CN102031526A - Low-temperature acidification corrosion inhibitor and preparation method thereof - Google Patents
Low-temperature acidification corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN102031526A CN102031526A CN 201010539122 CN201010539122A CN102031526A CN 102031526 A CN102031526 A CN 102031526A CN 201010539122 CN201010539122 CN 201010539122 CN 201010539122 A CN201010539122 A CN 201010539122A CN 102031526 A CN102031526 A CN 102031526A
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Abstract
The invention relates to a low-temperature acidification corrosion inhibitor which is composed of 10-50 parts by weight of alkynol, 10-50 parts by weight of quaternary ammonium salt and 5-10 parts by weight of heterocyclic compound, wherein the alkynol is selected from butyn alcohol, hexynol, popargyl alcohol, 1,4-butyne glycol, dormison, methyl butynol, butyne glycol, and 4-trimethylsilyl isocyanate-3-butyn alcohol; the quaternary ammonium is selected from dimethyl benzyl ammonium chloride, rosin modified oleic acid group imidazoline quaternary ammonium salt, quaternary ammonium tribenzal-imidazoline, (4-vinyl)-quinoline benzyl quinoline chloride quaternary ammonium salt, (4-vinyl)-quinoline benzyl pyridine chloride quaternary ammonium salt, epoxypropane group quinoline chloride, epoxypropane group pyridine chloride, allyl quinoline chloride and allyl pyridine chloride; the heterocyclic compound is selected from bromination hexadecy pyridine, cetylpyridine chloride, chlorinated dodecyl pyridine and bromination myristyl lycine pyridine. The invention also relates to a preparation method of the low-temperature acidification corrosion inhibitor.
Description
Technical field
The present invention relates to a kind of acidification corrosion inhibitor and preparation method thereof, relate in particular to a kind of low temperature acidification corrosion inhibitor and preparation method thereof.
Background technology
Acidizing treatment has been one of yield-increasing technology indispensable in the oilfield process, because therefore acid solution need use inhibiter to the corrosion of uphole equipment, down-hole pipe string etc. in acid solution, reaches reduction or eliminates the corrosive purpose.At present the low temperature that uses on the oil field (greater than 60 ℃ less than 90 ℃) acidification corrosion inhibitor is generally nitrogenous compound, sulfocompound, acetylenic compound, aldehydes, ketone and lipophilic cpd, tensio-active agent etc.; There are many deficiencies in they, comprise with acid solution and various additive compatibleness relatively poorly, generate floss as some inhibiter in acid solution, even precipitation; Relatively poor to instrumentation tubes string corrosion mitigating effect, solid inadequately as the film that some inhibiter form on the instrumentation tubes string, a little less than the anti-scouring capability; Inhibiter production cost height surpasses 2% as the addition of some inhibiter, causes the expense of acid fluid system high.These deficiencies have limited these low temperature inhibiter mass-producings on the oil field and have used and promote.
Therefore, need a kind of compatibleness and corrosion mitigating effect and low low temperature acidification corrosion inhibitor of production cost with improvement.
Summary of the invention
Primary and foremost purpose of the present invention provides a kind of low temperature acidification corrosion inhibitor.
Another object of the present invention provides a kind of preparation method of low temperature acidification corrosion inhibitor.
Low temperature acidification corrosion inhibitor of the present invention is made up of the alkynol of 10-50 weight part, the quaternary amine of 10-50 weight part and the heterogeneous ring compound of 5-10 weight part, wherein alkynol is selected from butynol, l-hexyn-3-ol, propiolic alcohol, 1, and 4-butynediol, methylparafynol, methylbutynol, butynediol, 4-trimethylammonium first be silica-based-the 3-butynol; Quaternary amine is selected from dodecyl benzyl dimethyl ammonium chloride, benzyl dimethyl dodecyl bromination ammonium, Abietyl modified oleic acid base imidazoline quaternary ammonium salt, three phenyl ring imidazoline quaternary ammonium salts, (4-vinyl)-benzyl chloroquine quaternary ammonium salt, (4-vinyl)-benzyl chlorination pyridine quaternary ammonium salt, propylene oxide base chloroquine, propylene oxide base pyridinium chloride, allyl group chlorination quinoline, allyl group chlorination pyridine; Heterogeneous ring compound is selected from bromohexadecane yl pyridines, chloro-hexadecane yl pyridines, chlorinated dodecane yl pyridines, bromotetradecane yl pyridines.
