CN108822148B - Synthetic method and application of rosinyl imidazoline derivative corrosion inhibitor - Google Patents
Synthetic method and application of rosinyl imidazoline derivative corrosion inhibitor Download PDFInfo
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- CN108822148B CN108822148B CN201810854353.6A CN201810854353A CN108822148B CN 108822148 B CN108822148 B CN 108822148B CN 201810854353 A CN201810854353 A CN 201810854353A CN 108822148 B CN108822148 B CN 108822148B
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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
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to the synthesis and application of a metal anti-corrosion compound, and particularly discloses a synthetic method and application of a rosinyl imidazoline derivative corrosion inhibitor.
Description
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a synthetic method and application of a rosinyl imidazoline derivative corrosion inhibitor.
Background
With the increasing degree of crude oil heaviness, the annual output of high-acid crude oil accounts for about 5% of the total crude oil of the earth, the annual increase rate is increased by 0.3%, and the output of high-acid crude oil in China accounts for about 40% of the total crude oil output, so that the corrosion of oil wells, storage tanks and pipelines in the crude oil extraction process is particularly serious, the corrosion of refining equipment in the crude oil processing process is particularly serious, the economic loss caused by the statistical corrosion accounts for 6% of the total economic value of the nation, and the loss of the petrochemical industry is particularly serious.
Since the beginning of the 20 th century, research on metal corrosion is continuously conducted and various methods for effectively preventing metal corrosion are sought. Among various anti-corrosion methods developed, the corrosion inhibitor protection is an anti-corrosion method with good effect, simple method, low cost and strong applicability, and the method is widely applied to the industries of petroleum, chemical industry, metallurgy and the like. At present, corrosion inhibitors used in oil and gas fields and petrochemical industry at home and abroad are mainly organic compounds such as propargyl alcohols, organic amines, imidazolines, quaternary ammonium salts and the like, and because the toxicity of the propargyl alcohols and the aromatic amines is high, the low-toxicity and environment-friendly imidazoline corrosion inhibitors are widely used.
Imidazoline corrosion inhibitors are imidazoline derivatives obtained by modifying imidazoline serving as an intermediate, have low toxicity, good thermal stability and no particularly pungent smell, can change the oxidation-reduction potential of hydrogen when an acidic medium is contacted with metal, can generate electrochemical reaction on the surface of the metal to form a monomolecular adsorption protective film, can also enable certain oxidants in a solution to react, and can slow down the corrosion of equipment by reducing the electrode potential of the certain oxidants. Imidazoline is generally synthesized by reacting long-chain fatty acid or fatty acid methyl ester with polyamine to dehydrate to form a five-membered ring, the synthesis process is complex, more energy is consumed, and the slow release performance of the corrosion inhibitor is limited.
Therefore, the technical personnel in the field need to solve the problem of how to provide the imidazoline derivative corrosion inhibitor which has low consumption, energy conservation, simple synthesis process and higher slow release performance.
Disclosure of Invention
In order to reduce the corrosion of high-acid crude oil to equipment in the petroleum refining process and continuously optimize the corrosion inhibition performance of the added corrosion inhibitor, the invention provides the rosinyl imidazoline derivative corrosion inhibitor, a synthesis method and application thereof, and the added corrosion inhibitor is successfully modified through low-consumption and energy-saving Mannich reaction to obtain the rosinyl imidazoline derivative corrosion inhibitor with excellent corrosion inhibition performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a rosinyl imidazoline derivative corrosion inhibitor has a structural formula as follows:
a synthetic method of a rosinyl imidazoline derivative corrosion inhibitor comprises the following steps:
(1) preparation of corrosion inhibitor intermediate: dehydrogenated abietic acid, triethylene tetramine and xylene react under the condition of temperature rise, and after complete reaction, reduced pressure distillation operation is carried out to obtain rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO, wherein the reaction formula is as follows:
(2) mannich reaction: the rosin-based imidazoline derivative corrosion inhibitor intermediate IMDO, phosphorous acid and formaldehyde are subjected to reflux reaction in an acidic catalytic environment, and extraction liquid separation is performed after the reaction is finished to obtain the rosin-based imidazoline derivative corrosion inhibitor IMDOM, wherein the reaction formula is as follows:
according to the invention, in triethylene tetramine, diethylenetriamine or other polyethylene polyamines, researches show that only triethylene tetramine can ensure that the synthesized corrosion inhibitor has high adsorption strength of a polar chain, moderate oil solubility and high dispersibility in a corrosive medium, so that triethylene tetramine is selected as a reactant of a chemical reaction.
