CN117658904A - Acidizing corrosion inhibitor, acidizing working solution, and preparation method and application thereof - Google Patents
Acidizing corrosion inhibitor, acidizing working solution, and preparation method and application thereof Download PDFInfo
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- CN117658904A CN117658904A CN202311652747.0A CN202311652747A CN117658904A CN 117658904 A CN117658904 A CN 117658904A CN 202311652747 A CN202311652747 A CN 202311652747A CN 117658904 A CN117658904 A CN 117658904A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 175
- 230000007797 corrosion Effects 0.000 title claims abstract description 172
- 239000003112 inhibitor Substances 0.000 title claims abstract description 106
- 239000012224 working solution Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- -1 biphenylyl benzylquinoline quaternary ammonium salt Chemical class 0.000 claims abstract description 64
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012530 fluid Substances 0.000 claims abstract description 56
- 230000020477 pH reduction Effects 0.000 claims abstract description 40
- ILBIXZPOMJFOJP-UHFFFAOYSA-N n,n-dimethylprop-2-yn-1-amine Chemical compound CN(C)CC#C ILBIXZPOMJFOJP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 30
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 11
- GTVGGVKAMZWLKX-UHFFFAOYSA-N C(C1=CC=CC=C1)C1=NC2=CC=CC=C2C(=C1C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C1=CC=CC=C1)C1=NC2=CC=CC=C2C(=C1C1=CC=CC=C1)C1=CC=CC=C1 GTVGGVKAMZWLKX-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 30
- 229910052751 metal Inorganic materials 0.000 abstract description 28
- 239000002184 metal Substances 0.000 abstract description 28
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 32
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910000939 field's metal Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D215/10—Quaternary compounds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/27—Methods for stimulating production by forming crevices or fractures by use of eroding chemicals, e.g. acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The application discloses an acidification corrosion inhibitor, an acidification working solution, a preparation method and application thereof, and belongs to the technical field of oil-gas field underground auxiliary agents. The acidizing corrosion inhibitor contains diphenyl benzyl quinoline quaternary ammonium dichloride; alternatively, the mass ratio is (0.2-5): (0.1-0.5) diphenyl benzylquinoline quaternary ammonium chloride and N, N-dimethyl propargylamine; alternatively, the mass ratio is (0.2-5): (0.1-0.5): (1.5-5) biphenylyl benzylquinoline quaternary ammonium salt dichloride, N-dimethyl propargylamine and hexamethylenetetramine. The acidizing corrosion inhibitor has high corrosion inhibition rate, can effectively inhibit corrosion of acidizing fluid on underground metal parts of oil and gas fields, and can obviously reduce the corrosion rate of the underground metal parts of the oil and gas fields.
Description
Technical Field
The application belongs to the technical field of underground auxiliary agents of oil and gas fields, and particularly relates to an acidification corrosion inhibitor, an acidification working solution, a preparation method and application thereof.
Background
Acidizing of oil and gas wells has been used in large quantities for the development and production of oil and gas resources as an effective measure for improving oil and gas recovery. However, when acidizing operation is performed by using the acidizing fluid, the problem of corrosion on the surfaces of metal equipment and metal pipe fittings of the oil and gas field is easily caused. Therefore, inhibition of acid corrosion of oil and gas field metal equipment and metal tubing is critical.
In order to solve the corrosion problem of metal equipment and metal pipe fittings caused in the acidification operation process of the oil and gas field, a technical strategy of compounding corrosion inhibitors into the acidizing fluid is developed in the related technology, and the acidizing corrosion inhibitors with excellent performance are developed and produced. For example, the prior art with publication number CN 115449363A discloses a quaternary ammonium salt type high-temperature acidification corrosion inhibitor, which realizes better acidification corrosion inhibition performance by utilizing the multi-benzene ring structure characteristic of chloromethyl naphthalene quinoline quaternary ammonium salt.
However, the quaternary ammonium salt type high-temperature acidification corrosion inhibitor described above has the following problems: firstly, the corrosion inhibitor has high required concentration, more compatibility component types and complex preparation, so that the acidizing operation cost of the oil and gas field is high and the acidizing effect is not easy to control; secondly, the corrosion rate is still higher when the corrosion inhibitor is used for acidizing treatment of oil and gas fields, so that the acidizing corrosion inhibition effect is poor.
