CN115612473A - High-temperature-resistant acidizing corrosion inhibitor, preparation method and application thereof, and corrosion-inhibiting acidizing fracturing fluid - Google Patents
High-temperature-resistant acidizing corrosion inhibitor, preparation method and application thereof, and corrosion-inhibiting acidizing fracturing fluid Download PDFInfo
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- CN115612473A CN115612473A CN202211238519.4A CN202211238519A CN115612473A CN 115612473 A CN115612473 A CN 115612473A CN 202211238519 A CN202211238519 A CN 202211238519A CN 115612473 A CN115612473 A CN 115612473A
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- 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
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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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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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
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention belongs to the technical field of oil well additives, and provides a high-temperature-resistant acidizing corrosion inhibitor, a preparation method and application thereof, and a corrosion-inhibition acidizing fracturing fluid. The high-temperature resistant acidizing corrosion inhibitor provided by the invention takes the quinoline benzyl chloride substance with the structure shown in the formula I and the structure shown in the formula II as a main agent, and nitrogen atoms in the quinoline benzyl chloride substance form multi-point adsorption on the surface of a metal pipeline, so that the film forming capability of the high-temperature resistant acidizing corrosion inhibitor on the surface of the metal pipeline is enhanced, the desorption speed of the high-temperature resistant acidizing corrosion inhibitor from the surface of the metal pipeline at high temperature is reduced, and a good corrosion inhibition effect can be exerted under a high-temperature environment.
Description
Technical Field
The invention relates to the technical field of oil well additives, in particular to a high-temperature-resistant acidizing corrosion inhibitor, a preparation method and application thereof, and a corrosion-inhibition acidizing fracturing fluid.
Background
In the development process of petroleum and natural gas, the purpose of increasing production is achieved by adopting an acidizing and fracturing technology. Oil well acid fracturing is one of the important measures for increasing the production and injection of each oil field in China, and during operation, acid fracturing fluid (with the general concentration of 15% HCl, 20% HCl, 7.5% HCl +1.5% HF, 12% HCl +3% HF and other media matched with various auxiliary materials) is injected into a stratum by a common mechanical method, so that plugging substances in the stratum near the bottom of a well and certain components in stratum rocks are dissolved, oil flow channels are enlarged, and oil flow resistance is reduced, and the aim of increasing the production is achieved.
However, in the construction process, the injection of the acidizing fracturing fluid causes surface pitting, hydrogen embrittlement and even brittle fracture of oil and gas well pipes and underground equipment, and sometimes can cause sudden fracture accidents of the underground pipes, thereby causing serious economic loss. At the same time, metallic iron ions that react with the acid in the acidified fracturing fluid may also cause permanent damage to the formation. In order to prevent the acidizing fracturing fluid from corroding oil and gas well pipes and underground equipment, the addition of the acidizing corrosion inhibitor into the acidizing fracturing fluid is a necessary measure for corrosion prevention. With the increasing demand of the world economy for oil and gas resources and the continuous progress of drilling and oil extraction technology, a large number of deep wells, ultra-deep wells (more than 7000 m) and ultra-deep wells (15000 m) are put into development, more and more high-temperature wells begin to appear, and the requirement on the acidizing corrosion inhibitor is higher and higher.
At present, a wide variety of acidizing corrosion inhibitor products with wide application are developed at home and abroad, but the acidizing corrosion inhibitor products are generally applicable at the temperature of 140 ℃ or below and have poor high-temperature resistance.
Disclosure of Invention
In view of the above, the invention aims to provide a high-temperature resistant acidizing corrosion inhibitor, a preparation method and an application thereof, and a corrosion inhibition acidizing fracturing fluid. The high-temperature resistant acidizing corrosion inhibitor provided by the invention is high-temperature resistant.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-temperature resistant acidizing corrosion inhibitor, which comprises quinoline benzyl chloride substances, alkynol, metal iodide and a solvent;
the mass ratio of the quinoline benzyl chloride substance to the alkynol to the metal iodide to the solvent is (0.5-1.5): 0.5-4.5: 0.5 to 4.0:3.0 to 5.0;
the quinoline benzyl chloride substance comprises a quinoline benzyl chloride compound or a quinoline benzyl chloride exchanger;
the quinoline benzyl chloride compound has a structure shown in a formula I:
the quinoline benzyl chloride exchanger has a structure shown in formula II:
preferably, the alkynol comprises one or more of propiolic alcohol, 1,4-butynediol and methanesulfonic acid-2-propyn-1-ol.