Preferably, low temperature acidification corrosion inhibitor of the present invention is made up of the alkynol of 10-40 weight part, the quaternary amine of 20-50 weight part and the heterogeneous ring compound of 5-10 weight part, wherein alkynol is selected from propiolic alcohol, butynol, 1, and 4-butynediol, methylbutynol and 4-trimethylammonium first be silica-based-the 3-butynol; Quaternary ammonium salt is selected from benzyl dimethyl dodecyl bromination ammonium, dodecyl benzyl dimethyl ammonium chloride and Abietyl modified oleic acid base imidazoline quaternary ammonium salt; Heterogeneous ring compound is selected from bromohexadecane yl pyridines, chlorinated dodecane yl pyridines and bromotetradecane yl pyridines.
The method for preparing the low temperature acidification corrosion inhibitor of the present invention comprises the alkynol of described ratio, quaternary amine and heterogeneous ring compound mixed dissolution in organic alcoholic solution, promptly gets the low temperature acidification corrosion inhibitor.
Organic alcohol is selected from refined methanol, ethylene glycol, and propyl carbinol, hexalin etc., wherein preferred refined methanol, because its dissolving power is strong, cost is low, buys easily on market.
Low temperature acidification corrosion inhibitor of the present invention and most acidizing additive compatibleness are good, and the solvability in acid solution is fine, does not have phenomenons such as layering, flocculation, precipitation, therefore do not need to add other auxiliary chemical agents; This inhibiter is not only applicable to hydrochloric acid system, mud acid system, is applicable to the organic acid system yet, can satisfy conventional acidifying, pickling operation needs, has reduced the corrosion of acid solution to equipment, has improved the service efficiency of equipment.
Low temperature acidification corrosion inhibitor production technique of the present invention is simple, and production cost is low and do not have the three wastes to produce, and environmental pollution is little.
Low temperature acidification corrosion inhibitor of the present invention is applicable to the pickling operation of formation temperature at 60 ℃ to 90 ℃ oil gas, well acidizing operation and equipment.During use, according to the gross weight of acid solution, directly add the inhibiter of the present invention of 0.5%-1.0% in acid solution, stirring gets final product.
Low temperature acidification corrosion inhibitor of the present invention also has following advantages:
1) good chemical stability is arranged in acidic medium;
2) corrosion of metal speed can be reduced to very low, even stop fully the corrosion, can not produce spot corrosion;
3) inhibiter can not influence physics, the mechanical property of metal;
4) can bear the variation of execution conditions, as variation of acidic medium concentration, temperature, flow velocity etc.
Embodiment
Each material that adopts in following examples all is commercial.
Embodiment 1:
The refined methanol that in reactor, adds 300kg, the benzyl dimethyl dodecyl bromination ammonium that adds 500kg then, the propiolic alcohol of 120kg, the bromohexadecane yl pyridines of 80kg, stirred 30 minutes with 60 rev/mins speed, after stirring, form uniform reddish-brown liquid, promptly get the low temperature acidification corrosion inhibitor.
Corrosion mitigating effect is estimated:
The static corrosion testing experiment: 90 ℃, the N80 steel disc was tested 4 hours, and density of corrosion inhibitor is 1.0%, erosion rate result such as table 1 in different acid fluid system:
The test of table 1 inhibiter relatively
Erosion rate result 5 kinds of acid fluid system under identical addition and identical experiment condition finds out that inhibiter of the present invention is better than present normally used low temperature acidification corrosion inhibitor, and the test piece smooth surface, no point corrosion.
Embodiment 2:
The refined methanol that in reactor, adds 350kg, add then 280kg dodecyl benzyl dimethyl ammonium chloride, 300kg 1, the chlorinated dodecane yl pyridines of 4-butynediol and 70kg, stirred 30 minutes with 60 rev/mins speed, after stirring, form uniform reddish-brown liquid, promptly get the low temperature acidification corrosion inhibitor.
Test the static corrosion testing experiment with the acid fluid system of using in the actual acidizing treatment in oil field: 90 ℃, the N80 steel disc was tested 4 hours.
