CN102071427A - Corrosion inhibitor for inhibiting corrosion of high-temperature high-pressure carbon dioxide and preparation method thereof - Google Patents
Corrosion inhibitor for inhibiting corrosion of high-temperature high-pressure carbon dioxide and preparation method thereof Download PDFInfo
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- CN102071427A CN102071427A CN 201010587348 CN201010587348A CN102071427A CN 102071427 A CN102071427 A CN 102071427A CN 201010587348 CN201010587348 CN 201010587348 CN 201010587348 A CN201010587348 A CN 201010587348A CN 102071427 A CN102071427 A CN 102071427A
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Abstract
The invention provides a corrosion inhibitor for inhibiting the corrosion of high-temperature high-pressure carbon dioxide and a preparation method thereof. The corrosion inhibitor comprises 1 to 80 weight percent of thioimidazolone derivative, 1 to 50 weight percent of quaternary alkylammonium salt, 0.01 to 20 weight percent of sulfur-containing low molecular weight organic matter, 0 to 70 weight percent of water, 0 to 30 weight percent of nonionic surfactant, 0 to 70 weight percent of solvent, and 1 to 20 weight percent of alkynol. The corrosion inhibitor has good effect of resisting the corrosion of the high-temperature high-pressure carbon dioxide, can form a layer of effective protective film on the surface of metal, prevent hypersalinity wastewater from corroding the metal at high temperature and high partial pressure of carbon dioxide, and can be used in oil wells with high temperature and high partial pressure of carbon dioxide.
Description
Technical field
The present invention relates to a kind of inhibiter that suppresses the High Temperature High Pressure carbon dioxide corrosion and preparation method thereof.Be specially adapted to suppress the corrosion that the High Temperature High Pressure carbonic acid gas causes.
Background technology
Carbonic acid gas often is present in the oil gas for the component of Sweet natural gas or oil field gas.CO
2After dissolving in water iron and steel there is extremely strong corrodibility., more serious than hydrochloric acid in the total acidity of identical pH value carbon dioxide to the corrosion of iron and steel than hydrochloric acid height.Carbon dioxide corrosion may make the life-span of oil gas well be significantly less than life, and the erosion rate of soft steel can be up to 7mm/a, sometimes even higher.Abroad, early relevant for CO
2Cause iron and steel general corrosion and serious local corrosion rapidly, make pipeline and equipment that the example report of early stage corrosion failure take place.The example that also has many carbon dioxide corrosions to lose efficacy at home, for example, the N80 oil pipe of a bite down-hole of North China Oilfield is corroded riddled with gaping woundsly, just as screen cloth, only uses and just has in 18 months scrap.Year surplus Zhongyuan Oil Field literary composition-23 gas field development ten is along with exploitation time lengthening, CO
2Etching problem is more and more serious, and since nineteen ninety-five, this gas field has 10 mouthfuls of wells, and tube corrosion perforation fracture accident takes place 17 wells.
Great deal of research results shows that temperature and dividing potential drop are the important parameters of carbon dioxide corrosion, near 100 ℃, high erosion rate and serious local corrosion occur.Work as CO
2When dividing potential drop was lower than 0.483MPa, CO easily took place
2Uniform corrosion; Be pressed in the pitting corrosion that then may take place between 0.483MPa～2.07MPa in various degree when branch; When dividing potential drop during greater than 2.07MPa, serious local corrosion takes place.At present, domestic high temperature resistance high carbon dioxide dividing potential drop corrosive inhibiter is less, has problems such as working concentration height, weak effect.
The object of the invention is to develop a kind of inhibiter of novel inhibition High Temperature High Pressure carbon dioxide corrosion, makes it can form the effective protective membrane of one deck in the metallic surface, prevents that high temperature high carbon dioxide branch from depressing high salinity sewage to corrosion of metal.Inhibiter of the present invention can be used in the oil well of high temperature and high carbon dioxide dividing potential drop, and it is few to have usage quantity, the effect height.
Summary of the invention
Task of the present invention provides a kind of inhibiter that is used to suppress the High Temperature High Pressure carbon dioxide corrosion, makes it can form the effective protective membrane of one deck in the metallic surface, prevents that high temperature high carbon dioxide branch from depressing high salinity sewage to corrosion of metal.The present invention provides preparation this method that is used to suppress the inhibiter of High Temperature High Pressure carbon dioxide corrosion simultaneously.
