CN113801047A - Metal corrosion inhibitor and preparation method thereof - Google Patents
Metal corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN113801047A CN113801047A CN202111182892.8A CN202111182892A CN113801047A CN 113801047 A CN113801047 A CN 113801047A CN 202111182892 A CN202111182892 A CN 202111182892A CN 113801047 A CN113801047 A CN 113801047A
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/82—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/83—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of an acyclic saturated carbon skeleton
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- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
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- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
- C07C323/59—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton with acylated amino groups bound to the carbon skeleton
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- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—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
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—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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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—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 invention provides a metal corrosion inhibitor and a preparation method thereof, relating to the technical field of metal materials, wherein the preparation method of the metal corrosion inhibitor comprises the following steps: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution; adding p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is completed to obtain a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor. The metal corrosion inhibitor has the advantages that the atoms of the metal corrosion inhibitor can form coordinate bonds with the metal atoms, and a compact monomolecular film layer is formed on the surface of the metal to slow down the corrosion of the metal.
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
However, due to the nature of the metal, the metal is exposed to the natural environment and is easy to generate chemical reaction or electrochemical reaction so as to be corroded, so that the performance of the metal material is damaged, and resource loss and potential safety hazard are caused.
The method for preventing metal corrosion by using the metal corrosion inhibitor is one of the best corrosion prevention methods in the current industrial application, and has the advantages of low cost, high efficiency, simple and convenient actual operation, wide application range and the like compared with other corrosion prevention means such as electrochemical protection, coating corrosion prevention technology and the like.
Disclosure of Invention
The invention solves the problems that the existing metal corrosion inhibitor has at least one aspect of high manufacturing and using cost, high difficulty and no environmental protection.
In order to solve the problems, the invention provides a preparation method of a metal corrosion inhibitor, which comprises the following steps:
step S1: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution;
step S2: adding p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is completed to obtain a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor.
Optionally, after obtaining the second mixed solution in step S2, the method further includes: and adding a reducing agent into the second mixed solution, adding a mixed solution of ethanol and water, heating and refluxing until the reaction is completed, and separating and purifying to obtain the metal corrosion inhibitor.
Optionally, in step S1, the α -amino acid includes one of glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine or tryptophan.
Optionally, in step S2, the adding p-tert-butylbenzoyl chloride to the first mixed solution, and continuously stirring until the reaction is completed, to obtain a second mixed solution, including:
and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is completed to obtain a second mixed solution, and adding excessive dilute hydrochloric acid into the second mixed solution for quenching.
Optionally, in step S2, the separating and purifying includes extracting the second mixed solution, and then purifying the second mixed solution by column chromatography.
Optionally, in step S1, the mixing and dissolving the α -amino acid, the alkaline reagent, and the solvent to obtain a first mixed solution includes:
and mixing and dissolving the alpha-amino acid, the alkaline reagent and the solvent to obtain the first mixed solution, and placing the first mixed solution in an ice-water bath.
Optionally, in step S2, the stirring time is 6-24 h.
Optionally, in step S2, the extracting the second mixed solution includes: and extracting the second mixed solution by using ethyl acetate.
Compared with the prior art, the preparation method of the metal corrosion inhibitor has the following advantages:
the amino acid amide compound is prepared as the metal corrosion inhibitor through the reaction of alpha-amino acid, an alkaline reagent and p-tert-butylbenzoyl chloride, N atoms and/or S atoms in the metal corrosion inhibitor can be coordinated with d empty orbits 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 the metal is slowed down.
The invention also aims to provide a metal corrosion inhibitor which is prepared by the preparation method of the metal corrosion inhibitor.
Compared with the prior art, the advantages of the metal corrosion inhibitor provided by the invention are the same as the preparation method of the metal corrosion inhibitor, and are not repeated herein.
The invention also relates to the use of the metal corrosion inhibitor as an additive for the surface treatment of metals.
