CN113801275B - Corrosion inhibitor for resisting carbon dioxide corrosion and preparation method and application thereof - Google Patents
Corrosion inhibitor for resisting carbon dioxide corrosion and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a corrosion inhibitor for resisting carbon dioxide corrosion, a preparation method and application thereof, and belongs to the technical field of carbon dioxide displacement. The corrosion inhibitor is prepared by the steps of prepolymerizing a first monomer and N-vinyl pyrrolidone to obtain a first intermediate, reacting the first intermediate, a second monomer and a third monomer to obtain a second intermediate, reacting the second intermediate with alkynol, and then adding antimony trichloride to compound. The preparation method of the corrosion inhibitor is simple, the prepared corrosion inhibitor can react with carbon dioxide, the generation of acid liquor is reduced, the corrosion inhibitor can be adsorbed on the surface of metal to form a protective film, and the acid liquor is prevented from contacting the metal, so that the corrosion of the metal is reduced; meanwhile, the high-temperature performance is stable, and the corrosion inhibitor can play a good corrosion inhibition role in a shaft bottom with higher temperature.
Description
Technical Field
The application relates to a corrosion inhibitor for resisting carbon dioxide corrosion, a preparation method and application thereof, belonging to the technical field of carbon dioxide displacement.
Background
The carbon dioxide oil displacement technology is characterized in that supercritical carbon dioxide fluid (the critical point of the carbon dioxide is 7.4MPa, and the temperature is 31.2 ℃) is used as an oil displacement agent to be injected into an oil layer, the injected carbon dioxide can reduce the viscosity of crude oil, improve the oil-water fluidity ratio, expand the volume of the crude oil and enhance the energy of the oil layer, and miscible phase displacement can be realized under certain conditions, so that the purposes of expanding the swept degree and improving the oil reservoir recovery ratio are achieved.
However, carbon dioxide and water form a mixed-phase fluid, namely acid liquor, underground, and the acid liquor can cause strong corrosion to pipelines, and sudden situations such as cracking of oil and gas in pipeline transportation can occur after long-time corrosion. Currently, corrosion inhibitors are commonly added to oil displacing agents to inhibit carbon dioxide corrosion.
With the increasing maturity of oil and gas exploitation technology, the exploitation well depth is continuously increased, the temperature of the well bottom is gradually increased, the problems of unstable corrosion inhibition performance and the like of the existing corrosion inhibitor are easy to occur in a high-temperature well bottom environment, the normal exploitation of oil and gas is not influenced, and formation damage is possibly caused.
Disclosure of Invention
In order to solve the problems, the corrosion inhibitor for resisting carbon dioxide corrosion and the preparation method and the application thereof are provided, the corrosion inhibitor can react with carbon dioxide, reduce the generation of acid liquor, can be adsorbed on the surface of metal to form a protective film, and can prevent the acid liquor from contacting the metal, thereby reducing the corrosion of the metal; meanwhile, the high-temperature performance is stable, and the corrosion inhibitor can play a good corrosion inhibition role in a shaft bottom with higher temperature.
According to one aspect of the present application, there is provided a method for preparing a corrosion inhibitor against carbon dioxide corrosion, comprising the steps of:
prepolymerizing a first monomer and N-vinyl pyrrolidone to obtain a first intermediate;
polymerizing the first intermediate, the second monomer and the third monomer to obtain a second intermediate;
adding alkynol into the second intermediate for polymerization, and then adding antimony trichloride for mixing to obtain the corrosion inhibitor;
wherein the first monomer is allyl polyether and/or diallyl polyether;
the second monomer is at least one of N, N-methylene bisacrylamide, acrylamide and N- (hydroxymethyl) acrylamide;
the third monomer is at least one selected from the group consisting of formaldehyde, trioxymethylene and paraformaldehyde.
Preferably, the third monomer is formaldehyde.
Optionally, the weight ratio of the first monomer to the N-vinyl pyrrolidone is 1: (1-10); and/or
The weight ratio of the first intermediate, the second monomer and the third monomer is (5-15) (10-50): (5-10); and/or
The weight ratio of the second intermediate, the alkynol and the antimony trichloride is (10-80): (5-10): (1-5).
