CN119529815A - Acidizing corrosion inhibitor, acidizing working fluid, preparation method and application thereof - Google Patents
Acidizing corrosion inhibitor, acidizing working fluid, preparation method and application thereof Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
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Abstract
本申请涉及油气田井下助剂技术领域，公开了一种酸化缓蚀剂、酸化工作液及其制备方法和应用。本申请的酸化缓蚀剂，包含4,4'‑二(2‑溴乙酰基)联苯季铵盐；含有质量比为(0.2～4)∶(0.2～1)的4,4'‑二(2‑溴乙酰基)联苯季铵盐和六次甲基四胺；或者，含有质量比为(0.2～4)∶(0.2～1)∶(0.1～0.5)的4,4'‑二(2‑溴乙酰基)联苯季铵盐、六次甲基四胺和炔丙基‑PEG2‑醇。本申请的酸化缓蚀剂具有优异的缓蚀性能，能够有效抑制酸化液对于油气田井下金属件的腐蚀，使得油气田井下金属件的腐蚀速率明显降低。本申请的酸化工作液中，三种组分起到协同增效作用，形成超分子结构(k)，从而在金属表面形成致密吸附层，能够有效避免酸化过程中油气田井下金属件的腐蚀，使得油气田井下金属件的腐蚀速率明显降低。
The present application relates to the technical field of downhole additives in oil and gas fields, and discloses an acidizing corrosion inhibitor, an acidizing working fluid, and a preparation method and application thereof. The acidizing corrosion inhibitor of the present application comprises 4,4'-bis(2-bromoacetyl)biphenyl quaternary ammonium salt; containing 4,4'-bis(2-bromoacetyl)biphenyl quaternary ammonium salt and hexamethylenetetramine in a mass ratio of (0.2-4): (0.2-1); or, containing 4,4'-bis(2-bromoacetyl)biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 alcohol in a mass ratio of (0.2-4): (0.2-1): (0.1-0.5). The acidizing corrosion inhibitor of the present application has excellent corrosion inhibition performance, can effectively inhibit the corrosion of downhole metal parts of oil and gas fields by acidizing fluid, so that the corrosion rate of downhole metal parts of oil and gas fields is significantly reduced. In the acidizing working fluid of the present application, the three components play a synergistic role to form a supramolecular structure (k), thereby forming a dense adsorption layer on the metal surface, which can effectively avoid the corrosion of metal parts in the oil and gas field wells during the acidizing process, and significantly reduce the corrosion rate of metal parts in the oil and gas field wells.
Description
Technical Field
The application relates to the technical field of underground auxiliary agents of oil and gas fields, in particular to an acidification corrosion inhibitor, an acidification working solution and a preparation method and application thereof.
Background
Acidification of oil and gas wells is an effective stimulation measure, and is widely applied to exploitation of oil and gas. However, when acidizing operation is performed by using the acidizing fluid, the surface of the metal equipment of the oil-gas well is extremely easy to corrode. Therefore, the method has very important significance in acid corrosion prevention and control of metal equipment and pipelines in oil and gas fields.
Aiming at the problem of corrosiveness to metals and metal components in the acidification process of oil and gas fields, corrosion inhibitors are generally added into acid solutions in the prior art to form efficient acidification working solutions. For example, the prior art with publication number CN 117488308A solves the problem of poor corrosion inhibition effect of the gemini imidazoline quaternary ammonium salt corrosion inhibitor in the related art by compounding the gemini imidazoline quaternary ammonium salt, thiourea compound and fatty alcohol polyoxyethylene ether to use as the corrosion inhibitor, and obtains a product with excellent corrosion inhibition effect.
However, the acidizing corrosion inhibitor has the problems of multiple types of compatible components, complex preparation, poor corrosion inhibition effect and the like.
Disclosure of Invention
The application provides an acidification corrosion inhibitor, an acidification working solution and a preparation method and application thereof, and aims to solve the problems of multiple types of compatible components, complex preparation and poor corrosion inhibition effect of the existing acidification corrosion inhibitor.
In order to achieve the above purpose, the present application is realized by the following technical scheme.