Compared with the prior art, the advantages of the application of the metal corrosion inhibitor are the same as those of the preparation method of the metal corrosion inhibitor, and are not repeated herein.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of a method for preparing a metal corrosion inhibitor according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a first method for preparing a metal corrosion inhibitor according to a first embodiment of the present invention;
FIG. 3 is a first micrograph of the surface topography of Q235 steel according to a first embodiment of the present invention;
FIG. 4 is a second micrograph of the surface topography of Q235 steel according to a first embodiment of the present invention;
FIG. 5 is a third micrograph of the surface topography of Q235 steel according to a first embodiment of the present invention;
FIG. 6 is a micrograph of the surface topography of Q235 steel according to a second embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It is noted that the description of the term "some specific embodiments" in the description of the embodiments herein is intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a metal corrosion inhibitor, including the following steps:
step S1: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution; the alkaline reagent comprises hydroxides of alkali metal elements such as sodium hydroxide and potassium hydroxide, and other alkaline reagents capable of participating in the reaction.
Step S2: slowly adding p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, naturally returning the reaction temperature to room temperature from-10-5 ℃ to obtain a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor. The p-tert-butylbenzoyl chloride is slowly added into the first mixed solution containing the alpha-amino acid, so that the reaction temperature is favorably controlled, and the reaction of the p-tert-butylbenzoyl chloride and the alpha-amino acid releases heat, so that the concentrated release of the heat can be prevented by controlling the adding speed of the p-tert-butylbenzoyl chloride, and the reaction temperature is overhigh.
The amino acid amide compound is prepared as the metal corrosion inhibitor through the reaction of alpha-amino acid, an alkaline reagent and p-tert-butylbenzoyl chloride, N atoms and/or S atoms in the metal corrosion inhibitor can be coordinated with d empty orbits 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 the metal is slowed down.
The metal corrosion inhibitor in the embodiment is an amino acid amide compound, is synthesized by reacting p-tert-butylbenzoyl chloride with alpha-amino acid, and generally has more than ten amide synthesis methods, wherein the amide synthesis method by using acyl chloride is one of the methods, and compared with other methods, the amide synthesis method by using acyl chloride is simpler and more convenient to operate, and has high reaction activity and high atom economy.
Because acyl chloride is easy to decompose in water to become corresponding carboxylic acid, but because the p-tert-butylbenzoyl chloride belongs to aromatic acyl chloride and is relatively stable, the p-tert-butylbenzoyl chloride can be completely decomposed for a long time even in water, and therefore, the p-tert-butylbenzoyl chloride is selected to react in a water system in the embodiment of the invention. After the reaction is completed, the remaining material is usually p-tert-butylbenzoic acid, which is recoverable and economical to use as a raw material for producing p-tert-butylbenzoyl chloride, in addition to the target product.
In some specific embodiments, in step S1, the alkaline reagent includes a hydroxide of an alkali metal element. Thus, the amino acid amide compound metal corrosion inhibitor is prepared by utilizing the reducibility of the hydroxide of the alkali metal element.
In this embodiment, the alkaline reagent participating in the amide preparation reaction from acyl chloride may be an inorganic base or an organic base, but the use of an inorganic base such as a hydroxide of an alkali metal element facilitates subsequent operations of the reaction, simplifies the operation steps, and facilitates separation and purification of the reactant.
In some specific embodiments, in step S1, the α -amino acid includes one of glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine, or tryptophan.
Wherein the alpha-amino acid comprises glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine, tryptophan and the like, and the experimental steps using the amino acids as reaction raw materials have no difference, wherein the corrosion inhibition efficiency is ranked from high to low as: methionine (Meth) > cysteine (Cys) > proline (Pro) > alanine (Ala) > histidine (His) > lysine (2lys) > phenylalanine (Phen) > glutamic acid (Glu) > tryptophan (Tryp), i.e. the best effect can be obtained by using methionine as a reactant for preparing the metal corrosion inhibitor.
In some specific embodiments, in step S2, the adding p-tert-butylbenzoyl chloride to the first mixed solution and continuously stirring until the reaction is completed to obtain a second mixed solution, which includes:
and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is completed to obtain a second mixed solution, and adding excessive dilute hydrochloric acid into the second mixed solution for quenching.
Thereby, the excess reagent in the reaction is eliminated and the reaction product is ensured to be stable.
In some embodiments, in step S2, the separating and purifying includes extracting the second mixture, and then purifying the second mixture by column chromatography. Therefore, the required product is separated by simple operation, the method is simple, and the purification rate is high.
