CN111621791B - Oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide - Google Patents
Oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide Download PDFInfo
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- CN111621791B CN111621791B CN202010373554.1A CN202010373554A CN111621791B CN 111621791 B CN111621791 B CN 111621791B CN 202010373554 A CN202010373554 A CN 202010373554A CN 111621791 B CN111621791 B CN 111621791B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/10—Inhibiting corrosion during distillation
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Abstract
The invention discloses an oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide, which comprises the following components in percentage by mass: greater than or equal to 98 percent of pyridyl ionic liquid, the balance of NaBr, and the pyridyl ionic liquid is N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate. The corrosion inhibitor has the characteristics of good corrosion resistance effect, small using amount, low cost, good water solubility and environmental friendliness in the industrial production and application processes.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to an oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide.
Background
Atmospheric and vacuum distillation is the first work in the petroleum refining process of crude oil and is the basis of the whole petroleum refining process. According to API 571-Refinery equipment damage mechanism, the types of damage involved in atmospheric and vacuum distillation units are more than 20, and the number of atmospheric distillation overhead systems is 8. HCl corrosion and H of the overhead system of an atmospheric and vacuum distillation unit2S corrosion always troubles important problems of refineries at home and abroad and restricts the bottleneck of long-term operation of refining enterprises. According to physical property analysis of the top of the distillation tower, the water in the oil-water mixture at the top of the distillation tower is low in acidity, even the pH value reaches 1-1.3, and serious liquid acidic water corrosion may exist. Particularly, the content of HCl is higher at a dew point position, even the content of HCl in liquid water at the dew point position is reported to reach 1-3 wt.%, and carbon steel can be subjected to rapid dew point corrosion in the acid environment.
At present, for corrosion of a distillation tower top system, refinery process corrosion prevention is mainly adopted, and material corrosion prevention is auxiliary. The most common corrosion prevention method is 'one-removing three-injecting', namely electric desalting, water injection, corrosion inhibitor injection and neutralizer injection. The corrosion inhibitor is mainly composed of quinoline quaternary ammonium salt or pyridine quaternary ammonium salt, thiourea and derivatives thereof are compounded to improve the corrosion inhibition performance of the quinoline quaternary ammonium salt or the pyridine quaternary ammonium salt, and meanwhile, an organic solvent, a surfactant, an organic base and the like are added to meet the requirements of physicochemical performance. With the promulgation of novel environmental protection laws, organic solvents have obvious pollution to the environment. The surfactant is organic chlorine generally, belongs to toxic and harmful substances, and is not friendly to the environment. Therefore, the compound corrosion inhibitor added with the solvent, the synergist and the surfactant belongs to chemical products which are not friendly to the environment, and the future development and application of the compound corrosion inhibitor are greatly influenced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide, which is suitable for higher temperature and HCl and H2The corrosion inhibition effect is good, no solvent is used, the environment is friendly, the water solubility is good, and the dosage is small.
The invention adopts the following technical scheme:
an oil refining distillation tower top corrosion inhibitor resisting corrosion of dilute hydrochloric acid and hydrogen sulfide comprises the following components in percentage by mass: greater than or equal to 98 percent of pyridyl ionic liquid, the balance of NaBr, and the pyridyl ionic liquid is N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate.
Specifically, the preparation process of the pyridyl ionic liquid is as follows:
s1, adding bromoalkane into a three-neck round-bottom flask, and fixing a constant-pressure dropping funnel containing pyridine and a condensation reflux device with a drying tube at the upper end of a transducer of an ultrasonic cleaner;
s2, carrying out ultrasonic treatment on bromoalkane, adding pyridine dropwise into the bromoalkane, carrying out ultrasonic intermittent reaction to enable clear liquid to become turbid, continuing ultrasonic treatment to generate white floccule, and filtering after continuing reaction to obtain light yellow solid;
s3, mixing the light yellow solid obtained in the step S2 with acetone and sodium tetrafluoroborate or sodium hexafluorophosphate, stirring for reaction at room temperature, and filtering to remove white precipitate NaBr in the filtrate;
s4, adding dichloromethane into the filtrate filtered in the step S3 to generate white precipitate, removing acetone and dichloromethane through filtration and rotary evaporation, and obtaining N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate through vacuum drying treatment.