Preferably, in the above method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor, the preparation of the corrosion inhibitor intermediate IMDO specifically comprises the following steps:
a. adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene as water carrying agents, and reacting for 3-6 h;
b. continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor;
c. and (3) distilling the xylene under reduced pressure to obtain the rosinyl imidazoline derivative corrosion inhibitor intermediate.
Experimental research shows that in the chemical reaction related to the invention, only xylene and water have azeotropic effect, so that the xylene is selected as a water carrying agent, and water is taken out from a reaction container by azeotropy of the water carrying agent and the water, thereby promoting the dehydration reaction.
And the reaction of gradual temperature rise is mild, the reaction is thorough and sufficient, if the reaction is not thorough below the set temperature, the yield of the corrosion inhibitor is low, the energy consumption is high when the reaction is higher than the set temperature, and effective products are decomposed, so that the corrosion inhibition effect is reduced when the reaction is lower than or higher than the set temperature.
Preferably, in the above method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor, the mannich reaction specifically comprises the following steps:
a. under the acidic catalysis environment, adding rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO and phosphorous acid, and heating and refluxing for 1.5-2.5h at the temperature of 100-;
b. slowly dripping formaldehyde by using a constant pressure funnel, and carrying out reflux reaction for 1-2 h;
c. and after the reaction is finished, cooling to room temperature, adding a certain amount of saturated saline solution for washing and liquid separation, and adding a certain amount of ethyl acetate into the separated crude product for extraction and liquid separation to obtain the rosinyl imidazoline derivative corrosion inhibitor IMDOM.
In the step a, if the heating reflux temperature is lower than 100 ℃, the reaction can not be completely carried out, the yield is low, and the slow release effect is reduced; if the heating temperature is higher than 110 ℃, the decomposition of effective products is caused, the energy consumption is high, and the slow release effect is reduced.
Preferably, in the above method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor, the molar ratio of dehydroabietic acid, triethylene tetramine and xylene is 1: 1.1-1.3: 0.8-1.1.
Preferably, in the above method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor, the molar ratio of dehydroabietic acid, triethylene tetramine and xylene is 1: 1.1: 0.8.
preferably, in the above method for synthesizing the rosin-based imidazoline derivative corrosion inhibitor, the molar ratio of the rosin-based imidazoline derivative corrosion inhibitor intermediate, phosphorous acid, and formaldehyde is 1:1: 1.5-3.
Preferably, in the above method for synthesizing the rosin-based imidazoline derivative corrosion inhibitor, the molar ratio of the rosin-based imidazoline derivative corrosion inhibitor intermediate, phosphorous acid, and formaldehyde is 1:1: 2.
through experimental research, the yield of effective components of the corrosion inhibitor synthesized by the reactants participating in the reaction according to the proportion is high, the corrosion inhibition performance is better, and the corrosion inhibition performance is reduced by being lower than or higher than the proportion.
Preferably, in the synthetic method of the rosinyl imidazoline derivative corrosion inhibitor, the related reactant raw materials are analytically pure, the analytically pure chemical substances can obtain a product with higher slow release performance, if the superior grade is selected, the performance of the product cannot be obviously improved, and the analytically pure raw materials are preferably selected to avoid the waste of materials.
Preferably, in the above method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor, the triethylene tetramine and the xylene are simultaneously dropped or sequentially dropped, and the xylene and the triethylene tetramine are dropped after the temperature is increased due to the low boiling point of the xylene, so that the actual reaction amount of the xylene is reduced and the reaction effect is deteriorated, and the adding sequence of the xylene cannot be behind that of the triethylene tetramine.
Preferably, in the synthetic method of the rosinyl imidazoline derivative corrosion inhibitor, the saturated saline solution and the ethyl acetate used in the separation and extraction process can be recycled.
Preferably, in the synthetic method of the rosin-based imidazoline derivative corrosion inhibitor, the acidic catalytic environment is a dilute hydrochloric acid solution prepared by mixing analytically pure hydrochloric acid and deionized water in a volume ratio of 1:1.
The invention also provides application of the rosinyl imidazoline derivative corrosion inhibitor, wherein the use concentration of the rosinyl imidazoline derivative corrosion inhibitor is 1-4 g/L.
