CN114934273A - Pickling agent method for in-situ preparation of nitrogen-doped carbon dot corrosion inhibitor - Google Patents
Pickling agent method for in-situ preparation of nitrogen-doped carbon dot corrosion inhibitor Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 60
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 41
- 238000005554 pickling Methods 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 120
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 150000002739 metals Chemical class 0.000 abstract 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C23F11/12—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
-
- C—CHEMISTRY; METALLURGY
- 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
- C23F11/18—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 inorganic inhibitors
- C23F11/182—Sulfur, boron or silicon containing compounds
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- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses a pickling agent method for in-situ preparation of a nitrogen-doped carbon-point corrosion inhibitor, which comprises the following specific steps: citric acid and urea are used as raw materials of the carbon point corrosion inhibitor, and after mixing and grinding, the raw materials are added into water and stirred, so that the mixture of the citric acid and the urea is dissolved in the water, and a mixed solution of the citric acid and the urea is obtained; adding concentrated sulfuric acid with the concentration not lower than 80% into the obtained mixed solution of citric acid and urea, and stirring uniformly while adding; uniformly heating the obtained mixed solution containing concentrated sulfuric acid at 35-75 ℃ for 5-120 min, and carrying out dehydration and carbonization reaction on citric acid and urea in the solution under the action of the concentrated sulfuric acid; and pouring the obtained solution after the reaction into water for dilution, and stirring while pouring to obtain a diluted solution, namely the pickling agent of the nitrogen-doped carbon dot corrosion inhibitor. The method can be used for preparing the pickling agent of the nitrogen-doped carbon point corrosion inhibitor in situ on a large scale. The nitrogen-doped carbon dots have stronger corrosion inhibition effect, and under the protection of the nitrogen-doped carbon dots, the pickling agent can effectively clean metals such as carbon steel, copper and the like, and does not damage a metal matrix.
Description
Technical Field
The invention relates to the field of preparation of functional materials and corrosion inhibition application, in particular to a pickling agent method for in-situ preparation of a nitrogen-doped carbon-point corrosion inhibitor.
Background
Carbon dots are a novel carbon nanomaterial and were first discovered in 2004. Typically, carbon dots are less than 10nm in size, with intrinsic fluorescence effects. The vast majority of carbon sites consist of two parts, a core, which typically consists of sp2 hybridized graphitic carbon or amorphous carbon, and a surface group, which is mostly an oxygen-or nitrogen-containing group. The nano-silver-doped zinc oxide nano-particles have the advantages of small size effect, unique fluorescence property, good biocompatibility, environmental friendliness, low toxicity, excellent catalytic property, lubricating property, corrosion inhibition property and the like, and are widely applied to the fields of chemical sensing, biological imaging, catalysis, photoelectric devices, plant systems, lubrication, corrosion protection and the like.
In 2017, researchers explore the application of carbon dots in the field of corrosion prevention for the first time. Based on the above teaching, some researchers change the type and reaction conditions of the precursor to prepare various carbon dots with better corrosion inhibition performance, such as nitrogen-doped carbon dots, ionic liquid modified carbon dots and the like, and the carbon dots are used as green corrosion inhibitors of aggressive acid solutions or salt solutions, so that the corrosion inhibitors have excellent corrosion resistance and the corrosion inhibition efficiency is higher than 90%. For example: the problem group takes citric acid and thiourea as precursors, nitrogen-doped carbon dots with the size of 2-4 nm are prepared by hydrothermal method, and corrosion inhibition behavior of the carbon dots on X80 carbon steel in 0.1M hydrochloric acid solution is researched by electrochemical experiment, weight loss method and surface morphology analysis: when the concentration of the carbon points is 10mg/L, the corrosion inhibition efficiency reaches 92.98%, which shows that the carbon points have remarkable corrosion resistance to the X80 carbon steel, and the corrosion resistance is enhanced due to the fact that more carbon points, but not water molecules, are adsorbed on the surface of the X80 carbon steel. A large number of researches prove that the citric acid nitrogen-doped carbon dots can provide more active sites, form a protective film on the metal surface through the double actions of physical adsorption and chemical adsorption, protect the metal matrix from being corroded by acid solution, and have wide application prospects in the fields of metal pickling and oil well acidification.
Based on this, document CN111662243A discloses a citric acid-based functionalized carbon dot corrosion inhibitor, and a preparation method and an application thereof. According to the invention, citric acid is subjected to hydrothermal reaction in the presence of deionized water, after reaction liquid is cooled, the deionized water, absolute ethyl alcohol and triethylamine are respectively added and stirred, then 4-dimethylaminopyridine is added, after the reaction liquid is stirred and dissolved, melamine powder is added and stirred and dissolved, and then heating is carried out for amidation reaction to prepare the citric acid nitrogen-doped carbon point corrosion inhibitor, which shows more efficient corrosion inhibition performance.