Test in table 2 acid fluid system
Find out that from the experimental result of table 2 under the situation of identical addition, the corrosion resistance of low temperature inhibiter of the present invention in acid solution is better than the normally used low temperature acidification corrosion inhibitor in present oil field.Furthermore, even increase the addition of the low temperature acidification corrosion inhibitor that uses at present, corrosion mitigating effect does not have inhibiter excellence of the present invention yet, and uses low temperature inhibiter of the present invention point corrosion can not take place.
Embodiment 3:
The refined methanol that in reactor, adds 400kg, the benzyl dimethyl dodecyl bromination ammonium that adds 400kg then, the methylbutynol of 100kg, the chlorinated dodecane yl pyridines of 100kg, stirred 30 minutes with 60 rev/mins speed, after stirring, form uniform reddish-brown liquid, promptly get the low temperature acidification corrosion inhibitor.
The test of table 3 inhibiter relatively
Erosion rate result 5 kinds of acid fluid system under identical addition and identical experiment condition finds out that inhibiter of the present invention is better than present normally used low temperature acidification corrosion inhibitor, and the test piece smooth surface, no point corrosion.
Embodiment 4:
The refined methanol that in reactor, adds 410kg, the benzyl dimethyl dodecyl bromination ammonium that adds 390kg then, the 4-trimethylammonium first of 110kg is silica-based-the 3-butynol, the bromotetradecane yl pyridines of 90kg, stirred 30 minutes with 60 rev/mins speed, after stirring, form uniform reddish-brown liquid, promptly get the low temperature acidification corrosion inhibitor.
The test of table 4 inhibiter relatively
Erosion rate result 5 kinds of acid fluid system under identical addition and identical experiment condition finds out that inhibiter of the present invention is better than present normally used low temperature acidification corrosion inhibitor, and the test piece smooth surface, no point corrosion.
Embodiment 5:
The refined methanol that in reactor, adds 390kg, the benzyl dimethyl dodecyl bromination ammonium that adds 390kg then, the butynol of 120kg, the bromotetradecane yl pyridines of 100kg, stirred 30 minutes with 60 rev/mins speed, after stirring, form uniform reddish-brown liquid, promptly get the low temperature acidification corrosion inhibitor.
The test of table 5 inhibiter relatively
Erosion rate result 5 kinds of acid fluid system under identical addition and identical experiment condition finds out that inhibiter of the present invention is better than present normally used low temperature acidification corrosion inhibitor, and the test piece smooth surface, no point corrosion.
On the other hand, the cost of low temperature inhibiter of the present invention is lower than the inhibiter that uses on the present oil field, and the consumption in acid fluid system is also lower.Therefore, inhibiter of the present invention takes advantage on cost.
Claims (4)
1. low temperature acidification corrosion inhibitor, the quaternary amine of its alkynol by the 10-50 weight part, 10-50 weight part and the heterogeneous ring compound of 5-10 weight part are formed, wherein alkynol is selected from butynol, l-hexyn-3-ol, propiolic alcohol, 1, and 4-butynediol, methylparafynol, methylbutynol, butynediol, 4-trimethylammonium first be silica-based-the 3-butynol; Quaternary amine is selected from dodecyl benzyl dimethyl ammonium chloride, benzyl dimethyl dodecyl bromination ammonium, Abietyl modified oleic acid base imidazoline quaternary ammonium salt, three phenyl ring imidazoline quaternary ammonium salts, (4-vinyl)-benzyl chloroquine quaternary ammonium salt, (4-vinyl)-benzyl chlorination pyridine quaternary ammonium salt, propylene oxide base chloroquine, propylene oxide base pyridinium chloride, allyl group chlorination quinoline, allyl group chlorination pyridine; Heterogeneous ring compound is selected from bromohexadecane yl pyridines, chloro-hexadecane yl pyridines, chlorinated dodecane yl pyridines, bromotetradecane yl pyridines.
2. low temperature acidification corrosion inhibitor as claimed in claim 1, the quaternary amine of its alkynol by the 10-40 weight part, 20-50 weight part and the heterogeneous ring compound of 5-10 weight part are formed, wherein alkynol is selected from propiolic alcohol, butynol, 1, and 4-butynediol, methylbutynol and 4-trimethylammonium first be silica-based-the 3-butynol; Quaternary ammonium salt is selected from benzyl dimethyl dodecyl bromination ammonium, dodecyl benzyl dimethyl ammonium chloride and Abietyl modified oleic acid base imidazoline quaternary ammonium salt; Heterogeneous ring compound is selected from bromohexadecane yl pyridines, chlorinated dodecane yl pyridines and bromotetradecane yl pyridines.