Preferably, in the application of the rosinyl imidazoline derivative corrosion inhibitor, the usage concentration of the rosinyl imidazoline derivative corrosion inhibitor is 3 g/L.
According to the technical scheme, compared with the prior art, the invention discloses and provides a rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO and a rosinyl imidazoline derivative corrosion inhibitor IMDOM, wherein both are anode type corrosion inhibitors, the corrosion current density is reduced by adding the corrosion inhibitors, so that the corrosion rate is reduced, and the corrosion inhibitors replace water molecules and other corrosive substances to be adsorbed on the metal surface to form a film; when the rosinyl imidazoline derivative corrosion inhibitor is singly used, when the addition amount of the corrosion inhibitor is 3g/L, the corrosion inhibition rate of IMDOM is 90.87%, the corrosion inhibition rate of IMDO is 84.85%, and the pitting degree is greatly reduced; the preparation method is simple, low in energy consumption and more suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared spectrum of an intermediate IMDO of the rosinyl imidazoline corrosion inhibitor of the present invention;
FIG. 2 is an infrared spectrum of IMDOM of the rosin-based imidazoline corrosion inhibitor of the present invention;
FIG. 3 is a graph showing the polarization curves of samples in experimental media with different corrosion inhibitors added;
FIG. 4 is a schematic diagram of an electrochemical impedance spectroscopy equivalent circuit of a working electrode in an experimental medium;
FIG. 5 is a graph showing electrochemical impedance spectra of electrodes at 60 ℃ in solutions of various amounts of corrosion inhibitor;
FIG. 6 is a graph showing the average corrosion rate of a sample after being soaked in experimental solutions containing different corrosion inhibitors at 60 ℃ for 4 hours;
FIG. 7 is an SEM image of a sample after being soaked in a blank solution at 60 ℃ for 4 hours;
FIG. 8 is an SEM image of a sample after being soaked in an experimental solution added with 3g/L of IMDO at 60 ℃ for 4 hours;
FIG. 9 is a SEM image of a sample after being soaked in an experimental solution added with 3g/L of IMDOM for 4 hours at 60 ℃;
FIG. 10 is an energy spectrum of the surface adsorption film of the test piece after adding 3g/L corrosion inhibitors IMDO and IMDOM in the corrosion medium for 4h at 60 ℃;
FIG. 11 is a graph showing the results of the reaction of 10# steel in 36% hydrochloric acid solutions of various corrosion inhibitors-1For the graph C.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a rosinyl imidazoline derivative corrosion inhibitor, and the specific embodiment of the corrosion inhibitor is as follows:
example 1
(1) Preparation of corrosion inhibitor intermediate
Adding dehydroabietic acid, triethylene tetramine and xylene in a molar ratio of 1: 1.1: 0.8, firstly adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene serving as water carrying agents, and reacting for 3-6 h; then, continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor; finally, xylene is distilled out under reduced pressure to obtain a rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO;
(2) mannich reaction
H3PO3And adding the intermediate IMDO and the formaldehyde in a molar ratio of 1:1:2, heating and refluxing the intermediate IMDO and the phosphorous acid for 1.5-2.5h at the temperature of 100 ℃ and 110 ℃ in an acidic catalytic environment, then slowly dripping the formaldehyde by using a constant-pressure funnel, refluxing and reacting for 1-2h, cooling to room temperature after the reaction is finished, adding a certain amount of saturated saline solution for washing and separating, and adding a certain amount of ethyl acetate into the separated crude product for extraction and separation to obtain the rosinyl imidazoline derivative corrosion inhibitor product IMDOM.
Example 2
(1) Preparation of corrosion inhibitor intermediate
Adding dehydroabietic acid, triethylene tetramine and xylene in a molar ratio of 1: 1.3: 1.1, adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene serving as water carrying agents, and reacting for 3-6 h; then, continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor; finally, xylene is distilled out under reduced pressure to obtain a rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO;
(2) mannich reaction
H3PO3And adding the intermediate IMDO and the formaldehyde in a molar ratio of 1:1:2, heating and refluxing the intermediate IMDO and the phosphorous acid for 1.5-2.5h at the temperature of 100 ℃ and 110 ℃ in an acidic catalytic environment, then slowly dripping the formaldehyde by using a constant-pressure funnel, refluxing and reacting for 1-2h, cooling to room temperature after the reaction is finished, adding a certain amount of saturated saline solution for washing and separating, and adding a certain amount of ethyl acetate into the separated crude product for extraction and separation to obtain the rosinyl imidazoline derivative corrosion inhibitor product IMDOM.