Realize that technical scheme of the present invention is:
This inhibiter that is used to suppress the High Temperature High Pressure carbon dioxide corrosion provided by the invention is that benchmark contains with its gross weight:
Thiocarbamoyl imidazole ketone derivatives 1-80 weight %;
Alkyl quaternary ammonium salts 1-50 weight %
Sulfur-bearing low molecule organic matter 0.01-20 weight %;
Water 0-70 weight %;
Nonionogenic tenside 0-30 weight %;
Organic solvent 0-70 weight %;
Alkynol 0-20 weight %
Thiocarbamoyl imidazole ketone derivatives in the inhibiter of the present invention is synthetic by following method: with the amine organism, organic solvent joins in the reactor of being furnished with condensation reflux device simultaneously, under the normal temperature, drip dithiocarbonic anhydride with dropper, after finishing, be heated to the 60-80 degree, backflow 10-12 hour, ice bath is cooled to room temperature, the precipitation washing with acetone, obtain the thiocarbamoyl imidazole ketone derivatives, amine organism wherein, the weight consumption ratio of solvent and dithiocarbonic anhydride is 3: 1: 4, and described amine organism is a quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine or hydroxy-ethylenediamine.
Alkyl quaternary ammonium salts in the inhibiter of the present invention is synthetic by following method: alkylamine, organic solvent, Benzyl Chloride are joined in the reactor of being furnished with condensation reflux device simultaneously, and reaction is 4-6 hour under the 100-120 degree; Cooling, adding organic solvent stirs, be cooled to the product that obtains after the room temperature and be alkyl quaternary ammonium salts, wherein the weight consumption of alkylamine, organic solvent and Benzyl Chloride ratio is 2: 2: 1, and described alkylamine is C1～C20 saturated alkyl amine or C1～C20 unsaturated alkyl amine.
Sulfur-bearing low molecule organic matter in the inhibiter of the present invention is a kind of or derivatives thereof in thiamines, thiocarbamide, mercaptan, the thiophene.
Nonionogenic tenside in the inhibiter of the present invention is fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene.
Organic solvent in the inhibiter of the present invention is methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, propylene glycol or glycerol.
Alkynol in the inhibiter of the present invention is propiolic alcohol, butynol or l-hexyn-3-ol.
This preparation method who is used to suppress the inhibiter of High Temperature High Pressure carbon dioxide corrosion provided by the invention is: with thiocarbamoyl imidazole ketone derivatives, alkyl quaternary ammonium salts, sulfur-bearing low molecule organic matter, water, nonionogenic tenside, organic solvent, alkynol by following mixed:
Thiocarbamoyl imidazole ketone derivatives 1-80 weight %;
Alkyl quaternary ammonium salts 1-50 weight %
Sulfur-bearing low molecule organic matter 0.01-20 weight %;
Water 0-70 weight %;
Nonionogenic tenside 0-30 weight %;
Organic solvent 0-70 weight %;
Alkynol 0-20 weight %
Thiocarbamoyl imidazole ketone derivatives described in the preparation method of the present invention is synthetic by following method: with the amine organism, organic solvent joins in the reactor of being furnished with condensation reflux device simultaneously, under the normal temperature, drip dithiocarbonic anhydride with dropper, after finishing, be heated to the 60-80 degree, backflow 10-12 hour, ice bath is cooled to room temperature, the precipitation washing with acetone, obtain the thiocarbamoyl imidazole ketone derivatives, amine organism wherein, the weight consumption ratio of solvent and dithiocarbonic anhydride is 3: 1: 4, and described amine organism is a quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine or hydroxy-ethylenediamine.
Alkyl quaternary ammonium salts described in the preparation method of the present invention is synthetic by following method: alkylamine, organic solvent, Benzyl Chloride are joined in the reactor of being furnished with condensation reflux device simultaneously, and reaction is 4-6 hour under the 100-120 degree; Cooling, adding organic solvent stirs, be cooled to the product that obtains after the room temperature and be alkyl quaternary ammonium salts, wherein the weight consumption of alkylamine, organic solvent and Benzyl Chloride ratio is 2: 2: 1, and described alkylamine is C1～C20 saturated alkyl amine or C1～C20 unsaturated alkyl amine.