3. method for preparing low temperature acidification corrosion inhibitor as claimed in claim 1, it comprises the alkynol of described ratio, quaternary amine and heterogeneous ring compound mixed dissolution in organic alcoholic solution, promptly gets the low temperature acidification corrosion inhibitor.
4. method as claimed in claim 3, wherein said organic alcohol is selected from refined methanol, ethylene glycol, propyl carbinol and hexalin.
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Cited By (18)
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|---|---|---|---|---|
| CN102676140A (en) * | 2012-04-26 | 2012-09-19 | 南京华洲新材料有限公司 | Nitrogenous heterocyclic quaternary ammonium salt acidizing corrosion inhibitor and preparation method thereof |
| CN102942908A (en) * | 2012-11-22 | 2013-02-27 | 中国海洋石油总公司 | Water injected pitting-corrosion composite inhibitor and application thereof |
| CN103014715A (en) * | 2012-08-09 | 2013-04-03 | 江苏科技大学 | Corrosion inhibitor composition for preventing hydrogen sulfide corrosion |
| CN103614129A (en) * | 2013-12-13 | 2014-03-05 | 成都华阳兴华化工有限公司 | Corrosion inhibition foam water discharging agent for oil-gas well and preparation method of corrosion inhibition foam water discharging agent |
| CN104212427A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Method for preventing corrosion of sand control pump tail pipe used for sand production well |
| CN104370809A (en) * | 2014-10-27 | 2015-02-25 | 四川理工学院 | Corrosion inhibitor and method for implementing corrosion inhibition |
| CN104651848A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Acidizing high-temperature corrosion inhibitor and preparation method thereof |
| CN104928682A (en) * | 2015-06-16 | 2015-09-23 | 河南省科学院能源研究所有限公司 | Corrosion inhibitor used for metal zinc in acid environment and preparing method thereof |
| CN104926730A (en) * | 2014-03-21 | 2015-09-23 | 中国科学院武汉岩土力学研究所 | Rosinyl imidazoline compound and synthesis method and application thereof |
| CN105239076A (en) * | 2015-10-10 | 2016-01-13 | 中国海洋石油总公司 | Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof |
| CN104031626B (en) * | 2014-06-25 | 2017-05-17 | 西安石油大学 | Water injection corrosion inhibitor for sewage corrosion control of oilfield production water injection system |
| CN106884170A (en) * | 2017-02-17 | 2017-06-23 | 西安超新科技发展有限公司 | A kind of acidification corrosion inhibitor and preparation method thereof |
| CN108977813A (en) * | 2018-09-05 | 2018-12-11 | 河南省化工研究所有限责任公司 | A kind of zinc inhibitor and the preparation method and application thereof in hydrochloric acid medium |
| CN109265402A (en) * | 2018-09-21 | 2019-01-25 | 中国石油天然气集团有限公司 | A kind of Organic Acid System Mannich bases acidification corrosion inhibitor and preparation method thereof |
| CN111441054A (en) * | 2020-04-14 | 2020-07-24 | 丁双龙 | High-acid high-salt corrosion inhibitor suitable for low-temperature part of oil refining device |
| CN113046046A (en) * | 2021-03-29 | 2021-06-29 | 中海油常州涂料化工研究院有限公司 | Corrosion inhibitor suitable for hydrochloric acid system with mass fraction of 20-28% and preparation method thereof |
| CN114763614A (en) * | 2021-01-13 | 2022-07-19 | 中国石油天然气股份有限公司 | Corrosion inhibitor suitable for acidification at 200 ℃, preparation method and application |
| CN114990554A (en) * | 2021-07-31 | 2022-09-02 | 武汉三友石化有限公司 | Neutralization corrosion inhibitor and preparation method and application thereof |
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| CN101613622A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of composite inhibiter and its production and use |
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| CN102676140A (en) * | 2012-04-26 | 2012-09-19 | 南京华洲新材料有限公司 | Nitrogenous heterocyclic quaternary ammonium salt acidizing corrosion inhibitor and preparation method thereof |
