CN114164430B - Metal corrosion inhibitor and preparation method thereof - Google Patents
Metal corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN114164430B CN114164430B CN202111444113.7A CN202111444113A CN114164430B CN 114164430 B CN114164430 B CN 114164430B CN 202111444113 A CN202111444113 A CN 202111444113A CN 114164430 B CN114164430 B CN 114164430B
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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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- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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Abstract
The application discloses a metal corrosion inhibitor and a preparation method thereof, wherein the metal corrosion inhibitor comprises the following components: 10-30 parts by weight of thiophenecarboxylic acid substance, 50-200 parts by weight of first solvent, 10-30 parts by weight of additive, 10-20 parts by weight of dioxane, 5-15 parts by weight of methionine, 20-120 parts by weight of alkaline reagent, 10-20 parts by weight of second solvent and 10-30 parts by weight of acid reagent, wherein the first solvent is methylene dichloride, chloroform or toluene, the second solvent is water or dioxane, the additive is oxalyl chloride or thionyl chloride, and when the additive oxalyl chloride is, the metal corrosion inhibitor further comprises: 0.1 to 0.5 weight part of catalyst, the metal corrosion inhibitor uses thiophene carboxylic acid substances, methionine and the like as raw materials, and the raw materials are wide in source, low in cost, nontoxic, harmless, green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a metal corrosion inhibitor and a preparation method thereof.
Background
The metal material is widely applied to various fields and is also an indispensable raw material in industrial production, however, due to the nature of the metal, the metal is easy to generate chemical reaction or electrochemical reaction under natural environment to be corroded, so that the performance of the metal material is damaged, and the resource loss and the potential safety hazard are caused.
The metal corrosion inhibitor is one of the best corrosion prevention methods in the current industrial application, however, most of the existing metal corrosion inhibitors have larger toxicity, are easy to cause environmental heavy metal pollution, and have the defect of high production cost, so that the metal corrosion inhibitor has certain limitations in application and popularization.
Disclosure of Invention
Based on the above, the main purpose of the invention is to provide a metal corrosion inhibitor with low cost and environmental protection and a preparation method thereof.
In order to achieve the above object, the present invention provides a metal corrosion inhibitor comprising:
thiophene carboxylic acid species: 10-30 parts by weight;
a first solvent: 50-200 parts by weight;
additives: 10-30 parts by weight;
dioxane: 10-20 parts by weight;
methionine: 5-15 parts by weight;
alkaline reagent: 20-120 parts by weight;
a second solvent: 10-20 parts by weight;
acid reagent: 10-30 parts by weight;
the metal corrosion inhibitor comprises a first solvent, a second solvent and an additive, wherein the first solvent is dichloromethane, chloroform or toluene, the second solvent is water or dioxane, the additive is oxalyl chloride or thionyl chloride, and when the additive oxalyl chloride is, the metal corrosion inhibitor further comprises: 0.1 to 0.5 part by weight of a catalyst.
Preferably, the thiophenecarboxylic acid material is 3-thiophenecarboxylic acid or 2, 5-dibromo-3-thiophenecarboxylic acid, when the thiophenecarboxylic acid material is 3-thiophenecarboxylic acid, the metal corrosion inhibitor obtained is TOP-Meth, and when the thiophenecarboxylic acid material is 2, 5-dibromo-3-thiophenecarboxylic acid, the metal corrosion inhibitor obtained is BTOP-Meth, wherein the 3-thiophenecarboxylic acid has the structural formula:
TOP-Meth has the formula: />
The structural formula of the 2, 5-dibromo-3-thiophenecarboxylic acid is as follows:
the structural formula of the BTOP-Meth is as follows: />
Preferably, the alkaline agent is an organic or inorganic base.
Preferably, the organic base is sodium hydroxide, potassium hydroxide or sodium hydride.
Preferably, the inorganic base is triethylamine, pyridine, diisopropylethylamine or sodium alkoxide.
Preferably, the catalyst is N, N-Dimethylformamide (DMF).
Preferably, the acidic reagent is hydrochloric acid or dilute sulfuric acid.
