CN109023381B - Neutralization corrosion inhibitor and preparation method and application thereof - Google Patents
Neutralization corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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Abstract
The invention provides a neutralization corrosion inhibitor, and a preparation method and application thereof, belongs to the technical field of chemical industry, and can solve the technical problems of poor slow release effect and insufficient protection effect of the existing water-soluble corrosion inhibitor. The neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 20-50 parts of amphoteric imidazoline corrosion inhibitor, 10-30 parts of organic amine, 5-30 parts of auxiliary surfactant and 2-5 parts of auxiliary agent. The corrosion inhibitor provided by the invention has good water solubility, has the advantages of convenience in use and excellent corrosion inhibition performance, is applied to corrosion prevention of petroleum processing equipment, can well adapt to a high-temperature and high-acid working environment, has a good protection effect, and has the advantages of simple production process, low cost, environmental friendliness and good economic value.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a neutralization corrosion inhibitor, and a preparation method and application thereof.
Background
Due to the increasing weight and the obvious crude oil deterioration trend of the conventional crude oil, and the large amount of acid liquor injected for improving the recovery ratio in the oil field exploitation process, the proportion of acid content, sulfur content, chlorine content and salt content in the crude oil is higher and higher, so that equipment in the petroleum processing process, such as an atmospheric and vacuum distillation device, a pipeline and the like, is seriously corroded, and becomes an important safety hazard for long-term operation of the device.
In addition to hydrocarbons, crude oil contains small amounts of organic and inorganic impurities of sulfur, chlorine, nitrogen and metal elements, and the content thereof is about 5%, and although the content thereof is small, these impurities have a significant influence on the quality of the process and product of oil refining. In the heating process, the chloride and sulfide in the crude oil are decomposed to generate hydrogen chloride and hydrogen sulfide, and the hydrogen chloride and the hydrogen sulfide rise along with oil gas in a fractionating tower and are condensed together with water vapor in the circulation at the top of the tower to form HCl-H2S-H2O corrosion environment, especially the low pH value of the initial condensed water at the dew point position, brings great threat to the equipment.
In order to ensure normal production operation, the corrosion of the fractionating tower equipment is industrially inhibited by measures such as upgrading the material of the equipment and pipelines, filling corrosion inhibitors and the like. In the selection of the corrosion inhibitor, the imidazoline corrosion inhibitor has better corrosion inhibition performance due to the coordination of the imidazoline ring on the iron surface, and the imidazoline corrosion inhibitor has the advantages of greenness, environmental protection, low toxicity and the like, thereby being attracted by people.
The prior imidazoline corrosion inhibitors can be divided into water-soluble imidazoline corrosion inhibitors and oil-soluble imidazoline corrosion inhibitors, and the two corrosion inhibitors have advantages and disadvantages respectively. For example, chinese patent CN2015105819428 discloses a "preparation method of an oil-soluble corrosion inhibitor for inhibiting circulating corrosion at the top of a fractionating tower", which can achieve a good corrosion inhibition effect, but has the disadvantages of troublesome post-treatment, complex operation process and inconvenient application; compared with the oil-soluble corrosion inhibitor, the post-treatment process of the water-soluble corrosion inhibitor is simpler and more suitable for the existing process, but the slow-release effect is poorer and the sufficient protection effect cannot be achieved. At present, the development of a corrosion inhibitor which has excellent performance and is easy to operate is urgently needed.
Disclosure of Invention
The invention provides a neutralization corrosion inhibitor, a preparation method and application thereof, the corrosion inhibitor has good water solubility, has the advantages of convenient use and excellent corrosion inhibition performance, is applied to corrosion prevention of petroleum processing equipment, can well adapt to the working environment with high temperature and high acid, has better protection effect, and has simple production process, low cost, environmental protection and good economic value.
In order to achieve the aim, the invention provides a neutralization corrosion inhibitor which comprises the following raw material components in parts by weight:
preferably, the amphoteric imidazoline corrosion inhibitor is one or more of disodium lauroyl amphoteric diacetic acid, disodium cocoyl amphoteric diacetic acid and sodium lauroyl amphoteric acetate.
Preferably, the organic amine is one or more of trimethylamine, ethylamine, ethylenediamine, triethylamine, thiourea and thiophene.
Preferably, the auxiliary surfactant is one or more of cetyl trimethyl ammonium bromide, sodium hexadecylbenzene sulfonate, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether.
Preferably, the auxiliary agent is one or more of an alkynol compound or a metal iodide.