Preferably, the metal iodide includes one or more of cuprous iodide, potassium iodide and sodium iodide.
Preferably, the solvent is an alcoholic solvent.
Preferably, the alcoholic solvent comprises n-butanol and/or ethanol.
The invention also provides a preparation method of the high-temperature resistant acidizing corrosion inhibitor, which comprises the following steps:
and mixing the quinoline benzyl chloride substance, the alkynol, the metal iodide and the solvent to obtain the high-temperature-resistant acidizing corrosion inhibitor.
Preferably, the mixing is carried out under the condition of ultrasound, the temperature of the ultrasound is room temperature, and the output power density is 0.3-0.6W/cm 2 The time is 10-30 min.
The invention also provides application of the high-temperature resistant acidizing corrosion inhibitor in the technical scheme in corrosion inhibition acidizing fracturing fluid.
The invention also provides a corrosion inhibition acidizing fracturing fluid which comprises the high temperature resistant acidizing corrosion inhibitor and an acidic medium in the technical scheme;
the mass percentage of the quinoline benzyl chloride substance in the high-temperature resistant acidizing and corrosion inhibitor in the corrosion-inhibition acidizing fracturing fluid is 0.5-1.5%.
Preferably, the acidic medium is an acid solution with the mass concentration of hydrochloric acid of 12% and the mass concentration of hydrofluoric acid of 3%.
The invention provides a high-temperature resistant acidizing corrosion inhibitor, which comprises quinoline benzyl chloride substances, alkynol, metal iodide and a solvent; the mass ratio of the quinoline benzyl chloride substance to the alkynol to the metal iodide to the solvent is 0.5-1.5: 0.5-4.5: 0.5 to 4.0:3.0 to 5.0; the quinoline benzyl chloride substance comprises a quinoline benzyl chloride compound or a quinoline benzyl chloride exchanger; the quinoline benzyl chloride compound has a structure shown in a formula I, and the quinoline benzyl chloride exchanger has a structure shown in a formula II. The high-temperature resistant acidizing corrosion inhibitor provided by the invention takes quinoline benzyl chloride substances as a main agent, and forms multi-point adsorption on the surface of a metal pipeline through nitrogen atoms in the quinoline benzyl chloride substances, so that the film forming capability of the high-temperature resistant acidizing corrosion inhibitor on the surface of the metal pipeline is enhanced, the desorption speed of the high-temperature resistant acidizing corrosion inhibitor from the surface of the metal pipeline at high temperature is reduced, and a good corrosion inhibition effect can be exerted under a high-temperature environment. In particular, the high-temperature resistant acidizing corrosion inhibitor taking the quinoline benzyl chloride exchanger shown in the formula II as a main agent utilizes a plurality of nitrogen atoms in the quinoline benzyl chloride exchanger to form more point adsorption on the surface of a metal pipeline, so that the high-temperature resistance of the high-temperature resistant acidizing corrosion inhibitor is stronger. The data of the examples show that: the high-temperature resistant acidizing corrosion inhibitor taking the quinoline benzyl chloride compound as the main agent can resist 160 ℃, and the high-temperature resistant acidizing corrosion inhibitor taking the quinoline benzyl chloride exchanger as the main agent can resist 200 ℃.
The invention also provides a preparation method of the high-temperature resistant acidizing corrosion inhibitor, which comprises the following steps: and mixing the quinoline benzyl chloride substance, the alkynol, the metal iodide and the solvent to obtain the high-temperature-resistant acidizing corrosion inhibitor. The preparation method provided by the invention has the advantages of easily available raw materials and simple operation.