In a first aspect of the present application, there is provided an acidified corrosion inhibitor comprising a quaternary ammonium salt of 4,4' -bis (2-bromoacetyl) biphenyl;
The 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt has a structure shown in a formula (1):
In some embodiments, the acidizing corrosion inhibitor further comprises hexamethylenetetramine, and the mass ratio of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt to the hexamethylenetetramine is (0.2-4) to (0.2-1).
In some embodiments, the acidified corrosion inhibitor further comprises propargyl-PEG 2 -ol, said propargyl-PEG 2 -ol having a structure represented by formula (2):
The mass ratio of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt to the hexamethylenetetramine to the propargyl-PEG 2 -alcohol is (0.2-4): 0.2-1): 0.1-0.5.
In some embodiments, the method of preparing the quaternary ammonium salt of 4,4' -bis (2-bromoacetyl) biphenyl comprises:
reacting 4,4' -bis (2-bromoacetyl) biphenyl and quinoline in acetonitrile, and collecting a solid-phase product;
And (3) sequentially recrystallizing and vacuum drying the solid phase product to obtain the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt.
In a second aspect of the application, there is provided the use of the above-described acidizing corrosion inhibitor for the preparation of an acidizing fluid.
In a third aspect of the present application, there is provided an acidified working fluid comprising an acidified fluid and the above-described acidified corrosion inhibitor dissolved in the acidified fluid.
In some embodiments, the mass concentration of the acidified corrosion inhibitor in the acidified working solution is 0.2 to 5wt%.
In some embodiments, the acidizing fluid comprises a hydrochloric acid solution with a mass concentration of 12-20wt%.
In a fourth aspect of the present application, there is provided a method for preparing the above-mentioned acidified working fluid, the method comprising:
According to the formula composition of the acidizing working solution, the acidizing corrosion inhibitor is added into the acidizing working solution, and the acidizing working solution is obtained through ultrasonic dissolution.
In a fifth aspect of the application, there is provided the use of an acidizing fluid as described above in acidizing treatments of oil and gas fields.
Compared with the prior art, the application has the beneficial effects that:
the acidizing corrosion inhibitor contains 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, or contains 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine with the mass ratio of (0.2-4) to (0.2-1), or contains 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol with the mass ratio of (0.2-4) to (0.2-1) to (0.1-0.5), has high corrosion inhibition performance, can effectively inhibit the acid solution corrosion of oil-gas well metal parts, and greatly reduces the corrosion speed of oil-field underground metal parts. In particular, the application has the advantages of smaller dosage of the acidification corrosion inhibitor, smaller required compatibility components, capability of improving the compatibility characteristic of the acidification corrosion inhibitor, reducing the raw material cost required by production, and the like, and can improve the industrialization degree of metal corrosion inhibition in acidification operation.
The acidified working solution contains 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, or contains 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine with the mass ratio of (0.2-4) to (0.2-1), or contains 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol with the mass ratio of (0.2-4) to (0.2-1) to (0.1-0.5). In the acidizing working solution, three components play a synergistic role, wherein hydrogen bonds are formed between carbonyl groups of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and propargyl-PEG 2 -alcohol, hydrogen bonds are formed between propargyl-PEG 2 -alcohol and water molecules and between hexamethylenetetramine, and the three components form a supermolecular structure (k) in acid liquor, so that the three components form a compact adsorption layer on the metal surface, the corrosion of underground metal parts of an oil-gas field in the acidizing process can be effectively avoided, and the corrosion rate of the underground metal parts of the oil-gas field is obviously reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a graph showing various characterization of quaternary 4,4' -bis (2-bromoacetyl) biphenyl ammonium salts (infrared spectrogram, 1 H. NMR and 13 C. NMR) provided in examples of the present application;
FIG. 2 is an electrochemical impedance spectrum of an acidified working fluid provided by an embodiment of the application;
FIG. 3 is a graph showing the electrochemical polarization of an acidified working fluid provided by an embodiment of the present application;
Fig. 4 is an SEM image of the acidified working fluid provided in example 7 of the present application before and after acidification and corrosion inhibition treatment of J55 steel.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the following description of the present embodiment, the terms "include," "comprise," "have," "contain," and the like are open-ended terms, meaning including, but not limited to.