Preferably, the alkynol compound is one or more of propargyl alcohol or butynediol.
Preferably, the metal iodide is one or two of potassium iodide and sodium iodide.
Preferably, the raw material components and the parts by weight thereof are as follows: the amphoteric imidazoline corrosion inhibitor is prepared from 30 parts of disodium lauroyl amphoteric diacetate, 5 parts of trimethylamine, 10 parts of ethylenediamine and 5 parts of thiourea as organic amine, 10 parts of hexadecyl trimethyl ammonium bromide as an auxiliary surfactant, and 2 parts of propiolic alcohol and potassium iodide as an auxiliary agent.
Preferably, the corrosion inhibition rate of the neutralization corrosion inhibitor is more than or equal to 96%.
The invention also discloses a preparation method of the neutralization corrosion inhibitor, which comprises the following steps: the raw materials of the components are mixed according to the proportion and stirred evenly at room temperature to obtain the neutralization corrosion inhibitor.
The invention also discloses an application of the neutralization corrosion inhibitor in corrosion prevention of petroleum processing equipment, wherein the addition amount of the corrosion inhibitor is 20-100 mg/L.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention provides a neutralization corrosion inhibitor, a preparation method and application thereof, the corrosion inhibitor has good water solubility, has the advantages of convenient use and good corrosion inhibition performance, is applied to corrosion prevention of petroleum processing equipment, can well adapt to the working environment of high temperature and high acid, has better protection effect, and has simple production process, low cost, environmental friendliness and good economic value.
Drawings
FIG. 1 is a gold phase diagram of the surface of a steel sheet sample protected without corrosion inhibitor;
FIG. 2 is a gold phase diagram of the surface of a steel sheet sample protected with a corrosion inhibitor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a neutralization corrosion inhibitor, which comprises the following raw material components in parts by weight:
the neutralization corrosion inhibitor provided by the embodiment takes amphoteric imidazoline corrosion inhibitors as main components, and has the advantage of convenient use brought by good water solubility and excellent corrosion inhibition performance by compounding with organic amine, auxiliary surfactant and auxiliary agent.
The amphoteric imidazoline corrosion inhibitor as the main raw material has good water solubility, so that the amphoteric imidazoline corrosion inhibitor has good water solubility, can be injected while injecting water, has a simple removal process, and has the advantage of convenient use. The molecules of the amphoteric imidazoline corrosion inhibitor are amphoteric molecules, have electropositive (quaternary ammonium salt) and electronegative (carboxyl) groups, can have different charges along with the change of the pH value of the environment, the molecules show electropositive properties under an acidic condition, the ionization of the carboxyl is inhibited, the combination mode of the amphoteric imidazoline corrosion inhibitor and the metal is mainly the chelation of an imidazoline ring and the metal, and the addition of the auxiliary surfactant and the auxiliary agent can play a role in auxiliary film formation, make up the defect of corrosion resistance, improve the compactness and hydrophobicity of a surface molecular layer of an imidazoline adsorption film, thereby improving the corrosion prevention effect, and leading the compounded corrosion inhibitor to have the advantages of convenient use and excellent corrosion inhibition performance. Furthermore, the amphoteric imidazoline corrosion inhibitor is compounded with the organic amine, so that the effect of regulating the pH value under the action of deacidification can be achieved, and meanwhile, compared with inorganic base, the organic amine has higher boiling point and stronger neutralization effect, can be condensed with HCl together, is beneficial to neutralizing dew point condensed water, and is easier to regulate and control the pH value. The imidazoline corrosion inhibitor and the organic amine are compounded, so that the under-deposit corrosion caused by corrosive products (such as ammonium chloride) can be avoided, and the action effect of the corrosion inhibitor is ensured.
It should be noted here that compared with the conventional naphthenic acid imidazoline or oleic acid imidazoline, the amphoteric imidazoline used in the present invention has a better binding ability with metal, and besides the nitrogen atom on the imidazoline ring can form a chelating effect with metal, the carboxyl group at the other end can also react with iron ions, so as to increase the binding ability with metal. When the concentration of the corrosion inhibitor is low, two ends of the amphoteric imidazoline are combined with the metal, the coverage area of the metal is increased, and the extended hydrophobic alkyl plays a role in isolating corrosive substances, so that relatively good effect is also shown when the consumption of the corrosion inhibitor is low. When the metal surface corrosion inhibitor is compounded with a proper auxiliary surfactant and an auxiliary agent, in addition to a certain corrosion inhibition effect of the surfactant on the metal surface, the amphoteric imidazoline can be combined with the surfactant through the electrostatic action to form a more compact and stable protective film outside the metal, so that the adaptability of the metal to harsh environments (such as high temperature and high acid value) is greatly improved.
