CN105586594B - A kind of compound acidification corrosion inhibitor of high temperature and preparation method thereof - Google Patents
A kind of compound acidification corrosion inhibitor of high temperature and preparation method thereof Download PDFInfo
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- CN105586594B CN105586594B CN201410575626.5A CN201410575626A CN105586594B CN 105586594 B CN105586594 B CN 105586594B CN 201410575626 A CN201410575626 A CN 201410575626A CN 105586594 B CN105586594 B CN 105586594B
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Abstract
A kind of compound acidification corrosion inhibitor of high temperature of present invention offer and preparation method thereof.The compound acidification corrosion inhibitor of high temperature is made of the raw material of following proportion by weight：Hydroxyl bi-quaternary ammonium salt 60-80, synergist 10-20, solvent 10-25；Its preparation process is：（1）The synthesis of hydroxyl bi-quaternary ammonium salt：Take nitrogen-containing heterocycle compound in reaction kettle, using absolute ethyl alcohol as solvent, heating is heated to 78 DEG C of reflux, and double halohydrins are then added, and continues to be heated to reflux the filtering of 12-24h postcoolings, hydroxyl bi-quaternary ammonium salt is recrystallized 3 times to obtain with absolute ethyl alcohol-acetone mixture；（2）The hydroxyl bi-quaternary ammonium salt of synthesis is uniformly mixed with synergist, solvent up to the compound acidification corrosion inhibitor of high temperature.The compound acidification corrosion inhibitor of high temperature prepared by the present invention have many advantages, such as it is acid-soluble it is good, dosage is few, the high and low poison ring of corrosion inhibition rate is protected.
Description
Technical field
The present invention relates to corrosion and protection technology field more particularly to a kind of compound acidification corrosion inhibitor of high temperature and
Preparation method.
Background technology
In the work progress of oil field, acidification be realize well production increment, injection well augmented injection an important effective measures, often
Acidizing reagent is the hydrochloric acid solution of 15-28%.Acid solution is injected into stratum under the conditions of certain pressure, acid solution can be with rock
Dissolving or corrosion occur for tamper in cement and formation pore, crack, with this come improve stratum porosity and
Permeability achievees the purpose that volume increase, augmented injection.However acid solution has corrosiveness to down-hole string and metal equipment, especially
When being acidified using the hydrochloric acid of high concentration under hot conditions, the serious curtailment service life of pipeline and construction equipment causes
Huge economic loss.Therefore to reduce acid solution to corrosions of metal such as acidizing treatment equipment, tubing strings, usually in work progress
It is middle that corrosion inhibiter is added into acid solution.
The main body of high-temperature acidification corrosion inhibitor is mostly the substances such as Mannich base, quaternary ammonium salt, imidazoline at present.Due to stratum drilling
The continuous improvement of depth, high temperature oil gas field continuously emerge, and the conventional acidulation corrosion inhibiter of one-component has been unable to meet hot conditions
Under anti-corrosion demand, it usually needs add synergist in host agent and improve anti-corrosion effect.Alkynol substance is most common height
Warm acidification corrosion inhibitor synergist, but this substance volatility is larger, and after being added in acid solution, part active ingredient can follow hydrochloric acid
It evaporates together, not only reduces its active ingredient, result in waste of resources, while itself being also a kind of extremely toxic substance, sternly
The health of construction personnel is compromised again.Therefore, it is quite necessary to study, a kind of dosage is few, the high and low poison ring of corrosion inhibition rate is protected
High-temperature acidification corrosion inhibitor.
Invention content
The object of the present invention is to provide compound acidification corrosion inhibitors of a kind of high temperature and preparation method thereof.Utilize the hydroxyl of preparation
There are multiple adsorption sites in bi-quaternary ammonium salt molecule, multiple spot absorption can be formed in metal surface, caused to be formed in metal surface
Privacy protection film hinders corrosion of metal；Green low toxicity, degradable rosin amine is selected to make instead of most common alkynol substance
It is small to environmental hazard for synergist；The compound acidification corrosion inhibitor of high temperature prepared by the present invention have it is acid-soluble it is good, dosage is few, slow
The advantages that high and low poison ring of erosion rate is protected.
One of in order to achieve the above objectives, the present invention can be realized by following technical measures：
A kind of compound acidification corrosion inhibitor of high temperature, is made of the proportioning of following mass parts raw material：
Hydroxyl bi-quaternary ammonium salt 60-80 synergist 10-20 solvents 10-25.
An object of the present invention can also be realized by following measure：
The synergist is rosin amine；
The solvent is the one or two of ethyl alcohol, formaldehyde.
