CN103409129A - organic amine acidizing corrosion inhibitor used for well drilling and preparation method thereof - Google Patents
organic amine acidizing corrosion inhibitor used for well drilling and preparation method thereof Download PDFInfo
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- CN103409129A CN103409129A CN2013103476797A CN201310347679A CN103409129A CN 103409129 A CN103409129 A CN 103409129A CN 2013103476797 A CN2013103476797 A CN 2013103476797A CN 201310347679 A CN201310347679 A CN 201310347679A CN 103409129 A CN103409129 A CN 103409129A
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Abstract
The invention provides an organic amine acidizing corrosion inhibitor used for well drilling and a preparation method thereof. The organic amine acidizing corrosion inhibitor used for well drilling is characterized by being prepared from the following raw materials in weight percentage: 15-25% of acetone, 11-22% of aniline, 10-20% of formaldehyde, 3-5% of sodium molybdate, 10-15% of ethyl alcohol, 15-25% of hydrochloric acid solution, and 5-10% of propargyl alcohol. The corrosion inhibitor is low in cost, can be used at temperature as high as 195 DEG C, has excellent corrosion inhibition under a high temperature condition, and is a premium grade product meeting requirements of the China Petroleum and Chemical Cooperation.
Description
Technical field
The present invention relates to a kind of organic amine drilling well acidifying with 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 on market is of a great variety with acidification corrosion inhibitor, and effect is different, and middle low-temperature performance is better, but along with the going deep into of exploitation of oil-gas field, increasing hot hole appears in face of us, and such as the deep-well had more than a lot of 5000m, and downhole temperature is up to 150 ℃.Along with the construction of offshore oilfield, the hot hole of many 180 ℃ has also appearred simultaneously.Limited for this class inhibiter performance effect of this type high temp deep-well, acidizing corrosion problem for hot hole, the present invention utilizes formaldehyde commonly used, 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 ℃, basically can meet, the acidifying medication of most Oil/gas Wells of home and overseas, this inhibiter be take aldehyde amine ketone condensate and is major ingredient, it is good that medicament has a solubility in acid, low to the drill core permeability rate infringement, product viscosity is low, the nonirritant stink, the advantages such as scene is easy to use.The acidification that can be used for 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 15%~28% hydrochloric acid or mud acid, use temperature is not higher than with 195 ℃.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of under higher temperature conditions corrosion inhibition drilling well acidifying preferably with inhibiter and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention has been to provide a kind of organic amine drilling well acidification corrosion inhibitor, it is characterized in that, is made by 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 20~30% hydrochloric acid soln 15-25%;
Propiolic alcohol 5-10%.
The present invention also provides the preparation method of above-mentioned organic amine drilling well acidification corrosion inhibitor, it is characterized in that, concrete steps are: take by weight percentage each raw material; By ethanol and weight concentration, be 20~30% hydrochloric acid soln suction glassed steel reaction vessels, drip aniline, in the dropping process, temperature is controlled at 20~40 ℃; Divide six to ten times by acetone suction glassed steel reaction vessels, drip formaldehyde, in the dropping process, temperature is controlled at 80~100 ℃; Cool to 60~70 ℃, be incubated two hours; Add propiolic alcohol and Sodium orthomolybdate, stir, discharging, obtain the reddish-brown liquid product, is organic amine drilling well acidification corrosion inhibitor.
At first preparation method of the present invention is the condenses of synthetic 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 ℃, and the corrosion inhibition under hot conditions is comparatively good, can reach the top grade product that China Petrochemical Industry requires.
2, the ordorless smell of inhibiter of the present invention, add the acidizing fluid color softer.
Embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.Described acetone is the pale yellow oily liquids acetone of commercially available technical grade (>99%), and East China branch office of China Petrochemical Industry produces; Described aniline is commercially available technical grade aniline, water white transparency, oxidative phenomena do not occur and adds nitrogen as protection gas, and aniline content>98%, Dongying Chinese honor new energy materials company limited produces; Described formaldehyde is commercially available technical grade formaldehyde, formaldehyde content>35.5%, and Zaozhuang U.S. occasion chemical industry company limited produces; Described Sodium orthomolybdate is the technical grade Sodium orthomolybdate, Sodium orthomolybdate content>98%, and the 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 the technical grade synthetic hydrochloric acid, iron ion<2ppm, and described ethanol is the technical grade dehydrated alcohol, content>99%, ethanol, hydrochloric acid are all purchased in Chemical market.
Embodiment 1
A kind of organic amine drilling well acidification corrosion inhibitor, made by following raw material with weight percent: acetone 15%; Aniline 11%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 26%; Weight concentration is 30% hydrochloric acid soln 25% and propiolic alcohol 10%.
Its preparation method is: take by weight percentage each raw material; It by ethanol 26wt%, weight concentration, is 30% hydrochloric acid soln 25wt% suction glassed steel reaction vessels, splash into slowly aniline 11wt%, in the dropping process, temperature is controlled at 20~30 ℃, divide six times by acetone 15wt% suction glassed steel reaction vessels, slowly drip formaldehyde 10wt%, in the dropping process, temperature is controlled at 90~100 ℃, drip to finish and cool to 60~70 ℃, be incubated two hours, add propiolic alcohol 10wt%, stirred one hour, then add Sodium orthomolybdate 3wt%, stir two hours blowings, obtain the 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, made by following raw material with weight percent: acetone 25%; Aniline 12%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 25%; Weight concentration is 30% hydrochloric acid soln 15% and propiolic alcohol 10%.