In the following description of the present embodiment, the term "and/or" is used to describe the association relationship of the association objects, and means that three relationships may exist, for example, a and/or B, and that a alone, B alone, and a and B together may exist. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the following description of the present embodiments, the term "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (a), b or c," or "at least one (a), b and c," may each represent a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may each be single or plural.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood by those skilled in the art that, in the following description of the present embodiment, the sequence number does not mean that the execution sequence is sequential, and some or all of the steps may be executed in parallel or sequentially, and the execution sequence of each process should be determined by its functions and inherent logic, and should not constitute any limitation on the implementation process of the embodiment of the present application.
It will be understood by those skilled in the art that the numerical ranges in the embodiments of the present application are to be understood as specifically disclosing each intermediate value between the upper and lower limits of the ranges. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, technical/scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
In a first aspect, the present application provides an acidified corrosion inhibitor comprising a quaternary ammonium salt of 4,4' -bis (2-bromoacetyl) biphenyl;
The 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt has a structure shown in a formula (1):
According to the acidizing corrosion inhibitor, the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt is compounded, so that pi electron quantity and quaternary ammonium group number in the acidizing corrosion inhibitor molecules can be greatly improved, the corrosion inhibitor molecules are easier to adsorb on the metal surface, corrosion of acidizing fluid on the surface of an underground metal part of an oil-gas field is effectively inhibited, and the corrosion rate of the underground metal part of the oil-gas field is reduced. On the basis, the acidizing corrosion inhibitor can greatly reduce the compound demand concentration and the number of kinds of components required by compatibility, greatly improve the compatibility of the acidizing corrosion inhibitor, save the material cost of acidizing corrosion inhibition operation, and has simple and controllable preparation and separation processes, saves the preparation time of the acidizing corrosion inhibitor and improves the purity and yield of target products.
As a preferred embodiment, the acidizing corrosion inhibitor of the present application comprises 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine. Wherein the mass ratio of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt to hexamethylenetetramine is preferably (0.2-4): 0.2-1.
The acidizing corrosion inhibitor provided by the application has the advantages that the 4,4 '-di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine with the mass ratio of (0.2-4) to (0.2-1) are arranged, so that the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine can generate a synergistic effect, the acidizing corrosion inhibitor provided by the application has a better corrosion inhibition effect, and the corrosion rate of the acidizing working solution containing the acidizing corrosion inhibitor to underground metal parts of an oil-gas field is greatly reduced.
The mass ratio of the 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine can be selected from any one of the mass ratio ranges, and particularly preferably the mass ratio is 0.4:0.6, 0.4:0.8, 0.3:0.5 or 0.4:0.5.
As a preferred embodiment, the acidizing corrosion inhibitor of the present application comprises 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol. Wherein the mass ratio of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol is preferably (0.2-4): 0.2-1): 0.1-0.5.
The propargyl-PEG 2 -ol has a structure represented by formula (2):
according to the acidizing corrosion inhibitor, the mass ratio of (0.2-4) (0.2-1) (0.1-0.5) of the 4,4 '-di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol is set, so that a more sufficient synergistic effect can be generated among the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol, a better corrosion inhibition effect is given to the acidizing corrosion inhibitor, and the corrosion rate of acidizing fluid containing the acidizing corrosion inhibitor to metal parts is further reduced.
Specifically, 4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol form a supermolecular structure (k) in acid liquid through supermolecular acting forces such as hydrogen bond and the like, and the formula is shown as follows:
The super-molecular structure enables three components to form a compact adsorption layer on the surface of the metal, so that corrosion of underground metal parts of the oil and gas field in the acidification process can be effectively avoided, and the corrosion rate of the underground metal parts of the oil and gas field is obviously reduced.
The mass ratio of 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol may be any one of the mass ratio within the range, and particularly preferably the mass ratio is 0.4:0.8:0.25, 0.3:0.5:0.4, 0.4:0.6:0.4, 0.4:0.6:0.25 or 0.4:0.5:0.3.
