CN104745175A - Propynylamine high-temperature acidizing corrosion inhibitor and preparation method thereof - Google Patents
Propynylamine high-temperature acidizing corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN104745175A CN104745175A CN201510099967.4A CN201510099967A CN104745175A CN 104745175 A CN104745175 A CN 104745175A CN 201510099967 A CN201510099967 A CN 201510099967A CN 104745175 A CN104745175 A CN 104745175A
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- corrosion inhibitor
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- acidification corrosion
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Abstract
The invention discloses a propynylamine high-temperature acidizing corrosion inhibitor and a preparation method thereof. The propynylamine high-temperature acidizing corrosion inhibitor is prepared by the following steps: by taking propargyl alcohol, organic amine and aldehyde as raw materials and a cuprous salt as a catalyst, carrying out mannich reaction within a relatively short time under promotion of ultrasonic waves to synthesize propynylamine compounds; and compounding the propynylamine compounds with potassium iodide and a surfactant. The corrosion inhibitor is a yellow or brown emulsion and is stable and uniform, can be well dispersed in an acidic liquid and can give play to a good corrosion inhibiting effect under the condition of a high temperature from 100-140 DEG C, so that the propynylamine high-temperature acidizing corrosion inhibitor is effectively prevented being corroded in the acidizing process. In addition, the corrosion inhibitor disclosed by the invention is prepared by using an ultrasonic wave synthetic method and has the characteristics of being low in synthetic temperature, short in time, high in reaction yield and the like.
Description
Technical field
The invention belongs to oilfield stimulation renovation technique field, particularly a kind of propargylamine type high temp acidification corrosion inhibitor and preparation method thereof.
Background technology
Oil well acidation is a kind of important measures improving oil-field development economic benefit, namely by press device, acid solution is injected stratum, utilize acid solution to the corrosion of rock, the infiltration lane of reservoir rock is expanded, and the tamper dissolved in seepage channel or manufacture of intraocular crack, thus make gas channel unimpeded.But the process that acid solution injects stratum can make surface duct and pit shaft tube wall produce serious corrosion, therefore must add inhibiter in acid solution.Along with the development of drilling technology and entering of oil recovery technique, a large amount of High Temperature High Pressure hydrocarbon-bearing pool drops into exploitation, proposes high requirement to the temperature resistance of acidifying inhibiter.
The high-temperature corrosion inhibitor of widespread use contains the inorganic components such as chromic salt, molybdate, and this constituents much can poison the catalyzer during refinery of downstream, can produce bring inconvenience to downstream.In recent years, various novel organic molecule is constantly developed, and at present, remains the main flow of inhibiter, present excellent corrosion inhibition containing heteroatomic organic molecules such as nitrogen, oxygen, phosphorus, sulphur.
Therefore research and develop and anti-ly a kind ofly can overcome conventional high-temperature acidification corrosion inhibitor and use the acidification corrosion inhibitor that the inorganic salt such as molybdate, chromic salt poison the high temperature resistance of the shortcoming of downstream refinery catalyzer to have important practical significance.
Summary of the invention
The object of the present invention is to provide and a kind ofly can play good corrosion inhibition under the high temperature conditions, effectively can avoid the propargylamine type high temp acidification corrosion inhibitor of the corrosion in acidization.
Present invention also offers a kind of ultrasound synthesis preparation method for the preparation of this propargylamine type high temp acidification corrosion inhibitor adopting low temperature, generated time short.
To achieve these goals, propargylamine type high temp acidification corrosion inhibitor of the present invention with propargyl alcohol, organic amine, aldehyde for raw material, with cuprous salt (cuprous salt) for catalyzer, under ultrasonic wave promotes, there is Mannich reaction in the short period of time synthesized a class propargylamine compounds, and be prepared from potassiumiodide, surfactant compound.
This propargylamine type high temp acidification corrosion inhibitor, is prepared from by the raw material of following massfraction:
Preferably, described alkynol is 2-methyl-3-butyne-2-alcohol or 2-propine-1-alcohol.