In addition, in an alkaline environment, the amphoteric imidazoline corrosion inhibitor shows electronegativity, can coordinate with metal through a nitrogen atom in an imidazole ring, can also be combined with the electrostatic action of the metal through deprotonated carboxyl, a monomolecular film is formed on the surface of the metal, a hydrophobic alkyl chain extends outwards, and a hydrophobic area is formed on the surface close to the metal, so that the metal is protected, namely the corrosion inhibitor is also suitable for the alkaline environment and also has an anticorrosion and corrosion inhibition effect.
In a preferred embodiment, the amphoteric imidazoline corrosion inhibitor is one or more of disodium lauroamphodiacetate, disodium cocoamphodiacetate, and sodium lauroamphoacetate. The lauroyl and cocoyl amphoteric imidazolines employed in this example are hydrophobic alkyl chains having 12 and 8-18 carbon atoms, and the difference in hydrophobic chain length results in imidazoline molecules having different hydrophilicity and hydrophobicity and film-forming properties on metal surfaces. On the one hand, the difference in the length of the hydrophobic chains results in imidazoline molecules with different hydrophobic and hydrophilic properties, the longer the hydrophobic chains, the more hydrophobic the molecules, with consequent changes in the partitioning properties in the oil and water phases. On the other hand, when compounded with other surfactants or adjuvants, the hydrophobic chain length affects the interaction between them. For example, when the imidazoline is compounded with the surfactant, when the length of the hydrophobic chain in the imidazoline is long, the hydrophobic interaction with the hydrophobic chain in the surfactant is strong, so that a compact hydrophobic membrane layer is favorably formed, but if the hydrophobic interaction of the imidazoline and the surfactant is too strong, the bonding strength of the imidazoline and the metal can be influenced, so that the imidazoline with the proper length of the hydrophobic chain is selected to be compounded with the proper surfactant molecule to achieve the synergistic effect. The components disclosed in the preferred embodiment are compounded to play a good role in coordination, so that the bonding strength of the corrosion inhibitor of the material and the metal material can be enhanced, and the excellent anti-corrosion effect can be achieved in a high-temperature and high-acid environment.
In a preferred embodiment, the organic amine is one or more of trimethylamine, ethylamine, ethylenediamine, triethylamine, thiourea and thiophene.
In a preferred embodiment, the auxiliary surfactant is one or more of cetyl trimethyl ammonium bromide, sodium hexadecylbenzene sulfonate, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether. The auxiliary surfactant adopted in the embodiment can play a role in auxiliary film formation, for example, the cationic surfactant in the auxiliary surfactant can fill up the gap of the imidazoline adsorption film on the metal surface, so that the corrosion inhibitor film is more compact and has better corrosion inhibition effect. In the auxiliary surfactant, the nonionic surfactant can be combined in the adsorption film layer through the interaction with a hydrophobic chain in imidazoline, so that the structure of the corrosion inhibitor film is improved, and the corrosion inhibition effect is further improved. The anionic surfactant usually contains sulfur atoms or carboxyl, and can generate chelation with metal to improve the bonding strength of a film layer and the metal. Different auxiliary surfactants, imidazoline and protected metals have different action mechanisms, and the corrosion inhibition effect of the corrosion inhibitor can be effectively improved through reasonable raw material compounding.
In a preferred embodiment, the auxiliary agent is one or more of an alkynol compound or a metal iodide. In an alternative embodiment, the alkynol compound is one or more of propargyl alcohol or butynediol, and the metal iodide is potassium iodide. The auxiliary agent adopted in the embodiment can play a role in assisting film formation, and the introduction of alkynol in the auxiliary agent can form a more uniform and compact adsorption film on the metal surface; under the condition that metal iodide is in an acidic solution and iodide ions are adsorbed on the metal surface, the metal surface is charged with negative charges, and the adopted imidazoline corrosion inhibitor is positively charged and forms a bridging phenomenon with the iodide ions adsorbed on the metal surface through classical attraction, so that the coverage area of the corrosion inhibitor on the metal surface is increased, and the corrosion inhibition rate can be improved.
It is understood that the above examples illustrate the practical materials of each component, and the formula using the above components can effectively achieve the technical effects expected by the present application. But is not limited to the above list and may be other substances that may be reasonably substituted by one skilled in the art.