The preparation method of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt comprises the steps of heating and refluxing 4,4' -di (2-bromoacetyl) biphenyl and quinoline in acetonitrile, collecting a solid-phase product, and sequentially recrystallizing and drying the solid-phase product in vacuum to obtain the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt. The preparation method has the advantages of easily available raw materials, convenient preparation, simple separation and purification, and capability of large-scale production and preparation.
In a second aspect, the present application provides an acidified corrosion inhibitor useful for preparing acidified working fluids. The acidizing corrosion inhibitor has high corrosion inhibition rate on underground metals of oil and gas fields, so that after the acidizing corrosion inhibitor is used for preparing the acidizing working fluid, the acidizing working fluid has excellent anti-corrosion effect on the basis of lower cost.
In a third aspect, the present application provides an acidified working fluid comprising an acidified fluid and an acidified corrosion inhibitor as described above dissolved in the acidified fluid.
The acidizing fluid is commonly used in the acidizing operation of oil and gas wells, is mainly used for dissolving plugs and reservoir rock minerals generated in the oil and gas well operation, and is used for recovering and improving the permeability of the reservoir so as to achieve the effects of increasing the yield and the injection of the oil and gas fields. The acidizing fluid can be common monoacid systems such as HCl, HF and the like, or known HCl-HF, organic acid-HF composite systems, acidizing acid systems and the like. Of course, the acidizing fluid of the embodiment of the application also contains various common auxiliary agents in the acidizing working fluid, and the embodiment of the application does not limit the system type, the concentration, the auxiliary agents and the like of the acidizing fluid in particular, so as to meet the requirement of the underground acidizing operation of the oil-gas field.
The acidizing working solution is provided with 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt, or contains 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine with the mass ratio of (0.2-4) to (0.2-1), or contains 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol with the mass ratio of (0.2-4) to (0.2-1) to (0.1-0.5), so that the acidizing solution has high corrosion inhibition rate, can effectively inhibit corrosion of the acidizing solution to underground metal parts of oil and gas fields, and obviously reduces the corrosion rate of the underground metal parts of the oil and gas fields.
In a specific embodiment, the mass concentration of the acidizing corrosion inhibitor dissolved in the acidizing fluid is preferably 0.2-5wt%, and examples of the acidizing corrosion inhibitor are 0.2wt%, 0.5wt%, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, 5.0wt%, and the like, and the acidizing corrosion inhibitor can be specifically selected according to the underground working conditions of the oil-gas field. For example, the mass concentration of the acidified corrosion inhibitor of the application contained in a 20% HCl acidified solution is 4.0wt% at 160℃and the mass concentration of the acidified corrosion inhibitor of the application contained in a 20% HCl acidified solution is 0.5wt% at 60 ℃.
In a specific embodiment, the acidizing fluid contains a hydrochloric acid solution with a mass concentration of preferably 12-20wt%, for example, HCl with a mass concentration of 12wt%, 15wt%, 18wt% or 20wt%.
The hydrochloric acid with the concentration of 20% is prepared by the hydrochloric acid and distilled water, and the distilled water meets the requirements of GB/T6682-2008 three-level water. When the preparation is carried out, hydrochloric acid is slowly added into distilled water while stirring, and the mixture is stirred uniformly. The actual concentration is determined by titration, and the error is not more than +/-0.2%.
In a fourth aspect, the present application provides a method for preparing the above-mentioned acidified working fluid, the method comprising:
according to the formula composition of the acidizing working solution, the acidizing corrosion inhibitor is added into the acidizing working solution, and the acidizing working solution is obtained through ultrasonic dissolution. Among them, ultrasonic dissolution at a temperature of 60 ℃ is preferable.