Disclosure of Invention
The application discloses an acidification corrosion inhibitor, an acidification working solution and a preparation method and application thereof, and aims to solve the technical problems of high required concentration, multiple types of compatible components, complex preparation and non-ideal acidification corrosion inhibition effect of the acidification corrosion inhibitor.
To achieve the above object, a first aspect of the present application provides an acidizing corrosion inhibitor. The acidizing corrosion inhibitor contains diphenyl benzyl quinoline quaternary ammonium dichloride;
the biphenyl benzyl quinoline dichloride quaternary ammonium salt has the structure of [ i ]:
in an embodiment of the first aspect, the acidizing corrosion inhibitor of the present application comprises biphenylyl dichloride benzylquinoline quaternary ammonium salt and N, N-dimethyl propargylamine;
the mass ratio of the biphenyl benzyl quinoline quaternary ammonium salt and the N, N-dimethyl propargylamine is (0.2-5): (0.1-0.5).
In an embodiment of the first aspect, the acidizing corrosion inhibitor of the present application contains diphenyl benzylquinoline quaternary ammonium dichloride, N-dimethyl propargylamine and hexamethylenetetramine;
the mass ratio of the biphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine is (0.2-5): (0.1-0.5): (1.5-5).
In an embodiment in combination with the first aspect, the preparation method of the biphenyl benzyl quinoline quaternary ammonium salt comprises the following steps:
reacting biphenyl dichlorobenzyl and quinoline in an organic solvent, and sequentially recrystallizing and vacuum drying the reaction product to obtain biphenyl benzyl quinoline quaternary ammonium salt.
In a second aspect, the present application provides the use of the acidizing corrosion inhibitor of the present application for the preparation of an acidizing working fluid.
A third aspect of the present application provides an acidified working fluid comprising an acidified fluid and an acidified corrosion inhibitor of the present application dissolved in the acidified fluid.
In combination with an embodiment of the third aspect, the concentration by mass of the acidifying corrosion inhibitor dissolved in the acidifying liquid is between 0.2 and 5% by weight.
In an embodiment in combination with the third aspect, the acidified solution contains a hydrochloric acid solution having a mass concentration of 12 to 20 wt%.
A fourth aspect of the present application provides a method for preparing an acidified working fluid, the method comprising the steps of:
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.
A fifth aspect of the present application provides the use of an acidizing fluid of the present application in acidizing treatments of oil and gas fields.
Compared with the prior art, the advantages or beneficial effects of the embodiment of the application at least comprise:
the acidizing corrosion inhibitor provided in the first aspect of the application comprises biphenyl benzyl quinoline quaternary ammonium salt dichloride or comprises the following components in percentage by mass (0.2-5): (0.1-0.5) diphenyl benzylquinoline dichloride quaternary ammonium salt and N, N-dimethyl propargylamine, or (0.2-5): (0.1-0.5): the diphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine in the formula (1.5-5) have high corrosion inhibition rate, so that the corrosion of the acidizing fluid to the underground metal parts of the oil and gas field is effectively inhibited, and the corrosion rate of the underground metal parts of the oil and gas field is greatly reduced. The preparation method has the advantages that the required concentration of the acidizing corrosion inhibitor is low, the required compatibility component types are few, the compatibility performance of the acidizing corrosion inhibitor is improved, the material cost of acidizing corrosion inhibition operation is saved, the preparation and separation of the acidizing corrosion inhibitor are simple and controllable, and the industrialization of metal corrosion protection operation in the acidizing operation process is improved.
The acidizing corrosion inhibitor provided in the second aspect of the application has a very high corrosion inhibition rate for underground metal parts of oil and gas fields based on the acidizing corrosion inhibitor when being used for preparing the working fluid comprising acidizing. Therefore, after the acidizing corrosion inhibitor is used for preparing the acidizing working solution, the acidizing working solution has a good anti-corrosion effect on the basis of lower cost.
The acidizing working solution provided in the third aspect of the application comprises biphenyl benzyl quinoline quaternary ammonium salt dichloride or comprises the following components in percentage by mass (0.2-5): (0.1-0.5) diphenyl benzylquinoline quaternary ammonium chloride and N, N-dimethyl propargylamine; alternatively, the mass ratio is (0.2-5): (0.1-0.5): the diphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine in the (1.5-5) are prepared, so that the acidizing fluid has high corrosion inhibition rate, the corrosion of the acidizing fluid to the underground metal parts of the oil-gas field is effectively inhibited, and the corrosion rate of the underground metal parts of the oil-gas field is obviously reduced.
