CN103289671B - Corrosion inhibiter and preparation method thereof - Google Patents
Corrosion inhibiter and preparation method thereof Download PDFInfo
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- CN103289671B CN103289671B CN201310204643.3A CN201310204643A CN103289671B CN 103289671 B CN103289671 B CN 103289671B CN 201310204643 A CN201310204643 A CN 201310204643A CN 103289671 B CN103289671 B CN 103289671B
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Abstract
The invention discloses a kind of corrosion inhibiter and preparation method thereof, wherein corrosion inhibiter is made up of by mass percentage following component: Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant 10%～30%；Shuangzi pyridine quaternary ammonium salt type surfactant 10%～60%；Mutual solvent 5%～10%；Synergist 2%～5%；Solvent 15%～60%.The corrosion inhibiter of the present invention has good corrosion mitigating effect, and can at high temperature use.
Description
Technical field
The present invention relates to the high temperature resistance of acidification in corrosion inhibiter technical field, particularly Oil/gas Well development process
Corrosion inhibiter and preparation method thereof.
Background technology
Oil well acidation operation is the major measure of oilfield stimulation.Along with deep-well and the continuous appearance of ultradeep well, for these
The complicated acidizing treatment of oil well, on market, existing corrosion inhibiter shows acid-soluble the best, temperature resistance ability, and corrosion inhibition is bad
Problem.If improving corrosion inhibiter to down-hole hardware and the protective capacities of pipeline by increasing the consumption of corrosion inhibiter, not only
The cost of acidizing treatment can be increased, acidizing treatment is brought adverse effect, and likely stratum is damaged.Meanwhile, one
A little corrosion inhibiter are incompatible with stratum ion, usually cause the injury problem to stratum.As, by aldehyde ketone amine condensation substance and the chlorine of synthesis
Change benzyl to react, obtain aldehyde ketone amine condensation substance quaternary ammonium salt, obtain height using the quaternary ammonium salt obtained as host and propilolic alcohol are compounding
Temperature acidification corrosion inhibitor, the maximum temperature that this corrosion inhibiter uses can only achieve 120 DEG C.Make with the homopolymer of N-pi-allyl chloroquine
For acidification corrosion inhibitor, using when temperature higher (more than 150 DEG C) can be dangerous.The most importantly, this inhibitor molecular amount
Too big (2000～5000), and such homopolymer does not has hydrophilic group, therefore this corrosion inhibiter dissolution dispersity energy and
Bigger defect can be there is in compatibility.By naphthenic acid imidazoline derivant as acidification corrosion inhibitor, such corrosion inhibiter is acid-soluble good,
Toxicity is little, has preferable corrosion mitigating effect, and temperature is more than 90 DEG C under conditions of temperature is less than 90 DEG C, and especially up to 100
After DEG C, then effect is excessively poor.A kind of new aldehyde ketone amine condensation substance has been obtained, in the aldehyde ketone amine contracting obtained by Mannich reaction
Compound adds solvent and obtains final acidification corrosion inhibitor product with surfactant.This corrosion inhibiter in the hydrochloric acid solution of 90 DEG C
There is good corrosion mitigating effect.But this corrosion inhibiter is after reaching 120 DEG C, then effect is undesirable.Therefore, need badly develop with ground
The sub-compatibility of leafing is good, can high temperature resistance, corrosion inhibiter that corrosion inhibition is good.
As can be seen here, above-mentioned existing corrosion inhibiter has obviously still suffered from inconvenience and defect on using, and is urgently entered
One step is improved.The present inventor's actively the most in addition research and innovation, to inventing corrosion inhibiter of a kind of novelty and preparation method thereof so that it is more
There is practicality.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the invention provides a kind of can high temperature resistance, corrosion inhibition good
Corrosion inhibiter.
In order to solve above-mentioned technical problem, present invention employs following technical scheme:
Corrosion inhibiter, is made up of by mass percentage following component:
As preferably, the chemical formula of the active ingredient of described Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant is [RN
(R1)2(R2)3]2 +X2 -, wherein, R is the straight chained alkyl of C12～C18, R1, R2, for alkyl or the H of C1～C4, X be halogen Cl or
Br element, the weight/mass percentage composition of active ingredient is 81～85%.