Preferably, the weight ratio of the first monomer to the N-vinyl pyrrolidone is 1: 4; and/or
The weight ratio of the first intermediate to the second monomer to the third monomer is 10: 35: 5; and/or
The weight ratio of the second intermediate, the alkynol and the antimony trichloride is (40-60): (6-8): (2-3);
more preferably, the weight ratio of the second intermediate, alkynol and antimony trichloride is 50: 7: 3.
optionally, the first monomer is a mixture of allyl polyether and diallyl polyether, and the weight ratio of the allyl polyether to the diallyl polyether is 1: (4-9).
Preferably, the weight ratio of the allyl polyether to the diallyl polyether is 1: 7.
optionally, the allyl polyether is at least one of allyl polyoxyethylene methyl ether, allyl polyoxyethylene propyl ether, allyl polyoxyethylene epoxy ether, allyl polyoxyethylene acetate and allyl polyoxyethylene polyoxypropylene acetate;
the diallyl polyether has an average molecular weight of 4000-10000. Here, the average molecular weight is an index average molecular weight.
Preferably, the allyl polyether is a mixture of allyl polyoxyethylene methyl ether and allyl polyoxyethylene epoxy ether, and the weight ratio of the allyl polyoxyethylene methyl ether to the allyl polyoxyethylene epoxy ether is 1: (2-5);
the average molecular weight of the diallyl polyether is 4000-8000;
more preferably, the weight ratio of the allyl polyoxyethylene methyl ether to the allyl polyoxyethylene epoxy ether is 1: 4;
the average molecular weight of the diallyl polyether is 6000.
Optionally, the weight ratio of N, N-methylenebisacrylamide, acrylamide, and N- (hydroxymethyl) acrylamide in the second monomer is (1-10): (2-5): (0-5).
Optionally, the second monomer is a mixture of N, N-methylene bisacrylamide and acrylamide, and the weight ratio of N, N-methylene bisacrylamide to acrylamide is 5: 2.
optionally, dissolving a first monomer, N-vinyl pyrrolidone and an initiator into a first solvent, uniformly stirring, introducing nitrogen, heating to 50-75 ℃, and reacting for 1-5 hours to obtain a first intermediate;
according to the parts by weight, the total monomer content is 30-60%, the initiator content is 0.2-1.0%, and the balance is a first solvent;
the first solvent is at least one of hexane, benzene, toluene, xylene, diethyl ether and acetone.
Preferably, the temperature is raised to 60-70 ℃, and the first intermediate is obtained after 2-4h of reaction;
the total monomer content is 50 percent, the initiator content is 0.5 percent, and the balance is the first solvent according to the parts by weight.
More preferably, the temperature is increased to 65 ℃, and the reaction is carried out for 3h to obtain the first intermediate;
optionally, the initiator is at least one of azo, peroxyacid, and peroxy initiators.
Optionally, dissolving the first intermediate, the second monomer, the third monomer and the catalyst into a second solvent, uniformly stirring, adjusting the pH =2-3, heating to 80-90 ℃, and reacting for 5-7h to obtain a second intermediate;
the total monomer content is 40-55%, the catalyst content is 0.2-1.0%, and the balance is the second solvent;
the second solvent is at least one of deionized water, methanol and absolute ethyl alcohol.
Preferably, the temperature is increased to 80-85 ℃, and the second intermediate is obtained after the reaction for 5-6 h;
the total monomer content is 50 percent, the catalyst content is 0.5 percent and the rest is a second solvent according to the parts by weight;
more preferably, the temperature is increased to 85 ℃, and the second intermediate is obtained after the reaction for 6 hours;
optionally, the catalyst is zinc fluoroborate, zirconium oxide, AlCl3、NbCl5And InCl3At least one of (1).
Optionally, alkynol is added into the second intermediate, polymerization is carried out for at least 3h at the temperature of 80-90 ℃, then the temperature is reduced to 40-50 ℃, antimony trichloride is added, and mixing is carried out for 0.5-1h, thus obtaining the corrosion inhibitor.
Preferably, alkynol is added into the second intermediate, polymerization is carried out for at least 3h at 85 ℃, then the temperature is reduced to 40 ℃, antimony trichloride is added, and mixing is carried out for 0.5h, thus obtaining the high-temperature acidification corrosion inhibitor.