Preferably, described aldehyde is acetaldehyde, propionic aldehyde or furfural.Described aldehyde is liquid under being preferably normal temperature and has the aldehyde of good phased soln in aqueous.
Described organic amine is monoamine or diamine.Preferably, described organic amine is n-Butyl Amine 99, quadrol or Putriscine.
Preferably, described cuprous salt is cuprous iodide, cuprous bromide or cuprous chloride.Described cuprous salt in the synthesis of propargylamine compounds as catalyzer.
Preferably, described tensio-active agent is cetyl chloride ammonium, octadecyl ammonium chloride or alkylpolyoxyethylene.Adding of tensio-active agent, while increasing the solubleness of organic phase, also possesses certain corrosion inhibition.
In this inhibiter, described potassiumiodide, as inhibition synergistic agent, can improve the corrosion mitigating effect of this inhibiter greatly.
Wherein, the propargylamine compounds in this inhibiter adopts mannich condensation reaction synthesis obtained.This compounds possesses the functional group of alkynol and aminated compounds simultaneously, therefore jointly can play the corrosion inhibition of amine and alkynol compound.Nitrogen Sauerstoffatom in molecule can be adsorbed on metallic surface formation layer protecting film because it has electronegativity.And alkynol class formation aggregate packet occurs can form conjugated diolefine in acid after overlays on metallic surface and forms fine and close " oligomer film ", thus greatly slow down corrosion of metal.Meanwhile, have neither part nor lot in the aldehyde of reaction, amine and alkynol compound in this system and all there is corrosion inhibitive function, reaction can be added as compound.
Following propargylamine compounds composition principle makes an explanation for 2-methyl-3-butyne-2-alcohol.
(1) when described organic amine is monoamine, its reaction equation is as follows:
(2) when described organic amine is diamine, its reaction equation is as follows:
A kind of preparation method of propargylamine type high temp acidification corrosion inhibitor as claimed in claim 1, propiolic alcohol compound, organic amine, aldehyde, cuprous salt, tensio-active agent and potassiumiodide are added in reactor, be dissolved in water, reactor is put into ultrasonic cleaning machine at 25 DEG C, namely reaction 1 ~ 1.5h obtains propargylamine type high temp acidification corrosion inhibitor, and described ultrasonic cleaning machine operating power is 60W.
Wherein, tensio-active agent and potassiumiodide can add after prepared by propargylamine compounds again, also can add simultaneously.Meanwhile, add and can not produce side reaction and impact to other monomer synthesize propargylamine compounds.
This propargylamine type high temp acidification corrosion inhibitor is yellow or brown milk sap, and stable uniform, can be dispersed in acid solution well, occurs without precipitation and demixing phenomenon.
The ultrasonic synthetic method preparation method that the present invention adopts is simple, the reaction times is short, temperature of reaction is low, and the synthesis solving conventional other inhibiter (as imidazolines, Mannich bases etc.) all needs the shortcoming of pyroreaction and long period.
Compared with prior art, this propargylamine type high temp acidification corrosion inhibitor:
1) be homogeneous, steady state, can be dispersed in acid solution well during use, occur without precipitation and demixing phenomenon;
2) 100 ~ 140 DEG C time, there is good corrosion mitigating effect, can effectively reduce acid liquid corrosion tubing string and equipment, reach one-level or secondary standard according to industry standard SY/T 5405-1996SY/T " acidifying inhibiter method for testing performance and evaluation index " corrosion mitigating effect, meet job requirements;
3) avoid the use of the composition that the high-temperature corrosion inhibitor such as chromic salt, molybdate is commonly used, provide a kind of inhibiter preparation method of high-efficiency low-toxicity.Water react under adopting ultrasonic wave to promote in preparation process, the reaction times is short, and at room temperature can carry out, and production cost is reduced greatly; Meanwhile, in production process, avoid the use of organic solvent, decrease the pollution to environment.
Embodiment
Below in conjunction with embodiment, foregoing invention content of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should comprise within the scope of the invention.