As preferably, described Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant is to use dichloroetane or the dibromobutane to be
Bridging agent, fatty acid is hydrophobic group, and diethylenetriamine is that the initial feed synthesis of hydrophilic group prepares.
As preferably, wherein with oleic acid or sinapic acid as hydrophobic group.
As preferably, the chemical formula of the active ingredient of described Shuangzi pyridine quaternary ammonium salt type surfactant is [R3N (R4)2
(R5)3]2 +X2 -, wherein, R3 is the alkyl naphthene of C8～C10, and R4, R5 are alkyl or the H of C1～C2, and X is halogen Cl or Br unit
Element, the weight/mass percentage composition of active ingredient is 79～81%.
As preferably, described Shuangzi pyridine quaternary ammonium salt type surfactant be use double chloromethylated intermediates or double bromine intermediate with
Pyridine or pyridine homologue, triethylamine and benzyl chloride are synthesized.
As preferably, described mutual solvent is isomery fatty alcohol-polyoxyethylene ether, and chemical formula is R6R7O (CH2CH2O)mH, its
In: R6, R7 are the straight chained alkyl of C2～C8, and the C number of R6+R7 is less than 14, the integer of m=6～20.
As preferably, described synergist is molybdic acid sodium salt or ammonium salt, and chemical formula is Na2MoO4·2H2O or (NH4)2MoO4·
2H2O。
As preferably, described solvent is dimethylformamide, and molecular formula is HCON (CH3)2。
Another object of the present invention is for providing the preparation method of a kind of above-mentioned corrosion inhibiter, and the method is easy to implement, by letter
Single corrosion inhibiter that operation prepares high temperature resistance, corrosion inhibition is good.The technical scheme realizing this purpose is as follows:
The preparation method of a kind of above-mentioned corrosion inhibiter, its step is as follows, is sequentially added into Shuangzi imidazolinyl season in a kettle.
Ammonium salt type surfactant, Shuangzi quaternized pyridinium salt surfactant, composite synergist, mutual solvent and solvent, at 50 60 DEG C
Under be sufficiently stirred for 1-2 hour, be configured to corrosion inhibiter.
Compared with prior art, the beneficial effects of the present invention is:
The present invention is by the compound acidifying inhibition that Shuangzi imidazoline quaternary ammonium salt and Shuangzi pyridine quaternary ammonium salt are key component
Agent, has good dispersibility in hydrochloric acid；Have heat stability height, high temperature corrosion inhibition is good, have good acid-resisting gas
Corrosive nature and anti-H2S hydrogen embrittlement performance.Can be used as the acid of oil (gas) well salt, equipment and other instrument in soil acid acidizing fracturing technology
Corrosion inhibiter；To height containing H2S/CO2The acidifying of Oil/gas Well, acid fracturing construction have the good suitability；To common straightcarbon steel, high sulfur resistive
The various material such as carbon steel, steel alloy all has anti-general corrosion and the selective corrosion of excellence.At present increasing high temperature and
Superhigh temperature Oil/gas Well occurs, the well depth of these Oil/gas Wells is typically about ten thousand metres, and have also exceeds well over ten thousand metres, and down-hole
Temperature is often as high as 160 DEG C.Existing corrosion inhibiter is difficult to play preferable corrosion mitigating effect in high temperature environments.The inhibition of the present invention
Agent is to be compounded by Shuangzi imidazoline quaternary ammonium salt surfactant with Shuangzi quaternized pyridinium salt surfactant and synergist and obtain
Obtain final products.Primary raw material Shuangzi imidazoline quaternary ammonium salt surfactant and Shuangzi pyrrole due to this superhigh temperature acidification corrosion inhibitor
Pyridine quaternary surfactant is autonomous synthesis, and therefore cost is substantially reduced, and corrosion mitigating effect and heat-resisting ability improve.
Performance is distinguished under the high temperature conditions.Therefore it is with a wide range of applications in acidification of oil field is constructed.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but not as a limitation of the invention.
Embodiment one:
In the 250mL tri-neck port grinding bottle with condensing reflux pipe, add sinapic acid and diethylenetriamine and catalyst three
Al 2 O, is simultaneously introduced water entrainer dimethylbenzene and is stirred backflow, react 4h～6h, and reaction temperature is 180 DEG C～200 DEG C,
Distillation of reducing pressure at 140 DEG C is sloughed dimethylbenzene and is obtained producing in the middle of imidazoline body.