According to another aspect of the application, a corrosion inhibitor for resisting carbon dioxide corrosion is provided, and the corrosion inhibitor is prepared by the preparation method of any one of the above.
According to a further aspect of the application, a corrosion inhibitor prepared by the preparation method of any one of the above or the application of the corrosion inhibitor in retarding corrosion of oil and water conveying pipelines is provided.
Benefits of the present application include, but are not limited to:
1. according to the preparation method of the corrosion inhibitor, the toxicity of the used raw materials is low, the synthesis operation of each step is simple, the synthesis is carried out step by step, the prepared corrosion inhibitor is large in molecular weight, long in molecular chain and large in number of side group, a protective film can be formed on the surface of metal, and the corrosion inhibition effect is good.
2. According to the corrosion inhibitor prepared by the application, a good anti-corrosion effect can be achieved by adding a small amount of the corrosion inhibitor into the oil displacement agent, formation pollution is avoided, production equipment can be effectively protected, the service life of the equipment is prolonged, the production efficiency is improved, safety production is ensured, the cost is saved, and the oil and gas exploitation amount is enlarged.
3. According to the corrosion inhibitor prepared by the application, a molecular chain is provided with amino groups and hydroxyl groups, wherein the amino groups are used as basic groups, so that the corrosion inhibitor has strong trapping capacity on acidic gas carbon dioxide, and can be used as an active center to perform condensation reaction with the carbon dioxide, thereby effectively reducing the generation of acid liquor and preventing the corrosion of the acid liquor on metal pipelines; in addition, as the molecules have polar groups and nonpolar groups, wherein the polar groups are more in number, the molecules can be adsorbed on the metal surface by utilizing the polar action of the molecules, so that adsorption points can be increased, the corrosion inhibitor is driven to be arranged on the metal surface to form a protective film, and acid liquor is prevented from contacting the metal, thereby reducing the corrosion of the metal.
4. According to the corrosion inhibitor prepared by the application, allyl polyether molecules in the first intermediate can be used as branched chains in a molecular chain of the corrosion inhibitor, and long-chain side groups can form hydrophobic association in crude oil, so that the acid resistance and the temperature resistance of the corrosion inhibitor are improved, and the corrosion inhibitor can effectively inhibit corrosion in high-temperature acid liquor. The diallyl polyether can be used as a straight chain in a molecule, the length of a molecular chain of the corrosion inhibitor is prolonged, the molecular chain of the corrosion inhibitor can move freely, and the molecular chains can be wound and disentangled with each other, so that the diallyl polyether can be flexibly adsorbed on the surface of metal to protect the metal from corrosion.
5. According to the corrosion inhibitor prepared by the application, the first intermediate contains pyrrolidone groups, so that the rigidity of a molecular chain can be enhanced, and when the corrosion inhibitor is adsorbed on the metal surface, the molecular chain is arranged on the metal surface more regularly to form a compact protective film, so that the gaps of the protective film are reduced, and further, acid liquor is prevented from contacting the metal surface, and the metal corrosion is inhibited.
6. According to the corrosion inhibitor prepared by the application, a second monomer, a third monomer and a first intermediate are subjected to a Mannich reaction, molecular chains are crosslinked, the acid solubility of the synthesized corrosion inhibitor is stable, the corrosion inhibition effect can be exerted in acid liquor for a long time, and the phenomena of layering, precipitation and coking are avoided; the molecular chain exists on the metal surface in the form of a protective film, the ester groups are uniformly distributed on the molecular chain of the corrosion inhibitor, and gaps of the protective film are filled, so that the acid liquor is further prevented from contacting the metal surface, and the purpose of corrosion inhibition is achieved.
7. According to the corrosion inhibitor prepared by the application, a part of alkynol participates in the reaction, so that the acid solubility of the corrosion inhibitor can be improved, and in addition, the alkynol which does not participate in the reaction and antimony trichloride are dispersed in a protective film formed by the corrosion inhibitor in a small molecular form, so that metal is protected from being corroded; the alkynol which does not participate in the reaction can carry out a conjugate reaction, and is connected with the macromolecular chain of the corrosion inhibitor through the conjugate effect, so that the temperature resistance of the corrosion inhibitor can be improved, and the corrosion inhibition effect of the corrosion inhibitor at high temperature can be improved.