In an embodiment, preparing the ultrasonic cleaning machine described in each propargylamine type high temp acidification corrosion inhibitor process is the AS5150A type ultrasonic cleaning machine that Tianjin Ao Tesaiensi Instrument Ltd. produces, and operating power is 60W.
Embodiment 1
8.4g 2-methyl-3-butyne-2-alcohol, 7g n-Butyl Amine 99,5.8g propionic aldehyde, 0.5g cuprous bromide, 5g potassiumiodide, 10g octadecyl ammonium chloride are added reactor and be dissolved in 80g water, in ultrasonic cleaner at 25 DEG C, reaction 1h, obtains propargylamine type high temp acidification corrosion inhibitor A.
Embodiment 2
8.4g 2-methyl-3-butyne-2-alcohol, 3g quadrol, 11g 40% acetaldehyde solution, 0.5g cuprous bromide, 5g potassiumiodide, 10g Steareth are added reactor and be dissolved in 80g water, in ultrasonic cleaner at 25 DEG C, reaction 1h, obtains propargylamine type high temp acidification corrosion inhibitor B.
Embodiment 3
8.4g 2-methyl-3-butyne-2-alcohol, 3g quadrol, 5.8.g propionic aldehyde, 1g cuprous bromide, 5g potassiumiodide, 10g cetyl chloride ammonium are added reactor and be dissolved in 80g water, in ultrasonic cleaner at 25 DEG C, reaction 1.5h, obtains propargylamine type high temp acidification corrosion inhibitor C.
Embodiment 4
By 5.6g 2-propine-1-alcohol, 4.4g 1,4-butanediamine, 11g 40% acetaldehyde solution, 1g cuprous iodide, 5g potassiumiodide, 10g Steareth add reactor and are dissolved in 80g water, in ultrasonic cleaner at 25 DEG C, reaction 1.5h, obtains propargylamine type high temp acidification corrosion inhibitor D.
Propargylamine type high temp acidification corrosion inhibitor prepared by embodiment 1 ~ 4 is yellow or brown milk sap, and stable uniform, can be dispersed in acid solution well, occur without precipitation and demixing phenomenon.
Embodiment 5
Erosion rate experiment is carried out to the propargylamine type high temp acidification corrosion inhibitor prepared by embodiment 1 ~ 4.
Dynamic experiment is carried out according to industry standard SY/T 5405-1996SY/T " acidifying inhibiter method for testing performance and evaluation index ".Steel disc is used abrasive paper for metallograph sanding and polishing, deoil with distilled water, dehydrated alcohol, acetone degreasing successively, blot with filter paper and put dry 2h in an oven.By its quality of analytical balance precise.Steel disc is hung vertically in High Temperature High Pressure Dynamic Corrosion determinator, immerses test medium.After experiment, lacing film is taken out, then clean deoil with distilled water, dehydrated alcohol, acetone, weigh after dry 2h.Evaluation experimental condition is:
Working temperature is 100 ~ 140 DEG C, and operating pressure is 16MPa.Rotating speed 200r/min.The corrosive medium adopted is the hydrochloric acid of 15%, and inhibiter consumption is 1 ~ 3%, measures the erosion rate of above-mentioned four kinds of formula inhibiter.
The calculating of erosion rate:
Wherein, V
i---monolithic erosion rate, g/ (m
2h);
Δ m
i---the corrosion quality of test piece, g;
A
i---strip amasss, mm
2;
Δ t---the reaction times, h.
The corrosion inhibition experimental result of the inhibiter prepared by embodiment 1 ~ 4 four kind formula is as shown in the table:
Claims (9)
1. a propargylamine type high temp acidification corrosion inhibitor, is characterized in that, is prepared from by the raw material of following massfraction:
2. propargylamine type high temp acidification corrosion inhibitor according to claim 1, is characterized in that, described alkynol is 2-methyl-3-butyne-2-alcohol or 2-propine-1-alcohol.
3. propargylamine type high temp acidification corrosion inhibitor according to claim 2, is characterized in that, described organic amine is monoamine or diamine.
4. propargylamine type high temp acidification corrosion inhibitor according to claim 3, is characterized in that, described organic amine is n-Butyl Amine 99, quadrol or Putriscine.