In order to achieve the above purpose, the invention also provides a preparation method of the metal corrosion inhibitor, which comprises the following steps:
s100: adding 10-30 parts by weight of thiophenecarboxylic acid substances into a flask;
s200: adding 50-200 parts by weight of a first solvent and 0-30 parts by weight of an additive into the flask, and continuously stirring to react to obtain a solution containing an intermediate, wherein the intermediate is a product obtained by reacting a thiophene carboxylic acid substance with the additive, the first solvent is dichloromethane, chloroform or toluene, the additive is oxalyl chloride or thionyl chloride, and when the additive oxalyl chloride is, 0.1-0.5 part by weight of a catalyst is required to be added into the flask;
s300: evaporating the solution containing the intermediate under reduced pressure to obtain the intermediate, and adding dioxane to dissolve the intermediate;
s400: adding 5-15 parts by weight of methionine and 20-120 parts by weight of alkaline reagent into 10-20 parts by weight of second solvent for dissolution, wherein the second solvent is water or dioxane;
s500: adding the solution obtained in the step S300 into the solution obtained in the step S400, and continuously stirring until the reaction is complete so as to obtain a solution containing thiophene carboxylate;
s600: adding 10-30 parts by weight of acid into the solution containing thiophene carboxylate to perform quenching reaction to obtain a solution containing the metal corrosion inhibitor, and then separating and purifying the solution containing the metal corrosion inhibitor to obtain the metal corrosion inhibitor.
Preferably, step S200 specifically includes: 50 to 200 parts by weight of a first solvent, 0 to 30 parts by weight of an additive and 0.1 to 0.5 parts by weight of a catalyst are added dropwise to the flask under an ice water bath, and the mixture is stirred for 2 to 4 hours to react, so that a solution containing an intermediate is obtained.
Preferably, step S500 specifically includes: dropwise adding the solution obtained in the step S300 into the solution obtained in the step S400 under ice water bath, and stirring for 6-24 hours to react so as to obtain a solution containing thiophene carboxylate.
The technical scheme of the invention has the advantages that the thiophene carboxylic acid substance and the additive react to generate the intermediate (acyl chloride substance), the intermediate (acyl chloride substance) and methionine react in an alkaline environment to generate thiophene carboxylate, the acid reagent and the thiophene carboxylate perform quenching reaction to obtain the metal corrosion inhibitor, the metal corrosion inhibitor prepared by the method comprises N atoms and/or S atoms, the N atoms and/or the S atoms can coordinate with d-space orbitals of metal ions to form coordination bonds, so that molecules of the metal corrosion inhibitor are adsorbed on the metal surface, a compact monomolecular film layer is formed on the metal surface, and a corrosion medium is isolated from the metal surface, so that the corrosion of metal is slowed down.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from the devices shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of a metal corrosion inhibitor of the present invention;
FIG. 2 shows that the Q235 steel of the present invention is 1mol L at 298K -1 Electrochemical impedance spectroscopy (Nyquist) plots of TOP-Meth at different concentrations in HCl solution;
FIG. 3 shows that the Q235 steel of the present invention is 1mol L at 298K -1 Electrochemical resistance of BTOP-Meth with different concentrations in HCl solutionAn anti-spectral (Nyquist) diagram;
FIG. 4 shows 1mol L of the invention without metal corrosion inhibitor added at 298K -1 An equivalent circuit diagram of the HCl solution;
FIG. 5 shows the addition of 1mol L of TOP-Meth or BTOP-Meth at 298K according to the invention -1 An equivalent circuit diagram of the HCl solution;
FIG. 6 shows that the Q235 steel of the present invention is at 1mol L -1 Scanning electron microscope images of HCl without or with metal corrosion inhibitor.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement, etc. between the components in a particular posture (as shown in the drawings), and if the particular posture is changed, the directional indicator is changed accordingly. Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, "and/or" throughout this document includes three schemes, taking a and/or B as an example, including a technical scheme, a technical scheme B, and a technical scheme that both a and B satisfy; in addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention provides a metal corrosion inhibitor, which comprises the following components: 10-30 parts by weight of thiophenecarboxylic acid substance, 50-200 parts by weight of first solvent, 10-30 parts by weight of additive, 10-20 parts by weight of dioxane, 5-15 parts by weight of methionine, 20-120 parts by weight of alkaline reagent, 10-20 parts by weight of second solvent and 10-30 parts by weight of acid reagent, wherein the first solvent is methylene dichloride, chloroform or toluene, the second solvent is water or dioxane, the additive is oxalyl chloride or thionyl chloride, and when the additive oxalyl chloride is, the metal corrosion inhibitor further comprises: 0.1 to 0.5 part by weight of a catalyst.
According to the invention, thiophene carboxylic acid substances and additives react to generate intermediates (acyl chloride substances), the intermediates (acyl chloride substances) and methionine react in an alkaline environment to generate thiophene carboxylate, an acidic reagent and the thiophene carboxylate perform quenching reaction to obtain the metal corrosion inhibitor, the metal corrosion inhibitor prepared by the method comprises N atoms and/or S atoms, the N atoms and/or S atoms can coordinate with d-space orbitals of metal ions to form coordination bonds, so that metal corrosion inhibitor molecules are adsorbed on the metal surface, a compact monomolecular film layer is formed on the metal surface, and corrosion media are isolated from the metal surface, so that metal corrosion is slowed down.