According to the preparation method of the acidizing working solution, the components can be fully dissolved and uniformly mixed in the acidizing solution to form a dispersion-stable acidizing working solution system, so that the acidizing working solution has high corrosion inhibition rate, corrosion of the acidizing solution to oil-gas field metal parts can be effectively inhibited, and the corrosion rate of the oil-gas field underground metal parts is obviously reduced. In particular, when the acidified working fluid contains a mass ratio of (0.2-5): (0.1-0.5) diphenyl benzylquinoline quaternary ammonium chloride and N, N-dimethyl propargylamine; alternatively, the mass ratio is (0.2-5): (0.1-0.5): when the biphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine are prepared in the formula (1.5-5), the components can have a synergistic effect, so that the corrosion inhibition rate of the acidizing working solution 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 acidified working fluid provided in the fifth aspect of the present application has a high corrosion inhibition rate, a low corrosion rate and a low cost based on the acidified working fluid when used in acidizing treatments including oil and gas fields. Therefore, after the acidizing working fluid is applied to acidizing treatment of the oil and gas field, corrosion of the treated oil and gas field underground metal parts can be greatly reduced, and the acidizing corrosion of the surface of the oil and gas field underground metal parts can be effectively 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 described in 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 an infrared spectrum of a biphenyl benzylquinoline quaternary ammonium dichloride provided in an embodiment of the present application;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a quaternary ammonium salt of biphenyl benzylquinoline dichloride provided in the examples of the present application;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of a quaternary ammonium salt of biphenyl benzylquinoline dichloride provided in an embodiment of the present application;
FIG. 4 is an electrochemical impedance spectrum of an acidified working fluid provided in an embodiment of the present application;
FIG. 5 is a graph of electrochemical polarization of an acidified working fluid provided in an embodiment of the present application;
FIG. 6 is an SEM image of J55 steel before and after acidification and corrosion inhibitor treatment provided in the examples herein, wherein FIG. 6A is an SEM image of J55 steel before acidification; FIG. 6B is an SEM image of J55 steel after 4h of acidification treatment with 20% hydrochloric acid at 160 ℃; FIG. 6C is an SEM image of J55 steel after 4 hours of acidification treatment at 160℃in the acidification working fluid of example 8.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
In the following description of the present embodiment, the term "and/or" is used to describe an association relationship of association objects, which means that three relationships may exist, for example, a and/or B may mean: a alone, B alone and both a and B. 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 (individual) of a, b, or c," or "at least one (individual) of 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 be single or multiple, respectively.
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 in the examples 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 embodiments of the present application, the sequence number does not mean that the sequence of execution is not 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 embodiments 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 each intermediate value between the upper and lower limits of the specifically disclosed 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 invention. 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, embodiments herein provide an acidizing corrosion inhibitor. The acidizing corrosion inhibitor contains diphenyl benzyl quinoline quaternary ammonium dichloride;
the biphenyl benzylquinoline quaternary ammonium salt has the structure of [ i ]:
according to the acidizing corrosion inhibitor provided by the embodiment of the application, the provided biphenyl benzyl quinoline quaternary ammonium dichloride is compounded, so that pi electron quantity and quaternary ammonium group number in 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 acidification corrosion inhibitor can greatly reduce the compound demand concentration and reduce the types of components with compatibility demands, so that the compatibility of the acidification corrosion inhibitor is greatly improved, the material cost of acidification corrosion inhibition operation is saved, the preparation and separation processes of the acidification corrosion inhibitor are simple and controllable, the preparation time of the acidification corrosion inhibitor is saved, and the purity and yield of a target product are improved.
In a specific embodiment, the acidizing corrosion inhibitor of the embodiment of the application contains diphenyl benzylquinoline dichloride quaternary ammonium salt and N, N-dimethyl propargylamine. Wherein the mass ratio of the biphenyl benzoquinoline quaternary ammonium salt and the N, N-dimethyl propargylamine is preferably (0.2-5): (0.1-0.5).
The acidizing corrosion inhibitor comprises the following components in percentage by mass (0.2-5): (0.1-0.5) diphenyl benzyl quinoline quaternary ammonium salt and N, N-dimethyl propargylamine, thereby generating synergistic effect between the diphenyl benzyl quinoline quaternary ammonium salt and the N, N-dimethyl propargylamine, endowing the acidizing corrosion inhibitor with better corrosion inhibition effect, and greatly reducing the corrosion rate of the acidizing working solution containing the acidizing corrosion inhibitor to underground metal parts of oil and gas fields.