The preparation method of the acidizing working solution can enable all the components to be fully dissolved and evenly mixed in the acidizing solution to form a stable-dispersion acidizing solution system, can effectively inhibit corrosion of the acidizing solution on the surface of a metal piece, and enables all the components to have a synergistic effect, so that the acidizing corrosion inhibition rate is improved. In addition, the preparation method of the acidizing working solution has controllable process conditions, and ensures that the prepared acidizing working solution dispersion system is stable, thereby ensuring the stability of the acidizing corrosion inhibition effect.
The acidizing working fluid can be used for acidizing treatment of oil and gas fields. The corrosion inhibition rate of the oil-gas field underground metal is high, so that the acidizing working solution has an excellent anti-corrosion effect on the basis of lower cost.
The application is further illustrated by the following examples.
Example 1
The embodiment provides a preparation method of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, which specifically comprises the following steps:
placing 4,4' -bis (2-bromoacetyl) biphenyl and quinoline into a dry round-bottom flask according to the molar ratio of 1:2 (total mass is 32.0 g), adding 250mL of acetonitrile as a solvent, mixing under stirring, heating and refluxing for 24 hours, taking out a solid phase product after the refluxing is finished, cooling, and drying under reduced pressure to obtain a crude product (28.2 g);
Recrystallizing the crude product with mixed solvent of absolute ethyl alcohol and ethyl acetate for 2 times, and drying under reduced pressure in a vacuum oven to obtain yellow brown solid product (27.5 g) which is 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt.
The quaternary ammonium salt of 4,4' -bis (2-bromoacetyl) biphenyl prepared in example 1 was subjected to elemental analysis, the results are shown in Table 1, and subjected to characterization by infrared spectroscopy, nuclear magnetic resonance hydrogen spectroscopy and nuclear magnetic resonance carbon spectroscopy, and the results are shown in FIG. 1. Wherein FIG. 1A is an infrared spectrum of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, FIG. 1B is a nuclear magnetic resonance hydrogen spectrum of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, and FIG. 1C is a nuclear magnetic resonance carbon spectrum of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt.
TABLE 1 elemental analysis of 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salts
As can be seen from FIG. 1A, 2920cm -1 is a-CH 2 -medium-C-H telescopic vibration absorption peak, a C=O double bond telescopic vibration peak is formed at 1690cm -1, absorption peaks appearing at 1620cm -1 and 1590cm -1 are a C=C double bond telescopic vibration peak and a C=N double bond telescopic vibration peak in an aromatic ring respectively, a-C-N + -C-quaternary nitrogen characteristic peak appears at 1440cm -1, bending vibration absorption of an N +-CH2 bond is formed at 1350cm -1, and 900-6755 cm -1 is an absorption peak caused by bending vibration outside an aromatic ring surface;
drawing of the figure 1B：1H NMR(600MHz,Methanol-d4)δ9.42(d,J＝5.8Hz,2H),9.38(d,J＝8.4Hz,2H),8.52(dd,J＝8.4,1.5Hz,2H),8.38–8.36(m,4H),8.33(d,J＝9.0Hz,2H),8.23(ddd,J＝5.3,3.3,1.7Hz,4H),8.09(dd,J＝9.4,2.6Hz,6H),6.98(d,J＝11.9Hz,4H);
Drawing of the figure 1C：13C NMR(151MHz,MeOD)δ189.46,150.56,148.78,145.47,139.30,136.19,133.40,130.67,130.17,130.07,129.25,129.14,127.78,127.43,121.69,118.48,63.21.
The characterization results prove that the preparation method of the embodiment 1 successfully synthesizes the target 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt.
Example 2
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
4g of 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt and 100g of hydrochloric acid solution with the mass concentration of 20wt% are placed in a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain an acidification working solution with the concentration of 4.0 wt%.
Example 3
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine according to the mass ratio of 0.4:0.6 to obtain a binary compound acidizing corrosion inhibitor I;
4g of binary compound acidizing corrosion inhibitor I and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are dissolved for 30min at the temperature of 60 ℃ by ultrasonic waves, so that the acidizing working solution with the mass concentration of 4.0wt% is obtained.