Its preparation method is: take by weight percentage each raw material, by ethanol 25wt%, weight concentration is 30% hydrochloric acid soln 15wt% suction glassed steel reaction vessels, splash into slowly aniline 12wt%, in the dropping process, temperature is controlled at 20~30 ℃, divide six times by acetone 25wt% suction glassed steel reaction vessels, slowly drip formaldehyde 10wt%, in the dropping process, temperature is controlled at 90~100 ℃, drip to finish and cool to 60~70 ℃, be incubated two hours, add propiolic alcohol 10wt%, stirred one hour, then add Sodium orthomolybdate 3wt%, stir two hours blowings, obtain the reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, organic amide monomer wherein
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, made by following raw material with weight percent: acetone 24%; Aniline 18%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 15%; Weight concentration is 30% hydrochloric acid soln 15% and propiolic alcohol 15%.
Its preparation method is: take by weight percentage each raw material, by ethanol 15wt%, weight concentration is 30% hydrochloric acid soln 15wt% suction glassed steel reaction vessels, splash into slowly aniline 18wt%, in the dropping process, temperature is controlled at 20~30 ℃, divide six times by acetone 24wt% suction glassed steel reaction vessels, slowly drip formaldehyde 10wt%, in the dropping process, temperature is controlled at 90~100 ℃, drip to finish and cool to 60~70 ℃, be incubated two hours, add propiolic alcohol 15wt%, stirred one hour, then add Sodium orthomolybdate 3wt%, stir two hours blowings, obtain the reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, organic amide monomer wherein
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, made by following raw material with weight percent: acetone 17%; Aniline 20%; Formaldehyde 10%; Sodium orthomolybdate 3%; Ethanol 15%; Weight concentration is 30% hydrochloric acid soln 20% and propiolic alcohol 15%.
Its preparation method is: take by weight percentage each raw material, by ethanol 15wt%, weight concentration is 30% hydrochloric acid soln 20wt% suction glassed steel reaction vessels, splash into slowly aniline 20wt%, in the dropping process, temperature is controlled at 20~30 ℃, divide six times by acetone 17wt% suction glassed steel reaction vessels, slowly drip formaldehyde 10wt%, in the dropping process, temperature is controlled at 90~100 ℃, drip to finish and cool to 60~70 ℃, be incubated two hours, add propiolic alcohol 15wt%, stirred one hour, then add Sodium orthomolybdate 3wt%, stir two hours blowings, obtain the reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, organic amide monomer wherein
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, made by following raw material with weight percent: acetone 15%; Aniline 22%; Formaldehyde 15%; Sodium orthomolybdate 5%; Ethanol 15%; Weight concentration is 30% hydrochloric acid soln 15% and propiolic alcohol 13%.
Its preparation method is: take by weight percentage each raw material, by ethanol 15wt%, weight concentration is 30% hydrochloric acid soln 15wt% suction glassed steel reaction vessels, splash into slowly aniline 22wt%, in the dropping process, temperature is controlled at 20~30 ℃, divide six times by acetone 15wt% suction glassed steel reaction vessels, slowly drip formaldehyde 15wt%, in the dropping process, temperature is controlled at 90~100 ℃, drip to finish and cool to 60~70 ℃, be incubated two hours, add propiolic alcohol 13wt%, stirred one hour, then add Sodium orthomolybdate 5wt%, stir two hours blowings, obtain the reddish-brown liquid product, be organic amine drilling well acidification corrosion inhibitor, organic amide monomer wherein
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 to corrosion inhibition experiment (this experiment adopt be the Gas Industry standard S Y/T5405-1996 of PetroChina Company Limited.), and the corrosion inhibition experimental result is as follows:
High Temperature High Pressure Dynamic Corrosion speed result (medium is 20% hydrochloric acid):
High Temperature High Pressure Dynamic Corrosion speed result (medium is that the mud acid composition is HCl: HF=12: 3):
From above experimental result, the corrosion inhibition of organic amine drilling well acidification corrosion inhibitor of the present invention under hot conditions is comparatively good, can reach the top grade product that China Petrochemical Industry requires.
Claims (2)
1. an organic amine drilling well acidification corrosion inhibitor, is characterized in that, made by 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 20~30% hydrochloric acid soln 15-25%;
Propiolic alcohol 5-10%.
2. the preparation method of organic amine drilling well acidification corrosion inhibitor claimed in claim 1, is characterized in that, concrete steps are: take by weight percentage each raw material; By ethanol and weight concentration, be 20~30% hydrochloric acid soln suction glassed steel reaction vessels, drip aniline, in the dropping process, temperature is controlled at 20~40 ℃; Divide six to ten times by acetone suction glassed steel reaction vessels, drip formaldehyde, in the dropping process, temperature is controlled at 80~100 ℃; Cool to 60~70 ℃, be incubated two hours; Add propiolic alcohol and Sodium orthomolybdate, stir, discharging, obtain the reddish-brown liquid product, is organic amine drilling well acidification corrosion inhibitor.
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CN105154049A (en) * | 2015-08-04 | 2015-12-16 | 中国石油化工股份有限公司 | Corrosion inhibitor 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 |
WO2016148698A1 (en) * | 2015-03-17 | 2016-09-22 | Halliburton Energy Services, Inc. | Metalate-based additives for use in subterranean formations |
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 |
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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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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