8. According to the corrosion inhibitor prepared by the application, the N-vinyl pyrrolidone, the first monomer, the second monomer and the third monomer are matched with each other, so that the acid resistance and the temperature resistance of the corrosion inhibitor can be improved, and the corrosion inhibition effect can be exerted even in a high-temperature and high-acid environment; the raw materials and the proportion thereof selected by each monomer can ensure that the polymer is polymerized efficiently, and simultaneously, a plurality of oxygen atoms and nitrogen atoms or groups with lone pair electrons can be ensured in the molecular chain of the corrosion inhibitor and can be adsorbed on the surface of metal to protect the metal from being corroded.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials and various auxiliaries in the examples of the present application were all purchased commercially, unless otherwise specified.
And (3) carrying out infrared spectrum analysis on the corrosion inhibitor by using a Fourier transform infrared spectrometer, and carrying out test analysis on the obtained corrosion inhibitor by adopting an attenuated total reflection mode at room temperature.
Example 1
(1) Respectively weighing 400.0g of N-vinyl pyrrolidone, 2.5g of allyl polyoxyethylene methyl ether, 10.0g of allyl polyoxyethylene epoxy ether and 87.5g of diallyl polyether (with the molecular weight average molecular weight of 6000), dissolving in 495.0g of absolute ethanol, introducing nitrogen, heating to 65 ℃, adding 5.0g of azobisisobutyronitrile, uniformly stirring, and reacting for 3 hours to obtain a first intermediate;
(2) respectively weighing 100.0g of first intermediate, 250.0g of 250.0g N, N-methylene bisacrylamide, 100.0g of acrylamide and 50.0g of formaldehyde, dissolving in 495.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, subsequently heating to 85 ℃, uniformly stirring, and reacting for 6 hours to obtain a second intermediate;
(3) weighing 500.0g of a second intermediate, heating to 85 ℃, adding 70.0g of alkynol, and uniformly stirring for reacting for 3 hours; then the temperature is reduced to 40 ℃, 30.0g of antimony trichloride is added, and the mixture is stirred for 0.5h, so that the corrosion inhibitor 1# is obtained.
Example 2
(1) Respectively weighing 150.0g of N-vinyl pyrrolidone, 5.0g of allyl polyoxyethylene methyl ether, 10.0g of allyl polyoxyethylene epoxy ether and 135.0g of diallyl polyether (with the average molecular weight of 10000), dissolving in 698.0g of absolute ethanol, introducing nitrogen, heating to 75 ℃, adding 2.0g of azobisisobutyronitrile, uniformly stirring, and reacting for 1 hour to obtain a first intermediate;
step (2) and step (3) are the same as in example 1, and corrosion inhibitor # 2 is prepared.
Example 3
(1) Respectively weighing 545.5g of N-vinyl pyrrolidone, 1.8g of allyl polyoxyethylene methyl ether, 9.1g of allyl polyoxyethylene epoxy ether and 43.6g of diallyl polyether (average molecular weight is 4000) and dissolving in 390.0g of ethanol, introducing nitrogen, then heating to 75 ℃, adding 10.0g of azobisisobutyronitrile, uniformly stirring and reacting for 1 hour to obtain a first intermediate;
(2) (3) the same as in example 1, corrosion inhibitor # 3 was prepared.
Example 4
(1) Same as example 1;
(2) respectively weighing 33.3g of the first intermediate, 41.7g N, N-methylenebisacrylamide, 83.4g of acrylamide, 208.3 g of N- (hydroxymethyl) acrylamide and 33.3g of trioxymethylene, dissolving into 598.0g of absolute ethyl alcohol, adding 2.0g of zinc fluoroborate, adjusting the pH to be =2-3, then heating to 80 ℃, uniformly stirring, and reacting for 7 hours to obtain a second intermediate;
(3) corrosion inhibitor # 4 was prepared as in example 1.