The mass ratio of the biphenylyl benzylquinoline quaternary ammonium salt dichloride to the N, N-dimethyl propargylamine is illustratively 0.25:0.5;
or alternatively
The mass ratio of the diphenyl benzylquinoline quaternary ammonium chloride to the N, N-dimethyl propargylamine is illustratively 0.25:0.3;
or alternatively
The mass ratio of the diphenyl benzylquinoline quaternary ammonium chloride to the N, N-dimethyl propargylamine is illustratively 0.25:0.2;
or alternatively
The mass ratio of the diphenyl benzylquinoline quaternary ammonium chloride to the N, N-dimethyl propargylamine is illustratively 0.3:0.2.
in a specific embodiment, the acidizing corrosion inhibitor of the embodiment of the application contains diphenyl benzylquinoline quaternary ammonium chloride, N-dimethyl propargylamine and hexamethylenetetramine. Wherein the mass ratio of the biphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine is preferably (0.2-5): (0.1-0.5): (1.5-5).
The acidizing corrosion inhibitor provided by the embodiment of the application contains the following components in percentage by mass (0.2-5): (0.1-0.5): the biphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine of (1.5-5) can generate more sufficient synergistic interaction between the biphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine, so that the acidizing corrosion inhibitor has better corrosion inhibition effect, and the corrosion rate of the acidizing fluid containing the acidizing corrosion inhibitor to metal parts is further reduced.
The mass ratio of biphenyl benzoquinolinium dichloride quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine is exemplified as follows:
the mass ratio of biphenyl benzylquinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine is illustratively 0.25:0.5:5, a step of;
or alternatively
The mass ratio of the biphenyl benzylquinoline quaternary ammonium salt to the N, N-dimethyl propargylamine and the hexamethylenetetramine is illustratively 0.25:0.3:4, a step of;
or alternatively
The mass ratio of biphenyl benzylquinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine is illustratively 0.25:0.2:5, a step of;
or alternatively
The mass ratio of biphenyl benzylquinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine is illustratively 0.25:0.2:4.5;
or alternatively
The mass ratio of the biphenyl benzylquinoline quaternary ammonium salt to the N, N-dimethyl propargylamine and the hexamethylenetetramine is illustratively 0.3:0.2:4, a step of;
the embodiment of the application provides a preparation method of biphenyl benzyl quinoline quaternary ammonium salt, which preferably comprises the following steps:
reacting biphenyl dichlorobenzyl and quinoline in an absolute ethyl alcohol-toluene mixed solvent, and sequentially recrystallizing and vacuum drying the reaction product to obtain biphenyl benzyl quinoline quaternary ammonium salt dichloride. Wherein, the molar ratio of biphenyl dichlorobenzyl to quinoline is preferably 1:2.
according to the preparation method of the biphenyl benzyl quinoline quaternary ammonium salt dichloride, the biphenyl benzyl quinoline and quinoline are heated and refluxed in the absolute ethyl alcohol-toluene mixed solvent, and the obtained product is recrystallized and dried in vacuum, so that the biphenyl benzyl quinoline quaternary ammonium salt dichloride product can be obtained, the raw materials are easy to obtain, the preparation is convenient, the separation and purification are simple, and the preparation can be realized in a large scale.
In a second aspect, embodiments of the present application provide that the above-described acidizing corrosion inhibitor is used for preparing an acidizing working fluid, and the acidizing corrosion inhibitor has a high corrosion inhibition rate for downhole metal parts of an oil and gas field. Therefore, after the acidizing corrosion inhibitor is used for preparing the acidizing working solution, the acidizing working solution has a good anti-corrosion effect on the basis of lower cost.
In a third aspect, embodiments of the present application provide an acidizing fluid, where the acidizing fluid includes an acidizing fluid and an acidizing corrosion inhibitor of the present application dissolved in the acidizing 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 acidifying liquid can be common monoacid systems such as HCl, HF and the like, or known HCl-HF, organic acid-HF composite systems, acidifying acid systems and the like. Of course, the acidizing fluid in the embodiment of the application further contains various common auxiliary agents in the acidizing working fluid, and the system type, concentration, auxiliary agents and the like of the acidizing fluid are not particularly limited in the embodiment of the application, so that the requirement of underground acidizing operation of the oil-gas field can be met.