Example 3
(1) Preparation of corrosion inhibitor intermediate
Adding dehydroabietic acid, triethylene tetramine and xylene in a molar ratio of 1: 1.2: 0.9, firstly adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene serving as water carrying agents, and reacting for 3-6 h; then, continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor; finally, xylene is distilled out under reduced pressure to obtain a rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO;
(2) mannich reaction
H3PO3Adding the intermediate IMDO and the formaldehyde with the molar ratio of 1:1:2 in an acidic catalytic environment, firstly adding the intermediate IMDO and the phosphorous acid, heating and refluxing for 1.5-2.5h at the temperature of 100-plus-one-phase (110 ℃), then slowly dripping the formaldehyde by using a constant-pressure funnel, refluxing for reaction for 1-2h, cooling to room temperature after the reaction is finished, adding a certain amount of saturated saline solution for washing and separating, adding a certain amount of ethyl acetate into the separated crude product for extracting and separating to obtain pine powderThe product IMDOM of the vanilloid imidazoline derivative corrosion inhibitor.
Example 4
(1) Preparation of corrosion inhibitor intermediate
Adding dehydroabietic acid, triethylene tetramine and xylene in a molar ratio of 1: 1.1: 0.8, firstly adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene serving as water carrying agents, and reacting for 3-6 h; then, continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor; finally, xylene is distilled out under reduced pressure to obtain a rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO;
(2) mannich reaction
H3PO3And adding the intermediate IMDO and the formaldehyde at a molar ratio of 1:1:1.5 under an acidic catalytic environment, firstly adding the intermediate IMDO and the phosphorous acid, heating and refluxing for 1.5-2.5h at the temperature of 100-110 ℃, then slowly dripping the formaldehyde by using a constant-pressure funnel, refluxing and reacting for 1-2h, cooling to room temperature after the reaction is finished, adding a certain amount of saturated saline solution for washing and separating, adding a certain amount of ethyl acetate into the separated crude product for extraction and separation to obtain a rosinyl imidazoline derivative corrosion inhibitor product IMDOM.
Example 5
(1) Preparation of corrosion inhibitor intermediate
Adding dehydroabietic acid, triethylene tetramine and xylene in a molar ratio of 1: 1.1: 0.8, firstly adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene serving as water carrying agents, and reacting for 3-6 h; then, continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor; finally, xylene is distilled out under reduced pressure to obtain a rosinyl imidazoline derivative corrosion inhibitor intermediate IMDO;
(2) mannich reaction
H3PO3Adding the intermediate IMDO and the formaldehyde with the molar ratio of 1:1:3 in an acidic catalytic environment, firstly adding the intermediate IMDO and the phosphorous acid, heating and refluxing for 1.5-2.5h at the temperature of 100-plus-material 110 ℃, then slowly dripping the formaldehyde by using a constant-pressure funnel, refluxing for 1-2h, and cooling after the reaction is finishedAnd cooling to room temperature, adding a certain amount of saturated saline solution for washing and liquid separation, and adding a certain amount of ethyl acetate into the separated crude product for extraction and liquid separation to obtain a rosinyl imidazoline derivative corrosion inhibitor product IMDOM.
Wherein, the explanation formula of the electron movement condition in the process of forming phosphate group is as follows:
the action mechanism of the corrosion inhibitor is as follows:
the corrosion inhibitor has hydrophilic and oleophobic polar functional groups and oleophilic and hydrophobic nonpolar functional groups in the structure, or has unsaturated bonds in the structure. In a corrosive medium, polar groups are directionally adsorbed on the surface of the metal to replace original corrosive particles, so that the effect of corrosion prevention is achieved; while adsorption energy and coverage are two main aspects of the corrosion inhibition performance. The hydrophilic group of the corrosion inhibitor molecule and the metal surface form a bond, so that the corrosion inhibitor is firmly adsorbed, the surface property and the charge distribution of the metal are changed, the activation energy of the corrosion reaction is improved due to the protection effect of the adsorption film, the activity reduction energy of the metal surface tends to be stable, and the decrease of the corrosion rate of the metal can be proved from the increase of the Gibbs free energy of the corrosion reaction; the hydrophobic groups are arranged on the outer side of the corrosion material to form a hydrophobic protective film between the metal and the corrosion medium, so that the corrosion medium is prevented from being in direct contact with the material, and the purpose of corrosion inhibition is further achieved.