Further, in step S1, the alkyl bromide is methyl bromide, butyl bromide or dodecyl bromide, and the molar ratio of pyridine to alkyl bromide is 1 (1.1-1.3).
Further, in step S2, performing ultrasonic treatment under the protection of Ar, dropping pyridine at a speed less than or equal to 10mL/min, performing ultrasonic intermittent operation for 5-10 min, and continuing to react for 1.8-2.2 h after generating white floccules.
Further, in step S3, a light yellow solid: acetone: the molar ratio of (sodium tetrafluoroborate or sodium hexafluorophosphate) is 1: (1.8-2.0): (1.05-1.15).
Further, the mixture is magnetically stirred at room temperature for reaction for 12-13 h and then filtered.
Further, in the step S4, the adding amount of the dichloromethane is 20-30 mL, the processing time of the rotary evaporation is 3-4 h, the vacuum drying temperature is 40-45 ℃, and the time is 20-25 h.
Furthermore, the corrosion rate of the corrosion inhibitor in the environment of the top of the petroleum refining distillation tower containing dilute hydrochloric acid and hydrogen sulfide is 2.107-2.869 mm/a.
Compared with the prior art, the invention has at least the following beneficial effects:
the corrosion inhibitor for the distillation tower top of oil refining, which is resistant to corrosion of dilute hydrochloric acid and hydrogen sulfide, does not contain solvents, synergists and other chemical agents, contains pyridine rings in molecules, and has strong binding force with the metal surface, so that the corrosion inhibitor can realize high-efficiency corrosion inhibition performance without adding the synergists, and has the characteristics of low corrosion rate, good corrosion inhibition effect, no solvent, environmental friendliness and small using amount.
Furthermore, the corrosion inhibitor only contains a corrosion inhibition effective component N-alkylpyridine tetrafluoroborate or N-alkylpyridine hexafluorophosphate, and is environment-friendly.
Furthermore, the preparation of the pyridyl ionic liquid corrosion inhibitor is simple and convenient, and no toxic and harmful by-products are generated.
Furthermore, the bromoalkane and the pyridine are mixed according to the mass ratio of (1.1-1.3) to 1, so that the pyridine can be fully reacted.
Furthermore, Ar is used as a protective gas, pyridine is added at a speed of less than or equal to 15mL/min, and the pyridine and the bromoalkane are ensured to uniformly react under the condition of air isolation.
Furthermore, acetone is used as a solvent, and the amount ratio of substances of the light yellow solid, (sodium tetrafluoroborate or sodium hexafluorophosphate) to acetone is 1 (1.05-1.15) to (1.8-2.2), so that the obtained ionic liquid in the light yellow solid can be fully reacted.
Further, the obtained ionic liquid is magnetically stirred for 12-13 hours, NaBr generated in the reaction is removed, and the imidazoline-based ionic liquid with high purity is obtained.
In conclusion, the corrosion inhibitor has the characteristics of good corrosion resistance effect, small using amount, low cost, good water solubility and environmental friendliness in the industrial production and application processes.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic diagram of the reaction scheme of the present invention.
Detailed Description
The invention provides an oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide, which contains more than 98% of pyridyl ionic liquid by mass percent, no synergist or solvent is added, the content reaches more than 98%, the balance is NaBr, the pyridyl ionic liquid is N-alkylpyridines tetrafluoroborate or N-alkylpyridines hexafluorophosphate, and the corrosion rate is 2.107-2.869 mm/a. The corrosion inhibitor can be used at higher temperature and high HCl + H2And in the environment of the top of the petroleum refining distillation tower, metal pipelines and equipment are effectively protected. The corrosion inhibitor has the characteristics of good corrosion resistance effect, small using amount, low cost, good water solubility and environmental friendliness in the industrial production and application processes.
Referring to FIG. 1, N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate is prepared by the following process:
s1, adding a certain amount of brominated alkane (R-Br, the amount of the substance is 33-39 mmol) into a three-neck round-bottom flask, placing 30mmol of pyridine in a constant-pressure dropping funnel and a condensation reflux device with a drying tube, and carrying out ultrasonic treatment for 5-10 min after the pyridine is fixed at the upper end of a transducer of an ultrasonic cleaner; the brominated alkane is methyl bromide, butyl bromide or brominated dodecyl alkane;
the brominated alkane is methyl bromide, butyl bromide or dodecyl bromide.