The invention also provides application of the high-temperature resistant acidizing corrosion inhibitor in the technical scheme in corrosion inhibition acidizing fracturing fluid. The high-temperature resistant acidizing corrosion inhibitor provided by the invention has excellent high-temperature resistance and corrosion inhibition performance, so that the high-temperature resistant acidizing corrosion inhibitor can be better applied to corrosion inhibition acidizing fracturing fluid.
The invention also provides a corrosion inhibition acidizing fracturing fluid which comprises the high temperature resistant acidizing corrosion inhibitor and an acidic medium in the technical scheme; the mass percentage of the quinoline benzyl chloride substance in the high-temperature resistant acidizing and corrosion inhibitor in the corrosion-inhibition acidizing fracturing fluid is 0.5-1.5%. The corrosion-inhibition acidizing fracturing fluid provided by the invention has excellent corrosion inhibition and high temperature resistance.
Detailed Description
The invention provides a high-temperature resistant acidizing corrosion inhibitor, which comprises quinoline benzyl chloride substances, alkynol, metal iodide and a solvent;
the mass ratio of the quinoline benzyl chloride substance to the alkynol to the metal iodide to the solvent is 0.5-1.5: 0.5 to 4.5:0.5 to 4.0:3.0 to 5.0;
the quinoline benzyl chloride substance comprises a quinoline benzyl chloride compound or a quinoline benzyl chloride exchanger;
the quinoline benzyl chloride compound has a structure shown in a formula I, and the quinoline benzyl chloride exchanger has a structure shown in a formula II.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The high-temperature resistant acidizing corrosion inhibitor provided by the invention comprises quinoline benzyl chloride substances. In the invention, the quinoline benzyl chloride substance comprises a quinoline benzyl chloride compound with a structure shown in a formula I or a quinoline benzyl chloride exchanger with a structure shown in a formula II.
In the present invention, the preparation method of the quinoline chlorobenzyl compound preferably comprises the steps of:
and dissolving benzyl chloride and quinoline, and carrying out a first reaction to obtain the quinoline benzyl chloride compound.
In the present invention, the molar ratio of benzyl chloride to quinoline is preferably 1:1. in the present invention, the dissolved reagent preferably comprises acetonitrile. In the present invention, the first reaction is preferably carried out under heating under reflux. In the present invention, the time for the first reaction is preferably 24 hours. After the first reaction, the method preferably further comprises cooling to room temperature, and performing suction filtration to obtain the quinoline benzyl chloride compound.
In the invention, the process for preparing the quinoline benzyl chloride compound by taking benzyl chloride and quinoline as the preparation raw materials is shown as the following formula:
in the present invention, the preparation method of the quinoline benzyl chloride exchanger preferably comprises the following steps:
mixing benzotriazole and sodium hydroxide, and carrying out a second reaction to obtain an intermediate product;
and mixing the intermediate product with the quinoline benzyl chloride compound, and carrying out ion exchange reaction to obtain the quinoline benzyl chloride exchanger.
The present invention mixes benzotriazole and sodium hydroxide to carry out the second reaction, and an intermediate product is obtained. In the present invention, the molar ratio of the benzotriazole to the sodium hydroxide is preferably 1:1. in the present invention, the sodium hydroxide is used in the form of an aqueous sodium hydroxide solution, and the mass concentration of the aqueous sodium hydroxide solution is preferably 30% to 50%, and more preferably 40%. In the present invention, the temperature of the second reaction is preferably 60 to 80 ℃ and the time is preferably 12 hours. After the second reaction, the obtained second reaction liquid is preferably directly used as an intermediate product for subsequent reaction.