In this embodiment, the additive reacts with 3-thiophenecarboxylic acid or 2, 5-dibromo-3-thiophenecarboxylic acid to form an intermediate (acid chloride substance), and in this embodiment, when the additive is thionyl chloride, the first solvent may not be added, and thionyl chloride may serve as a solvent while the reactant is thionyl chloride.
In this embodiment, when the second solvent is water, deionized water is used, and deionized water refers to pure water from which impurities in ionic form have been removed, so as to avoid interference of impurities in ionic form in water with the reaction.
Further, the thiophenecarboxylic acid material is 3-thiophenecarboxylic acid or 2, 5-dibromo-3-thiophenecarboxylic acid, when the thiophenecarboxylic acid material is 3-thiophenecarboxylic acid, the metal corrosion inhibitor obtained is TOP-Meth, and when the thiophenecarboxylic acid material is 2, 5-dibromo-3-thiophenecarboxylic acid, the metal corrosion inhibitor obtained is BTOP-Meth, wherein the structural formula of the 3-thiophenecarboxylic acid is as follows:
TOP-Meth has the formula: />
The structural formula of the 2, 5-dibromo-3-thiophenecarboxylic acid is as follows: />
The structural formula of the BTOP-Meth is as follows: />
Further, the alkaline agent is an organic or inorganic base, and in this embodiment, the alkaline agent is used to provide an alkaline environment.
Further, the organic base is sodium hydroxide, potassium hydroxide or sodium hydride.
Further, the inorganic base is triethylamine, pyridine, diisopropylethylamine or sodium alkoxide.
Further, the catalyst is N, N-Dimethylformamide (DMF).
Further, the acidic reagent is hydrochloric acid or dilute sulfuric acid.
Referring to fig. 1, the invention provides a preparation method of a metal corrosion inhibitor, which comprises the following steps:
s100: adding 10-30 parts by weight of thiophenecarboxylic acid substances into a flask;
s200: adding 50-200 parts by weight of a first solvent and 0-30 parts by weight of an additive into a flask, continuously stirring and reacting to obtain a solution containing an intermediate, wherein the intermediate is a product obtained by reacting a thiophene carboxylic acid substance with the additive, the first solvent is dichloromethane, chloroform or toluene, the additive is oxalyl chloride or thionyl chloride, and when the additive is oxalyl chloride, 0.1-0.5 part by weight of a catalyst is required to be added into the flask;
s300: evaporating the solution containing the intermediate under reduced pressure to obtain the intermediate, and adding dioxane to dissolve the intermediate;
s400: adding 5-15 parts by weight of methionine and 20-120 parts by weight of alkaline reagent into 10-20 parts by weight of second solvent for dissolution, wherein the second solvent is water or dioxane;
s500: adding the solution obtained in the step S300 into the solution obtained in the step S400, and continuously stirring until the reaction is complete so as to obtain a solution containing thiophene carboxylate;
s600: adding 10-30 parts by weight of an acidic reagent into a solution containing thiophene carboxylate to perform quenching reaction to obtain a solution containing a metal corrosion inhibitor, and then separating and purifying the solution containing the metal corrosion inhibitor to obtain the metal corrosion inhibitor.
Further, the step S200 specifically includes: under ice water bath, 50-200 parts by weight of a first solvent and 0-30 parts by weight of an additive are added into a flask, and stirring is carried out for 2-4 hours to react, so as to obtain a solution containing an intermediate, wherein the intermediate is a product obtained by reacting a thiophene carboxylic acid substance with the additive, the first solvent is dichloromethane, chloroform or toluene, the additive is oxalyl chloride or thionyl chloride, when the oxalyl chloride is the additive, 0.1-0.5 part by weight of a catalyst is also required to be added into the flask, and concretely, the dropwise adding mode is adopted, so that the thiophene carboxylic acid substance and the additive are uniformly mixed and fully react.
In this embodiment, since a large amount of heat is released during the reaction between the thiophenecarboxylic acid substance and the additive, if the temperature of the reaction system is too high, side reaction is caused to generate unnecessary products, therefore, before the additive is added, the flask is placed in an ice water bath, the low temperature environment is favorable for inhibiting the reaction activity, and the concentrated heat release is prevented from causing the excessive temperature of the reaction system.
In this embodiment, the thiophenecarboxylic acid material is 3-thiophenecarboxylic acid or 2, 5-dibromo-3-thiophenecarboxylic acid, the intermediate is 3-thiophenecarboxylic acid chloride when the thiophenecarboxylic acid material is 3-thiophenecarboxylic acid, and the intermediate is 2, 5-dibromo-3-thiophenecarboxylic acid chloride when the thiophenecarboxylic acid material is 2, 5-dibromo-3-thiophenecarboxylic acid chloride, wherein the structural formula of the 3-thiophenecarboxylic acid chloride is
The structural formula of the 2, 5-dibromo-3-thiophenecarboxyl chloride is +.>
In this example, in step S300, the solution containing the intermediate is evaporated under reduced pressure in order to remove the excess first solvent and additives from the solution containing the intermediate.