In some specific embodiments, in step S1, the mixing and dissolving the α -amino acid, the alkaline reagent, and the solvent to obtain a first mixed solution includes:
and mixing and dissolving the alpha-amino acid, the alkaline reagent and the solvent to obtain the first mixed solution, and placing the first mixed solution in an ice-water bath. In the embodiment, a large amount of heat is released during the reaction of the p-tert-butylbenzoyl chloride and the alpha-amino acid, and if the temperature of the reaction system is too high, a side reaction is caused, and an unnecessary product is generated. In the prior art, a method for synthesizing amide by using a low-temperature condensing agent exists, the method is usually carried out at a temperature of-20 ℃ or even lower, the requirement on equipment is high, and the operation is complex, while the method for synthesizing amide by using p-tert-butylbenzoyl chloride is usually carried out at a temperature of 0-5 ℃, that is, cooling is carried out by using an ice-water bath in the embodiment, so that the operation is convenient, the reaction is mild, and the economy is good.
In some specific embodiments, in step S2, the stirring time is 6-24 h. Therefore, the p-tert-butylbenzoyl chloride is uniformly dispersed in the first mixed solution, and the reaction is more sufficient.
In some specific embodiments, in step S2, the extracting the second mixed solution includes: and extracting the second mixed solution by using ethyl acetate. Therefore, the extraction rate is improved, and the purification of the reaction product is facilitated.
The preparation method of the metal corrosion inhibitor provided by the embodiment of the invention has the advantages of short synthesis steps, mild reaction conditions, simple and convenient operation, wide sources, low cost, no toxicity, no harm, environmental friendliness and the like, and uses alpha-amino acid, an alkaline reagent and p-tert-butylbenzoyl chloride as raw materials.
The embodiment of the invention also provides a metal corrosion inhibitor which is prepared by adopting the preparation method of the metal corrosion inhibitor.
Compared with the prior art, the advantages of the metal corrosion inhibitor provided by the embodiment of the invention are the same as the preparation method of the metal corrosion inhibitor, and are not repeated herein.
The embodiment of the invention provides application of a metal corrosion inhibitor, and the metal corrosion inhibitor is used as an additive for metal surface treatment. The method is particularly suitable for fine treatment of metal surfaces, including acidification of oil and gas wells, corrosion prevention treatment of circulating cooling water systems, acid treatment of metal surfaces, chemical cleaning of the interior of boilers and the like.
Compared with the prior art, the advantages of the application of the metal corrosion inhibitor provided by the embodiment of the invention are the same as those of the preparation method of the metal corrosion inhibitor, and are not repeated herein.
The technical scheme of the invention is further described below by combining a plurality of specific embodiments, so that the purpose and the advantages of the invention are clear.
The first embodiment is as follows:
the preparation method of the metal corrosion inhibitor of the embodiment is carried out according to the following steps:
s1: 1.49g of methionine (Meth) was added to a 50mL round bottom flask using a scale, 0.8g of sodium hydroxide was added to the round bottom flask using a scale, and 5mL of deionized water was added for dissolution, and the round bottom flask was placed in an ice water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using an injector, slowly injecting the p-tert-butylbenzoyl chloride into the round-bottom flask, keeping stirring in the injection process, keeping stirring for 6 hours after the injection is finished, naturally recovering the temperature from-10 ℃ to the room temperature state in the reaction process, adding excessive hydrochloric acid to carry out quenching reaction after the reaction is finished, extracting by using ethyl acetate, and separating out the metal corrosion inhibitor by using a column chromatography after the extraction is finished.
In this embodiment, methionine (Meth) is used as a reaction raw material, as shown in fig. 2, p-tert-butylbenzoyl chloride and methionine are used as raw materials, sodium hydroxide is added, water is used as a solvent, the temperature naturally returns to room temperature from-10 ℃ in the reaction process, the reaction is carried out for 6 hours, and the metal corrosion inhibitor is obtained after separation and purification.
To verify the corrosion inhibition effect of the metal corrosion inhibitor described in this example, Q235 steel was placed in 1mol L containing metal corrosion inhibitors of different concentrations-1In HCl solution, various tests were performed:
1. the results of the weight loss test and the measurement of the corrosion rate of the Q235 steel are shown in Table 1, and it can be seen from Table 1 that the Q235 steel is at 1mol L at room temperature-1The corrosion rate in HCl is 4.930gh-1m-2The corrosion rate in the solution added with the metal corrosion inhibitor is 2.667gh-1m-2、1.574gh-1m-2、0.384gh-1m-2、0.180gh-1m-2Compared with a blank HCl solution, the corrosion rate v of the Q235 steel in the solution added with the metal corrosion inhibitor is obviously reduced, and the higher the concentration of the metal corrosion inhibitor is, the lower the corrosion rate of the Q235 steel is, namely, the stronger the corrosion inhibition effect of the metal corrosion inhibitor is.