Sulfur-bearing low molecule organic matter described in the preparation method of the present invention is a kind of or derivatives thereof in thiamines, thiocarbamide, mercaptan, the thiophene; Described nonionogenic tenside is fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene; Described organic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, propylene glycol or glycerol; Described alkynol is propiolic alcohol, butynol or l-hexyn-3-ol.
This inhibiter that is used to suppress the High Temperature High Pressure carbon dioxide corrosion provided by the invention makes it can form the effective protective membrane of one deck in the metallic surface, prevents that high temperature high carbon dioxide branch from depressing high salinity sewage to corrosion of metal.Inhibiter of the present invention can be used in the oil well of high temperature and high carbon dioxide dividing potential drop, and it is few to have usage quantity, characteristics such as effect height.
Concrete true mode:
To come more detailed description the present invention by specific embodiment below.But these embodiment are used for limiting the scope of the invention by any way.
Embodiment 1
This embodiment is used to prepare corrosive medium.
2 gram sodium bicarbonates, 0.3g sodium sulfate, 0.2g calcium chloride, 0.2g magnesium chloride, 13g sodium-chlor are joined in the 1000g water, and stirring is dissolved sodium-chlor fully, and the sodium chloride solution that can obtain 3.0 weight % is as corrosive medium.
Embodiment 2
This example is used for preparing the thiocarbamoyl imidazole ketone derivatives
With the 120g quadrol, 40g ethanol is put into the reactor of 500ml, under returned cold coalescence stirring condition, in room temperature, slowly drips 160g dithiocarbonic anhydride.After finishing, connect power supply, be heated to 60 ℃, refluxed 10 hours.Obtain the cooling of product ice bath, precipitation is used washing with acetone, obtains the thiocarbamoyl imidazole ketone derivatives.
Embodiment 3
This example is used for preparing the alkylthio quaternary ammonium salt
With the 120g octadecylamine, 50g ethanol, Benzyl Chloride 60g put into the reactor of 500ml, under returned cold coalescence stirring condition, react 4 hours down at 100 ℃, and cooling adds the 70g alcohol solvent and stirs, and the product that obtains after the cooling is alkyl quaternary ammonium salts.
Embodiment 4
This embodiment is used to prepare inhibiter provided by the invention
4g thiocarbamide and 20g Virahol are added in the water of 60 ℃ of 36g, after treating that it dissolves fully, add the 10g Soxylat A 25-7 and mix, and then add 15g imidazolone derivatives and the embodiment 15g alkyl quaternary ammonium salts that embodiment 2 makes, mix and promptly obtain inhibiter provided by the invention.
Embodiment 5
This embodiment is used to prepare inhibiter provided by the invention
25g imidazolone derivatives and embodiment 20g alkyl quaternary ammonium salts, 8g Soxylat A 25-7,37g Virahol that embodiment 2 is made join in the water of 50 ℃ of 10g together, mix and promptly obtain inhibiter provided by the invention.
Embodiment 6
This embodiment is used to prepare inhibiter provided by the invention
35g imidazolone derivatives, 10g Soxylat A 25-7,30g Virahol, 15g ethylene glycol, 10g propiolic alcohol that embodiment 2 is made mix down at 70 ℃ together, mix and promptly obtain inhibiter provided by the invention.
Test result
Embodiment 4-6 is used to measure the effect of inhibiter provided by the invention to the High Temperature High Pressure carbon dioxide corrosion, uses water sample to be water sample described in the example 1, test(ing) liquid flow velocity 1m/s.According to the oil and gas industry standard SY/T5273-2000 of the People's Republic of China (PRC), the steel disc before and after the corrosion is carried out weightlessness analysis, calculate erosion rate.
The result is as shown in table 1
From the result shown in the table 1 as can be seen, inhibiter lower concentration provided by the invention has the effect of good control High Temperature High Pressure carbon dioxide corrosion.