Further, the step S500 specifically includes: dropwise adding the solution obtained in the step S300 into the solution obtained in the step S400 under ice water bath, and stirring for 6-24 hours to react so as to obtain a solution containing thiophene carboxylate, specifically, dropwise adding the solution obtained in the step S300, so that the solution obtained in the step S300 and the solution obtained in the step S400 are uniformly mixed, and reacting fully, wherein in the embodiment, the thiophene carboxylate is related to an alkaline reagent, such as: when the basic agent is sodium hydroxide, the thiophene carboxylate is a sodium salt, when the basic agent is potassium hydroxide, the thiophene carboxylate is a potassium salt, and when the basic agent is triethylamine, the thiophene carboxylate is an amine salt.
In this embodiment, since a large amount of heat is released during the reaction between the solution obtained in step S300 and the solution obtained in step S400, if the temperature of the reaction system is too high, side reactions are initiated to generate unnecessary products, therefore, before the solution obtained in step S300 is added, the solution obtained in step S400 is placed in an ice water bath, the low temperature environment is favorable for inhibiting the reaction activity, and the reaction system is prevented from being too high due to concentrated heat release.
In step S600, the acidic reagent is hydrochloric acid or dilute sulfuric acid, and the acid is used to eliminate the alkaline reagent in the reaction, so as to ensure the stability of the reaction product, and in this embodiment, an excessive amount of dilute hydrochloric acid is added to the solution containing thiophene carboxylate for quenching, so as to ensure that the excessive alkaline reagent in the reaction can be completely eliminated.
The separation and purification in step S600 includes: after extracting the solution containing the metal corrosion inhibitor, purifying the solution containing the metal corrosion inhibitor by column chromatography, and particularly, the separation and purification are simple in operation and high in purification rate.
Extracting the solution containing the metal corrosion inhibitor comprises: the solution containing the metal corrosion inhibitor is extracted with a water-insoluble organic solvent, which may be, but is not limited to, dichloromethane or ethyl acetate.
The technical scheme of the invention is further described below with reference to several specific embodiments, and the purposes and advantages of the invention are clear.
Embodiment one:
the preparation method of the metal corrosion inhibitor comprises the following steps:
s100: 0.64g of 3-thiophenecarboxylic acid was weighed out by a balance and charged into a 100mL round-bottomed flask.
S200: 50mL of methylene chloride was added to the round bottom flask under an ice water bath, followed by dropwise addition of oxalyl chloride (COCl) 2 0.8mL, 3 drops of N, N-Dimethylformamide (DMF) were added dropwise, and the mixture was stirred for 2 to 4 hours.
S300: the dichloromethane solvent and excess oxalyl chloride were removed by evaporation under reduced pressure to give the intermediate, and 10mL of dioxane was added to dissolve the intermediate.
S400: 0.746g methionine was weighed out with a balance, 0.4g sodium hydroxide (NaOH) was weighed out with a balance, and 5mL deionized water was added for dissolution.
S500: sucking the solution obtained in the step S300 by using a syringe, dropwise adding the solution into the solution obtained in the step S400 under an ice water bath, keeping stirring in the injection process, and keeping stirring for 6-24 hours after the injection is finished to obtain a solution containing thiophene carboxylate.
S600: and adding excessive hydrochloric acid (HCL) after the reaction is finished to quench the solution containing thiophene carboxylate to obtain a solution containing the metal corrosion inhibitor, extracting the solution containing the metal corrosion inhibitor by using ethyl acetate, and separating by using column chromatography after the extraction is finished to obtain the metal corrosion inhibitor (TOP-Meth).
In the embodiment, 3-thiophenecarboxylic acid is used as a reaction raw material, 3-thiophenecarboxylic acid and methionine are used as raw materials, sodium hydroxide is added, deionized water is used as a solvent, the temperature in the reaction process is naturally restored to the room temperature state from 0 ℃ and the reaction is carried out for 6 hours, and the metal corrosion inhibitor is obtained after separation and purification.
The reaction procedure of this example is as follows:
wherein, 0 ℃ to r.t means that the reaction temperature is from 0 ℃ to room temperature,
in the form of methionine, the amino acid is methionine,
is thiophene carboxylate.