When the corrosion inhibitor molecule has a polar group of an element with unshared lone pair electrons and high electronegativity, the polar group and a metal atom with an unoccupied empty orbit form a coordinate bond or a covalent bond, and the metal surface activity is reduced through the action of polymerization (condensation polymerization), chelation and the like. The dehydroabietic acid contains benzene ring pi bonds, so that the charge state of the metal surface is changed, the adsorption effect of electrons on the benzene ring or unsaturated bonds also belongs to a power supply type, and the adsorption energy and the coverage are two main aspects for measuring the corrosion inhibition performance. The adsorption effect of electrons on the benzene ring also belongs to electron-donating type single-layer adsorption, and the adsorption force is strong, the adsorption heat is high, the adsorption is irreversible, the metal surface potential is changed, and the adsorption selectivity exists. On one hand, the benzene ring is negatively charged and is adsorbed on the electropositive metal surface, on the other hand, the imidazoline corrosion inhibitor enables the positively charged imidazoline ring and the corrosion ions negatively charged in the medium to be attracted on the metal surface under the action of electrostatic attraction, and finally the corrosion inhibitor is adsorbed on the steel. Experiments show that the addition of the imidazoline derivative corrosion inhibitor can reduce the activation energy of the metal surface as a whole, which indirectly proves that the imidazoline derivative corrosion inhibitor generates chemical adsorption on the metal surface.
The stronger polar group can be firmly adsorbed, the better corrosion inhibition effect is, because the polar group of the compound has large polarity and the adsorption energy is larger, the more firm adsorption is realized on an oil/metal interface, but when the polarity is too strong, the oil solubility is deteriorated, and the solubility in an oily corrosion medium is reduced, so that the triethylene tetramine is selected to ensure that the synthesized corrosion inhibitor has higher adsorption strength of a polar chain, the oil solubility of the corrosion inhibitor is moderate, and the dispersibility in the corrosion medium is higher.
The slow release performance characterization and analysis evaluation of the intermediate IMDO of the rosinyl imidazoline derivative corrosion inhibitor and the slow release performance characterization and analysis evaluation of the IMDOM of the rosinyl imidazoline derivative corrosion inhibitor are shown in the embodiment of the invention.
1. Infrared spectroscopy
The IR spectra of the IMDO and IMDOM prepared in examples 1-4 are shown in FIGS. 1 and 2, and 1636.26cm as seen in FIG. 1-1The characteristic stretching vibration absorption peak of C-N of IMDO is a characteristic structure of an imidazoline ring, and the C-N stretching vibration peak on the imidazoline ring appears at 1226.33cm-1Here, the N-H bond stretching vibration absorption peak appears at 3355.12cm-1，1461.29cm-1is-CH2-in-plane variation angle absorption peak, stretching vibration peak of-NH-in the branched chain is 1524.02cm-1Indicating that IMDO has been synthesized;
the peak position of C-N expansion and contraction vibration absorption of FIG. 2 was 1610.21cm-1The C-N stretching vibration peak appears at 1195.63cm-1And the absorption peak of the stretching vibration of the N-H bond is 3375.30cm-1，-CH2-an in-plane variation absorption peak at 1454.68cm-1The stretching vibration peak of-NH-in the branched chain appears at 1531.58 cm-1Characteristic functional group-PH for IMDOM compounds2O3Is 900-1200 cm-1Peaks in this band, mainly composed of two parts, P ═ O and P — OH, indicate that the successful mannich reaction of IMDO occurs.
2. Electrochemical process
2.1 polarization curve method
As can be seen from FIG. 3 and Table 1, in example 1, as the corrosion inhibitor in the medium increases, the corrosion current density decreases, the corrosion inhibition rate increases, when the corrosion inhibitor is added to 3g/L, the corrosion inhibition rate reaches the maximum, although the corrosion current of the cathode and the corrosion current of the anode are both reduced, the polarization process is both inhibited, and the corrosion potential E iscorrThe positive shift and the increase of the anode polarizability are obvious, which indicates that the corrosion inhibitor has stronger inhibition effect on the anode reaction, so the corrosion inhibitor is a mixed corrosion inhibitor mainly inhibiting the anode. The corrosion inhibition effect of the IMDOM is better than that of the IMDO, because the IMDO has stronger charge effect, uneven charge distribution and unstable energy, the formed protective film is not as dense as the protective film formed by the IMDOM and has strong adsorption force.