The acidizing working solution provided by the embodiment of the application contains biphenyl benzyl quinoline dichloride quaternary ammonium salt or contains the components with the mass ratio of 0.2-5:0.1-0.5 of biphenyl benzoquinolinium dichloride quaternary ammonium salt and N, N-dimethyl propargylamine; or, the mass ratio of the components is 0.2-5:0.1-0.5:1.5-5, diphenyl benzyl quinoline quaternary ammonium chloride, N-dimethyl propargylamine and hexamethylenetetramine, so that the acidizing fluid has high corrosion inhibition rate, can effectively inhibit corrosion of the acidizing fluid to underground metal parts of the oil-gas field, and obviously reduces the corrosion rate of the underground metal parts of the oil-gas field.
In a specific embodiment, the mass concentration of the acidizing corrosion inhibitor dissolved in the acidizing fluid is preferably 0.2-5wt%, and examples are 0.2wt%, 0.5wt%, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, 5.0wt%, and the like, and may be specifically selected according to the downhole working conditions of the oil and gas field, for example, the mass concentration of the acidizing corrosion inhibitor contained in the 20% hcl acidizing fluid is 4.0wt% at the temperature of 160 ℃; the mass concentration of the acidizing corrosion inhibitor contained in the 20% HCl acidizing fluid is 0.5wt% at the temperature of 60 ℃.
In a specific embodiment, the acidizing fluid contains a hydrochloric acid solution with a mass concentration of preferably 12-20wt%, for example, 12wt% hcl and 20wt% hcl, which are typical for acidizing working fluids.
It should be noted that, in the embodiment of the application, hydrochloric acid with concentration of 20% and distilled water are prepared according to formulas (1) and (2), and the distilled water meets the requirements of GB/T6682 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%.
The amount of hydrochloric acid is calculated according to the formula (1):
in formula (1):
V 0 hydrochloric acid in milliliters (mL);
ρ 0 hydrochloric acid density in grams per cubic centimeter (g/cm) 3 )；
W 0 Hydrochloric acid mass fraction, expressed as a percentage;
v- -volume of hydrochloric acid formulated in milliliters (mL);
ρ - -the density of the hydrochloric acid formulated in grams per cubic centimeter (g/cm) 3 )；
W- -the mass fraction of hydrochloric acid prepared was expressed as a percentage (20% hydrochloric acid density 1.1004 g/cm) 3 )。
The distilled water consumption is calculated according to the formula (2):
wherein: v (V) 1 Distilled water in the hydrochloric acid prepared, the unit is milliliter (mL);
ρ 1 density of water at room temperature in grams per cubic centimeter (g/cm) 3 )。
In a fourth aspect, embodiments of the present application provide a method for preparing an acidified working fluid, the method preferably 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 is preferably performed at a temperature of 60 ℃.
According to the preparation method of the acidizing working solution, the components can be fully dissolved and uniformly mixed in the acidizing solution to form a stable-dispersion acidizing solution system, corrosion of the acidizing solution to the surface of a metal piece can be effectively inhibited, and synergistic effects are achieved among the components, 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 technical scheme of the present application will be further described in conjunction with specific embodiments.
Example 1
The embodiment provides a preparation method of biphenyl benzyl quinoline quaternary ammonium salt, which specifically comprises the following steps:
s101: biphenyl dichlorobenzyl and quinoline are mixed according to the mole ratio of 1:2 (total mass 38.0 g) is put into a dry round bottom flask, 250mL of absolute ethanol and toluene are added as solvents, and after mixing under stirring, heating and refluxing are carried out for 12h;
s102: after the reflux was completed, the product was taken out and cooled, and dried under reduced pressure to obtain a crude product (35.2 g);
s103: recrystallizing the crude product with a mixed solvent of absolute ethyl alcohol and ethyl acetate for 2 times, and drying in a vacuum oven under reduced pressure to obtain a pink solid product (34.5 g), namely the biphenyl benzyl quinoline quaternary ammonium salt dichloride, which is used for preparing the acidification corrosion inhibitor.