Example 5
(1) Same as example 1;
(2) respectively weighing 235.7g of the first intermediate, 78.6g N, N-methylenebisacrylamide, 39.3g of acrylamide, 39.3g of N- (hydroxymethyl) acrylamide and 157.1g of paraformaldehyde, dissolving in 440.0g of absolute ethanol, adding 10.0g of zinc fluoroborate, adjusting the pH to be =2-3, then heating to 90 ℃, uniformly stirring, and reacting for 5 hours to obtain a second intermediate;
(3) corrosion inhibitor # 5 was prepared as in example 1.
Example 6
(1) (2) same as example 1;
(3) weighing 100.0g of a second intermediate, heating to 80 ℃, adding 50.0g of alkynol, and uniformly stirring for reacting for 5 hours; then cooling to 50 ℃, adding 50.0g of antimony trichloride, and stirring for 1h to obtain the corrosion inhibitor 6 #.
Example 7
(1) (2) same as example 1;
(3) weighing 800.0g of a second intermediate, heating to 90 ℃, adding 100.0g of alkynol, and uniformly stirring for reacting for 3 hours; then cooling to 50 ℃, adding 10.0g of antimony trichloride, and stirring for 0.5h to obtain the corrosion inhibitor 7 #.
Example 8
The difference from example 1 is that the weight ratio of N-vinylpyrrolidone and first monomer in step (1) is = 15: 1, the method comprises the following specific steps:
(1) respectively weighing 468.7g of N-vinyl pyrrolidone, 0.8g of allyl polyoxyethylene methyl ether, 3.1g of allyl polyoxyethylene epoxy ether and 27.4g of diallyl polyether (with the average molecular weight of 6000), dissolving in 495.0g of absolute ethanol, introducing nitrogen, heating to 65 ℃, adding 5.0g of azobisisobutyronitrile, uniformly stirring, and reacting for 3 hours to obtain a first intermediate;
(2) (3) the same as in example 1, corrosion inhibitor # 8 was prepared.
Example 9
The difference from the example 1 is that the weight ratio of the allyl polyether to the diallyl polyether in the first monomer of the step (1) is 1: 1, and the weight ratio of allyl polyoxyethylene methyl ether to allyl polyoxyethylene epoxy ether in the allyl polyether is 1: 1, the method comprises the following specific steps:
(1) respectively weighing 400.0g of N-vinyl pyrrolidone, 25.0g of allyl polyoxyethylene methyl ether, 25.0g of allyl polyoxyethylene epoxy ether and 50.0g of diallyl polyether (with the average molecular weight of 6000), dissolving in 495.0g of absolute ethanol, introducing nitrogen, heating to 65 ℃, adding 5.0g of azobisisobutyronitrile, uniformly stirring, and reacting for 3 hours to obtain a first intermediate;
(2) (3) the same as in example 1, corrosion inhibitor # 9 was prepared.
Example 10
The difference from the example 1 is that the total monomer content in the step (1) is 70%, and the specific steps are as follows:
(1) respectively weighing 560.0g of N-vinyl pyrrolidone, 3.5g of allyl polyoxyethylene methyl ether, 14.0g of allyl polyoxyethylene epoxy ether and 122.5g of diallyl polyether (with the average molecular weight of 6000), dissolving in 295.0g of absolute ethanol, introducing nitrogen, heating to 65 ℃, adding 5.0g of azobisisobutyronitrile, uniformly stirring, and reacting for 3 hours to obtain a first intermediate;
(2) (3) the same as in example 1, corrosion inhibitor # 10 was prepared.
Example 11
The difference from example 1 is that the reaction temperature of step (1) is 40 ℃, and the specific steps are as follows:
(1) respectively weighing 400.0g of N-vinyl pyrrolidone, 2.5g of allyl polyoxyethylene methyl ether, 10.0g of allyl polyoxyethylene epoxy ether and 87.5g of diallyl polyether (with the average molecular weight of 6000), dissolving in 495.0g of absolute ethanol, introducing nitrogen, heating to 40 ℃, adding 5.0g of azobisisobutyronitrile, uniformly stirring, and reacting for 3 hours to obtain a first intermediate;
(2) (3) Corrosion inhibitor # 11 with an average molecular weight of 150000 was prepared in the same manner as in example 1.