5. the propargylamine type high temp acidification corrosion inhibitor according to any one of Claims 1 to 4 claim, is characterized in that, described aldehyde is acetaldehyde, propionic aldehyde or furfural.
6. the propargylamine type high temp acidification corrosion inhibitor according to any one of Claims 1 to 4 claim, is characterized in that, described cuprous salt is cuprous iodide, cuprous bromide or cuprous chloride.
7. the propargylamine type high temp acidification corrosion inhibitor according to any one of Claims 1 to 4 claim, is characterized in that, described tensio-active agent is cetyl chloride ammonium, octadecyl ammonium chloride or alkylpolyoxyethylene.
8. the preparation method of a propargylamine type high temp acidification corrosion inhibitor as claimed in claim 1, it is characterized in that, propiolic alcohol compound, organic amine, aldehyde, cuprous salt, tensio-active agent and potassiumiodide is comprised the steps: to add in reactor, be dissolved in water, reactor is put into ultrasonic cleaning machine at 20 ~ 25 DEG C, reaction 1 ~ 1.5h, namely obtains propargylamine type high temp acidification corrosion inhibitor.
9. propargylamine type high temp acidification corrosion inhibitor according to claim 8, is characterized in that, described ultrasonic cleaning machine operating power is 60W.
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Cited By (6)
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| CN105152991A (en) * | 2015-09-08 | 2015-12-16 | 中国石油化工股份有限公司 | Amine derivative corrosion inhibitor and application thereof |
| CN107385447A (en) * | 2017-06-19 | 2017-11-24 | 上海电力学院 | A kind of water process copper compound corrosion inhibitor |
| CN107502333A (en) * | 2017-08-29 | 2017-12-22 | 中国石油集团渤海钻探工程有限公司 | A kind of quinoline and the compound acidification corrosion inhibitor of new Mannich base |
| CN109023381A (en) * | 2018-10-25 | 2018-12-18 | 中国石油大学(华东) | Neutralize corrosion inhibiter and its preparation method and application |
| CN109294549A (en) * | 2018-08-30 | 2019-02-01 | 赵晴晴 | A kind of high temperature oil field acidification corrosion inhibitor and preparation method |
| CN114907830A (en) * | 2021-02-07 | 2022-08-16 | 中国石油天然气股份有限公司 | Chloride stress corrosion cracking inhibitor for 13Cr stainless steel, preparation and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152991A (en) * | 2015-09-08 | 2015-12-16 | 中国石油化工股份有限公司 | Amine derivative corrosion inhibitor and application thereof |
| CN105152991B (en) * | 2015-09-08 | 2017-12-29 | 中国石油化工股份有限公司 | A kind of amine derivant corrosion inhibiter and its application |
| CN107385447A (en) * | 2017-06-19 | 2017-11-24 | 上海电力学院 | A kind of water process copper compound corrosion inhibitor |
| CN107502333A (en) * | 2017-08-29 | 2017-12-22 | 中国石油集团渤海钻探工程有限公司 | A kind of quinoline and the compound acidification corrosion inhibitor of new Mannich base |
| CN107502333B (en) * | 2017-08-29 | 2019-10-22 | 中国石油集团渤海钻探工程有限公司 | A kind of quinoline and the compound acidification corrosion inhibitor of novel Mannich base |
| CN109294549A (en) * | 2018-08-30 | 2019-02-01 | 赵晴晴 | A kind of high temperature oil field acidification corrosion inhibitor and preparation method |
| CN109023381A (en) * | 2018-10-25 | 2018-12-18 | 中国石油大学(华东) | Neutralize corrosion inhibiter and its preparation method and application |
| CN109023381B (en) * | 2018-10-25 | 2020-05-19 | 中国石油大学(华东) | Neutralization corrosion inhibitor and preparation method and application thereof |
| CN114907830A (en) * | 2021-02-07 | 2022-08-16 | 中国石油天然气股份有限公司 | Chloride stress corrosion cracking inhibitor for 13Cr stainless steel, preparation and application thereof |
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Application publication date: 20150701 |