The citric acid based nitrogen-doped carbon point corrosion inhibitor prepared by the document has the defects of complex preparation, high cost, low yield and the like. In addition, if the carbon point corrosion inhibitor is used as a corrosion inhibitor of a pickling agent, the prepared carbon point corrosion inhibitor needs to be added into an acid solution, and then is stirred and mixed to obtain the pickling agent containing the carbon point corrosion inhibitor, so that the use process is complicated, and the application of the pickling agent in the fields of metal pickling and oil well acidification is limited.
Disclosure of Invention
The invention aims to provide a pickling agent method for preparing a citric acid nitrogen-doped carbon point corrosion inhibitor in situ, which is simple, convenient, low in cost and high in yield, and aims to solve the problems of complex preparation, high cost, low yield, incapability of in-situ preparation and the like in the conventional method for preparing the carbon point corrosion inhibitor.
The technical scheme of the invention is as follows:
a pickling agent method for preparing a nitrogen-doped carbon point corrosion inhibitor in situ comprises the following steps:
the method comprises the following steps: citric acid and urea are used as raw materials of the carbon point corrosion inhibitor, and after mixing and grinding, the raw materials are added into water and stirred, so that the mixture of the citric acid and the urea is dissolved in the water, and a mixed solution of the citric acid and the urea is obtained;
step two: adding concentrated sulfuric acid with the concentration not lower than 80% into the mixed solution of the citric acid and the urea obtained in the step one, and stirring uniformly while adding to prevent the concentrated sulfuric acid from generating an bumping phenomenon;
step three: uniformly heating the mixed solution containing concentrated sulfuric acid obtained in the step two at 35-75 ℃ for 5-120 min, and carrying out dehydration and carbonization reaction on citric acid and urea in the solution under the action of the concentrated sulfuric acid, wherein the color of the solution is changed from colorless to yellow or brown, so that a new substance, namely carbon points is generated, and the obtained carbon points are citric acid nitrogen-doped carbon points due to the fact that the used urea contains nitrogen and the citric acid is used as a carbon source, so that the corrosion inhibition efficiency is higher;
step four: and (3) pouring the solution obtained after the reaction in the step three into water for dilution, stirring while pouring to prevent concentrated sulfuric acid from generating a bumping phenomenon, and uniformly stirring to obtain a diluted solution, namely the pickling agent of the nitrogen-doped carbon corrosion inhibitor.
The pickling agent method for in-situ preparation of the nitrogen-doped carbon point corrosion inhibitor comprises the following steps of: 1.
in the pickling agent method for in-situ preparation of the nitrogen-doped carbon point corrosion inhibitor, the total mass of the citric acid and the urea in the step one accounts for 0.1-8% of the mass fraction of the diluted solution obtained in the step three.
According to the acid pickling agent method for preparing the nitrogen-doped carbon point corrosion inhibitor in situ, the mass of the concentrated sulfuric acid added in the step two is 3.5 times larger than that of the water added in the step one, so that the concentrated sulfuric acid can effectively enable citric acid and urea to be subjected to dehydration and carbonization reaction, and the citric acid based nitrogen-doped carbon point can be efficiently generated.
In the pickling agent method for in-situ preparation of the nitrogen-doped carbon point corrosion inhibitor, the mass of the water used for dilution in the fourth step is added according to the mass fraction of the concentrated sulfuric acid, so that the mass fraction range of the sulfuric acid contained in the obtained diluted solution is 5-15%.
The invention has the beneficial effects that: (1) the method is simple and convenient; (2) the cost is low, the yield is high, and the pickling agent of the nitrogen-doped carbon point corrosion inhibitor can be prepared in situ; (3) large-scale preparation can be realized; (4) the high-efficiency corrosion inhibition of the metal matrix can be realized in the process of carrying out acid washing or oil well acidification on the metal rust.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
FIG. 2 is a Transmission Electron Microscope (TEM) image of citric acid based nitrogen doped carbon dots in an acid rinse prepared in accordance with an example.
In the figure: S1-S4 correspond to the first to the fourth steps of the method.