After obtaining the intermediate product, mixing the intermediate product with the quinoline benzyl chloride compound, and carrying out ion exchange reaction to obtain the quinoline benzyl chloride exchanger. In the invention, the molar ratio of the benzotriazole to the quinoline chlorobenzyl chloride compound is preferably 1:1. in the present invention, the temperature of the ion exchange reaction is preferably 60 to 80 ℃ and the time is preferably 24 hours. After the ion exchange reaction, the method preferably further comprises the steps of extracting the obtained ion exchange reaction feed liquid, and drying and distilling the obtained organic phase in turn to obtain the quinoline benzyl chloride exchanger. In the present invention, the extractant of the extraction is preferably dichloroethane; the number of extractions is preferably 3. In the present invention, the drying is preferably performed by drying with a desiccant; the drying agent is preferably anhydrous sodium sulfate. The present invention does not specifically limit the parameters of the distillation as long as the solvent in the organic phase can be completely removed.
In the present invention, the procedure for preparing said quinoline benzyl chloride exchanger is shown as follows:
in the invention, nitrogen atoms in the quinoline benzyl chloride substance can form multi-point adsorption on the surface of the metal pipeline, so that the film forming capability of the high-temperature resistant acidizing corrosion inhibitor on the surface of the metal pipeline is enhanced, and the desorption speed of the high-temperature resistant acidizing corrosion inhibitor from the surface of the metal pipeline at high temperature is reduced, thereby playing a good corrosion inhibition role in a high-temperature environment.
The high-temperature resistant acidizing corrosion inhibitor provided by the invention comprises alkynol. In the present invention, the alkynol preferably includes one or more of propargyl alcohol, 1,4-butynediol and methanesulfonic acid-2-propyn-1-ol, and is further preferably propargyl alcohol. In the invention, the alkynol is used as a synergist, is mainly adsorbed in gaps among quinoline benzyl chloride substances by utilizing pi electrons to form a complete and compact adsorption film, and has a good corrosion inhibition effect.
The high-temperature resistant acidizing corrosion inhibitor provided by the invention comprises metal iodide. In the present invention, the metal iodide preferably includes one or more of cuprous iodide, potassium iodide, and sodium iodide, and more preferably cuprous iodide. In the invention, the metal iodide has a characteristic adsorption effect with a corrosive active metal in a pipeline in an application environment, and can coordinate with the active metal, so that the adsorption force of the high-temperature resistant acidizing corrosion inhibitor and the surface of the pipeline can be enhanced, the quinoline benzyl chloride substance is promoted to form a complete and compact adsorption film, and a good corrosion inhibition effect is achieved.
The high-temperature resistant acidizing corrosion inhibitor provided by the invention comprises a solvent. In the present invention, the solvent is preferably an alcohol solvent; the alcoholic solvent preferably includes n-butanol and/or ethanol.
The mass ratio of quinoline benzyl chloride substances, alkynol, metal iodide and solvent in the high-temperature resistant acidizing corrosion inhibitor provided by the invention is 0.5-1.5: 0.5-4.5: 0.5 to 4.0:3.0 to 5.0, particularly preferably 0.5:4.5:1.0:3.0, 0.5:4.5:0.5:3.0, 0.5:4.0:1.0:3.0, 1.0:3.0:0.5:3.0, 0.5:0.5:4.0:3.0, 1.5:1.5:1.0:3.0, 1.0:1.0:2:3.0, 1.0:1.0:1.0:3.0, 0.5:0.5:2.0:3.0, 0.5:0.5:1.0:3.0, 1.0:1.0:0.5:3.0 or 0.5:0.5:0.5:3.0.
the invention also provides a preparation method of the high-temperature resistant acidizing corrosion inhibitor, which comprises the following steps:
and mixing the quinoline benzyl chloride substance, the alkynol, the metal iodide and the solvent to obtain the high-temperature-resistant acidizing corrosion inhibitor.
In the present invention, the mixing is preferably performed under the condition of ultrasound. In the present invention, the temperature of the ultrasound is preferably room temperature. In the present invention, the output power density of the ultrasound is preferably 0.3 to 0.6W/cm 2 The time is preferably 10 to 30min.
The invention also provides application of the high-temperature resistant acidizing corrosion inhibitor in the technical scheme in corrosion inhibition acidizing fracturing fluid.
