CN103409129B - A kind of organic amine drilling well acidification corrosion inhibitor and preparation method thereof - Google Patents
A kind of organic amine drilling well acidification corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN103409129B CN103409129B CN201310347679.7A CN201310347679A CN103409129B CN 103409129 B CN103409129 B CN 103409129B CN 201310347679 A CN201310347679 A CN 201310347679A CN 103409129 B CN103409129 B CN 103409129B
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- organic amine
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- acidification corrosion
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Abstract
The invention provides a kind of organic amine drilling well acidification corrosion inhibitor and preparation method thereof.Described organic amine drilling well acidification corrosion inhibitor, it is characterized in that, be made up of the following raw material with weight percent: acetone 15-25%, aniline 11-22%, formaldehyde 10-20%, Sodium orthomolybdate 3-5%, ethanol 10-15%, hydrochloric acid soln 15-25% and propiolic alcohol 5-10%.Inhibiter of the present invention is with low cost, and maximum operation (service) temperature can reach 195 DEG C, and corrosion inhibition is under the high temperature conditions comparatively excellent, can reach the top grade product that China Petrochemical Industry requires.
Description
Technical field
The present invention relates to a kind of organic amine drilling well acidifying inhibiter and preparation method thereof, be applied to oil field, gas drilled hole liquid acidifying inhibition, belong to oil field chemical new product development field.
Background technology
Drilling well acidification corrosion inhibitor on market is of a great variety, and effect is different, and middle low-temperature performance is better, but going deep into along with exploitation of oil-gas field, and increasing hot hole appears in face of us, and than if any deep-wells more than a lot of 5000m, and downhole temperature is up to 150 DEG C.Simultaneously along with the construction of offshore oilfield, also there is the hot hole of many 180 DEG C.Limited efficiency is played for this kind of inhibiter of this kind of high temperature deep well, for the acidizing corrosion problem of hot hole, the present invention utilizes conventional formaldehyde, acetone, aniline has synthesized a kind of organic amine, composite with alcohols and metal-salt, be applied in the acidifying inhibition of drilling fluid, high temperature resistantly reach 195 DEG C, substantially can meet, the acidifying medication of most Oil/gas Wells of home and overseas, this inhibiter with aldehyde amine ketone condensate for major ingredient, it is good that medicament has solubility in acid, low to drill core permeability rate infringement, product viscosity is low, nonirritant stink, the advantages such as onsite application is convenient.Can be used for the acidification of high-temperature high concentration hydrochloric acid and mud acid.This inhibiter is mainly used in anticorrosion and other acidizing treatments of oil well casing in oil field, acidification of oil gas well fracturing process. and be suitable for hydrochloric acid or the mud acid of 15% ~ 28%, use temperature is not higher than with 195 DEG C.
Summary of the invention
The technical problem to be solved in the present invention is to provide one corrosion inhibition good drilling well acidifying inhibiter and preparation method thereof under higher temperature conditions.
In order to solve the problems of the technologies described above, technical scheme of the present invention there is provided a kind of organic amine drilling well acidification corrosion inhibitor, it is characterized in that, is made up of the following raw material with weight percent:
Acetone 15-25%;
Aniline 11-22%;
Formaldehyde 10-20%;
Sodium orthomolybdate 3-8%;
Ethanol 10-35%;
Weight concentration is the hydrochloric acid soln 15-25% of 20 ~ 30%;
Propiolic alcohol 5-10%.
Present invention also offers the preparation method of above-mentioned organic amine drilling well acidification corrosion inhibitor, it is characterized in that, concrete steps are: take each raw material by weight percentage; Be the hydrochloric acid soln suction glassed steel reaction vessels of 20 ~ 30% by ethanol and weight concentration, drip aniline, in dropping process, temperature controls at 20 ~ 40 DEG C; Divide six to ten times by acetone suction glassed steel reaction vessels, drip formaldehyde, in dropping process, temperature controls at 80 ~ 100 DEG C; Cool to 60 ~ 70 DEG C, be incubated two hours; Add propiolic alcohol and Sodium orthomolybdate, stir, discharging, obtains reddish-brown liquid product, is organic amine drilling well acidification corrosion inhibitor.