Claims (10)
1. an inhibiter that is used to suppress the High Temperature High Pressure carbon dioxide corrosion is characterized in that, this inhibiter is that benchmark contains with its gross weight:
Thiocarbamoyl imidazole ketone derivatives 1-80 weight %;
Alkyl quaternary ammonium salts 1-50 weight %
Sulfur-bearing low molecule organic matter 0.01-20 weight %;
Water 0-70 weight %;
Nonionogenic tenside 0-30 weight %;
Organic solvent 0-70 weight %;
Alkynol 0-20 weight %
2. inhibiter according to claim 1, it is characterized in that, described thiocarbamoyl imidazole ketone derivatives is synthetic by following method: amine organism, organic solvent are joined in the reactor of being furnished with condensation reflux device simultaneously, under the normal temperature, drip dithiocarbonic anhydride with dropper, after finishing, be heated to the 60-80 degree, backflow 10-12 hour, ice bath is cooled to room temperature, precipitation is used washing with acetone, obtains the thiocarbamoyl imidazole ketone derivatives, and wherein the weight consumption of amine organism, solvent and dithiocarbonic anhydride ratio is 3: 1: 4.
3. inhibiter according to claim 2 is characterized in that, described amine organism is quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine or hydroxy-ethylenediamine.
4. inhibiter according to claim 1, it is characterized in that, described alkyl quaternary ammonium salts is synthetic by following method: alkylamine, organic solvent, Benzyl Chloride are joined in the reactor of being furnished with condensation reflux device simultaneously, and reaction is 4-6 hour under the 100-120 degree; Cooling adds organic solvent and stirs, and is cooled to the product that obtains after the room temperature and is alkyl quaternary ammonium salts, and wherein the weight consumption of alkylamine, organic solvent and Benzyl Chloride ratio is 2: 2: 1.
5. inhibiter according to claim 4 is characterized in that, described alkylamine is C1～C20 saturated alkyl amine or C1～C20 unsaturated alkyl amine.
6. inhibiter according to claim 1 is characterized in that, described sulfur-bearing low molecule organic matter is a kind of or derivatives thereof in thiamines, thiocarbamide, mercaptan, the thiophene; Described nonionogenic tenside is fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene; Described organic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, propylene glycol or glycerol; Described alkynol is propiolic alcohol, butynol or l-hexyn-3-ol.
7. the preparation method of the described inhibiter of claim 1 is: thiocarbamoyl imidazole ketone derivatives, alkyl quaternary ammonium salts, sulfur-bearing low molecule organic matter, water, nonionogenic tenside, organic solvent, alkynol are pressed following mixed:
Thiocarbamoyl imidazole ketone derivatives 1-80 weight %;
Alkyl quaternary ammonium salts 1-50 weight %
Sulfur-bearing low molecule organic matter 0.01-20 weight %;
Water 0-70 weight %;
Nonionogenic tenside 0-30 weight %;
Organic solvent 0-70 weight %;
Alkynol 0-20 weight %
8. preparation method according to claim 7, it is characterized in that, described thiocarbamoyl imidazole ketone derivatives is synthetic by following method: with the amine organism, organic solvent joins in the reactor of being furnished with condensation reflux device simultaneously, under the normal temperature, drip dithiocarbonic anhydride with dropper, after finishing, be heated to the 60-80 degree, backflow 10-12 hour, ice bath is cooled to room temperature, and precipitation is used washing with acetone, obtains the thiocarbamoyl imidazole ketone derivatives, amine organism wherein, the weight consumption ratio of solvent and dithiocarbonic anhydride is 3: 1: 4, and described amine organism is a quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine or hydroxy-ethylenediamine.
9. preparation method according to claim 7, it is characterized in that, it is characterized in that described alkyl quaternary ammonium salts is synthetic by following method: alkylamine, organic solvent, Benzyl Chloride are joined in the reactor of being furnished with condensation reflux device simultaneously, and reaction is 4-6 hour under the 100-120 degree; Cooling, adding organic solvent stirs, be cooled to the product that obtains after the room temperature and be alkyl quaternary ammonium salts, wherein the weight consumption of alkylamine, organic solvent and Benzyl Chloride ratio is 2: 2: 1, and described alkylamine is C1～C20 saturated alkyl amine or C1～C20 unsaturated alkyl amine.
10. preparation method according to claim 7 is characterized in that, described sulfur-bearing low molecule organic matter is a kind of or derivatives thereof in thiamines, thiocarbamide, mercaptan, the thiophene; Described nonionogenic tenside is fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene; Described organic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, propylene glycol or glycerol; Described alkynol is propiolic alcohol, butynol or l-hexyn-3-ol.