To verify the corrosion inhibition effect of the metal corrosion inhibitor of this example, Q235 steel was placed in 1mol L containing different concentrations of metal corrosion inhibitor -1 In HCl solution, a number of tests were performed:
1. weightlessness experiment
1mol L of TOP-Meth and BTOP-Meth in the absence or presence of different concentrations -1 The corrosion rate and corrosion inhibition efficiency of Q235 steel in the system were calculated by using the formula 2-1 and the results are shown in Table 1, and it can be seen from Table 1 that both methionine derivatives were effective on Q235 steel at 1mol L -1 Corrosion in HCl solution has excellent inhibition. Corrosion rate and TOP-Meth and BTOP-MethWith increasing concentrations of the two substances, the corrosion inhibition efficiency increases gradually, reaching a maximum at 200 mg/L. The inhibition of the corrosion of Q235 steel by TOP-Meth and BTOP-Meth can be attributed to the adsorption of TOP-Meth and BTOP-Meth on the surface of Q235 steel, limiting the dissolution of Q235 steel by blocking its corrosion sites, thereby reducing the corrosion rate. The free electrons of the corrosion inhibitor easily interact with d-space orbitals of metals to form surface complexes, so that it is presumed that the compounds TOP-Meth and BTOP-Meth interact with d-space orbitals of Fe on the surface of Q235 through lone pair electrons of N, S and O atoms to form a donor-receptor surface complex. Thereby blocking the corrosion sites on the surface of the Q235 steel.
Calculated from equation 2-1:
v-corrosion Rate (g m) -2 h -1 )；
Δw—poor quality (g);
s-surface area of sample (m 2 )；
Table 1 weight loss test results of Q235 Steel in HCl solutions without or with Metal Corrosion inhibitors at different concentrations
2. Tafel extrapolation
Obtaining the corrosion current density (i) of the surface of the Q235 steel electrode by Tafil extrapolation corr ) The corrosion rate and corrosion inhibition efficiency of the Q235 steel in the system are calculated by using the formula 2-2, and the related parameters such as corrosion potential, cathode and anode Tafil slopes and the like are shown in the table 2. As can be seen from the table, in the blank, the corrosion current density (i corr ) Is 74.65mA cm -2 200mg L was added -1 After TOP-Meth and BTOP-Meth, the corrosion current density was drastically reduced to 20.45mA cm, respectively -2 And 11.11mA cm -2 Corrosion inhibition rates are respectivelyUp to 75.07% and 86.46%, indicating good corrosion protection. In addition, the change of corrosion potential values after TOP-Meth and BTOP-Meth are added is obviously less than 85mV, and the two thiophene amino acid derivatives are also indicated to belong to the mixed corrosion inhibitor. In summary, TOP-Meth and BTOP-Meth are two cathode-based mixed corrosion inhibitors.
Calculated from equation 2-2:
eta in the formula is corrosion inhibition efficiency; i.e corr -corrosion current;
-corrosion current of blank HCI solution.
TABLE 2 potentiodynamic polarization parameters of Q235 Steel in HCl without or with Metal Corrosion inhibitors of different concentrations
3. Electrochemical impedance experiments, measuring impedance parameters
FIGS. 2 and 3 show 1mol L of Q235 steel at 298K, respectively -1 Electrochemical impedance spectra of TOP-Meth and BTOP-Meth at different concentrations in solution. As can be seen from FIGS. 2 and 3, the addition of TOP-Meth and BTOP-Meth to HCl solution significantly increases the diameter of the capacitive arc, indicating that TOP-Meth and BTOP-Meth can form an effective barrier layer on the Q235 steel/solution surface, improving the charge transfer resistance (R ct ) Corrosion of the Q235 steel is effectively suppressed. And the radius of the capacitive arc shows a tendency to increase as the concentrations of TOP-Meth and BTOP-Meth increase. In addition, all of the capacitive arcs were flat semi-circular in shape, indicating that the addition of TOP-Meth and BTOP-Meth did not significantly alter the corrosion mechanism. While the centers of all semicircles are significantly lower than the X-axis, which is the result of the non-uniformity of the protective film layer formed by TOP-Meth and BTOP-Meth on the surface of the Q235 steel/solution. From the electrochemical impedance spectrumIt can be seen that the capacitance arc radius of the addition of BTOP-Meth in the system is greater than that of the addition of TOP-Meth, indicating that the corrosion inhibition capability of BTOP-Meth is stronger than that of TOP-Meth.
The charge transfer resistance obtained by electrochemical impedance spectroscopy measurement can be used to calculate corrosion inhibition efficiency, and the equivalent circuit for simulating impedance parameters and simulating electrochemical behavior is described with reference to fig. 4 and 5, wherein the solution resistance (R s ) Charge transfer resistor (R) ct ) Solution film layer resistance (R f ) Constant phase angle element CPE (Q dl ) Solution film layer constant phase angle element (Q) f ) The data for the iso-electrochemical impedance fits are presented in Table 3, and the corrosion rate and corrosion inhibition efficiency of the Q235 steel in this system were calculated using formulas 2-3.