First preparation method of the present invention is the condenses of synthesis keto-aldehyde amine, in addition Sodium orthomolybdate and propiolic alcohol is composite mixes.
Compared with prior art, the invention has the beneficial effects as follows:
1, inhibiter of the present invention is with low cost, and maximum operation (service) temperature can reach 195 DEG C, and corrosion inhibition is under the high temperature conditions comparatively excellent, can reach the top grade product that China Petrochemical Industry requires.
2, the ordorless smell of inhibiter of the present invention, it is softer to add acidizing fluid color.
Embodiment
For making the present invention become apparent, hereby with preferred embodiment, be described in detail below.Described acetone is commercially available technical grade light yellow oil liquid acetone (> 99%), and East China branch office of China Petrochemical Industry produces; Described aniline is commercially available technical grade aniline, water white transparency, there is not oxidative phenomena and add nitrogen as protection gas, aniline content > 98%, Dongying Han Zun new energy materials company limited produce; Described formaldehyde is commercially available technical grade formaldehyde, formaldehyde content > 35.5%, and Zaozhuang Mei Chen Chemical Co., Ltd. produces; Described Sodium orthomolybdate is technical grade Sodium orthomolybdate, Sodium orthomolybdate content > 98%, and Shanghai traditional Chinese medicines are produced; Described propiolic alcohol is commercially available technical grade propiolic alcohol, propiolic alcohol content > 99%, the blue Xiang Chemical Manufacture in Taizhou; Described hydrochloric acid is technical grade synthetic hydrochloric acid, iron ion < 2ppm, and described ethanol is technical grade dehydrated alcohol, content > 99%, and ethanol, hydrochloric acid are all purchased in Chemical market.
Embodiment 1
A kind of organic amine drilling well acidification corrosion inhibitor, is made up of the following raw material with weight percent: acetone 15%; Aniline 11%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 26%; Weight concentration is hydrochloric acid soln 25% and the propiolic alcohol 10% of 30%.
Its preparation method is: take each raw material by weight percentage; It is the hydrochloric acid soln 25wt% suction glassed steel reaction vessels of 30% by ethanol 26wt%, weight concentration, instill aniline 11wt% slowly, in dropping process, temperature controls at 20 ~ 30 DEG C, divide six times by acetone 15wt% suction glassed steel reaction vessels, slow dropping formaldehyde 10wt%, in dropping process, temperature controls at 90 ~ 100 DEG C, drip to finish and cool to 60 ~ 70 DEG C, be incubated two hours, add propiolic alcohol 10wt%, stir one hour, then Sodium orthomolybdate 3wt% is added, stir two hours blowings, obtain reddish-brown liquid product, wherein organic amide monomer
sodium orthomolybdate 3wt%, propiolic alcohol 10wt% effective ingredient are greater than 50%, are organic amine drilling well acidification corrosion inhibitor.
Embodiment 2:
A kind of organic amine drilling well acidification corrosion inhibitor, is made up of the following raw material with weight percent: acetone 25%; Aniline 12%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 25%; Weight concentration is hydrochloric acid soln 15% and the propiolic alcohol 10% of 30%.
Its preparation method is: take each raw material by weight percentage, by ethanol 25wt%, weight concentration is the hydrochloric acid soln 15wt% suction glassed steel reaction vessels of 30%, instill aniline 12wt% slowly, in dropping process, temperature controls at 20 ~ 30 DEG C, divide six times by acetone 25wt% suction glassed steel reaction vessels, slow dropping formaldehyde 10wt%, in dropping process, temperature controls at 90 ~ 100 DEG C, drip to finish and cool to 60 ~ 70 DEG C, be incubated two hours, add propiolic alcohol 10wt%, stir one hour, then Sodium orthomolybdate 3wt% is added, stir two hours blowings, obtain reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, wherein organic amide monomer
sodium orthomolybdate 3wt%, propiolic alcohol 10wt% effective ingredient are greater than 50%, are organic amine drilling well acidification corrosion inhibitor.