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Cited By (8)
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| CN104829539A (en) * | 2015-04-13 | 2015-08-12 | 成都石大力盾科技有限公司 | Adipic acid bis-imidazoline derivative and preparation method thereof, and applications of adipic acid bis-imidazoline derivative as corrosion inhibitor |
| CN106478510A (en) * | 2016-09-14 | 2017-03-08 | 武汉楚博士科技有限公司 | Alkynol base imidazolinium compounds, the corrosion inhibiter for carbon dioxide drive and preparation |
| CN106995923A (en) * | 2017-04-26 | 2017-08-01 | 金浦新材料股份有限公司 | A kind of air cooling device corrosion inhibiter, its preparation method and its application |
| CN107267994A (en) * | 2017-04-19 | 2017-10-20 | 西安瑞杰油田物资实业开发有限公司 | A kind of gas gathering line multiple-effect composite corrosion inhibitor and preparation method thereof |
| CN107620070A (en) * | 2017-09-08 | 2018-01-23 | 武汉楚博士科技有限公司 | Carbon dioxide corrosion inhibitor based on expired Medicines and preparation method and application |
| CN111808593A (en) * | 2020-07-17 | 2020-10-23 | 中国石油化工股份有限公司 | Corrosion inhibitor for carbon dioxide flooding combined bacterial acidification and preparation method thereof |
| CN113292976A (en) * | 2021-05-26 | 2021-08-24 | 西南石油大学 | High-temperature-resistant high-salinity corrosion inhibitor |
| CN113528106A (en) * | 2021-07-19 | 2021-10-22 | 中海油田服务股份有限公司 | Corrosion inhibitor for inhibiting carbon dioxide corrosion at high temperature |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829539A (en) * | 2015-04-13 | 2015-08-12 | 成都石大力盾科技有限公司 | Adipic acid bis-imidazoline derivative and preparation method thereof, and applications of adipic acid bis-imidazoline derivative as corrosion inhibitor |
| CN106478510A (en) * | 2016-09-14 | 2017-03-08 | 武汉楚博士科技有限公司 | Alkynol base imidazolinium compounds, the corrosion inhibiter for carbon dioxide drive and preparation |
| CN106478510B (en) * | 2016-09-14 | 2018-01-30 | 武汉楚博士科技有限公司 | Alkynol base imidazolinium compounds, the corrosion inhibiter for carbon dioxide drive and preparation |
| CN107267994A (en) * | 2017-04-19 | 2017-10-20 | 西安瑞杰油田物资实业开发有限公司 | A kind of gas gathering line multiple-effect composite corrosion inhibitor and preparation method thereof |
| CN106995923A (en) * | 2017-04-26 | 2017-08-01 | 金浦新材料股份有限公司 | A kind of air cooling device corrosion inhibiter, its preparation method and its application |
| CN106995923B (en) * | 2017-04-26 | 2020-05-15 | 金浦新材料股份有限公司 | Corrosion inhibitor for air cooling device, preparation method and application thereof |
| CN107620070B (en) * | 2017-09-08 | 2018-06-29 | 武汉楚博士科技有限公司 | Carbon dioxide corrosion inhibitor based on expired Medicines and preparation method and application |
| CN107620070A (en) * | 2017-09-08 | 2018-01-23 | 武汉楚博士科技有限公司 | Carbon dioxide corrosion inhibitor based on expired Medicines and preparation method and application |
| CN111808593A (en) * | 2020-07-17 | 2020-10-23 | 中国石油化工股份有限公司 | Corrosion inhibitor for carbon dioxide flooding combined bacterial acidification and preparation method thereof |
| CN111808593B (en) * | 2020-07-17 | 2022-06-10 | 中国石油化工股份有限公司 | Corrosion inhibitor for carbon dioxide flooding combined bacterial acidification and preparation method thereof |
| CN113292976A (en) * | 2021-05-26 | 2021-08-24 | 西南石油大学 | High-temperature-resistant high-salinity corrosion inhibitor |
| CN113528106A (en) * | 2021-07-19 | 2021-10-22 | 中海油田服务股份有限公司 | Corrosion inhibitor for inhibiting carbon dioxide corrosion at high temperature |
| CN113528106B (en) * | 2021-07-19 | 2022-07-29 | 中海油田服务股份有限公司 | Corrosion inhibitor for inhibiting carbon dioxide corrosion at high temperature |
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