Example 4
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
Mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2-alcohol according to the mass ratio of 0.4:0.8:0.25 to obtain a ternary compound acidizing corrosion inhibitor I;
4g of ternary compound acidizing corrosion inhibitor I and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
Example 5
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
Mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2-alcohol according to the mass ratio of 0.3:0.5:0.4 to obtain a ternary compound acidizing corrosion inhibitor II;
4g of ternary compound acidizing corrosion inhibitor II and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are subjected to ultrasonic dissolution for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
Example 6
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
Mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2-alcohol according to the mass ratio of 0.4:0.6:0.4 to obtain a ternary compound acidizing corrosion inhibitor III;
4g of ternary compound acidizing corrosion inhibitor III and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are subjected to ultrasonic dissolution for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
Example 7
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2-alcohol according to the mass ratio of 0.4:0.6:0.25 to obtain a ternary compound acidizing corrosion inhibitor IV;
4g of ternary compound acidizing corrosion inhibitor IV and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
Example 8
The embodiment provides a preparation method of an acidizing working solution with the mass concentration of 4.0wt%, which specifically comprises the following steps:
mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2-alcohol according to the mass ratio of 0.4:0.5:0.3 to obtain a ternary compound acidizing corrosion inhibitor V;
4g of ternary compound acidizing corrosion inhibitor V and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are subjected to ultrasonic dissolution for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
Comparative example 1
Comparative example 1 provides a method for preparing an acidified working fluid having a mass concentration of 4.0wt%, comprising:
4g of hexamethylenetetramine and 100g of hydrochloric acid solution with the mass concentration of 20wt% are placed in a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain an acidification working solution with the mass concentration of 4.0 wt%.
Comparative example 2
Comparative example 2 provides a method for preparing an acidified working fluid having a mass concentration of 4.0wt%, comprising:
4g of propargyl-PEG 2-ol and 100g of hydrochloric acid solution with the mass concentration of 20wt% are placed in a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain an acidification working solution with the mass concentration of 4.0 wt%.
Comparative example 3
Comparative example 3 provides a method for preparing an acidified working fluid having a mass concentration of 4.0wt%, comprising:
Mixing hexamethylenetetramine and propargyl-PEG 2-alcohol according to a mass ratio of 1:1 to obtain a binary compound acidizing corrosion inhibitor II;
4g of binary compound acidizing corrosion inhibitor II and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
Comparative example 4
Comparative example 4 provides a method for preparing an acidified working fluid having a mass concentration of 4.0wt%, comprising:
mixing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and propargyl-PEG 2-alcohol according to a mass ratio of 1:1 to obtain a binary compound acidizing corrosion inhibitor III;
4g of binary compound acidizing corrosion inhibitor III and 100g of hydrochloric acid solution with the concentration of 20wt% are placed into a 250mL wide-mouth bottle, and are dissolved by ultrasonic waves for 30min at the temperature of 60 ℃ to obtain the acidizing working solution with the mass concentration of 4.0 wt%.
The corrosion inhibition performance of the acidizing corrosion inhibitors prepared in examples 2 to 8 and comparative examples 1 to 4 was tested by using SY/T5405-2019 test method and evaluation index for acidizing corrosion inhibitor, the test temperature was 160℃and the concentration of the corrosion inhibitor was 4.0wt%. The testing method specifically comprises the following steps:
① And (3) marking the steel sheet, namely wearing weighing gloves, measuring the size of the hanging piece by using a vernier caliper, and recording the serial number of the hanging piece and the corresponding geometric size and quality.
② The acidified working fluid of the above examples was introduced into the autoclave based on a 20mL dosage of acidified working fluid per square centimeter of hanging surface area.
③ The hanging piece single piece is arranged on a hanging piece device of the high-pressure reaction kettle, so that the whole surface of the hanging piece is ensured to be contacted with the acidizing working solution, and the hanging piece is not contacted with the container wall. And filling N 2 to 12MPa into the high-pressure reaction kettle. The temperature program was started, the temperature rise rate was 160℃at a temperature rise rate of 3℃/min, and the reaction start time was recorded.
④ And (3) reacting for 4 hours, cutting off the power supply, releasing pressure when the temperature is reduced to 80 ℃, taking out hanging pieces, observing corrosion conditions and recording in detail.