2. Electrochemical experiments, measuring potentiodynamic polarization parameters to reflect corrosion rate, wherein Tafel extrapolation is used, the results are shown in Table 2, Table 2 is the dynamic parameters of a polarization curve, shows the corrosion potential, the corrosion current density and the Tafel slope obtained by measurement, and the results in Table 2 show that the Q235 steel is in a blank 1mol L at room temperature-1The current density in HCl solution is 68.61mAcm-2The current density in the solution added with the metal corrosion inhibitor is 28.51mAcm-2、21.61mAcm-2、17.23mAcm-2、12.29mAcm-2The corrosion current density decreases with the increase of the concentration of the metal corrosion inhibitor, and the concentration of the metal corrosion inhibitor is 100mgL-1The corrosion inhibition efficiency reaches 82.12 percent.
3. Electrochemical impedance experiment, measuring impedance parameters, the results are shown in table 3, and it can be seen from table 3 that the solution resistance decreases with the increase of the concentration of the metal corrosion inhibitor; the charge transfer resistance increases with increasing concentration of the metal corrosion inhibitor, while the constant phase angle element value decreases. The increase of the charge transfer resistance and the increase of the capacitance show that molecules are gradually adsorbed on the surface of the Q235 steel, water molecules on the surface are gradually replaced, and an adsorption film is formed on the metal surface to block the charge transfer of the Q235 steel, so that the dissolution of the Q235 steel in HCl is inhibited, and the corrosion of the Q235 steel is inhibited. In addition, the experimental data show that the change trend of the corrosion inhibition efficiency is consistent with the change trend presented by the potentiodynamic polarization curve and is also consistent with the trend presented by the result in the weight loss method test.
4. Surface topography analysis by scanning electron microscope, FIG. 3 shows the surface topography of untreated Q235 steel, and FIG. 4 shows the surface topography of Q235 steel at 1mol L-1The surface appearance of the steel is shown in FIG. 5 after being soaked in HCl solution for 6h, which is 1mol L of Q235 steel containing 100mg of the metal corrosion inhibitor- 1After the steel sample is soaked in the HCl solution for 6 hours, the surface appearance is observed, the Q235 steel sample in the blank HCl solution is seriously corroded, a plurality of obvious groove pits can be seen, and the corrosion degree of the surface of the Q235 steel sample in the HCl solution containing the metal corrosion inhibitor is obviously reduced compared with that of the sample without the corrosion inhibitor.
In conclusion, the amino acid amide compound prepared by adopting methionine (Meth) as a reaction raw material has a certain corrosion inhibition effect as a metal corrosion inhibitor.
Example two:
the difference between this embodiment and the first embodiment is: the preparation method of the metal corrosion inhibitor of the embodiment uses cysteine (Cys) instead of methionine (Meth) as a reaction raw material.
The preparation method of the metal corrosion inhibitor of the embodiment is carried out according to the following steps:
s1: 0.61g of cysteine (Cys) was added to a 50mL round-bottom flask by a balance, 0.4g of sodium hydroxide was added to the round-bottom flask by a balance, 5mL of deionized water was added for dissolution, and the round-bottom flask was placed in an ice-water bath.
S2: sucking 0.98mL of p-tert-butylbenzoyl chloride by using an injector, slowly injecting the p-tert-butylbenzoyl chloride into the round-bottom flask, keeping stirring in the injection process, keeping stirring for 24 hours after the injection is finished, naturally recovering the temperature from 5 ℃ to the room temperature state in the reaction process, adding excessive hydrochloric acid to carry out quenching reaction after the reaction is finished, extracting by using ethyl acetate, and separating by using a column chromatography to obtain the metal corrosion inhibitor after the extraction is finished.
