阅读说明：本技术 焦化缓蚀剂 (Coking corrosion inhibitor ) 是由 徐文忠 于 2019-11-13 设计创作，主要内容包括：本发明公开了一种焦化缓蚀剂,包括：重量份计的含硫氨基酸组合物30～35份,胺复合剂12～15份、聚丙烯酰胺10～12份和增效剂6～12份。本发明成本低廉,易降解,采用氨基酸组合物、胺复合剂和聚丙烯酰胺进行复配使用,缓蚀效果明显,本发明采用的焦化缓蚀剂以氨基酸组合物为主要原料配合第一代缓蚀剂大大降低了胺复合剂的使用量,采用碳基材料负载氨基酸的方式解决了现有技术中绿色缓蚀剂吸附膜致密性差的缺点,使得该缓蚀剂更加环保而且缓蚀效果相较于第一代缓蚀剂有明显增加。(The invention discloses a coking corrosion inhibitor, which comprises: 30-35 parts of sulfur-containing amino acid composition, 12-15 parts of amine complexing agent, 10-12 parts of polyacrylamide and 6-12 parts of synergist. The coking corrosion inhibitor has low cost and easy degradation, adopts the amino acid composition, the amine complexing agent and the polyacrylamide for complex use, has obvious corrosion inhibition effect, greatly reduces the using amount of the amine complexing agent by taking the amino acid composition as a main raw material and matching with a first-generation corrosion inhibitor, and solves the defect of poor compactness of an adsorption film of a green corrosion inhibitor in the prior art by adopting a way of loading amino acid on a carbon-based material, so that the corrosion inhibitor is more environment-friendly and the corrosion inhibition effect is obviously improved compared with the first-generation corrosion inhibitor.)

1. The coking corrosion inhibitor is characterized by comprising:

30-35 parts of sulfur-containing amino acid composition, 12-15 parts of amine complexing agent, 10-12 parts of polyacrylamide and 6-12 parts of synergist;

wherein, the amine complexing agent comprises: 40-55 parts of ethanolamine, 30-45 parts of diethanolamine and 10-20 parts of triethanolamine; the synergist comprises: glycerol and citric acid.

2. A coking corrosion inhibitor according to claim 1, characterized in that the specific parts by weight are 32 parts of sulfur-containing amino acid composition, 12 parts of amine complexing agent, 12 parts of polyacrylamide and 6 parts of synergist.

3. A coking corrosion inhibitor according to claim 1 characterised in that the sulphur-containing amino acid composition comprises a combination of two or more of methionine, cysteine, cystine and acetyl cysteine.

4. A coking corrosion inhibitor according to claim 3, characterized in that the weight ratio of methionine, cysteine and cystine is 1:1: 3.

5. A coking corrosion inhibitor according to claim 1, characterized in that the weight ratio of glycerol to citric acid is 1: 3.

6. a coking corrosion inhibitor according to claim 1, characterized in that the amine complexing agent is prepared by taking 50-70% ammonia water and adding ethylene oxide into the ammonia water, wherein the mass ratio of ammonia to ethylene oxide is 4.5: 1, reacting for 2 hours at 150 ℃ and under the pressure of 16 MPa.

7. A coking corrosion inhibitor according to claim 1 characterised in that the sulfur-containing amino acid composition is used after loading by a method comprising:

adding a carbon-based load material into a mixed acid consisting of sulfuric acid and nitric acid, and carrying out ultrasonic treatment for 4-5 h in a water bath at 70 ℃; filtering and washing the acidified mixture, and drying the washed and washed mixture at 100 ℃ for 24 hours to obtain an acidified carbon-based load material;

adding the acidified carbon-based load material into deionized water, performing ultrasonic dispersion for 30min, adding the sulfur-containing amino acid composition and DCC (DCC-type carbon) accounting for 0.2% of the total molar mass of the sulfur-containing amino acid composition, reacting at 60 ℃ for 10-12 h, filtering, washing and drying to obtain the load-type sulfur-containing amino acid composition.