Example 12
The difference from example 1 is that the weight ratio of the first intermediate, the second monomer and the third monomer in step (2) is 10: 5: the specific steps are as follows:
(1) same as example 1;
(2) respectively weighing 250.0g of first intermediate, 89.3g N g of N-methylene bisacrylamide, 35.7g of acrylamide and 125.0g of formaldehyde, dissolving in 495.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, subsequently heating to 85 ℃, uniformly stirring, and reacting for 6h to obtain a second intermediate;
(3) corrosion inhibitor # 12 was prepared as in example 1.
Example 13
The difference from example 1 is that the weight ratio of N, N-methylenebisacrylamide, acrylamide, and N- (hydroxymethyl) acrylamide in the second monomer of step (2) is 1: 1: 1, the method comprises the following specific steps:
(1) same as example 1;
(2) respectively weighing 100.0g of the first intermediate, 116.6g N, N-methylene bisacrylamide, 111.6g of acrylamide, 111.7g of N- (hydroxymethyl) acrylamide and 50.0g of formaldehyde, dissolving in 495.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, then heating to 85 ℃, uniformly stirring, and reacting for 6 hours to obtain a second intermediate;
(3) the corrosion inhibitor # 13 was prepared in the same manner as in example 1.
Example 14
The difference from example 1 is that the total monomer content in step (2) is 60%, and the specific steps are as follows:
(1) same as example 1;
(2) respectively weighing 120.0g of first intermediate, 300.0g of 300.0g N, N-methylene bisacrylamide, 120.0g of acrylamide and 60.0g of formaldehyde, dissolving in 395.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, subsequently heating to 85 ℃, uniformly stirring, and reacting for 6 hours to obtain a second intermediate;
step (3) was performed in the same manner as in example 1 to obtain corrosion inhibitor # 14.
Example 15
The difference from the example 1 is that the reaction temperature in the step (2) is 70 ℃, and the specific steps are as follows:
(1) same as example 1;
(2) weighing 100.0g of the first intermediate, 250.0g of 250.0g N, N-methylene bisacrylamide, 100.0g of acrylamide and 50.0g of formaldehyde respectively, dissolving in 495.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, then heating to 70 ℃, uniformly stirring, and reacting for 6h to obtain a second intermediate;
(3) the corrosion inhibitor No. 15 was prepared in the same manner as in example 1.
Example 16
The difference from the example 1 is that the weight ratio of the second intermediate, the alkynol and the antimony trichloride in the step (3) is 5: 5: 5, the method comprises the following specific steps:
(1) (2) same as example 1;
(3) weighing 200.0g of a second intermediate, heating to 85 ℃, adding 200.0g of alkynol, and uniformly stirring for reacting for 3 hours; then cooling to 40 ℃, adding 200.0g of antimony trichloride, and stirring for 0.5h to obtain the corrosion inhibitor 16 #.
Example 17
The difference from the example 1 is that the reaction temperature after the alkynol is added in the step (3) is 70 ℃, the reaction time is 2h, and the specific steps are as follows:
(1) (2) same as example 1;
(3) weighing 500.0g of a second intermediate, heating to 70 ℃, adding 70.0g of alkynol, and uniformly stirring for reacting for 2 hours; then the temperature is reduced to 40 ℃, 30.0g of antimony trichloride is added, and the mixture is stirred for 0.5h, so that the corrosion inhibitor 17# is obtained.
Comparative example 1
The difference from example 1 is that the first monomer in step (1) is replaced by ethylene; the method comprises the following specific steps:
(1) respectively weighing 400.0g of N-vinyl pyrrolidone and 100.0g of ethylene, dissolving in 495.0g of absolute ethyl alcohol, introducing nitrogen, heating to 65 ℃, adding 5.0g of azodiisobutyronitrile, uniformly stirring, and reacting for 3 hours to obtain a first intermediate;
(2) (3) A corrosion inhibitor D1# was prepared in the same manner as in example 1.
Comparative example 2
The difference from the embodiment 1 is that the second monomer in the step (2) is replaced by benzotriazole, and the specific steps are as follows:
(1) same as example 1;
(2) weighing 100.0g of a first intermediate, 350.0g of benzotriazole and 50.0g of formaldehyde respectively, dissolving in 495.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, heating to 85 ℃, uniformly stirring, and reacting for 6 hours to obtain a second intermediate;
(3) a corrosion inhibitor D2# was prepared in the same manner as in example 1.