The embodiment of the invention also provides a preparation method of the neutralization corrosion inhibitor, which comprises the steps of adding the raw materials of the components into a reaction kettle according to a certain proportion, stirring and mixing for 15-60 minutes at room temperature, and thus obtaining the neutralization corrosion inhibitor. The preparation method provided by the embodiment can be carried out at normal temperature, the preparation process adopts the mixing of some commercialized chemicals, the processes such as synthesis, heating and the like are not involved, the preparation process is simple, the cost is low, meanwhile, because the processes such as heating, cooling and the like are not involved, the discharge of waste gas and waste liquid is not generated in the mixing process, and the whole production process meets the requirements of energy conservation and environmental protection.
The embodiment of the invention also provides application of the neutralization corrosion inhibitor in corrosion prevention of petroleum processing equipment, wherein the dosage of the corrosion inhibitor in use is 20-100 mg/L. The neutralization corrosion inhibitor provided by the embodiment can be applied to corrosion prevention of petroleum processing equipment, can be well suitable for a high-temperature and high-acid working environment, has a good protection effect, has a corrosion inhibition rate of over 96 percent through tests, has good water solubility, can be injected while injecting water, is simple in removal process, and has the advantage of convenience in use.
Example 1
A neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 20 parts of cocoyl amphodiacetate disodium, 10 parts of ethylenediamine, 5 parts of sodium hexadecylbenzene sulfonate, 5 parts of fatty alcohol-polyoxyethylene ether and 2 parts of butynediol.
Example 2
A neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 50 parts of lauroyl amphoacetate, 30 parts of thiophene, 5 parts of sodium dodecyl sulfate and 5 parts of potassium iodide.
Example 3
A neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 30 parts of disodium lauroyl amphodiacetate, 5 parts of trimethylamine as organic amine, 10 parts of ethylenediamine and 5 parts of thiourea, 10 parts of hexadecyl trimethyl ammonium bromide as an auxiliary surfactant and 2 parts of propiolic alcohol and potassium iodide as an auxiliary agent, wherein the propiolic alcohol is 2 parts and the potassium iodide is 2 parts.
Example 4
A neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 25 parts of disodium lauroamphodiacetate, 15 parts of trimethylamine, 10 parts of diethylamine, 15 parts of hexadecyl trimethyl ammonium bromide, 1 part of propiolic alcohol and 3 parts of sodium iodide.
Example 5
A neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 40 parts of lauroyl amphodiacetate disodium, 10 parts of ethylamine, 10 parts of thiourea, 10 parts of hexadecyl trimethyl ammonium bromide, 5 parts of fatty alcohol-polyoxyethylene ether, 3 parts of butynediol and 2 parts of potassium iodide.
Example 6
A neutralization corrosion inhibitor comprises the following raw material components in parts by weight: 30 parts of sodium lauroamphoacetate, 15 parts of trimethylamine, 10 parts of ethylenediamine, 15 parts of dodecyl trimethyl ammonium bromide, 1 part of propiolic alcohol and 3 parts of potassium iodide
Comparative example 1
The corrosion inhibitor I comprises the following raw material components in parts by weight: 30 parts of naphthenic acid imidazoline (water-soluble), 5 parts of trimethylamine as organic amine, 10 parts of ethylenediamine and 5 parts of thiourea, 10 parts of hexadecyl trimethyl ammonium bromide as an auxiliary surfactant and 2 parts of propiolic alcohol and potassium iodide as an auxiliary agent, wherein the propiolic alcohol is 2 parts, and the potassium iodide is 2 parts.
Comparative example 2
The corrosion inhibitor II comprises the following raw material components in parts by weight: 30 parts of oleic acid imidazoline, 5 parts of trimethylamine as organic amine, 10 parts of ethylenediamine and 5 parts of thiourea, 10 parts of hexadecyl trimethyl ammonium bromide as an auxiliary surfactant and 2 parts of propiolic alcohol and potassium iodide as an auxiliary agent, wherein the propiolic alcohol is 2 parts and the potassium iodide is 2 parts.