TABLE 1 polarization curve-related electrochemical parameters
In the table: rpIs polarization resistance, omega, βaβ being the slope of the tafel plot of the anodecThe slope of the cathode tafel curve is shown; j. the design is a squarecorrIn terms of current density, mA.cm-2。
Specifically, when the addition amount of the corrosion inhibitor is 3g/L, the slow release rates of the IMDO and the IMDOM obtained in the above embodiment of the present invention are shown in table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| IMDO | 78.75％ | 70.43％ | 83.16％ | 80.40％ | 78.56％ |
| IMDOM | 90.95％ | 85.02％ | 88.25％ | 87.64％ | 86.15％ |
2.2 electrochemical impedance Spectroscopy
And evaluating the corrosion resistance of the film layer by an electrochemical alternating current impedance technology, and analyzing to obtain the electrochemical behavior of the film layer and the metal surface. The film information is generally concentrated in high-frequency capacitive reactance arcs to be reflected, and the two aspects of the shielding performance and the dielectric performance of the film are mainly expressed; the interface information of the medium and the metal is reflected in the charge transfer condition of the metal electrochemical corrosion in the change of the low-frequency region capacitive arc. FIG. 4 is an equivalent circuit diagram, wherein RfTo absorb resistance, RctIs a charge transfer resistance, RSIs solution resistance, CfIs a film capacitance, CdlFor electric double layer capacitance, fig. 5 is an electrochemical impedance spectrum, and table 3 is a fitting parameter of example 1. Due to the dispersion effect, the double layer capacitance is not equivalent to the ideal capacitance, so when fitting impedance values, the capacitance is replaced by a common phase angle element (CPE), making the fitting more accurate.
As can be seen from FIG. 5 and Table 3, the film adsorption resistance R in the high frequency region after adding the corrosion inhibitorfIncrease, film capacitance CfAnd reduction proves that the originally adsorbed water molecules on the interface layer between the metal surface and the corrosion medium are replaced by the corrosion inhibitor molecules and are adsorbed on the metal surface, so that the shielding effect is generated, and the protection effect is achieved. The low-frequency region has increased arc radius of capacitive reactance and charge transfer resistance RctIncrease of (2) CdlThe decrease of the corrosion inhibitor proves that the corrosion inhibition efficiency is improved, when the addition amount of the corrosion inhibitor reaches 3g/L, the corrosion inhibition rate reaches a maximum value, which shows that polar groups of molecules of the corrosion inhibitor are adsorbed on metal, nonpolar groups extend to a corrosion medium to form a more compact corrosion inhibition film layer on the metal surface to cover the metal surface, so that charge transfer and material exchange with the corrosion medium are blocked, and when the corrosion inhibitor is continuously added, the corrosion inhibitor is desorbed on the metal surface, so that the corrosion inhibition rate is reduced.
TABLE 3 values of the parameters obtained by fitting
Specifically, when the amount of the corrosion inhibitor is 3g/L, the IE values of the IMDO and IMDOM parameters obtained in the above examples 1 to 4 of the present invention are shown in Table 4:
TABLE 4
3. Dynamic weightlessness method
In FIG. 6At 60 deg.C, 500 rpm/shunt speed, the average corrosion rate of the test piece can be up to 19.26g (m)2·h)-1In the whole dynamic soaking process, the surface of the test piece is seriously corroded by a corrosive medium and a large amount of bubbles are continuously generated; when the corrosion inhibitor is added, the generation rate of bubbles on the surface of the test piece is obviously reduced, and when the addition amount of the corrosion inhibitor is 3g/L, the average corrosion rate of the test piece in the IMDO corrosion inhibitor is reduced to 1.96g (m)2·h)-1The corrosion inhibition rate reaches 84.85%; the average corrosion rate of the test piece in the IMDOM corrosion inhibitor is reduced to 1.76g (m)2·h)-1The corrosion inhibition rate reaches 90.87%, and the most suitable adding amount of the corrosion inhibitor is 3 g/L. This is consistent with the trend of electrochemical test results.
Specifically, when the amount of the corrosion inhibitor added is 3g/L, the average slow release rate g (m) of the IMDO and IMDOM obtained in the above examples 1 to 4 of the present invention2·h)-1And% sustained release see table 5:
TABLE 5
4. Observation of surface topography
The surface topography of the coupons of examples 1-4 were analyzed after dynamic weight loss experiments using a Scanning Electron Microscope (SEM).
