | Composite acidizing corrosion inhibitor capable of resisting temperature of 120-140 DEG C |
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