⑤ Washing the hanging piece with water immediately after observation, brushing with a soft brush, if the hanging piece cannot be cleaned, cleaning with 10% of tri-ammonium citrate, finally cleaning the hanging piece by piece with acetone and absolute ethyl alcohol, and placing the hanging piece on clean filter paper.
⑥ Hanging piece weighing, namely drying by cold air, weighing to 0.0001g after drying for 20min in a dryer, and finally calculating the corrosion rate and the corrosion inhibition rate. The corrosion rate is calculated according to the formula (3), and the corrosion inhibition rate is calculated according to the formula (4):
wherein v i - - -single-chip corrosion rate, g/(m 2.h);
Δt— reaction time, h;
Δm t — hanging piece corrosion loss, g;
A t - -hanging surface area, mm 2.
Wherein eta represents uniform corrosion inhibition rate in percentage;
Δm 0 — mass loss of test piece in blank test, g;
Δm 1 - - -mass loss of test piece in dosing test, g.
The hanging sheet test results of this example are shown in Table 2.
Table 2160 ℃ corrosion inhibition performance test results of acidizing corrosion inhibitor
As can be seen from Table 2, the corrosion inhibition rate of the acidizing working solution containing the ternary compound acidizing corrosion inhibitor is above 98%, the corrosion rate is lower than 65 g/(m 2.h), and the standard of SY/T5405-2019 corrosion inhibitor performance test method and evaluation index for acidizing is achieved, which shows that the acidizing corrosion inhibitor prepared by the embodiment of the application can obviously reduce the corrosion rate of the acidizing solution to metal parts. Among them, the best corrosion inhibition effect was obtained when the mass ratio of 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol was 0.4:0.6:0.25 (example 7).
In contrast, the comparison example 1 and the comparison example 2 show that the corrosion rate of the acidification working solution containing the corrosion inhibitor is higher than 65 g/(m 2.h), and the acidification working solution does not meet the SY/T5405-2019 standard of the corrosion inhibitor performance test method and evaluation index for acidification. The binary compound acidizing corrosion inhibitor of the comparative example 3 does not contain the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, the corrosion rate of the prepared acidizing working solution is 64.80 g/(m 2.h), which is far higher than that of examples 2-8, and the corrosion inhibition effect is obviously lower than that of the acidizing working solution.
Comparative example 4 contains the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt of the application, the corrosion rate is 16.33 g/(m 2.h), the corrosion inhibition rate reaches 97.46%, however, the corrosion rate of the ternary compound corrosion inhibitor of examples 4-8 of the application is 6.92-10.23 g/(m 2.h), the corrosion inhibition rate is higher than 98%, and the corrosion inhibition effect is obviously better than that of comparative example 4. The acidizing working solution containing the ternary compound acidizing corrosion inhibitor provided by the application has the advantages that 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol form a supermolecular structure (k) in acid liquor through the supermolecular acting force of hydrogen bonds and the like, and the supermolecular structure enables three components to form a compact adsorption layer on the metal surface, so that corrosion of underground metal parts of an oil-gas field in the acidizing process can be effectively avoided, and the corrosion rate of the underground metal parts of the oil-gas field is obviously reduced.
The combined acidizing corrosion inhibitors described in examples 2 to 8 in table 2 were subjected to an electrochemical impedance spectroscopy test, and according to SY/T5405-2019, corrosion inhibitor performance test method for acidizing and evaluation index, the total concentration of the selected application acidizing corrosion inhibitors was 0.5wt%, the test temperature was 60 ℃, the specific test method included:
The J55 steel is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as an auxiliary electrode, and the test condition is 60 ℃. The system is tested by AC impedance spectrum with 0.01Hz-100kHz and AC amplitude of 5mV as shown in figure 2, then polarization curve test is carried out, the test is carried out in the scanning range of open circuit potential-250 to +250mV, the test is carried out at the scanning rate of 1.0mV.s -1, the corrosion current density is obtained by Tafel extrapolation, corrosion inhibition efficiency eta T% is calculated by formula (5), and the test results are shown in figure 3 and table 3.