The corrosion morphology diagrams of the test piece of the dynamic weightlessness experiment without pre-film treatment are shown in figures 7-9, and it can be seen that the test piece added with the corrosion inhibitor has obvious scratches due to scratches polished by abrasive paper before the test piece experiment, the test piece of the experiment group without the corrosion inhibitor in the blank group (Black) has no obvious scratches, only has an uneven corrosion surface, a large amount of serious uniform corrosion exists on the surface of the test piece, the pitting phenomenon is also obvious, and the serious corrosion is indicated; after the corrosion inhibitor is added, the overall corrosion condition is improved, and only a few loose and porous corrosion structures appear. Compared with IMDO, the IMDOM has more outstanding control effect on corrosion, the reduction degree of the pitting structure is larger, the surface of the sample is smoother, and the corrosion is effectively controlled. The corrosion inhibitor prepared by the method has obvious corrosion inhibition effect on No. 10 carbon steel, and the corrosion inhibition effect of the IMDOM is better than that of the IMDO.
5. Surface energy spectroscopy
As can be seen from fig. 10, compared with the blank experimental group, the proportion of Fe, O and P is greatly increased after the corrosion inhibitor is added, and O, P is contained in the corrosion inhibitor, which indicates that the corrosion inhibitor is combined with the metal surface to form a corrosion-resistant protective film to protect the metal substrate, and this also demonstrates that the corrosion inhibitor generates a large amount of chemisorption on the metal surface, and the surface of the blank group without the corrosion inhibitor has more corrosion chlorides, so that the corrosion inhibitor generates effective protection for the metal.
6. Thermodynamics of adsorption
The organic corrosion inhibitor can generate two adsorption modes of chemical adsorption and physical adsorption and is influenced by multiple factors of the electrical property, the temperature and the corrosion medium of a substance. In order to explore the adsorption rule of the corrosion inhibitor, an isothermal adsorption equation is established to simulate the adsorption result. For the corrosion inhibitor adsorption mode in the experiment, firstly, assuming that the adsorption rule of the corrosion inhibitor is in accordance with Langmuir adsorption isothermal formula, the following should be:
in the formula: c is the concentration of the corrosion inhibitor; theta is the surface coverage of the corrosion inhibitor; k is the adsorption equilibrium constant.
The surface coverage θ can be given by the formula:
θ＝(Rct-Rct 0)/Rct
by the above formula with C.theta-1Plotting C, the results are shown in FIG. 11, which is derived from FIG. 11, C.theta.-1Linearly related to C, the correlation coefficient gamma is close to 1, which shows that the adsorption rule of the corrosion inhibitor on the surface of 10# carbon steel conforms to Langmuir isothermal adsorption equation, and the calculated result shows that delta G0The negative value indicates that the corrosion inhibitor performs spontaneous adsorption on the metal surface, and belongs to a chemical adsorption process.
In conclusion, the intermediate IMDO is synthesized by using dehydroabietic acid and triethylene tetramine, and then IMDOM is synthesized through a Mannich reaction; the most suitable adding amount of the corrosion inhibitor is 3g/L, and the corrosion inhibitor has better corrosion inhibition effect on 10# carbon steel in 36% hydrochloric acid medium at 60 ℃ in a dynamic state; the metal surface added with the corrosion inhibitor finds characteristic elements contained in the corrosion inhibitor, so that the corrosion inhibitor is attached to the metal surface compactly, has a strong adsorption effect, effectively shields a liquid phase corrosion medium, reduces substance transfer and charge exchange between the metal surface and the corrosion medium, and reduces the corrosion reaction rate; and they all belong to anodic corrosion inhibitors; adsorption follows the Langmiuir isothermal adsorption equation, with chemisorption occurring at the metal surface.
It is further noted that imidazoline derivatives are composed of polar functional groups centered on O, S, N, etc. with electronegativity and nonpolar functional groups centered on C, H, on one hand, by changing the surface properties and charge distribution of the metal, the energy of the metal surface tends to be stable, and the activation energy of the corrosion reaction is increased to reduce the corrosion rate; on the other hand, the nonpolar functional group is arranged on the metal surface to form a hydrophobic dynamic adsorption layer, thereby avoiding the charge transfer with a corrosion medium and inhibiting the corrosion.