8. A coking corrosion inhibitor according to claim 7 characterised in that the carbon-based support material is a carbon nanotube or a carbon nanotube.

Technical Field

The invention relates to the technical field of fine chemical engineering. More particularly, the present invention relates to a coking corrosion inhibitor.

Background

The corrosive environment of the refinery is at low temperature (T)<120 ℃ C. light oil H₂S-H₂An O-type corrosive environment; high-temperature (240-500 ℃) heavy oil type corrosive environment, high-temperature vulcanization, and in a sulfur recovery device, in the burnt high-temperature sulfur-containing process gas, the gas flow composition is H₂S、SO₂Sulfur vapour, CS₂、COS、CO₂、H₂O, nitrogen, and the like.

Chinese patent CN107338072B describes a corrosion inhibitor for reforming apparatus, which comprises: the amine complexing agent is prepared by mixing monoethanolamine, diethanolamine and triethanolamine according to a certain weight part ratio, and glycerol and citric acid as synergist, and has polar group capable of being adsorbed on the surface of reforming equipment to form a layer of monomolecular water-resistant protective film which reacts with hydrogen ions to generate ions with positive charges, and the reaction formula is RNH²⁺+H⁺→RNH³⁺However, the amine corrosion inhibitor adopts organic amine which is not easy to degrade and is combined with metal after reacting with acid to form salt in useThe stability is high, the influence on the health of operators is realized, and the use amount is large;

chinese patent CN106086899B discloses a neutralization anticorrosion corrosion inhibitor, which is mainly prepared by reacting malic acid, tartaric acid and ethylene glycol as main components and adding synergist hexamethyltetramine and thiourea, and has safe and environment-friendly production process, safe operation without three-waste discharge, and limited application range due to the fact that the corrosion inhibitor mainly adopts an acidic material;

in addition, the article reported by Shanghai institute of Electrical Power, "progress in research on Corrosion inhibition technology and application thereof in energy industry" shows that the development trend of the existing corrosion inhibitors is more towards green corrosion inhibitors such as natural products and biomembrane technology;

therefore, further improvement is needed on the basis of the first generation corrosion inhibitor of the company, namely the Chinese patent CN 107338072B.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.

The coking corrosion inhibitor has the advantages that the cost is low, the coking corrosion inhibitor is easy to degrade, the amino acid composition, the amine complexing agent and the polyacrylamide are compounded for use, the corrosion inhibition effect is obvious, the coking corrosion inhibitor adopts the amino acid composition as the main raw material and is matched with the first-generation corrosion inhibitor, the use amount of the amine complexing agent is greatly reduced, the defect of poor compactness of an adsorption film of a green corrosion inhibitor in the prior art is overcome by adopting a mode of loading amino acid on a carbon-based material, the corrosion inhibitor is more environment-friendly, and the corrosion inhibition effect is obviously improved compared with that of the first-generation corrosion inhibitor.

To achieve these objects and other advantages in accordance with the present invention, there is provided a scorch inhibitor comprising:

30-35 parts of sulfur-containing amino acid composition, 12-15 parts of amine complexing agent, 10-12 parts of polyacrylamide and 6-12 parts of synergist;

wherein, the amine complexing agent comprises: 40-55 parts of ethanolamine, 30-45 parts of diethanolamine and 10-20 parts of triethanolamine; the synergist comprises: glycerol and citric acid.

Preferably, the weight parts are 32 parts of the sulfur-containing amino acid composition, 12 parts of the amine complexing agent, 12 parts of polyacrylamide and 6 parts of the synergist.

Preferably, the sulfur-containing amino acid composition comprises a combination of two or more of methionine, cysteine, cystine, and acetylcysteine;

preferably, the weight part ratio of the methionine, the cysteine and the cystine is 1:1: 3.