Performance testing
Corrosion resistance test
The corrosion inhibitors of examples 1-6 were compared to the corrosion inhibitor of the comparative example, a blank control (distilled water) using a weight loss method, and the experimental conditions were as follows:
simulating a corrosive liquid: adding a certain amount of concentrated hydrochloric acid and H into deionized water2S saturated solution, and mixing to make the specific concentration of HCl: 1000mg/L, H2S：500mg/L
The metal material is as follows: a3 steel sheet, 50X 10X 3mm
Experimental apparatus: the experiment was carried out in a 250 ml three-necked flask placed in a thermostatic bath
Experiment temperature: 90 deg.C
Experiment time: 24h
Adding amount of the corrosion inhibitor: 20-100mg/L
Evaluation method: analyzing the weight of the steel sheet before and after the weighing test, calculating the corrosion inhibition rate of the corrosion inhibitor according to the weight loss of the steel sheet, and obtaining the following results:
the experimental results show that the corrosion inhibitor of the embodiment can play a good corrosion inhibition role under the conditions of high temperature and high acid, the corrosion inhibition rate can reach more than 96 percent, and the corrosion inhibition effect of the compound corrosion inhibitor prepared by adopting the amphoteric imidazoline corrosion inhibitor is obviously better than that of a conventional naphthenic acid imidazoline or oleic acid imidazoline adopted by a comparative example.
After the anticorrosion test is finished, a metallographic microscope is used for observing A3 steel samples acted by a blank control sample and an example 3, a metallographic microscope photo of the surface of the blank control sample is shown in a figure 1, a metallographic microscope photo of a sample acted by a corrosion inhibitor of the example 3 is shown in a figure 2, and as can be seen from the figures 1 and 2, after the A3 steel sheet is soaked in a simulated corrosion solution added with the corrosion inhibitor of the example 3 for 24 hours, the surface condition is basically not changed and is still a flat and smooth surface, and after the A3 steel sheet is soaked in a simulated slow-release solution not added with the corrosion inhibitor of the example 3 for 24 hours, a plurality of corrosion pits appear on the surface of the steel sheet, and the corrosion pits have the tendency of being connected to form continuous. Further illustrates that the neutralization corrosion inhibitor provided by the invention has good corrosion inhibition effect.
The above description is only exemplary of the present invention and is not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments using the above disclosure as equivalent variations, but all simple modifications, equivalent variations and changes made to the above embodiments according to the technical spirit of the present invention may still fall within the protection scope of the present invention.
Claims (8)
1. The neutralization corrosion inhibitor is characterized by comprising the following raw material components in parts by weight:
the amphoteric imidazoline corrosion inhibitor is one or more of disodium lauroyl amphoteric diacetic acid, disodium cocoyl amphoteric diacetic acid and sodium lauroyl amphoteric acetate; the auxiliary surfactant is one or more of cetyl trimethyl ammonium bromide, sodium hexadecylbenzene sulfonate, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether.
2. The neutralization corrosion inhibitor according to claim 1, wherein the organic amine is one or more of trimethylamine, ethylamine, ethylenediamine, triethylamine, thiourea and thiophene.
3. The neutralization corrosion inhibitor according to claim 1, wherein the auxiliary agent is one or more of an alkynol compound or a metal iodide.
4. The neutralization corrosion inhibitor according to claim 3, wherein the alkynol compound is one or more of propargyl alcohol or butynediol.
5. The neutralization corrosion inhibitor according to claim 3, wherein the metal iodide is one or both of potassium iodide and sodium iodide.
6. The neutralization corrosion inhibitor according to claim 1, characterized by comprising the following raw material components in parts by weight: the amphoteric imidazoline corrosion inhibitor is prepared from 30 parts of disodium lauroyl amphoteric diacetate, 5 parts of trimethylamine, 10 parts of ethylenediamine and 5 parts of thiourea as organic amine, 10 parts of hexadecyl trimethyl ammonium bromide as an auxiliary surfactant, and 2 parts of propiolic alcohol and potassium iodide as an auxiliary agent.
7. The method of preparing a neutralization corrosion inhibitor according to any one of claims 1 to 6, characterized by comprising: the raw materials of the components are mixed according to the proportion and stirred evenly at room temperature to obtain the neutralization corrosion inhibitor.
8. The application of the neutralization corrosion inhibitor in corrosion prevention of petroleum processing equipment as claimed in any one of claims 1 to 6, wherein the dosage of the corrosion inhibitor is 20-100 mg/L.
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| CN114959713B (en) * | 2021-02-26 | 2023-10-10 | 上海梅山钢铁股份有限公司 | Corrosion inhibitor for inhibiting low-carbon steel metallographic phase sample pitting corrosion |
| CN113278977A (en) * | 2021-03-24 | 2021-08-20 | 江阴市亦乐科技发展有限公司 | Special corrosion inhibition dispersant for catalytic depentanizer |
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