Comparative example 3
The difference from the example 1 is that the third monomer in the step (2) is replaced by butanone, and the specific steps are as follows:
(1) same as example 1;
(2) respectively weighing 100.0g of first intermediate, 250.0g of 250.0g N, N-methylene bisacrylamide, 100.0g of acrylamide and 50.0g of butanone, dissolving in 495.0g of absolute ethanol, adding 5.0g of zinc fluoborate, adjusting the pH to be =2-3, subsequently heating to 85 ℃, uniformly stirring, and reacting for 6h to obtain a second intermediate;
(3) a corrosion inhibitor D3# was prepared in the same manner as in example 1.
Comparative example 4
The difference from the example 1 is that the alkynol is replaced by antimony trioxide in the step (3), and the specific steps are as follows:
(1) (2) same as example 1;
(3) weighing 500.0g of a second intermediate, heating to 85 ℃, adding 70.0g of antimony trioxide, uniformly stirring, and reacting for 3 hours; then the temperature is reduced to 40 ℃, 30.0g of antimony trichloride is added, and the mixture is stirred for 0.5h, thus obtaining the corrosion inhibitor D4 #.
Comparative example 5
The difference from example 1 is that all monomers and auxiliaries are polymerized together, the specific steps are as follows:
400.0g of N-vinylpyrrolidone, 2.5g of allyl polyoxyethylene methyl ether, 10.0g of allyl polyoxyethylene epoxy ether, 87.5g of diallyl polyether (average molecular weight: 6000) and 5.0g of azobisisobutyronitrile were weighed and dissolved in 495.0g of anhydrous ethanol to obtain a first component; weighing 100.0g of the first intermediate, 250.0g of 250.0g N, N-methylenebisacrylamide, 100.0g of acrylamide, 50.0g of formaldehyde and 5.0g of zinc fluoroborate, and dissolving in 495.0g of absolute ethanol to obtain a second component; adjusting the pH of the second component to be 2-3, heating to 85 ℃, adding 100.0 of the first component and 35.0g of alkynol, stirring for reaction for 6 hours, then cooling to 40 ℃, adding 30.0g of antimony trichloride, and stirring for 0.5 hour to obtain the corrosion inhibitor D5 #.
Examples of the experiments
In order to evaluate the corrosion inhibition performance of the corrosion inhibitor of the present application in a carbon dioxide environment, the corrosion inhibitors prepared in examples 1 to 17 and comparative examples 1 to 5 were tested for corrosion rate and corrosion inhibition rate, respectively, as follows, and the test results are shown in table 1.
Corrosion rate: introducing carbon dioxide into the experimental medium for 1h, and clarifying the solution for later use; taking a test piece N80, grinding and polishing the test piece by using metallographic abrasive paper, degreasing and deoiling the test piece by using distilled water, absolute ethyl alcohol and acetone in sequence, drying and weighing the test piece; adding a corrosion inhibitor into carbon dioxide saturated oil field layer water, wherein the amount of the corrosion inhibitor is 1.5wt%, uniformly stirring, immersing the treated test pieces in the water, arranging two groups of experimental groups, respectively sealing and hanging the test pieces at 100 ℃ and 180 ℃, taking out the test pieces after 72 hours, removing corrosion products, cleaning and drying the test pieces at normal temperature, weighing the test pieces, and calculating the corrosion inhibition rate as V1。
And (3) corrosion inhibition rate: directly putting the test piece into carbon dioxide saturated oil field layer water, respectively sealing and hanging the test piece at 100 ℃ and 180 ℃ under the pressure of 16MPa, taking out after 72 hours, removing corrosion products, cleaning and drying the test piece at normal temperature, weighing the test piece again, calculating a corrosion inhibition rate, and marking the corrosion inhibition rate as V0Wherein the corrosion inhibition rate = (V)0-V1）/V0×100%。
TABLE 1
According to the test data in table 1, the corrosion inhibitor of the present application can relieve corrosion of a steel sheet as a whole, wherein the corrosion inhibition effect of the corrosion inhibitor # 1 is the best, which indicates that the corrosion inhibitor obtained in the present application can form a protective film on a metal surface to achieve the effect of relieving metal corrosion. The corrosion inhibitor prepared by the synthesis method can continuously play a role at high temperature for a long time, and phenomena such as layering, precipitation, coking and the like can not occur, so that metal can be protected from corrosion for a long time by using the corrosion inhibitor in oil and gas exploitation, and the cost is saved.