S2, under the condition of ultrasonic treatment under Ar protection, pyridine is dripped at a speed of less than or equal to 10mL/min, the clear liquid turns turbid after the reaction is carried out for 5-10 min under the Ar protection ultrasonic intermittent operation mode, white floccule is generated by continuing ultrasonic treatment, the reaction is stopped after 1.8-2.2 h of reaction, and light yellow solid is obtained by filtration;
s3, adding the light yellow solid, sodium tetrafluoroborate (NaBF4) or sodium hexafluorophosphate (NaPF6) and acetone into a single-neck round-bottom flask with a condensation reflux device according to the mass ratio of 1 (1.05-1.15) to (1.8-2.0), magnetically stirring at room temperature for reaction for 12-13 h, and filtering to remove white precipitate NaBr;
s4, adding 20-30 mL of dichloromethane into the filtrate, performing rotary evaporation for 3-4 h to remove acetone and dichloromethane in the filtrate, and performing vacuum drying at 40-45 ℃ for 20-25 h to obtain N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for measuring the corrosion rate of the corrosion inhibitor in each embodiment of the invention comprises the following steps:
medium composition: HCl: 1g/L, H2S：1g/L；
Test temperature: 85 ℃;
test time: 6 hours;
test materials: 20# steel.
Polishing 20# steel, cleaning the polished 20# steel by petroleum ether, acetone and ethanol, drying, weighing, putting the prepared solution into a reaction container with a reflux device, adding 100ppm of the prepared corrosion inhibitor, uniformly stirring, hanging the weighed 20# steel into the reaction container, heating to 85 ℃, stabilizing for 6 hours under the condition, taking out a sample, removing a corrosion product film on the surface of the sample, drying, weighing and calculating the corrosion rate.
Example 1
The N-alkylpyridinium tetrafluoroborate is prepared by the following process: adding a certain amount of bromomethane (33mmol) into a three-neck round-bottom flask, installing a constant-pressure dropping funnel containing 30mmol of pyridine and a condensing reflux device with a drying tube, starting ultrasound after the dropping funnel is fixed at the upper end of a transducer of an ultrasonic cleaner, dropwise adding pyridine at the speed of 10mL/min, reacting for 5min under the Ar protection ultrasonic intermittent operation mode, then enabling the original clear liquid to become turbid, continuing ultrasound to generate white floccules, stopping the reaction after reacting for 1.8h, and filtering to obtain a light yellow solid. Adding the light yellow solid, 31.5mmol of sodium tetrafluoroborate (NaBF4) and 54mmol of acetone into a single-neck round-bottom flask with a condensing reflux device, magnetically stirring at room temperature for reaction for 11 hours, filtering, removing a white precipitate NaBr, adding 20mL of dichloromethane into the filtrate to generate a white precipitate, filtering, performing rotary evaporation for 3 hours to separate acetone and dichloromethane, and performing vacuum drying at 40 ℃ for 24 hours 20 hours to obtain the N-methylpyridine tetrafluoroborate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test medium, and the corrosion rate in the test medium is 2.869 mm/a.
Example 2
The N-alkylpyridinium tetrafluoroborate is prepared by the following process: adding a certain amount of n-butyl bromide (33mmol) into a three-neck round-bottom flask, adding a constant-pressure dropping funnel with 30mmol of pyridine and a condensing reflux device with a drying tube, fixing the flask on the upper end of a transducer of an ultrasonic cleaner, then starting ultrasonic treatment, slowly adding pyridine dropwise at the speed of 10mL/min, reacting for 5min under an Ar protection ultrasonic intermittent operation mode, then enabling the original clear liquid to become turbid, continuing ultrasonic treatment to generate white floccule, stopping the reaction after reacting for 2h, and filtering to obtain a light yellow solid. The pale yellow solid was mixed with 31.5mmol of sodium tetrafluoroborate (NaBF)4) And 54mmol of acetone is added into a single-neck round-bottom flask with a condensation reflux device, the mixture is magnetically stirred at room temperature for reaction for 12 hours and then filtered, white precipitate NaBr is removed, 20mL of dichloromethane is added into the filtrate, white precipitate is generated, the mixture is filtered, acetone and dichloromethane are separated by rotary evaporation for 3 hours, and the mixture is dried in vacuum at 40 ℃ for 24 hours to obtain the N-butylpyridinium tetrafluoroborate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test medium, and the corrosion rate in the test medium is 2.586 mm/a.