Preferably, the synergist comprises glycerol and citric acid, and the weight part ratio of the glycerol to the citric acid is 1: 3.

preferably, the preparation method of the amine complexing agent comprises the following steps of taking 50-70% ammonia water, and adding ethylene oxide into the ammonia water, wherein the mass ratio of ammonia to ethylene oxide is 4.5: 1, reacting for 2 hours at 150 ℃ and under the pressure of 16 MPa.

Preferably, the sulfur-containing amino acid composition is used after being loaded, and the method for loading the sulfur-containing amino acid composition comprises the following steps:

adding a carbon-based load material into a mixed acid consisting of sulfuric acid and nitric acid, and carrying out ultrasonic treatment for 4-5 h in a water bath at 70 ℃; filtering and washing the acidified mixture, and drying the washed and washed mixture at 100 ℃ for 24 hours to obtain an acidified carbon-based load material;

adding the acidified carbon-based load material into deionized water, performing ultrasonic dispersion for 30min, adding the sulfur-containing amino acid composition and DCC (DCC-type carbon) accounting for 0.2% of the total molar mass of the sulfur-containing amino acid composition, reacting at 60 ℃ for 10-12 h, filtering, washing and drying to obtain the load-type sulfur-containing amino acid composition.

Preferably, the carbon-based supporting material is a carbon nanotube or a carbon nanotube.

The invention at least comprises the following beneficial effects:

firstly, the corrosion inhibitor is low in cost and easy to degrade, and has an obvious corrosion inhibition effect due to the synergistic effect of the amino acid composition, the amine complexing agent and the polyacrylamide;

secondly, after the coking corrosion inhibitor adopted by the invention takes the amino acid composition as a main raw material and is matched with a first-generation corrosion inhibitor, the use amount of the amine complexing agent is effectively reduced, and the quality of oil products produced by a device and downstream devices are not influenced;

thirdly, the method of loading amino acid on the carbon nano tube or the carbon micro tube is adopted to preliminarily solve the defect of poor compactness of an adsorption film formed on the inner wall of the petroleum decoking device by taking amino acid as the corrosion inhibitor, so that the corrosion inhibitor has longer service life, is not easy to fall off, is more environment-friendly and has obviously increased corrosion inhibition effect compared with the first generation corrosion inhibitor.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

< example 1>

A coking corrosion inhibitor comprises the following raw materials in parts by weight:

30 parts of sulfur-containing amino acid composition, 12 parts of amine complexing agent, 10 parts of polyacrylamide and 6 parts of synergist;

wherein the sulfur-containing amino acid composition is cysteine and cystine, and the weight ratio of the cysteine to the cystine is 1: 2; the amine complexing agent comprises: 40 parts of ethanolamine, 45 parts of diethanolamine and 10 parts of triethanolamine; the synergist comprises: glycerol and citric acid, wherein the weight part ratio of the glycerol to the citric acid is 1: 2.

the specific preparation method of the coking corrosion inhibitor comprises the following steps:

s1, uniformly mixing 40 parts of ethanolamine, 45 parts of diethanolamine and 10 parts of triethanolamine at room temperature, and adding 6 parts of a synergist, wherein the weight part ratio of glycerol to citric acid in the synergist is 1: 1.5, obtaining a component A;

s2, taking cysteine and cystine, and mixing the components in parts by weight of 1: 2, mixing, and adding the sulfur-containing amino acid composition into the polyacrylamide in parts by weight to obtain a component B;

and S3, uniformly mixing the component A and the component B, heating and stirring in water bath at 40-45 ℃ for 1.5-2 h, and activating to obtain the coking corrosion inhibitor.