From the results in Table 3, it can be seen that the corrosion inhibition efficiency increases as the concentration of the corrosion inhibitor increases. At 200mg L -1 When the corrosion inhibition efficiency is highest, the corrosion inhibition efficiency reaches 90.21% and 95.34% respectively. TOP-Meth and BTOP-Meth contain N, S atoms and impart lone pair and pi electrons to the empty orbitals of iron so that these molecules can strongly adsorb on the Q235 steel surface, preventing corrosive media such as O 2 、H + And the like. R is R p With increasing values, more of the corrosion inhibitor molecules on the surface are adsorbed onto the surface of the Q235 steel, forming a more complete film.
Calculated from equation 2-3:
wherein R is p ＝R s +R ct +R f ；
R corresponding to blank HCI solution p ；R s -solution resistance; r is R ct -a charge transfer resistance; r is R f -solution film layer resistance.
TABLE 3 impedance parameters of the addition of Metal Corrosion inhibitors to HCl solutions without or with different concentrations
4. Scanning electron microscope surface topography analysis
FIG. 6 shows the surface morphology of Q235 steel after 12h immersion in a solution without and with TOP-Meth and BTOP-Meth. The initial morphology of the Q235 steel is shown in fig. 6 a), and it can be seen that the surface is entirely smooth, with only fine marks due to factory cutting. As shown in fig. 6 b), after the blank HCl solution is soaked for 12 hours, the corrosion degree of the Q235 steel is obviously increased, a plurality of irregular cracks and pits appear on the surface, and the corrosion holes are obviously enlarged and deepened. In contrast, after 12h of soaking in HCl solution with TOP-Meth and BTOP-Meth addition, the surface of Q235 steel suffered a greatly reduced level of corrosion, which demonstrated that TOP-Meth and BTOP-Meth at 1mol L for Q235 steel -1 The HCl solution has excellent corrosion resistance. As can be seen by comparing FIG. 6 c) with FIG. 6 d), the surface of Q235 steel added with TOP-Meth can still see fine holes caused by corrosion, while the surface of Q235 steel added with BTOP-Meth is smoother and smoother, and is closer to the initial morphology. It also shows that BTOP-Meth has a better corrosion inhibition effect than TOP-Meth, which is also consistent with the results of the previous weightlessness experiment, electrochemical experiment.
In conclusion, the amino acid amide compound prepared by taking methionine (Meth) as a reaction raw material has a certain corrosion inhibition effect when being taken as a metal corrosion inhibitor.
Embodiment two:
the difference between this embodiment and the first embodiment is that: the preparation method of the metal corrosion inhibitor of the embodiment uses 2, 5-dibromo-3-thiophenecarboxylic acid instead of 3-thiophenecarboxylic acid as a reaction raw material.
The preparation method of the metal corrosion inhibitor comprises the following steps:
s100: 0.857g of 2, 5-dibromo-3-thiophenecarboxylic acid were weighed out by a balance and charged into a 100mL round bottom flask.
S200: 50mL of methylene chloride was added under an ice-water bath, and oxalyl chloride (COCl) was added dropwise 2 0.5mL, 2 drops of N, N-Dimethylformamide (DMF) were added dropwise, and the mixture was stirred for 2 to 4 hours.
S300: the dichloromethane solvent and excess oxalyl chloride were removed by evaporation under reduced pressure to give the intermediate, and 10mL of dioxane was added to dissolve the intermediate.
S400: 0.447g of methionine was weighed out with a balance, 0.24g of sodium hydroxide (NaOH) was weighed out with a balance, and 5mL of deionized water was added for dissolution.
S500: sucking the solution obtained in the step S300 by using a syringe, dropwise adding the solution into the solution obtained in the step S400 under an ice water bath, keeping stirring in the injection process, and keeping stirring for 6-24 hours after the injection is finished to obtain a solution containing thiophene carboxylate.
S600: and adding excessive hydrochloric acid (HCL) after the reaction is finished to quench the solution containing thiophene carboxylate to obtain a solution containing the metal corrosion inhibitor, extracting the solution containing the metal corrosion inhibitor by using ethyl acetate, and separating by using column chromatography after the extraction is finished to obtain the metal corrosion inhibitor (BTOP-Meth).
The reaction procedure of this example is as follows:
embodiment III:
the preparation method of the metal corrosion inhibitor comprises the following steps:
s100: 0.857g of 2, 5-dibromo-3-thiophenecarboxylic acid were weighed out by a balance and charged into a 100mL round bottom flask.
S200: 10mL of thionyl chloride is added under ice water bath, heated to reflux temperature and stirred for 2 to 4 hours.