The invention also provides a corrosion inhibition acidizing fracturing fluid which comprises the high temperature resistant acidizing corrosion inhibitor and an acidic medium. In the invention, the mass percentage content of the quinoline benzyl chloride substance in the high temperature resistant acidizing and corrosion inhibitor in the corrosion inhibition acidizing fracturing fluid is 0.5-1.5%, and the preferred content is 1%.
In the present invention, the acidic medium is preferably an acid solution having a hydrochloric acid mass concentration of 12% and a hydrofluoric acid mass concentration of 3%.
The high temperature resistant acidizing corrosion inhibitor, the preparation method and the application thereof, and the corrosion-inhibiting acidizing fracturing fluid provided by the present invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain the quinoline benzyl chloride compound. Weighing 0.1mol of benzotriazole, adding into 7mL of NaOH aqueous solution (with mass concentration of 40%), reacting at 70 ℃ for 12h to obtain benzotriazole sodium aqueous solution; adding 0.1mol of quinoline benzyl chloride compound into aqueous solution of benzotriazole sodium, carrying out ion exchange reaction for 24h at 70 ℃, extracting for 3 times by using dichloromethane, drying an organic phase overnight by using anhydrous sodium sulfate, filtering out a drying agent, and distilling to remove a solvent to obtain a main agent quinoline benzyl chloride exchanger.
High-temperature resistant acidizing corrosion inhibitor:
mixing a main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol according to a mass ratio of 0.5:4.5:1.0:3.0, and sequentially adding into 3mL centrifuge tube, and ultrasonic cleaning at 25 deg.C with output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 2
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain the quinoline benzyl chloride compound. Weighing 0.1mol of benzotriazole, adding into 7mL of NaOH aqueous solution (with mass concentration of 40%), reacting at 70 ℃ for 12h to obtain benzotriazole sodium aqueous solution; adding 0.1mol of quinoline benzyl chloride compound into aqueous solution of benzotriazole sodium, carrying out ion exchange reaction for 24h at 70 ℃, extracting for 3 times by using dichloromethane, drying an organic phase overnight by using anhydrous sodium sulfate, filtering out a drying agent, and distilling to remove the solvent to obtain a main agent quinoline benzyl chloride exchanger.
High-temperature resistant acidizing corrosion inhibitor:
mixing a main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol according to a mass ratio of 0.5:4.5:0.5:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then mixing for 30min to obtain the high temperature resistant acidizing corrosion inhibitor.
Example 3
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain the quinoline benzyl chloride compound. Weighing 0.1mol of benzotriazole, adding into 7mL of NaOH aqueous solution (with mass concentration of 40%), reacting at 70 ℃ for 12h to obtain benzotriazole sodium aqueous solution; adding 0.1mol of quinoline benzyl chloride compound into aqueous solution of benzotriazole sodium, carrying out ion exchange reaction for 24h at 70 ℃, extracting for 3 times by using dichloromethane, drying an organic phase overnight by using anhydrous sodium sulfate, filtering out a drying agent, and distilling to remove the solvent to obtain a main agent quinoline benzyl chloride exchanger.
High-temperature resistant acidizing corrosion inhibitor:
mixing a main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol according to a mass ratio of 0.5:4.0:1.0:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 4
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain the quinoline benzyl chloride compound. Weighing 0.1mol of benzotriazole, adding into 7mL of NaOH aqueous solution (with mass concentration of 40%), reacting at 70 ℃ for 12h to obtain benzotriazole sodium aqueous solution; adding 0.1mol of quinoline benzyl chloride compound into aqueous solution of benzotriazole sodium, carrying out ion exchange reaction for 24h at 70 ℃, extracting for 3 times by using dichloromethane, drying an organic phase overnight by using anhydrous sodium sulfate, filtering out a drying agent, and distilling to remove the solvent to obtain a main agent quinoline benzyl chloride exchanger.