To verify the corrosion inhibition effect of the metal corrosion inhibitor described in this example, Q235 steel was placed in 1mol lhcl solution containing the metal corrosion inhibitor at different concentrations, and various tests were performed:
1. the results of the weight loss test and the measurement of the corrosion rate of Q235 steel are shown in Table 1, and it can be seen from Table 1 that the corrosion rate of Q235 steel in the solution added with the metal corrosion inhibitor is 4.902gh-1m-2、3.042gh-1m-2、1.653gh-1m-2、0.439gh-1m-2Compared with a blank HCl solution, the corrosion rate v of the Q235 steel in the solution added with the metal corrosion inhibitor is obviously reduced, and the higher the concentration of the metal corrosion inhibitor is, the lower the corrosion rate of the Q235 steel is, namely, the stronger the corrosion inhibition effect of the metal corrosion inhibitor is.
TABLE 1-weight loss test results for Q235 steels in HCl solutions without or with different concentrations of metal corrosion inhibitors
2. Electrochemical experiments, measuring the zeta potential polarization parameter, the results are shown in Table 2, and the results in Table 2 show that the current density in the solution added with the metal corrosion inhibitor is 58.74mAcm-2、39.19mAcm-2、17.79mAcm-2、9.64mAcm-2The corrosion current density decreases with the increase of the concentration of the metal corrosion inhibitor, and the concentration of the metal corrosion inhibitor is 100mgL-1The corrosion inhibition efficiency reaches 85.99 percent.
TABLE 2-zeta potential polarization parameters of Q235 steels in the absence or presence of various concentrations of metal corrosion inhibitors HCl
3. Electrochemical impedance experiment, measuring impedance parameters, and the result is shown in table 3, wherein the solution resistance is reduced along with the increase of the concentration of the metal corrosion inhibitor; the charge transfer resistance is increased along with the increase of the concentration of the metal corrosion inhibitor, and the value of the constant phase angle element is reduced, so that the change trend of the corrosion inhibition efficiency is consistent with the change trend presented by a potentiodynamic polarization curve and the trend presented by the result in the weight loss method test.
TABLE 3 impedance parameters of HCl solutions without or with different concentrations of metal corrosion inhibitors
4. Surface topography analysis by scanning electron microscope, FIG. 6 shows Q235 steel in 1mol L containing 100mg of the above metal corrosion inhibitor- 1The surface appearance after the steel is soaked in the HCl solution for 6 hours is observed, compared with a sample without the corrosion inhibitor, the corrosion degree of the Q235 steel sample surface is obviously reduced in the HCl solution containing the metal corrosion inhibitor, but compared with the Q235 steel sample without the corrosion inhibitor, the Q235 steel surface using the metal corrosion inhibitor taking the methionine as the raw material is more regular than the Q235 steel surface using the metal corrosion inhibitor taking the cysteine as the raw material and is closer to the original sample surface, which shows that the corrosion inhibition effect of the metal corrosion inhibitor taking the cysteine as the raw material is worse than that of the metal corrosion inhibitor taking the methionine as the raw material.
In conclusion, the amino acid amide compound prepared by taking cysteine (Cys) as a reaction raw material has a certain corrosion inhibition effect when used as a metal corrosion inhibitor.
Example three:
the difference between this embodiment and the first embodiment is: the preparation method of the metal corrosion inhibitor of the embodiment uses proline (Pro) instead of methionine (Meth) as a reaction raw material.
The preparation method of the metal corrosion inhibitor of the embodiment is carried out according to the following steps:
s1: 1.15g proline (Pro) was added to a 50mL round bottom flask using a scale, 0.8g sodium hydroxide was added to the round bottom flask using a scale, and 5mL deionized water was added for dissolution, and the round bottom flask was placed in an ice water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using an injector, slowly injecting the p-tert-butylbenzoyl chloride into the round-bottom flask, keeping stirring in the injection process, keeping stirring for 12 hours after the injection is finished, naturally recovering the temperature from-5 ℃ to the room temperature state in the reaction process, adding excessive hydrochloric acid to quench the reaction after the reaction is finished, extracting the reaction product by using ethyl acetate, and separating the reaction product by using a column chromatography to obtain the metal corrosion inhibitor after the extraction is finished.
Example four:
the difference between this embodiment and the first embodiment is: the preparation method of the metal corrosion inhibitor of the embodiment uses alanine (Ala) instead of methionine (Meth) as the reaction raw material.