S300: excess thionyl chloride was removed by evaporation under reduced pressure to give the intermediate, and 10mL of dioxane was added to dissolve the intermediate.
S400: 0.447g of methionine was weighed out with a balance, 0.24g of sodium hydride was weighed out with a balance, and 5mL of deionized water was added for dissolution.
S500: sucking the solution obtained in the step S300 by using a syringe, dropwise adding the solution into the solution obtained in the step S400 under an ice water bath, keeping stirring in the injection process, and keeping stirring for 6-24 hours after the injection is finished to obtain a solution containing thiophene carboxylate.
S600: and adding excessive hydrochloric acid (HCL) after the reaction is finished to quench the solution containing thiophene carboxylate to obtain a solution containing the metal corrosion inhibitor, extracting the solution containing the metal corrosion inhibitor by using ethyl acetate, and separating by using column chromatography after the extraction is finished to obtain the metal corrosion inhibitor (BTOP-Meth).
Embodiment four:
the preparation method of the metal corrosion inhibitor comprises the following steps:
s100: 0.857g of 2, 5-dibromo-3-thiophenecarboxylic acid were weighed out by a balance and charged into a 100mL round bottom flask.
S200: 50mL of methylene chloride was added under ice-water bath, and oxalyl chloride (COCl) was added dropwise 2 0.5mL, 2 drops of N, N-Dimethylformamide (DMF) were added dropwise, and the mixture was stirred for 2 to 4 hours.
S300: the dichloromethane solvent and excess oxalyl chloride were removed by evaporation under reduced pressure to give the intermediate, and 10mL of dioxane was added to dissolve the intermediate.
S400: 0.447g of methionine was weighed out with a balance, 0.34g of potassium hydroxide was weighed out with a balance, and 5mL of dioxane was added for dissolution.
S500: sucking the solution obtained in the step S300 by using a syringe, dropwise adding the solution into the solution obtained in the step S400 under an ice water bath, keeping stirring in the injection process, and keeping stirring for 6-24 hours after the injection is finished to obtain a solution containing thiophene carboxylate.
S600: and adding excessive hydrochloric acid (HCL) after the reaction is finished to quench the solution containing thiophene carboxylate to obtain a solution containing the metal corrosion inhibitor, extracting the solution containing the metal corrosion inhibitor by using ethyl acetate, and separating by using column chromatography after the extraction is finished to obtain the metal corrosion inhibitor (BTOP-Meth).
Fifth embodiment:
the preparation method of the metal corrosion inhibitor comprises the following steps:
s100: 0.64g of 3-thiophenecarboxylic acid was weighed out by a balance and charged into a 100mL round-bottomed flask.
S200: 50mL of methylene chloride was added under ice-water bath, and oxalyl chloride (COCl) was added dropwise 2 0.5mL, 2 drops of N, N-Dimethylformamide (DMF) were added dropwise, and the mixture was stirred for 2 to 4 hours.
S300: the dichloromethane solvent and excess oxalyl chloride were removed by evaporation under reduced pressure to give the intermediate, and 10mL of dioxane was added to dissolve the intermediate.
S400: 0.447g methionine was weighed out using a balance, 0.84mL triethylamine was measured out using a cylinder, and 5mL deionized water was added for dissolution.
S500: sucking the solution obtained in the step S300 by using a syringe, dropwise adding the solution into the solution obtained in the step S400 under an ice water bath, keeping stirring in the injection process, and keeping stirring for 6-24 hours after the injection is finished to obtain a solution containing thiophene carboxylate.
S600: and adding excessive hydrochloric acid (HCL) after the reaction is finished to quench the solution containing thiophene carboxylate to obtain a solution containing the metal corrosion inhibitor, extracting the solution containing the metal corrosion inhibitor by using ethyl acetate, and separating by using column chromatography after the extraction is finished to obtain the metal corrosion inhibitor (TOP-Meth).
The foregoing description of the preferred embodiments of the present invention should not be construed as limiting the scope of the invention, but rather as utilizing equivalent device variations from the description and drawings of the present invention or directly/indirectly utilizing the same in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The preparation method of the metal corrosion inhibitor is characterized by comprising the following steps of:
s100: adding 10-30 parts by weight of thiophenecarboxylic acid substances into a flask;
s200: adding 50-200 parts by weight of a first solvent and 0-30 parts by weight of an additive into the flask, and continuously stirring to react to obtain a solution containing an intermediate, wherein the intermediate is a product obtained by reacting a thiophene carboxylic acid substance with the additive, the first solvent is dichloromethane, chloroform or toluene, the additive is oxalyl chloride or thionyl chloride, and when the additive oxalyl chloride is, 0.1-0.5 part by weight of a catalyst is required to be added into the flask;
s300: evaporating the solution containing the intermediate under reduced pressure to obtain the intermediate, and adding dioxane to dissolve the intermediate;
s400: adding 5-15 parts by weight of methionine and 20-120 parts by weight of alkaline reagent into 10-20 parts by weight of second solvent for dissolution, wherein the second solvent is water or dioxane;
s500: adding the solution obtained in the step S300 into the solution obtained in the step S400, and continuously stirring until the reaction is complete so as to obtain a solution containing thiophene carboxylate;
s600: adding 10-30 parts by weight of an acidic reagent into the solution containing thiophene carboxylate to perform quenching reaction to obtain a solution containing the metal corrosion inhibitor, and then separating and purifying the solution containing the metal corrosion inhibitor to obtain the metal corrosion inhibitor.