To verify the technical effect of example 1, the diphenyl benzylquinoline dichloride quaternary ammonium salt prepared in example 1 is subjected to infrared spectrum, nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum characterization, and the characterization results are shown in fig. 1 to 3. Wherein, figure 1 is an infrared spectrogram of biphenyl benzyl quinoline dichloride quaternary ammonium salt; FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a quaternary ammonium salt of diphenyl benzylquinoline dichloride; FIG. 1 is a nuclear magnetic resonance carbon spectrum of biphenyl benzylquinoline quaternary ammonium dichloride.
As can be seen from FIG. 1, 3500-3200cm -1 The wide absorption band is associated with two molecules, 3000-3100cm -1 The peak of (2) is C-H stretching vibration characteristic peak in quinoline ring; 1525.27cm -1 Peak C-N + -quaternary nitrogen characteristic peak of C; 1400-1600cm -1 The multiple peaks of (2) are characteristic peaks of benzene rings; 900-675cm -1 Is the absorption peak caused by vibration outside the aromatic ring, 781.58cm -1 Is the absorption peak caused by the swinging vibration of the alkyl in the plane;
fig. 2: 1 H NMR(600MHz,CD 3 OD)δ9.67(d,J＝5.6Hz,2H),9.35(d,J＝8.1Hz,2H),8.57(d,J＝8.9Hz,2H),8.50(d,J＝8.1Hz,2H),8.26–8.21(m,4H),8.05(t,J＝7.5Hz,2H),7.69(d,J＝7.8Hz,4H),7.50(d,J＝8.0Hz,4H),6.46(s,4H)；
fig. 3: 13 C NMR(151MHz,CD 3 OD)δ151.07,149.71,140.79,138.29,136.02,133.68,133.19,130.89,130.58,130.14,127.93,127.70,121.99,119.00,62.89。
as can be seen from the characterization results of fig. 1 to 3, the preparation method of example 1 successfully synthesizes the target biphenyl benzyl quinoline dichloride 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 biphenyl benzyl quinoline dichloride quaternary ammonium salt and 100g of hydrochloric acid solution with the mass 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 an acidification working solution with the mass 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:
the biphenyl benzyl quinoline quaternary ammonium salt and the N, N-dimethyl propargylamine are mixed according to the mass ratio of 0.25:0.5, mixing to obtain a binary compound acidizing corrosion inhibitor;
4g of the binary compound acidizing corrosion inhibitor 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 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:
the biphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine are mixed according to the mass ratio of 0.25:0.5:5, mixing 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 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 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:
the biphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine are mixed according to the mass ratio of 0.25:0.3:4, mixing 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:
the biphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine are mixed according to the mass ratio of 0.25:0.2:5, mixing 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:
the biphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine are mixed according to the mass ratio of 0.25:0.2:4.5, mixing 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 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 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:
the biphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine are mixed according to the mass ratio of 0.3:0.2:4, mixing 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%.
Example 9
According to SYT 5405-2019 'test method and evaluation index of corrosion inhibitor performance for acidification', the embodiment provides a test experiment (test temperature is 160 ℃, test corrosion inhibitor concentration is 4.0 wt%) for testing corrosion inhibition performance of the acidizing corrosion inhibitors of the embodiments 2-8 by a static hanging piece weightlessness method, which specifically comprises:
(1) and (3) marking a steel sheet: 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. Filling N into the high-pressure reaction kettle 2 To 12MPa. The temperature program was started, the temperature rise rate was 160℃at a temperature rise rate of 3℃per minute, 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 the hanging piece, observing the corrosion condition and recording in detail.
(5) After observation, the hanging piece is immediately washed by water and then is brushed by a soft brush; if the cleaning cannot be performed, cleaning with 10% of tri-ammonium citrate; finally, washing the filter paper piece by using acetone and absolute ethyl alcohol, and placing the hanging pieces on clean filter paper.
(6) Hanging piece weighing: drying with cold air, drying in a dryer for 20min, weighing to 0.0001g, and calculating corrosion rate and 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 (v) i Monolithic corrosion rate in grams per square meter hour [ g/(m) 2 ·h)]；
Δt— reaction time in hours (h);
Δm t the hanging piece corrosion loss is expressed in grams (g);
A t hanging piece surface area in square millimeters (mm) 2 )。
Wherein: η - -the uniform sustained release rate expressed in percent;
Δm 0 mass loss in the blank in grams (g);
Δm 1 mass loss of the test piece in the dosing test, in grams (g).
The hanging sheet test results of this example are shown in Table 1.