Example 3
The N-alkylpyridinium tetrafluoroborate is prepared by the following process: adding a certain amount of bromododecane (39mmol) into the three-mouth round pieceIn a bottom flask, a constant-pressure dropping funnel filled with 30mmol of pyridine and a condensation reflux device with a drying tube are arranged, the ultrasonic treatment is started after the constant-pressure dropping funnel and the condensation reflux device are fixed at the upper end of a transducer of an ultrasonic cleaner, the pyridine is dropped at the speed of 8mL/min, the original clear liquid turns turbid after the reaction is carried out for 8min under the Ar protection ultrasonic intermittent operation mode, the ultrasonic treatment is continued to generate white floccules, the reaction is stopped after the reaction is carried out for 2.2h, and the light yellow solid is obtained by filtering. The pale yellow solid was mixed with 34.5mmol of sodium tetrafluoroborate (NaBF)4) Adding 60mmol of acetone into a single-neck round-bottom flask with a condensation reflux device, magnetically stirring at room temperature for reaction for 13h, filtering, removing white precipitate NaBr, adding 30mL of dichloromethane into the filtrate to generate white precipitate, filtering, performing rotary evaporation for 5h to remove acetone and dichloromethane, and performing vacuum drying at 45 ℃ for 25h to obtain the N-dodecyl pyridine tetrafluoroborate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test medium, and the corrosion rate in the test medium is 2.223 mm/a.
Example 4
The N-alkyl pyridine hexafluorophosphate salt is prepared by the following process: adding a certain amount of bromomethane (33mmol) into a three-neck round-bottom flask, adding a constant-pressure dropping funnel with 30mmol of pyridine and a condensing reflux device with a drying tube, fixing the dropping funnel at the upper end of a transducer of an ultrasonic cleaner, then starting ultrasound, dropwise adding pyridine at the speed of 10mL/min, reacting for 10min under an Ar protection ultrasonic intermittent operation mode, then turning the original clear liquid into turbid liquid, continuing ultrasound to generate white floccule, reacting for 2.2h, stopping the reaction, and filtering to obtain a light yellow solid. The pale yellow solid was mixed with 31.5mmol of sodium hexafluorophosphate (NaPF)6) And adding 60mmol of acetone into a single-neck round-bottom flask with a condensation reflux device, magnetically stirring at room temperature for reaction for 13h, filtering, removing a white precipitate NaBr, adding 20mL of dichloromethane into the filtrate to generate a white precipitate, filtering, performing rotary evaporation for 5h to remove acetone and dichloromethane, and performing vacuum drying at 45 ℃ for 25h to obtain the N-methylpyridine hexafluorophosphate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test medium, and the corrosion rate in the test medium is 2.756 mm/a.
Example 5
N-alkylpyridinium hexafluoroThe phosphate is prepared by the following process: adding a certain amount of n-butyl bromide (33mol) into a three-neck round-bottom flask, adding a constant-pressure dropping funnel with 30mmol of pyridine and a condensation reflux device with a drying tube, fixing the flask on the upper end of a transducer of an ultrasonic cleaner, then starting ultrasound, dropwise adding pyridine at the speed of 10mL/min, reacting for 10min under an Ar protection ultrasonic intermittent operation mode, then turning the original clear liquid to be turbid, continuing ultrasound to generate white floccule, reacting for 2.2h, stopping the reaction, and filtering to obtain a light yellow solid. The pale yellow solid was mixed with 31.5mmol of sodium hexafluorophosphate (NaPF)6) Adding 54mmol of acetone into a single-neck round-bottom flask with a condensation reflux device, magnetically stirring at room temperature for reaction for 11h, filtering, removing white precipitate NaBr, adding 30mL of dichloromethane into the filtrate to generate white precipitate, filtering, performing rotary evaporation to remove acetone and dichloromethane, and performing vacuum drying at 40 ℃ for 24h to obtain N-butylpyridinium hexafluorophosphate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test medium, and the corrosion rate in the test medium is 2.431 mm/a.