From the test results of the corrosion inhibitors in various proportions, it can be known that the monomer for preparing the corrosion inhibitor and the synthesis conditions can influence the corrosion inhibition effect of the corrosion inhibitor, and the corrosion inhibition effect of the corrosion inhibitor synthesized in various proportions on the steel sheet is weaker than that of the corrosion inhibitor of the embodiment.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the corrosion inhibitor for resisting carbon dioxide corrosion is characterized by comprising the following steps:
prepolymerizing a first monomer and N-vinyl pyrrolidone to obtain a first intermediate;
reacting the first intermediate, the second monomer and the third monomer to obtain a second intermediate;
adding alkynol into the second intermediate for polymerization, and then adding antimony trichloride for mixing to obtain the corrosion inhibitor;
wherein the first monomer is allyl polyether and/or diallyl polyether;
the second monomer is at least one of N, N-methylene bisacrylamide, acrylamide and N- (hydroxymethyl) acrylamide;
the third monomer is at least one selected from the group consisting of formaldehyde, trioxymethylene and paraformaldehyde.
2. The method according to claim 1, wherein the weight ratio of the first monomer to the N-vinylpyrrolidone is 1: (1-10); and/or
The weight ratio of the first intermediate, the second monomer and the third monomer is (5-15): (10-50): (5-10); and/or
The weight ratio of the second intermediate, the alkynol and the antimony trichloride is (10-80): (5-10): 1-5.
3. The preparation method of claim 1, wherein the first monomer is a mixture of allyl polyether and diallyl polyether, and the weight ratio of the allyl polyether to the diallyl polyether is 1 (4-9).
4. The method according to claim 3, wherein the allyl polyether is at least one of allyl polyoxyethylene methyl ether, allyl polyoxyethylene propyl ether, allyl polyoxyethylene epoxy ether, allyl polyoxyethylene acetate, and allyl polyoxyethylene polyoxypropylene acetate;
the diallyl polyether has an average molecular weight of 4000-10000.
5. The method of claim 1, wherein the second monomer is a mixture of N, N-methylene bisacrylamide and acrylamide, and the weight ratio of N, N-methylene bisacrylamide to acrylamide is 5: 2.
6. the preparation method of claim 1, wherein the first monomer, the N-vinyl pyrrolidone and the initiator are dissolved in a first solvent, uniformly stirred, introduced with nitrogen, heated to 50-75 ℃, and reacted for 1-5h to obtain the first intermediate;
according to the parts by weight, the total monomer content is 30-60%, the initiator content is 0.2-1.0%, and the balance is a first solvent;
the first solvent is at least one of hexane, benzene, toluene, xylene, diethyl ether and acetone.
7. The preparation method of claim 1, wherein the first intermediate, the second monomer, the third monomer and the catalyst are dissolved in the second solvent, uniformly stirred, adjusted to pH =2-3, heated to 80-90 ℃, and reacted for 5-7h to obtain the second intermediate;
the total monomer content is 40-55%, the catalyst content is 0.2-1.0%, and the balance is the second solvent;
the second solvent is any one or more of deionized water, methanol and absolute ethyl alcohol.
8. The preparation method of claim 1, wherein alkynol is added into the second intermediate, and the polymerization is carried out for at least 3h at 80-90 ℃, then the temperature is reduced to 40-50 ℃, and antimony trichloride is added and mixed for 0.5-1h to obtain the corrosion inhibitor.
9. A corrosion inhibitor against carbon dioxide corrosion, characterized in that it is prepared by the process according to any one of claims 1 to 8.
10. Use of the corrosion inhibitor prepared by the preparation method according to any one of claims 1 to 8 or the corrosion inhibitor according to claim 9 for retarding corrosion of oil and water pipelines.
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