High-temperature resistant acidizing corrosion inhibitor:
mixing a main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol according to a mass ratio of 1.0:3.0:0.5:3.0, and sequentially adding into 3mL centrifuge tube, and ultrasonic cleaning at 25 deg.C with output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 5
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain the quinoline benzyl chloride compound. Weighing 0.1mol of benzotriazole, adding into 7mL of NaOH aqueous solution (with mass concentration of 40%), reacting at 70 ℃ for 12h to obtain benzotriazole sodium aqueous solution; adding 0.1mol of quinoline benzyl chloride compound into aqueous solution of benzotriazole sodium, carrying out ion exchange reaction for 24h at 70 ℃, extracting for 3 times by using dichloromethane, drying an organic phase overnight by using anhydrous sodium sulfate, filtering out a drying agent, and distilling to remove a solvent to obtain the main agent quinoline benzyl chloride exchanger.
High-temperature resistant acidizing corrosion inhibitor:
mixing a main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol according to a mass ratio of 0.5:0.5:4.0:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Evaluation of Performance
Retest rate experiments were conducted on the high temperature resistant acidizing corrosion inhibitors prepared in examples 1-5.
Dynamic experiments are carried out according to the industrial standard SY/T5405-1996 performance test method and evaluation index of the corrosion inhibitor for acidification. And (3) polishing the steel sheet by using metallographic abrasive paper, degreasing and deoiling by using distilled water, absolute ethyl alcohol and acetone in sequence, sucking by using filter paper, and drying in an oven for 2 hours. The mass was accurately weighed with an analytical balance. The steel sheet is vertically suspended in a high-temperature high-pressure dynamic corrosion tester and is immersed in an experimental medium. After the experiment, the hanging piece is taken out, cleaned by distilled water, absolute ethyl alcohol and acetone to remove oil, dried for 2h and weighed. The evaluation experimental conditions were: the working temperature is as follows: the test pressure is 16.0MPa at 200 ℃, the stirring speed is 60r/min, and the reaction time is 4h. The acidic medium used was: 12% concentrated hydrochloric acid +3% hydrofluoric acid; adopting N80 steel; the addition amount of the high-temperature resistant acidizing corrosion inhibitor in the acid medium is 4.0-6.0 percent based on the total mass of the main agent, the propargyl alcohol and the cuprous iodide.
The corrosion rate is calculated as follows:
wherein, V i Monolithic corrosion rate, g/(m) 2 ·h)；
Δm i The corrosion quality of the coupon, g;
Δ i surface area of test piece, mm 2 ；
Δ t- -reaction time, h.
The corrosion inhibition performance of the high temperature resistant acidizing corrosion inhibitor obtained in examples 1-5 is shown in Table 1.
TABLE 1 Corrosion inhibition Properties of the high temperature resistant acidizing corrosion inhibitors obtained in examples 1 to 5
Example 6
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
a main agent, propargyl alcohol, cuprous iodide andthe absolute ethyl alcohol is mixed according to the mass ratio of 1.5:1.5:1.0:3.0, and sequentially adding into 3mL centrifuge tube, and ultrasonic cleaning at 25 deg.C with output power density of 0.5W/cm 2 Then mixing for 30min to obtain the high temperature resistant acidizing corrosion inhibitor.
Example 7
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
the main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol are mixed according to the mass ratio of 1.0:1.0:2:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 8
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
the main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol are mixed according to the mass ratio of 1.0:1.0:1.0:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 9
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
the main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol are mixed according to the mass ratio of 0.5:0.5:2.0:3.0 advanceWeighing, sequentially adding into 3mL centrifuge tube, and ultrasonic cleaning at 25 deg.C with output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 10
Putting 0.1mol of benzyl chloride and 0.1mol of quinoline into a 250mL round-bottom flask, adding 150mL of acetonitrile serving as a solvent, heating and refluxing for 24 hours, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
the main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol are mixed according to the mass ratio of 0.5:0.5:1.0:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 11
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
the main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol are mixed according to the mass ratio of 1.0:1.0:0.5:3.0, and sequentially adding into a 3mL centrifuge tube, and cleaning with an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Example 12
Placing 0.1mol of benzyl chloride and 0.1mol of quinoline in a 250mL round-bottom flask, adding 150mL of acetonitrile as a solvent, heating and refluxing for 24h, cooling to room temperature, separating out quinoline benzyl chloride quaternary ammonium salt, and performing suction filtration to obtain a main agent quinoline benzyl chloride compound.