Example 6
The N-alkyl pyridine hexafluorophosphate salt is prepared by the following process: adding a certain amount of bromododecane (39mmol) into a three-neck round-bottom flask, installing a constant-pressure dropping funnel containing 30mmol of pyridine and a condensation reflux device with a drying tube, fixing the flask on the upper end of a transducer of an ultrasonic cleaner, then starting ultrasonic treatment, dropwise adding pyridine at the speed of 10mL/min, reacting for 5min under an Ar protection ultrasonic intermittent operation mode, then enabling the original clear liquid to become turbid, continuing ultrasonic treatment to generate white floccules, stopping the reaction after reacting for 1.8h, and filtering to obtain a light yellow solid. The pale yellow solid was mixed with 34.5mmol of sodium hexafluorophosphate (NaPF)6) Adding 55mmol of acetone into a single-neck round-bottom flask with a condensation reflux device, magnetically stirring at room temperature for reaction for 13h, filtering, removing white precipitate NaBr, adding 30mL of dichloromethane into the filtrate to generate white precipitate, filtering, performing rotary evaporation for 4h to remove acetone and dichloromethane, and performing vacuum drying at 45 ℃ for 24h to obtain N-dodecyl pyridine hexafluorophosphate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test medium, and the corrosion rate in the test medium is 2.107 mm/a.
Example 7
The N-alkyl pyridine hexafluorophosphate salt is prepared by the following process: adding a certain amount of bromododecane (36mmol) into a three-neck round-bottom flask, adding a constant-pressure dropping funnel filled with 30mmol of pyridine and a condensing reflux device with a drying tube, fixing the dropping funnel on the upper end of a transducer of an ultrasonic cleaner, then starting ultrasound, dropwise adding pyridine at the speed of 10mL/min, reacting for 8min under an Ar protection ultrasonic intermittent operation mode, then turning the original clear liquid into turbid liquid, continuing ultrasound to generate white floccule, stopping the reaction after reacting for 2h, and filtering to obtain light yellow solid. The pale yellow solid was mixed with 33mmol of sodium hexafluorophosphate (NaPF)6) And 57mmol of the mixture is added into a single-neck round-bottom flask with a condensation reflux device, the mixture is magnetically stirred at room temperature for reaction for 12 hours and then filtered, white precipitate NaBr is removed, 20mL of dichloromethane is added into the filtrate, white precipitate is generated, the mixture is filtered, acetone and dichloromethane are removed through rotary evaporation for 4 hours, and the mixture is dried in vacuum at 42 ℃ for 24 hours to obtain N-dodecyl pyridine hexafluorophosphate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test ring, and the corrosion rate in the test ring is 2.116 mm/a.
Example 8
The N-alkyl pyridine hexafluorophosphate salt is prepared by the following process: adding a certain amount of bromododecane (36mmol) into a three-neck round-bottom flask, adding a constant-pressure dropping funnel filled with 30mmol of pyridine and a condensing reflux device with a drying tube, fixing the dropping funnel on the upper end of a transducer of an ultrasonic cleaner, then starting ultrasound, dropwise adding pyridine at the speed of 10mL/min, reacting for 6min under an Ar protection ultrasonic intermittent operation mode, then turning the original clear liquid to be turbid, continuing ultrasound to generate white floccule, reacting for 2.0h, stopping the reaction, and filtering to obtain a light yellow solid. The pale yellow solid was mixed with 33mmol of sodium hexafluorophosphate (NaPF)6) Adding 56mmol of acetone into a single-neck round-bottom flask with a condensation reflux device, magnetically stirring at room temperature for 12h, filtering, removing white precipitate NaBr, adding 30mL of dichloromethane into the filtrate to generate white precipitate, filtering, performing rotary evaporation for 3h to remove acetone and dichloromethane, and performing vacuum drying at 43 ℃ for 22h to obtain N-dodecyl pyridine hexafluorophosphate.
The corrosion inhibitor prepared by the invention has good dispersibility in a test ring, and the corrosion rate in the test ring is 2.109 mm/a.