< example 2>

A coking corrosion inhibitor comprises the following raw materials in parts by weight:

35 parts of sulfur-containing amino acid composition, 14 parts of amine complexing agent, 11 parts of polyacrylamide and 12 parts of synergist;

wherein the weight part ratio of the methionine to the cysteine to the cystine is 1:1: 3; the synergist comprises: glycerol and citric acid, wherein the weight part ratio of the glycerol to the citric acid is 1: 3.

the specific preparation method of the coking corrosion inhibitor comprises the following steps:

s1, the preparation method of the amine complexing agent comprises the steps of taking 50-70% ammonia water, adding ethylene oxide into the ammonia water, wherein the mass ratio of ammonia to ethylene oxide is 4.5: 1, reacting for 2 hours at 150 ℃ under the pressure of 16MPa, wherein ethanolamine 40%, diethanolamine 42%, triethanolamine 14%, 14 parts of amine complexing agent are taken, 12 parts of synergist are added into the amine complexing agent, and the synergist is glycerol and citric acid according to the weight part ratio of 1:3, mixing and preparing, and stirring and mixing uniformly to obtain a component A;

s2, mixing methionine, cysteine and cystine according to the weight part ratio of 1:1:3, and adding the sulfur-containing amino acid composition into the polyacrylamide according to the weight part ratio to obtain a component B;

and S3, uniformly mixing the component A and the component B, heating and stirring in water bath at 40-45 ℃ for 1.5-2 h, and activating to obtain the coking corrosion inhibitor.

< example 3>

A coking corrosion inhibitor comprises the following raw materials in parts by weight:

32 parts of sulfur-containing amino acid composition, 15 parts of amine complexing agent, 12 parts of polyacrylamide and 8 parts of synergist;

wherein, the sulfur-containing amino acid composition is methionine and cystine, and the weight ratio of the methionine to the cystine is 1.5: 2; the amine complexing agent comprises: 55 parts of ethanolamine, 30 parts of diethanolamine and 20 parts of triethanolamine; the synergist comprises: glycerol and citric acid, wherein the weight part ratio of the glycerol to the citric acid is 1: 3.

the specific preparation method of the coking corrosion inhibitor comprises the following steps:

s1, uniformly mixing 55 parts of ethanolamine, 30 parts of diethanolamine and 20 parts of triethanolamine at room temperature, and adding 8 parts of synergist to obtain a component A, wherein the weight part ratio of glycerol to citric acid in the synergist is 1: 3;

s2, taking methionine and cystine according to the weight ratio of 1.5: 2, mixing, and adding the sulfur-containing amino acid composition into the polyacrylamide in parts by weight to obtain a component B;

and S3, uniformly mixing the component A and the component B, heating and stirring in water bath at 40-45 ℃ for 1.5-2 h, and activating to obtain the coking corrosion inhibitor.

Wherein, the amino acid composition is obtained by pretreating before mixing polyacrylamide, activating by using 1mol/L sodium carbonate dichloro solution, stirring for 3h at room temperature, filtering, and vacuum concentrating.

< example 4>

A coking corrosion inhibitor comprises the following raw materials in parts by weight:

32 parts of sulfur-containing amino acid composition, 15 parts of amine complexing agent, 12 parts of polyacrylamide and 8 parts of synergist;

wherein, the sulfur-containing amino acid composition is methionine and cystine, and the weight ratio of the methionine to the cystine is 1.5: 2; the amine complexing agent comprises: 55 parts of ethanolamine, 30 parts of diethanolamine and 20 parts of triethanolamine; the synergist comprises: glycerol and citric acid, wherein the weight part ratio of the glycerol to the citric acid is 1: 3.

the specific preparation method of the coking corrosion inhibitor comprises the following steps:

s1, the preparation method of the amine complexing agent comprises the steps of taking 50-70% ammonia water, adding ethylene oxide into the ammonia water, wherein the mass ratio of the ammonia to the ethylene oxide is 4.5: 1, reacting for 2 hours at 150 ℃ under the pressure of 16MPa, wherein ethanolamine is 41%, diethanolamine is 42% and triethanolamine is 13%; adding 8 parts of synergist into an amine complexing agent to obtain a component A, wherein the weight part ratio of glycerol to citric acid in the synergist is 1: 3;