Embodiment 3:
A kind of organic amine drilling well acidification corrosion inhibitor, is made up of the following raw material with weight percent: acetone 24%; Aniline 18%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 15%; Weight concentration is hydrochloric acid soln 15% and the propiolic alcohol 15% of 30%.
Its preparation method is: take each raw material by weight percentage, by ethanol 15wt%, weight concentration is the hydrochloric acid soln 15wt% suction glassed steel reaction vessels of 30%, instill aniline 18wt% slowly, in dropping process, temperature controls at 20 ~ 30 DEG C, divide six times by acetone 24wt% suction glassed steel reaction vessels, slow dropping formaldehyde 10wt%, in dropping process, temperature controls at 90 ~ 100 DEG C, drip to finish and cool to 60 ~ 70 DEG C, be incubated two hours, add propiolic alcohol 15wt%, stir one hour, then Sodium orthomolybdate 3wt% is added, stir two hours blowings, obtain reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, wherein organic amide monomer
sodium orthomolybdate 3wt%, propiolic alcohol 15wt%, effective ingredient is greater than 50%, is organic amine drilling well acidification corrosion inhibitor.
Embodiment 4:
A kind of organic amine drilling well acidification corrosion inhibitor, is made up of the following raw material with weight percent: acetone 17%; Aniline 20%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 15%; Weight concentration is hydrochloric acid soln 20% and the propiolic alcohol 15% of 30%.
Its preparation method is: take each raw material by weight percentage, by ethanol 15wt%, weight concentration is the hydrochloric acid soln 20wt% suction glassed steel reaction vessels of 30%, instill aniline 20wt% slowly, in dropping process, temperature controls at 20 ~ 30 DEG C, divide six times by acetone 17wt% suction glassed steel reaction vessels, slow dropping formaldehyde 10wt%, in dropping process, temperature controls at 90 ~ 100 DEG C, drip to finish and cool to 60 ~ 70 DEG C, be incubated two hours, add propiolic alcohol 15wt%, stir one hour, then Sodium orthomolybdate 3wt% is added, stir two hours blowings, obtain reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, wherein organic amide monomer
sodium orthomolybdate 3wt%, propiolic alcohol 15wt% effective ingredient are greater than 50%, are organic amine drilling well acidification corrosion inhibitor.
Embodiment 5:
A kind of organic amine drilling well acidification corrosion inhibitor, is made up of the following raw material with weight percent: acetone 15%; Aniline 22%; Formaldehyde 15%; Sodium orthomolybdate 5%; Ethanol 15%; Weight concentration is hydrochloric acid soln 15% and the propiolic alcohol 13% of 30%.
Its preparation method is: take each raw material by weight percentage, by ethanol 15wt%, weight concentration is the hydrochloric acid soln 15wt% suction glassed steel reaction vessels of 30%, instill aniline 22wt% slowly, in dropping process, temperature controls at 20 ~ 30 DEG C, divide six times by acetone 15wt% suction glassed steel reaction vessels, slow dropping formaldehyde 15wt%, in dropping process, temperature controls at 90 ~ 100 DEG C, drip to finish and cool to 60 ~ 70 DEG C, be incubated two hours, add propiolic alcohol 13wt%, stir one hour, then Sodium orthomolybdate 5wt% is added, stir two hours blowings, obtain reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, wherein organic amide monomer
sodium orthomolybdate 5wt%, propiolic alcohol 13wt% effective ingredient are greater than 50%, are organic amine drilling well acidification corrosion inhibitor.