Example 9
The N-alkyl pyridine hexafluorophosphate salt is prepared by the following process: adding a certain amount of bromododecane (36mmol) into a three-neck round-bottom flask, adding a constant-pressure dropping funnel filled with 30mmol of pyridine and a condensing reflux device with a drying tube, fixing the dropping funnel on the upper end of a transducer of an ultrasonic cleaner, then starting ultrasound, dropwise adding pyridine at the speed of 8mL/min, reacting for 6min under an Ar protection ultrasonic intermittent operation mode, then turning the original clear liquid into turbid liquid, continuing ultrasound to generate white floccule, stopping the reaction after reacting for 2h, and filtering to obtain light yellow solid. The pale yellow solid was mixed with 33mmol of sodium hexafluorophosphate (NaPF)6) And 57mmol of acetone is added into a single-mouth round-bottom flask with a condensation reflux device, the mixture is magnetically stirred at room temperature for reaction for 12 hours, then the mixture is filtered, white precipitate NaBr is removed, 25mL of dichloromethane is added into the filtrate, white precipitate is generated, the mixture is filtered, acetone and dichloromethane are separated by rotary evaporation for 4 hours, and the mixture is dried in vacuum at 45 ℃ for 24 hours, so that the N-dodecyl pyridine hexafluorophosphate is obtained.
The corrosion inhibitor prepared by the invention has good dispersibility in a test ring, and the corrosion rate in the test ring is 2.113 mm/a.
In conclusion, the N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate ionic liquid corrosion inhibitor has the characteristics of good water solubility, low corrosion rate and good corrosion inhibition effect.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (4)
1. The corrosion inhibitor for the top of the distillation tower of oil refining, which resists the corrosion of dilute hydrochloric acid and hydrogen sulfide, is characterized by comprising the following components in percentage by mass: greater than or equal to 98 percent of pyridyl ionic liquid, the balance of NaBr, wherein the pyridyl ionic liquid is N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate;
the preparation process of the pyridyl ionic liquid is as follows:
s1, adding bromoalkane into a three-neck round-bottom flask, and fixing a constant-pressure dropping funnel containing pyridine and a condensation reflux device with a drying tube at the upper end of a transducer of an ultrasonic cleaner;
s2, carrying out ultrasonic treatment on bromoalkane, adding pyridine dropwise into the bromoalkane, carrying out ultrasonic intermittent reaction to enable clear liquid to become turbid, continuing ultrasonic treatment to generate white floccule, and filtering after continuing reaction to obtain light yellow solid;
s3, mixing the light yellow solid obtained in the step S2 with acetone and sodium tetrafluoroborate or sodium hexafluorophosphate, wherein the light yellow solid is: acetone: the molar ratio of (sodium tetrafluoroborate or sodium hexafluorophosphate) is 1: (1.8-2.0): (1.05-1.15), magnetically stirring at room temperature for 12-13 h for reaction, and then filtering to remove white precipitate NaBr in the filtrate;
s4, adding 20-30 mL of dichloromethane into the filtrate obtained after filtration in the step S3 to generate a white precipitate, removing acetone and dichloromethane through filtration and rotary evaporation for 3-4 h, and performing vacuum drying treatment at 40-45 ℃ for 20-25 h to obtain the N-alkylpyridinium tetrafluoroborate or N-alkylpyridinium hexafluorophosphate.
2. An oil refining distillation tower top corrosion inhibitor for resisting corrosion of dilute hydrochloric acid and hydrogen sulfide as claimed in claim 1, wherein in step S1, the alkyl bromide is methyl bromide, butyl bromide or dodecyl bromide, and the molar ratio of pyridine to alkyl bromide is 1 (1.1-1.3).
3. An oil refining distillation tower top corrosion inhibitor for resisting dilute hydrochloric acid and hydrogen sulfide corrosion according to claim 1, wherein in step S2, ultrasonic treatment is performed under the protection of Ar, the speed of dripping pyridine is less than or equal to 10mL/min, the intermittent operation time of ultrasonic wave is 5-10 min, and the reaction is continued for 1.8-2.2 h after white floccule is generated and then is stopped.
4. An oil refining distillation tower top corrosion inhibitor for resisting dilute hydrochloric acid and hydrogen sulfide corrosion according to claim 1, wherein the corrosion rate of the corrosion inhibitor in the environment of the top of a petroleum refining distillation tower containing dilute hydrochloric acid and hydrogen sulfide is 2.107-2.869 mm/a.
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