The preparation method of the metal corrosion inhibitor of the embodiment is carried out according to the following steps:
s1: 0.89g of alanine (Ala) was added to a 50mL round-bottom flask by a balance, 0.8g of sodium hydroxide was added to the round-bottom flask by a balance, 5mL of deionized water was added to dissolve, and the round-bottom flask was placed in an ice-water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using an injector, slowly injecting the p-tert-butylbenzoyl chloride into the round-bottom flask, keeping stirring in the injection process, keeping stirring for 18 hours after the injection is finished, naturally recovering the temperature from-2 ℃ to the room temperature state in the reaction process, adding excessive hydrochloric acid to quench the reaction after the reaction is finished, extracting the reaction product by using ethyl acetate, and separating the reaction product by using a column chromatography to obtain the metal corrosion inhibitor after the extraction is finished.
Example five:
the difference between this embodiment and the first embodiment is: the preparation method of the metal corrosion inhibitor of the embodiment uses histidine (His) instead of methionine (Meth) as a reaction raw material.
The preparation method of the metal corrosion inhibitor of the embodiment is carried out according to the following steps:
s1: 2.04g of histidine (His) was added to a 50mL round bottom flask by a balance, 0.8g of sodium hydroxide was added to the round bottom flask by a balance, 5mL of deionized water was added for dissolution, and the round bottom flask was placed in an ice water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using an injector, slowly injecting the p-tert-butylbenzoyl chloride into the round-bottom flask, keeping stirring in the injection process, keeping stirring for 20 hours after the injection is finished, naturally recovering the temperature from 0 ℃ to the room temperature state in the reaction process, adding excessive hydrochloric acid to quench the reaction after the reaction is finished, extracting the reaction product by using ethyl acetate, and separating the reaction product by using a column chromatography to obtain the metal corrosion inhibitor after the extraction is finished.
In combination with the electrochemical impedance screening data shown in table 4, which corresponds to the third, fourth and fifth examples, it can be observed that amino acid amide compounds prepared by using proline (Pro), alanine (Ala) and histidine (His) as reaction raw materials have a certain corrosion inhibition effect as metal corrosion inhibitors.
TABLE 4 impedance parameters of HCl solutions without or with different types of metal corrosion inhibitors
In addition, other amino acids can be used as reactants, and metal corrosion inhibitors with anti-corrosion effect can also be obtained, such as threonine, serine, tyrosine, arginine and the like, but more complicated and tedious steps are required to synthesize the same type of compounds. Compared with the preparation steps of the metal corrosion inhibitor, the compound is relatively complicated to synthesize, and is not simple, convenient and quick.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (10)
1. The preparation method of the metal corrosion inhibitor is characterized by comprising the following steps:
step S1: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution;
step S2: adding p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is completed to obtain a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor.
2. The method of claim 1, wherein in step S1, the alkaline reagent comprises a hydroxide of an alkali metal element.
3. The method of claim 1, wherein in step S1, the alpha-amino acid includes at least one of glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine, and tryptophan.
4. The method for preparing a metal corrosion inhibitor according to claim 1, wherein in step S2, the step of adding p-tert-butylbenzoyl chloride to the first mixed solution and stirring the mixture until the reaction is completed to obtain a second mixed solution comprises:
and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is completed to obtain a second mixed solution, and adding excessive dilute hydrochloric acid into the second mixed solution for quenching.
5. The method of claim 1, wherein the step of separating and purifying comprises extracting the second mixture, and purifying the second mixture by column chromatography in step S2.
6. The method for preparing a metal corrosion inhibitor according to claim 1, wherein in step S1, the step of mixing and dissolving the α -amino acid, the alkaline reagent and the solvent to obtain a first mixed solution comprises:
and mixing and dissolving the alpha-amino acid, the alkaline reagent and the solvent to obtain the first mixed solution, and placing the first mixed solution in an ice-water bath.
7. The method of claim 1, wherein the stirring time in step S2 is 6-24 h.
8. The method of claim 5, wherein the step S2 of extracting the second mixture includes: and extracting the second mixed solution by using ethyl acetate.
9. A metal corrosion inhibitor, characterized in that it is prepared based on the preparation method of the metal corrosion inhibitor as claimed in claims 1 to 8.
10. Use of a metal corrosion inhibitor as claimed in claim 9 as an additive for the surface treatment of metals.
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