In order to achieve the above objectives two, the present invention can be realized by following technical measures：
A kind of preparation method of the compound acidification corrosion inhibitor of high temperature, including following operating procedure：
(1) synthesis of hydroxyl bi-quaternary ammonium salt takes nitrogen-containing heterocycle compound in reaction kettle, using absolute ethyl alcohol as solvent, rises
Temperature is heated to 78 DEG C of reflux 0.5-1h, and double halohydrins are then added, and continues to be heated to reflux the filtering of 12-24h postcoolings, be matched with volume
Than being 1：1 absolute ethyl alcohol-acetone mixture recrystallizes 3 times to obtain hydroxyl bi-quaternary ammonium salt；The hydroxyl bi-quaternary ammonium salt molecule
Shown in structure following (A), (B).
(2) the hydroxyl bi-quaternary ammonium salt of synthesis is uniformly mixed with synergist, solvent up to the compound acidification corrosion inhibitor of high temperature.
The second object of the present invention can also be realized by following measure：
The nitrogen-containing heterocycle compound is quinoline or pyridine；
Double halohydrins are 1,3-, bis- chloro- 2- propyl alcohol, 1,3- bis- bromo- 2- propyl alcohol, the chloro- 2- butanol of Isosorbide-5-Nitrae-two, Isosorbide-5-Nitrae-two
One kind in bromo- 2- butanol；
The nitrogen-containing heterocycle compound：Double halohydrin=2.0-2.4: 1 (molar ratio).
The dosage of the solvent absolute ethyl alcohol presses nitrogen-containing heterocycle compound (mol)：Absolute ethyl alcohol (mL)=1：100-200.
The each dosage of absolute ethyl alcohol-acetone mixture presses nitrogen-containing heterocycle compound (mol)：Absolute ethyl alcohol-acetone is mixed
Close liquid (mL)=1：30-50.
The corrosion inhibiter performance test of the present invention is tested in strict accordance with SY/T5405-1996《Acidification corrosion inhibiter performance test
And evaluation index》Operation.
The advantageous effect of the compound acidification corrosion inhibitor of high temperature of the present invention is：Have in the hydroxyl bi-quaternary ammonium salt molecule of preparation
Multiple adsorption sites can form multiple spot absorption, to form fine and close protective film in metal surface to hinder metal in metal surface
Corrosion；In addition, selecting green low toxicity, degradable rosin amine to replace most common alkynol substance as synergist, to ring
Border harm is small.The compound acidification corrosion inhibitor of high temperature prepared by the present invention have it is acid-soluble it is good, dosage is few, the high and low poison ring of corrosion inhibition rate
The advantages that guarantor.
Specific implementation mode
With reference to specific embodiment, present invention is further described in detail.
Embodiment 1
Take 2mol quinoline in reaction kettle, 200mL absolute ethyl alcohols are solvent, and heating is heated to 78 DEG C of reflux 1h, then adds
Enter 1mol 1, bis- bromo- 2- propyl alcohol of 3- continues to be heated to reflux postcooling filtering for 24 hours, is every time 1 with 60mL volume ratios：1 it is anhydrous
Ethanol-acetone mixed liquor recrystallizes 3 times to obtain bis- quinoline propyl alcohol of bromination 1,3-.By bis- quinoline propyl alcohol of bromination 1,3-, rosin amine, ethyl alcohol
In mass ratio 60: 15: 25 obtain the compound acidification corrosion inhibitor of high temperature after mixing.
In 15%HCl solution, the compound acidification corrosion inhibitor of the high temperature of 0.3% mass fraction can make N80 Oil Tube Steels 90
Corrosion inhibition rate at DEG C is up to 99.19%；The compound acidification corrosion inhibitor of the high temperature of 0.5% mass fraction, can make N80 Oil Tube Steels at 90 DEG C
Under corrosion inhibition rate up to 99.64%.
Embodiment 2
Take 2.4mol quinoline in reaction kettle, 240mL absolute ethyl alcohols are solvent, and heating is heated to 78 DEG C of reflux 1h, then
1mol 1 is added, bis- bromo- 2- butanol of 3- continues to be heated to reflux the filtering of 12h postcoolings, is every time 1 with 120mL volume ratios：1 nothing
Water-ethanol-acetone mixture recrystallizes 3 times to obtain bis- quinoline butanol of bromination 1,4-.By bis- quinoline butanol of bromination 1,4-, rosin amine, first
Aldehyde in mass ratio 70: 20: 10 obtains the compound acidification corrosion inhibitor of high temperature after mixing.
In 15%HCl solution, the compound acidification corrosion inhibitor of the high temperature of 0.3% mass fraction can make N80 Oil Tube Steels 90
Corrosion inhibition rate at DEG C is up to 99.23%；The compound acidification corrosion inhibitor of the high temperature of 0.5% mass fraction, can make N80 Oil Tube Steels at 90 DEG C
Under corrosion inhibition rate up to 99.67%.