Wherein i 0 is the current density of the corrosion inhibitor without adding the corrosion inhibitor, mA.cm -2;
i is the current density after adding corrosion inhibitor, mA.cm -2.
FIG. 2 is an electrochemical impedance spectrum of the acidizing corrosion inhibitor of the present application. As can be seen from FIG. 2, the 0.5wt% acidizing corrosion inhibitor containing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt has obviously increased arc resistance compared with the acidizing corrosion inhibitor containing 0.5wt% of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, which shows that the combination of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine can generate better synergistic effect compared with the blank group (20 wt% hydrochloric acid solution), the acidizing corrosion inhibitor containing 0.5wt% of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt can generate better synergistic effect, and the acidizing agent containing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol ternary combination can generate more fully synergistic effect compared with the acidizing corrosion inhibitor containing 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine, which shows that the combination of 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine can generate better synergistic effect.
FIG. 3 is a graph of electrochemical polarization of the acidizing corrosion inhibitor of the application, and Table 3 is a graph of polarization curve parameters of the acidizing corrosion inhibitor of the application.
Table 3-60 ℃ results of electrochemical polarization Curve test of the acidizing Corrosion inhibitor
From the results of fig. 3 and table 3, it can be seen that the acidizing corrosion inhibitor of 0.5wt% of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, the acidizing corrosion inhibitor of the binary combination of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt and hexamethylenetetramine and the acidizing corrosion inhibitor of the ternary combination of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -alcohol, which are moved in the low current direction compared with the cathode and anode polarization curves under the blank condition, the corrosion current is gradually reduced, which indicates that the acidizing corrosion inhibitor of the ternary combination has the strongest protection effect on J55 steel, and the self-corrosion potential of the ternary acidizing corrosion inhibitor is positive-shifting to indicate that the synthesized corrosion inhibitor is an anode corrosion inhibitor under the blank condition. When the mass ratio of the 4,4' -di (2-bromoacetyl) biphenyl quaternary ammonium salt, the hexamethylenetetramine and the propargyl-PEG 2 -ol is 0.4:0.6:0.25 (example 7), the corrosion inhibition rate reaches 99.00%, and the corrosion inhibition effect is best.
The acidified working fluid prepared in example 7 was used for surface topography test experiments of J55 steel before and after acidifying the J55 steel, and the test results are shown in fig. 4 (500 times magnification). In fig. 4, (a) is an SEM image of J55 steel before acidification, (B) is an SEM image of J55 steel after acidification with 20% hydrochloric acid at 60 ℃ for 4 hours, and (C) is an SEM image of J55 steel after acidification with working fluid of example 7 at 90 ℃ for 4 hours.
As can be seen from FIG. 4 (A), the J55 steel surface before the acidification treatment is relatively smooth and has a few scratches;
as can be seen from (B) of FIG. 4, the J55 steel subjected to acidification treatment by 20% hydrochloric acid cannot see the appearance of the metal matrix, and the J55 steel sheet is severely corroded;
As can be seen from FIG. 4 (C), the surface of the J55 steel sheet acidified by the acidified working solution of example 7 is relatively smooth and flat, no obvious corrosion phenomena such as pitting and pitting are seen, and the acidified working solution of example 7 can reduce the corrosion of 20% hydrochloric acid on the surface of the J55 steel sheet, so that the combined corrosion inhibitor of 4,4' -bis (2-bromoacetyl) biphenyl quaternary ammonium salt, hexamethylenetetramine and propargyl-PEG 2 -ol with the mass ratio of 0.4:0.6:0.25 has a protective effect on the J55 steel sheet.
Based on the above test, the acidizing corrosion inhibitor has excellent corrosion inhibition performance at 160 ℃, and the corrosion rate reaches the standard of SY/T5405-2019 corrosion inhibitor performance test method and evaluation index for acidizing, which shows that the acidizing corrosion inhibitor can obviously reduce the corrosion rate of metal.
While the application has been described in detail in this specification with reference to the general description and the specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the application and are intended to be within the scope of the application as claimed.
Claims (10)
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