Most imidazoline derivatives mainly generate chemical adsorption on the metal surface, when molecules of the corrosion inhibitor approach the metal surface, electrons on a large pi bond on an imidazoline ring enter an empty d orbit of Fe, and an inverted n orbit (pi x) receives electrons on the d orbit of Fe to form a feedback bond, so that multi-center chemical adsorption is formed. Two adsorption effects exist by researching the IMDOM with the amphiphilic property, and on one hand, the IMDOM is mainly subjected to physical adsorption effect by Van der Waals force; on the other hand, due to the influence of lattice defects, the outer layer orbit of the iron atom is in a stronger vacancy force field, the iron atom is easy to accept lone pair electrons provided by N and S atoms to form covalent coordination bonds, the covalent coordination bonds are chemical adsorption of a multi-adsorption center, and the five-membered heterocyclic ring of the imidazoline contains two N atoms which can be combined with three active sites of an eroded surface to form bonds.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The rosinyl imidazoline derivative corrosion inhibitor is characterized in that the structural formula of the rosinyl imidazoline derivative corrosion inhibitor is as follows:
2. the method for synthesizing the rosin-based imidazoline derivative corrosion inhibitor of claim 1, comprising the steps of:
(1) preparation of corrosion inhibitor intermediate: dehydrogenated abietic acid, triethylene tetramine and xylene react under the condition of temperature rise, and after complete reaction, reduced pressure distillation operation is carried out to obtain a rosinyl imidazoline derivative corrosion inhibitor intermediate, wherein the reaction formula is as follows:
(2) mannich reaction: the rosin-based imidazoline derivative corrosion inhibitor intermediate, phosphorous acid and formaldehyde are subjected to reflux reaction in an acidic catalytic environment, and extraction liquid separation is performed after the reaction is finished to obtain the rosin-based imidazoline derivative corrosion inhibitor, wherein the reaction formula is as follows:
3. the method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor of claim 2, wherein the preparation of the corrosion inhibitor intermediate specifically comprises the following steps:
a. adding dehydroabietic acid into a dry four-mouth bottle provided with a water separator, heating to the temperature of 220 ℃ and 240 ℃, slowly dropwise adding triethylene tetramine and xylene by using a constant-pressure funnel, and reacting for 3-6 h;
b. continuously heating to 270 ℃ and 280 ℃, carrying out reflux cyclization reaction for 3-6h, and distributing water by using a water distributor;
c. and (3) distilling the xylene under reduced pressure to obtain the rosinyl imidazoline derivative corrosion inhibitor intermediate.
4. The method for synthesizing the rosin-based imidazoline derivative corrosion inhibitor according to claim 2 or 3, wherein the molar ratio of dehydroabietic acid, triethylene tetramine and xylene is 1: 1.1-1.3: 0.8-1.1.
5. The method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor according to claim 3, wherein triethylene tetramine and xylene are simultaneously added dropwise, or sequentially added dropwise according to the order of xylene and triethylene tetramine.
6. The method for synthesizing the rosinyl imidazoline derivative corrosion inhibitor of claim 2, wherein the mannich reaction specifically comprises the following steps:
a. under the acidic catalysis environment, adding rosinyl imidazoline derivative corrosion inhibitor intermediate and phosphorous acid, and heating and refluxing for 1.5-2.5h at the temperature of 100-;
b. slowly dripping formaldehyde by using a constant pressure funnel, and carrying out reflux reaction for 1-2 h;
c. and after the reaction is finished, cooling to room temperature, adding a certain amount of saturated saline solution for washing and liquid separation, and adding a certain amount of ethyl acetate into the separated crude product for extraction and liquid separation to obtain the rosinyl imidazoline derivative corrosion inhibitor.
7. The method for synthesizing the rosin-based imidazoline derivative corrosion inhibitor according to claim 2 or 6, wherein the molar ratio of the rosin-based imidazoline derivative corrosion inhibitor intermediate to the phosphorous acid to the formaldehyde is 1:1: 1.5-3.
8. Use of the rosin-based imidazoline derivative corrosion inhibitor according to any one of claims 1-7, wherein the rosin-based imidazoline derivative corrosion inhibitor is used at a concentration of 1-4 g/L.
9. The use of the rosin-based imidazoline derivative corrosion inhibitor according to claim 8, wherein the rosin-based imidazoline derivative corrosion inhibitor is used at a concentration of 3 g/L.
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