Detailed Description
The following is a specific embodiment of the present invention, and the technical solution of the present invention is further described with reference to the accompanying drawings. Citric acid, urea, concentrated sulfuric acid and the like used in the examples were purchased from chemical reagents limited of the national drug group, and were used directly without purification for analytical grade.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
A pickling agent method for in-situ preparation of nitrogen-doped carbon point corrosion inhibitors is shown in figure 1 and comprises the following specific steps:
the method comprises the following steps: taking 0.4g of citric acid and urea as raw materials of a carbon point corrosion inhibitor (the mass ratio of the citric acid to the urea is 1: 1), mixing and grinding, adding 0.8mL of deionized water, and stirring to dissolve the mixture of the citric acid and the urea in the deionized water to obtain a mixed solution of the citric acid and the urea;
step two: adding 4mL of concentrated sulfuric acid with the concentration of 98% into the mixed solution of the citric acid and the urea obtained in the step one, and stirring uniformly while adding to prevent the concentrated sulfuric acid from generating an bumping phenomenon;
step three: uniformly heating the mixed solution containing concentrated sulfuric acid obtained in the step two at 50 ℃ for 40min, and carrying out dehydration and carbonization reaction on citric acid and urea in the solution under the action of the concentrated sulfuric acid, wherein the color of the solution is changed from colorless to brown, so that a new substance, namely a carbon point is generated, and the obtained carbon point is a citric acid nitrogen-doped carbon point due to the fact that the used urea contains nitrogen and the citric acid is used as a carbon source, so that the corrosion inhibition efficiency is higher;
step four: and (3) pouring the solution obtained after the reaction in the step three into 74mL of deionized water for dilution, stirring while pouring to prevent concentrated sulfuric acid from generating a bumping phenomenon, and uniformly stirring to obtain a diluted solution, namely the pickling agent of the nitrogen-doped carbon corrosion inhibitor. The mass fraction of concentrated sulfuric acid in the final pickling agent is about 5%, and no other additives are added.
In order to prove that nitrogen-doped carbon dots are generated in the prepared pickling agent, the pickling agent is subjected to neutralization (sodium hydroxide solution is used as a neutralization solution), rotary evaporation, ethanol extraction, freeze drying and other operations to obtain a solid product, the solid product is subjected to TEM characterization (figure 2), the product is a nearly circular black dot with the particle size of less than 10nm, the generation of the carbon dots is determined, and X-ray photoelectron spectroscopy is used for further verifying that the carbon dots contain N elements, so that the generation of the nitrogen-doped carbon dots is determined.
In order to prove the corrosion inhibition effect of the nitrogen-doped carbon point corrosion inhibitor and the cleaning effect of the pickling agent, the prepared pickling agent containing the carbon point corrosion inhibitor and concentrated sulfuric acid (5%) with the same concentration are used for a Q235 carbon steel derusting experiment (Q235 carbon steel blocks of 10mm x 3mm under the same rusting condition are respectively soaked in the two pickling agents for 2 hours). The result shows that the concentrated sulfuric acid (5%) pickling agent with the same concentration can cause great corrosion to a Q235 carbon steel substrate due to no carbon point corrosion inhibitor, so that the surface is uneven; the pickling agent containing the citric acid nitrogen-doped carbon point corrosion inhibitor prepared by the specific embodiment only removes rust on the surface of Q235 carbon steel, does not corrode a substrate, and enables the surface to be flat and smooth. Therefore, the corrosion inhibition effect of the carbon point corrosion inhibitor and the corrosion cleaning effect of the prepared pickling agent are proved.
Claims (5)
1. A pickling agent method for preparing a nitrogen-doped carbon point corrosion inhibitor in situ is characterized by comprising the following steps:
the method comprises the following steps: citric acid and urea are used as raw materials of the carbon point corrosion inhibitor, and after mixing and grinding, the raw materials are added into water and stirred, so that the mixture of the citric acid and the urea is dissolved in the water, and a mixed solution of the citric acid and the urea is obtained;
step two: adding concentrated sulfuric acid with the concentration not lower than 80% into the mixed solution of citric acid and urea obtained in the step one, and stirring uniformly while adding;
step three: uniformly heating the mixed solution containing concentrated sulfuric acid obtained in the step two at 35-75 ℃ for 5-120 min, and carrying out dehydration and carbonization reaction on citric acid and urea in the solution under the action of the concentrated sulfuric acid;
step four: and (4) pouring the solution obtained after the reaction in the step three into water for dilution, and stirring while pouring to obtain a diluted solution, namely the pickling agent of the nitrogen-doped carbon dot corrosion inhibitor.
2. The acid pickling method for in-situ preparation of the nitrogen-doped carbon point corrosion inhibitor according to claim 1, wherein the mass ratio of the citric acid to the urea in the step one is 5-1: 1.
3. the acid pickling method for in-situ preparation of the nitrogen-doped carbon point corrosion inhibitor according to claim 1 or 2, wherein the total mass of the citric acid and the urea in the first step accounts for 0.1-8% of the mass fraction of the diluted solution obtained in the third step.
4. The acid pickling method for in-situ preparation of nitrogen-doped carbon point corrosion inhibitors according to claim 1, wherein the mass of concentrated sulfuric acid added in the second step is more than 3.5 times the mass of water added in the first step.
5. The acid pickling method for in-situ preparation of the nitrogen-containing doped carbon point corrosion inhibitor according to claim 1, wherein the mass of the water used for dilution in the fourth step is added according to the mass fraction of the concentrated sulfuric acid, so that the mass fraction of the sulfuric acid contained in the obtained diluted solution is in the range of 5-15%.
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| CN115504454A (en) * | 2022-09-13 | 2022-12-23 | 中国石油大学(华东) | Preparation of novel green rare earth doped carbon point corrosion inhibitor and method for modifying carbon point corrosion inhibitor by ionic liquid |
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