Table 1-160 ℃ corrosion inhibition test results of the acidizing corrosion inhibitor
As can be seen from Table 1, the corrosion inhibition rates of the acidizing working fluids containing the ternary compound acidizing corrosion inhibitors are all above 98%, and the corrosion rate is lower than 65 g/(m) 2 H), the standard of SYT 5405-2019 'performance test method and evaluation index of corrosion inhibitor for acidification' is reached, which shows that the corrosion inhibitor for acidification prepared by the embodiment of the application can obviously reduce the corrosion rate of acidizing fluid to metal parts. Wherein, when the mass ratio of the biphenyl dichloride benzyl quinoline quaternary ammonium salt to the N, N-dimethyl propargylamine to the hexamethylenetetramine is 0.3:0.2:4, the corrosion inhibition effect is best.
Example 10
The present example provides an electrochemical impedance spectrum test experiment of the combined acidizing corrosion inhibitor shown in table 1, considering the working environment of an electrochemical workstation, according to SYT 5405-2019, corrosion inhibitor performance test method for acidizing and evaluation index, the total concentration of the selected application acidizing corrosion inhibitor is 0.5wt%, the test temperature is 60 ℃, and the specific test method comprises:
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 was tested by AC impedance spectroscopy at 0.01Hz-100kHz with an AC amplitude of 5mV, as shown in FIG. 4. Wherein, fig. 4 is an electrochemical impedance spectrum of the acidified working fluid. Then, it was subjected to a polarization curve test at 1.0 mV.s in the scan range of-250 to +250mV of open circuit potential -1 The corrosion current density is obtained by Tafel extrapolation, corrosion inhibition efficiency eta T % is calculated by equation (5), and the detection results are shown in fig. 5 and table 2. Wherein, FIG. 5 is an electrochemical polarization graph of the acidizing corrosion inhibitor of the present application.
Wherein: i.e 0 Current density without corrosion inhibitor;
i is the current density (mA.cm) after adding corrosion inhibitor -2 )。
As can be seen from fig. 4, the 0.5wt% of the acidizing corrosion inhibitor containing the diphenyl benzylquinoline quaternary ammonium dichloride has increased arc resistance relative to the blank group (20 wt% hydrochloric acid solution), which indicates that the 0.5wt% of the diphenyl benzylquinoline quaternary ammonium dichloride is compounded into the acidizing fluid to effectively inhibit the corrosion of metal parts; compared with 0.5wt% of acidizing corrosion inhibitor containing binary combination of biphenyl benzyl quinoline quaternary ammonium salt and N, N-dimethyl propargylamine, 0.5wt% of acidizing corrosion inhibitor containing biphenyl benzyl quinoline quaternary ammonium salt has obviously increased arc resistance, which proves that the combination of biphenyl benzyl quinoline quaternary ammonium salt and N, N-dimethyl propargylamine can generate better synergistic effect; compared with an acidification corrosion inhibitor containing ternary combination of diphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine, the acidification corrosion inhibitor containing binary combination of diphenyl benzyl quinoline quaternary ammonium salt and N, N-dimethyl propargylamine has further increased arc resistance, which shows that the ternary combination of diphenyl benzyl quinoline quaternary ammonium salt, N-dimethyl propargylamine and hexamethylenetetramine can generate more sufficient synergistic effect.
The results of the electrochemical polarization curve test of this example are shown in Table 2.
Table 2-results of electrochemical polarization Curve test of the acidizing Corrosion inhibitor at a temperature of 60℃
From the results of fig. 5 and table 2, it can be seen that the 0.5wt% of the acidizing corrosion inhibitor of the diphenyl benzylquinoline quaternary ammonium dichloride, the acidizing corrosion inhibitor of the diphenyl benzylquinoline quaternary ammonium dichloride and the binary combination of the N, N-dimethyl propargylamine, and the acidizing corrosion inhibitor of the ternary combination of the diphenyl benzylquinoline quaternary ammonium dichloride, the N, N-dimethyl propargylamine, and the hexamethylenetetramine, the three acidizing corrosion inhibitors move in the low current direction compared with the negative and positive polarization curves under the blank condition, the corrosion current is gradually reduced, which indicates that the protection effect of the ternary combination of the acidizing corrosion inhibitor on the J55 steel is strongest; compared with the blank condition, the ternary acidification corrosion inhibitor has the advantages that the self-corrosion potential is positively shifted (less than 85 mV), the cathode polarization slope is not obviously changed, and the anode polarization slope is gradually increased, so that the synthesized corrosion inhibitor is a mixed corrosion inhibitor mainly used for inhibiting anode reaction. When the mass ratio of the biphenyl dichloride benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine is 0.3:0.2: and 4, the corrosion inhibition rate reaches 98.64%, and the corrosion inhibition effect is best.