Embodiment 3
Take 2mol pyridines in reaction kettle, 400mL absolute ethyl alcohols are solvent, and heating is heated to 78 DEG C of reflux 0.5h, then
1mol 1 is added, bis- chloro- 2- propyl alcohol of 3- continues to be heated to reflux.Postcooling filters for 24 hours for reaction, is every time 1 with 100mL volume ratios：
1 absolute ethyl alcohol-acetone mixture recrystallizes 3 times to obtain bis- pyridine propyl alcohols of chlorination 1,3-.By bis- pyridine propyl alcohols of chlorination 1,3-, rosin
Amine, ethyl alcohol in mass ratio 60: 20: 20 obtains the compound acidification corrosion inhibitor of high temperature after mixing.
In 15%HCl solution, the compound acidification corrosion inhibitor of the high temperature of 0.4% mass fraction can make N80 Oil Tube Steels 90
Corrosion inhibition rate at DEG C is up to 99.02%；The compound acidification corrosion inhibitor of the high temperature of 0.5% mass fraction, can make N80 Oil Tube Steels at 90 DEG C
Under corrosion inhibition rate up to 99.39%.
Embodiment 4
Take 2.4mol pyridines in reaction kettle, 240mL absolute ethyl alcohols are solvent, and heating is heated to 78 DEG C of reflux 0.5h, so
- two chloro- 2- butanol of 1mol Isosorbide-5-Nitraes is added afterwards, continues to be heated to reflux the filtering of 14h postcoolings, is every time 1 with 72mL volume ratios：1
Absolute ethyl alcohol-acetone mixture recrystallizes 3 times to obtain bis- pyridine butanol of chlorination 1,4-.By bis- pyridine butanol of chlorination 1,4-, rosin amine,
Formaldehyde in mass ratio 80: 10: 10 obtains the compound acidification corrosion inhibitor of high temperature after mixing.
In 15%HCl solution, the compound acidification corrosion inhibitor of the high temperature of 0.4% mass fraction can make N80 Oil Tube Steels 90
Corrosion inhibition rate at DEG C is up to 99.10%；The compound acidification corrosion inhibitor of the high temperature of 0.5% mass fraction, can make N80 Oil Tube Steels at 90 DEG C
Under corrosion inhibition rate up to 99.42%.
The explanation of above example is only applicable to help to understand the present invention；Meanwhile for those of ordinary skill in the art,
Embodiment according to the present invention can change place, in conclusion this explanation in specific implementation mode and application range
Book content should not be construed as limiting the invention.
Claims (2)
1. a kind of compound acidification corrosion inhibitor of high temperature, which is characterized in that be made of the raw material of following proportion by weight：
Hydroxyl bi-quaternary ammonium salt 60-80 synergist 10-20 solvents 10-25；Described hydroxyl bi-quaternary ammonium salt molecular structure following A, B
It is shown：
A
B
The synergist is rosin amine, and the solvent is the one or two of ethyl alcohol, formaldehyde.
2. a kind of method preparing the compound acidification corrosion inhibitor of high temperature as described in claim 1, which is characterized in that walked by following operation
It is rapid to carry out：
(1) synthesis of hydroxyl bi-quaternary ammonium salt：Take nitrogen-containing heterocycle compound in reaction kettle, using absolute ethyl alcohol as solvent, heating
78 DEG C of reflux 0.5-1h are heated to, double halohydrins are then added, continues to be heated to reflux the filtering of 12-24h postcoolings, uses volume proportion
It is 1：1 absolute ethyl alcohol-acetone mixture recrystallizes 3 times to obtain hydroxyl bi-quaternary ammonium salt；The hydroxyl bi-quaternary ammonium salt molecule knot
Shown in structure following A, B：
A
B
(2) the hydroxyl bi-quaternary ammonium salt of synthesis is uniformly mixed with the synergist, solvent up to the compound acidification corrosion inhibitor of high temperature；
Step (1) described nitrogen-containing heterocycle compound is quinoline or pyridine；Double halohydrins are bis- chloro- 2- propyl alcohol of 1,3-, 1,3-
One kind in two bromo- 2- propyl alcohol, bis- chloro- 2- butanol of 1,4-, bis- bromo- 2- butanol of 1,4-；The nitrogen-containing heterocycle compound：It is double halogenated
Alcohol=2.0-2.4 moles：1 mole；The nitrogen-containing heterocycle compound：Absolute ethyl alcohol=1 mole：100-200 milliliters；It is described nitrogenous
Heterocyclic compound：Single recrystallization absolute ethyl alcohol-acetone mixture=1 mole：30-50 milliliters.
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| CN112410009B (en) * | 2020-11-23 | 2022-12-20 | 滨州市广友化工有限公司 | Gas well corrosion inhibitor for shale gas development and preparation method thereof |
| CN113278409B (en) * | 2021-06-22 | 2022-04-29 | 西南石油大学 | High-temperature acidizing corrosion inhibitor |
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| 季铵盐型酸化缓蚀剂的合成及其缓蚀机理研究;宗鹏;《中国优秀硕士学位论文全文数据库，工程科技I辑》;20090630;第9，19,21-23,41页 * |
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