High-temperature resistant acidizing corrosion inhibitor:
the main agent, propargyl alcohol, cuprous iodide and absolute ethyl alcohol are mixed according to the mass ratio of 0.5:0.5:0.5:3.0, and adding into a 3mL centrifuge tube in sequence,in an ultrasonic cleaner at 25 deg.C and output power density of 0.5W/cm 2 Then, mixing for 30min to obtain the high-temperature resistant acidizing corrosion inhibitor.
Evaluation of Performance
Retest rate experiments were conducted on the high temperature resistant acidizing corrosion inhibitors prepared in examples 6-12.
The test method is consistent with the test method of the high-temperature resistant acidizing corrosion inhibitor obtained in the examples 1-5, and the differences are only: the working temperature is as follows: the addition amount of the high-temperature resistant acidizing corrosion inhibitor in the acid medium is 1.5-4.0 percent based on the total mass of the main agent, the propargyl alcohol and the cuprous iodide at 160 ℃.
The results are shown in Table 2.
TABLE 2 Corrosion inhibition Performance of the high temperature resistant acidizing corrosion inhibitors obtained in examples 6 to 12
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A high temperature resistant acidizing corrosion inhibitor is characterized by comprising quinoline benzyl chloride substances, alkynol, metal iodide and a solvent;
the mass ratio of the quinoline benzyl chloride substance to the alkynol to the metal iodide to the solvent is 0.5-1.5: 0.5-4.5: 0.5 to 4.0:3.0 to 5.0;
the quinoline benzyl chloride substance comprises a quinoline benzyl chloride compound or a quinoline benzyl chloride exchanger;
the quinoline benzyl chloride compound has a structure shown in a formula I:
the quinoline benzyl chloride exchanger has a structure shown in formula II:
2. the high temperature resistant acidizing corrosion inhibitor of claim 1 wherein said acetylenic alcohol comprises one or more of propiolic alcohol, 1,4-butynediol and methanesulfonic acid-2-propin-1-ol.
3. The high temperature acidification resistant corrosion inhibitor according to claim 1, wherein the metal iodide comprises one or more of cuprous iodide, potassium iodide and sodium iodide.
4. The high temperature resistant acidizing corrosion inhibitor according to claim 1 wherein said solvent is an alcohol solvent.
5. The high temperature acidification resistant corrosion inhibitor according to claim 4, wherein the alcohol solvent comprises n-butanol and/or ethanol.
6. The process for preparing the high temperature resistant acidizing corrosion inhibitor according to any one of the claims 1 to 5, characterized in that it comprises the following steps:
and mixing the quinoline benzyl chloride substance, the alkynol, the metal iodide and the solvent to obtain the high-temperature-resistant acidizing corrosion inhibitor.
7. The method of claim 6, wherein the mixing is performed under ultrasonic conditions, the ultrasonic temperature is room temperature, and the output power density is 0.3-0.6W/cm 2 The time is 10-30 min.
8. Use of a high temperature resistant acidizing corrosion inhibitor according to any one of claims 1 to 5 in a corrosion inhibiting acidizing fracturing fluid.
9. A corrosion-inhibition acidizing fracturing fluid which is characterized by comprising the high-temperature-resistant acidizing corrosion inhibitor and an acidic medium, wherein the high-temperature-resistant acidizing corrosion inhibitor is one of claims 1 to 5;
the mass percentage of the quinoline benzyl chloride substance in the corrosion-inhibition acidification fracturing fluid is 0.5-1.5%.
10. The corrosion-inhibiting acidified fracturing fluid of claim 9, wherein the acidic medium is an acid fluid having a hydrochloric acid concentration of 12% by mass and a hydrofluoric acid concentration of 3% by mass.
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