Product in embodiment 1-5 is carried out corrosion inhibition experiment (this experiment adopt be PetroChina Company Limited. Gas Industry standard SY/T5405-1996), corrosion inhibition experimental result is as follows:
High Temperature High Pressure Dynamic Corrosion rating results (medium is 20% hydrochloric acid):
High Temperature High Pressure Dynamic Corrosion rating results (medium is mud acid composition is HCl: HF=12: 3):
From above experimental result, organic amine drilling well acidification corrosion inhibitor of the present invention corrosion inhibition is under the high temperature conditions comparatively excellent, can reach the top grade product that China Petrochemical Industry requires.
Claims (1)
1. an organic amine drilling well acidification corrosion inhibitor, is characterized in that, is made up of the following raw material with weight percent:
Acetone 15-25%;
Aniline 11-22%;
Formaldehyde 10-20%;
Sodium orthomolybdate 3-5%;
Ethanol 10-15%;
Weight concentration is the hydrochloric acid soln 15-25% of 20 ~ 30%;
Propiolic alcohol 5-10%;
The preparation method of described organic amine drilling well acidification corrosion inhibitor is: take each raw material by weight percentage; Be the hydrochloric acid soln suction glassed steel reaction vessels of 20 ~ 30% by ethanol and weight concentration, drip aniline, in dropping process, temperature controls at 20 ~ 40 DEG C; Divide six to ten times by acetone suction glassed steel reaction vessels, drip formaldehyde, in dropping process, temperature controls at 80 ~ 100 DEG C; Cool to 60 ~ 70 DEG C, be incubated two hours; Add propiolic alcohol and Sodium orthomolybdate, stir, discharging, obtains reddish-brown liquid product, is organic amine drilling well acidification corrosion inhibitor.
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| CN104109529B (en) * | 2014-06-23 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of acidification corrosion inhibitor and preparation method thereof |
| US10072199B2 (en) | 2015-03-17 | 2018-09-11 | Halliburton Energy Services, Inc. | Metalate-based additives for use in subterranean formations |
| CN105154049B (en) * | 2015-08-04 | 2018-03-23 | 中国石油化工股份有限公司 | A kind of corrosion inhibiter and preparation method thereof |
| CN105419774A (en) * | 2015-11-10 | 2016-03-23 | 西南石油大学 | Preparation method of acidizing corrosion inhibitor in high-temperature and concentrated acid environment |
| CN107987822A (en) * | 2017-12-06 | 2018-05-04 | 唐山市金沙工贸有限公司 | High-temperature acidification corrosion inhibitor and preparation method thereof and application |
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| GB847762A (en) * | 1958-11-26 | 1960-09-14 | Amchem Prod | Inhibitor compositions |
| 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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| CN100549124C (en) * | 2007-03-23 | 2009-10-14 | 中国石油天然气股份有限公司 | High-temperature corrosion inhibitor for acid fracturing |
| CN101643642B (en) * | 2009-08-31 | 2012-02-15 | 寿光市裕鑫化工有限公司 | High-temperature acidifying inhibiter and preparation method thereof |
| CN102226081A (en) * | 2011-04-19 | 2011-10-26 | 中国海洋石油总公司 | High-temperature acidic corrosion inhibitor and preparation method thereof |
| CN103014715B (en) * | 2012-08-09 | 2014-09-10 | 江苏科技大学 | Corrosion inhibitor composition for preventing hydrogen sulfide corrosion |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB847762A (en) * | 1958-11-26 | 1960-09-14 | Amchem Prod | Inhibitor compositions |
| 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 |
| CN102586782A (en) * | 2011-01-10 | 2012-07-18 | 中国石油化工股份有限公司 | Corrosion inhibitor and preparation and application thereof |
| CN102953066A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Multi-branched Mannich base corrosion inhibitor and preparation method thereof |
| CN103045227A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Multicomponent composite retarded acid for sandstone reservoir acidification |
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