| CN103014715A (en) * | 2012-08-09 | 2013-04-03 | 江苏科技大学 | Corrosion inhibitor composition for preventing hydrogen sulfide corrosion |
| CN103014715B (en) * | 2012-08-09 | 2014-09-10 | 江苏科技大学 | Corrosion inhibitor composition for preventing hydrogen sulfide corrosion |
| CN102942908A (en) * | 2012-11-22 | 2013-02-27 | 中国海洋石油总公司 | Water injected pitting-corrosion composite inhibitor and application thereof |
| CN102942908B (en) * | 2012-11-22 | 2014-08-13 | 中国海洋石油总公司 | Water injected pitting-corrosion composite inhibitor and application thereof |
| CN104212427B (en) * | 2013-06-05 | 2016-12-28 | 中国石油天然气股份有限公司 | Method for preventing corrosion of sand control pump tail pipe used for sand production well |
| CN104212427A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Method for preventing corrosion of sand control pump tail pipe used for sand production well |
| CN104651848A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Acidizing high-temperature corrosion inhibitor and preparation method thereof |
| CN103614129A (en) * | 2013-12-13 | 2014-03-05 | 成都华阳兴华化工有限公司 | Corrosion inhibition foam water discharging agent for oil-gas well and preparation method of corrosion inhibition foam water discharging agent |
| CN103614129B (en) * | 2013-12-13 | 2015-09-23 | 成都华阳兴华化工有限公司 | Oil/gas Well inhibition foaming water discharge agent and preparation method thereof |
| CN104926730A (en) * | 2014-03-21 | 2015-09-23 | 中国科学院武汉岩土力学研究所 | Rosinyl imidazoline compound and synthesis method and application thereof |
| CN104031626B (en) * | 2014-06-25 | 2017-05-17 | 西安石油大学 | Water injection corrosion inhibitor for sewage corrosion control of oilfield production water injection system |
| CN104370809A (en) * | 2014-10-27 | 2015-02-25 | 四川理工学院 | Corrosion inhibitor and method for implementing corrosion inhibition |
| CN104928682A (en) * | 2015-06-16 | 2015-09-23 | 河南省科学院能源研究所有限公司 | Corrosion inhibitor used for metal zinc in acid environment and preparing method thereof |
| CN105239076A (en) * | 2015-10-10 | 2016-01-13 | 中国海洋石油总公司 | Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof |
| CN106884170A (en) * | 2017-02-17 | 2017-06-23 | 西安超新科技发展有限公司 | A kind of acidification corrosion inhibitor and preparation method thereof |
| CN106884170B (en) * | 2017-02-17 | 2019-10-18 | 西安超新科技发展有限公司 | A kind of acidification corrosion inhibitor and preparation method thereof |
| CN108977813A (en) * | 2018-09-05 | 2018-12-11 | 河南省化工研究所有限责任公司 | A kind of zinc inhibitor and the preparation method and application thereof in hydrochloric acid medium |
| CN109265402A (en) * | 2018-09-21 | 2019-01-25 | 中国石油天然气集团有限公司 | A kind of Organic Acid System Mannich bases acidification corrosion inhibitor and preparation method thereof |
| CN111441054A (en) * | 2020-04-14 | 2020-07-24 | 丁双龙 | High-acid high-salt corrosion inhibitor suitable for low-temperature part of oil refining device |
| CN114763614A (en) * | 2021-01-13 | 2022-07-19 | 中国石油天然气股份有限公司 | Corrosion inhibitor suitable for acidification at 200 ℃, preparation method and application |
| CN113046046A (en) * | 2021-03-29 | 2021-06-29 | 中海油常州涂料化工研究院有限公司 | Corrosion inhibitor suitable for hydrochloric acid system with mass fraction of 20-28% and preparation method thereof |
| CN114990554A (en) * | 2021-07-31 | 2022-09-02 | 武汉三友石化有限公司 | Neutralization corrosion inhibitor and preparation method and application thereof |
| CN114990554B (en) * | 2021-07-31 | 2023-11-14 | 武汉三友石化有限公司 | Neutralizing corrosion inhibitor and preparation method and application thereof |
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Application publication date: 20110427 |