2. The method for preparing a metal corrosion inhibitor according to claim 1, wherein step S200 specifically comprises: 50 to 200 parts by weight of a first solvent, 0 to 30 parts by weight of an additive and 0.1 to 0.5 parts by weight of a catalyst are added dropwise to the flask under an ice water bath, and the mixture is stirred for 2 to 4 hours to react, so that a solution containing the intermediate is obtained.
3. The method for preparing a metal corrosion inhibitor according to claim 1, wherein step S500 specifically comprises: dropwise adding the solution obtained in the step S300 into the solution obtained in the step S400 under ice water bath, and stirring for 6-24 hours to react so as to obtain a solution containing thiophene carboxylate.
4. The method for preparing a metal corrosion inhibitor according to claim 1, wherein the alkaline agent is an organic base or an inorganic base.
5. The method for preparing a metal corrosion inhibitor according to claim 4, wherein the organic base is sodium hydroxide, potassium hydroxide or sodium hydride.
6. The method for preparing a metal corrosion inhibitor according to claim 4, wherein the inorganic base is triethylamine, pyridine, diisopropylethylamine or sodium alkoxide.
7. The method for preparing a metal corrosion inhibitor according to claim 1, wherein the catalyst is N, N-Dimethylformamide (DMF).
8. The method for preparing a metal corrosion inhibitor according to claim 1, wherein the acidic reagent is hydrochloric acid or dilute sulfuric acid.
9. A metal corrosion inhibitor, characterized in that it is prepared by the method of preparing a metal corrosion inhibitor according to any one of claims 1-8.
10. The metal corrosion inhibitor according to claim 9, wherein the thiophenecarboxylic acid species is 3-thiophenecarboxylic acid or 2, 5-dibromo-3-thiophenecarboxylic acid, wherein when the thiophenecarboxylic acid species is 3-thiophenecarboxylic acid, the metal corrosion inhibitor obtained is TOP-Meth, and when the thiophenecarboxylic acid species is 2, 5-dibromo-3-thiophenecarboxylic acid, the metal corrosion inhibitor obtained is BTOP-Meth, wherein the 3-thiophenecarboxylic acid has the structural formula:
TOP-Meth has the formula:
the structural formula of the 2, 5-dibromo-3-thiophenecarboxylic acid is as follows: />
The structural formula of the BTOP-Meth is as follows:
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| GB684640A (en) * | 1949-11-14 | 1952-12-24 | Socony Vacuum Oil Co Inc | Reaction products of n-acylated polyalkylenepolyamines with alkenyl succinic acids or anhydrides or derivatives thereof |
| US5300323A (en) * | 1992-10-21 | 1994-04-05 | Henkel Corporation | Reducing or avoiding pinhole formation in autodeposition on zinciferous surfaces |
| CN108754510A (en) * | 2018-06-22 | 2018-11-06 | 重庆工业职业技术学院 | A kind of compound restrainer and preparation method thereof containing Schiff |
| CN110127869A (en) * | 2019-06-17 | 2019-08-16 | 黑龙江益瑞化工有限公司 | A kind of environment-friendly type oil recovery neutral anti-incrustation corrosion inhibitor and preparation method thereof |
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| GB684640A (en) * | 1949-11-14 | 1952-12-24 | Socony Vacuum Oil Co Inc | Reaction products of n-acylated polyalkylenepolyamines with alkenyl succinic acids or anhydrides or derivatives thereof |
| US5300323A (en) * | 1992-10-21 | 1994-04-05 | Henkel Corporation | Reducing or avoiding pinhole formation in autodeposition on zinciferous surfaces |
| CN108754510A (en) * | 2018-06-22 | 2018-11-06 | 重庆工业职业技术学院 | A kind of compound restrainer and preparation method thereof containing Schiff |
| CN110127869A (en) * | 2019-06-17 | 2019-08-16 | 黑龙江益瑞化工有限公司 | A kind of environment-friendly type oil recovery neutral anti-incrustation corrosion inhibitor and preparation method thereof |
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