s2, adding the carbon nano tube into mixed acid consisting of sulfuric acid and nitric acid, and carrying out ultrasonic treatment for 4-5 h in a water bath at 70 ℃; filtering and washing the acidified mixture, and drying the mixture at 100 ℃ for 24 hours to obtain an acidified carbon nano tube;

adding the acidified carbon nano tube into deionized water, ultrasonically dispersing for 30min, and adding DCC (dichloro-diphenyl-trichloroethane) with the molar mass of 0.2% of the total molar mass of the sulfur-containing amino acid composition and the sulfur-containing amino acid composition, wherein the weight part ratio of the carbon nano tube to the sulfur-containing composition is 1.2: 1; the sulfur-containing amino acid composition is methionine and cystine, and the weight part ratio of the methionine to the cystine is 1.5: 2; reacting at 60 ℃ for 10-12 h, filtering, washing and drying to obtain a supported sulfur-containing amino acid composition, and adding the supported sulfur-containing amino acid composition into the polyacrylamide in parts by weight to obtain a component B;

and S3, uniformly mixing the component A and the component B, heating and stirring in water bath at 40-45 ℃ for 1.5-2 h, and activating to obtain the coking corrosion inhibitor.

< example 5>

A coking corrosion inhibitor comprises the following raw materials in parts by weight:

32 parts of sulfur-containing amino acid composition, 15 parts of amine complexing agent, 12 parts of polyacrylamide and 8 parts of synergist;

wherein, the sulfur-containing amino acid composition is methionine and cystine, and the weight ratio of the methionine to the cystine is 1.5: 2; the amine complexing agent comprises: 55 parts of ethanolamine, 30 parts of diethanolamine and 20 parts of triethanolamine; the synergist comprises: glycerol and citric acid, wherein the weight part ratio of the glycerol to the citric acid is 1: 3.

the specific preparation method of the coking corrosion inhibitor comprises the following steps:

s1, the preparation method of the amine complexing agent comprises the steps of taking 50-70% ammonia water, adding ethylene oxide into the ammonia water, wherein the mass ratio of the ammonia to the ethylene oxide is 4.5: 1, reacting for 2 hours at 150 ℃ under the pressure of 16MPa, wherein the ethanolamine comprises 41 percent of ethanolamine, 42 percent of diethanolamine and 15 percent of triethanolamine; adding 8 parts of synergist into an amine complexing agent to obtain a component A, wherein the weight part ratio of glycerol to citric acid in the synergist is 1: 3;

s2, adding the carbon micron tube into mixed acid consisting of sulfuric acid and nitric acid, and carrying out ultrasonic treatment for 4-5 h in a water bath at 70 ℃; filtering and washing the acidified mixture, and drying the mixture at 100 ℃ for 24 hours to obtain an acidified carbon nanotube;

adding the acidified carbon micron tube into deionized water, ultrasonically dispersing for 30min, and adding DCC with the molar mass of 0.2% of the total molar mass of the sulfur-containing amino acid composition and the sulfur-containing amino acid composition, wherein the weight part ratio of the carbon micron tube to the sulfur-containing composition is 1.1: 1; the sulfur-containing amino acid composition is methionine and cystine, and the weight part ratio of the methionine to the cystine is 1.5: 2; reacting at 60 ℃ for 10-12 h, filtering, washing and drying to obtain a supported sulfur-containing amino acid composition, and adding the supported sulfur-containing amino acid composition into the polyacrylamide in parts by weight to obtain a component B;

and S3, uniformly mixing the component A and the component B, heating and stirring in water bath at 40-45 ℃ for 1.5-2 h, and activating to obtain the coking corrosion inhibitor.

< comparative example 1>

The remaining components and preparation were the same as in example 2, except that no sulfur-containing amino acid composition was added.

< comparative example 2>

The remaining components and preparation were the same as in example 2, except that the amine complexing agent was not added.

< comparative example 3>

The remaining components and preparation were the same as in example 2, except that polyacrylamide was not added.

< Experimental example >

First, the performance index of the coking corrosion inhibitor obtained in examples 1 to 5

TABLE 1