Example 11
This example provides the surface topography test experiment of J55 steel before and after the acidification working fluid of example 8 is used for acidizing J55 steel, and the test result is shown in FIG. 6 (500 times magnification). Wherein, fig. 6A is an SEM image of J55 steel before acidification; FIG. 6B is an SEM image of J55 steel after 4h of acidification treatment with 20% hydrochloric acid at 160 ℃; FIG. 6C is an SEM image of J55 steel after 4 hours of acidification treatment at 160℃in the acidification working fluid of example 8.
As can be seen from fig. 6A, the surface of the J55 steel before the acidification treatment is relatively smooth and has a few scratches;
as can be seen from FIG. 6B, the pits on the surface of the J55 steel subjected to the acidification treatment of 20% hydrochloric acid are densely distributed, and the J55 steel sheet is severely corroded;
according to fig. 6C, the surface of the J55 steel sheet acidified by the acidified working solution of example 8 is relatively smooth and flat, no obvious corrosion phenomena such as pitting and pitting are observed, and it is demonstrated that the acidified working solution of example 8 can inhibit corrosion of 20% hydrochloric acid on the surface of the J55 steel sheet, and the mass ratio of diphenyl benzylquinoline quaternary ammonium chloride, N-dimethyl propargylamine and hexamethylenetetramine is 0.3:0.2:4 has a protective effect on J55 steel.
Based on the above test, the acidizing corrosion inhibitor has excellent corrosion inhibition performance at 160 ℃, and the corrosion rate reaches the standard of SYT 5405-2019 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.
Various embodiments in this specification are described in an incremental manner, and identical or similar parts of the various embodiments are referred to each other, with each embodiment focusing on differences from the other embodiments.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the present application; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions.
Claims (10)
1. An acidification corrosion inhibitor is characterized by comprising biphenyl benzyl quinoline dichloride quaternary ammonium salt;
the biphenyl benzyl quinoline dichloride quaternary ammonium salt has the structure of [ i ]:
2. an acidification corrosion inhibitor is characterized by comprising diphenyl benzylquinoline quaternary ammonium chloride and N, N-dimethyl propargylamine;
the mass ratio of the biphenyl benzyl quinoline quaternary ammonium salt and the N, N-dimethyl propargylamine is (0.2-5): (0.1-0.5).
3. An acidification corrosion inhibitor is characterized by comprising diphenyl benzylquinoline quaternary ammonium chloride, N-dimethyl propargylamine and hexamethylenetetramine;
the mass ratio of the biphenyl benzyl quinoline quaternary ammonium salt, the N, N-dimethyl propargylamine and the hexamethylenetetramine is (0.2-5): (0.1-0.5): (1.5-5).
4. An acidizing corrosion inhibitor according to any one of claims 1 to 3, characterised in that the preparation method of the diphenyl benzylquinoline quaternary ammonium dichloride comprises:
reacting biphenyl dichlorobenzyl and quinoline in an absolute ethyl alcohol-toluene mixed solvent, and sequentially recrystallizing and vacuum drying the reaction product to obtain biphenyl benzyl quinoline quaternary ammonium salt dichloride.
5. Use of an acidified corrosion inhibitor according to any of claims 1-3 for the preparation of an acidified working fluid.
6. An acidified working fluid comprising an acidified fluid and an acidified corrosion inhibitor according to any one of claims 1 to 3 dissolved in said acidified fluid.
7. The acidified working solution of claim 6 wherein the acidified corrosion inhibitor is dissolved in the acidified solution at a mass concentration of 0.2 to 5 weight percent.
8. The acidified working solution of claim 6 wherein the acidified solution comprises a hydrochloric acid solution having a concentration of 12 to 20 weight percent.
9. A method for preparing an acidified working fluid according to any one of claims 6 to 8, said method comprising:
adding the acidizing corrosion inhibitor into the acidizing fluid according to the formula composition of the acidizing fluid according to any one of claims 6 to 8, and performing ultrasonic dissolution to obtain the acidizing fluid.
10. Use of an acidified working fluid according to any of claims 6-8 for acidizing oil and gas fields.
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