In above-mentioned intermediate product, add addition Isosorbide-5-Nitrae dichloroetane after benzyl chloride reacts 3 hours at 90-100 DEG C carry out
Contraction chainization is reacted, and reacts 3h～4h, and reaction temperature is 80 DEG C～90 DEG C, and obtaining end product is brown thick liquid, effectively becomes
Point weight/mass percentage composition be 81% 85%.The structural formula of effective ingredient is as follows:
Sinapic acid is replaced to can get the Shuangzi imidazoline quaternary ammonium salt of other structures, at this no longer with oleic acid or other fatty acids
Repeat.
Embodiment two:
In the 250mL tri-neck port grinding bottle with condensing reflux pipe, add pyridine and triethylamine, be simultaneously introduced water entrainer two
Toluene is stirred backflow, reacts 3h～4h, and reaction temperature is 140 DEG C～180 DEG C, and diformazan is sloughed in distillation of reducing pressure at 120 DEG C
Benzene obtains producing in the middle of pyridine base body.
In above-mentioned intermediate product, add benzyl chloride, react 3-4 hour at 120-140 DEG C, add Isosorbide-5-Nitrae dichloroetane
Carrying out the reaction of contraction chainization, react 2h～3h, reaction temperature is 80 DEG C～90 DEG C, and obtaining end product is brown thick liquid, has
The weight/mass percentage composition of effect composition is 79% 81%.The structural formula of effective ingredient is as follows:
Replace pyridine to can get the Shuangzi pyridine quaternary ammonium salt of other structures with pyridine homologue, do not repeat them here.
Embodiment three:
It is sequentially added into the component of following mass percent in a kettle.:
Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant (prepared by embodiment one) 10%；
Shuangzi pyridine quaternary ammonium salt type surfactant (prepared by embodiment two) 20%；
Synergist Na2MoO4·2H2O 2%；
Mutual solvent 8%；
Dimethylformamide 60%；
It is sufficiently stirred at 50 60 DEG C 1-2 hour, is configured to corrosion inhibiter.
The present embodiment gained corrosion inhibiter ADH-3 is carried out performance test at 90 DEG C, the results are shown in Table 1:
Table 1 embodiment three gained corrosion inhibiter performance test
Embodiment four:
It is sequentially added into the component of following mass percent in a kettle.:
Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant (prepared by embodiment one) 10%；
Shuangzi pyridine quaternary ammonium salt type surfactant (prepared by embodiment two) 50%；
Synergist (NH4)2MoO4·2H2O 5%
Mutual solvent 10%；
Dimethylformamide 25%；
It is sufficiently stirred at 50 60 DEG C 1-2 hour, is configured to corrosion inhibiter.
The present embodiment gained corrosion inhibiter ADH-4 is carried out performance test at 120 DEG C, the results are shown in Table 2:
Table 2 embodiment four gained corrosion inhibiter performance test
Embodiment five:
It is sequentially added into the component of following mass percent in a kettle.:
Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant (prepared by embodiment one) 10%；
Shuangzi pyridine quaternary ammonium salt type surfactant (prepared by embodiment two) 60%；
Na2MoO4·2H2O 10%
Mutual solvent 5%；
Dimethylformamide 15%；
It is sufficiently stirred at 50 60 DEG C 1-2 hour, is configured to corrosion inhibiter.
The present embodiment gained corrosion inhibiter ADH-5 is carried out performance test at 160 DEG C, the results are shown in Table 3:
Table 3 embodiment five gained corrosion inhibiter performance test
Above example is only the exemplary embodiment of the present invention, is not used in the restriction present invention, protection scope of the present invention
It is defined by the claims.The present invention can be made respectively in the essence of the present invention and protection domain by those skilled in the art
Planting amendment or equivalent, this amendment or equivalent also should be regarded as being within the scope of the present invention.
Claims (4)
1. corrosion inhibiter, it is characterised in that be made up of by mass percentage following component:
Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant 10%～30%；
Shuangzi pyridine quaternary ammonium salt type surfactant 10%～60%；
Mutual solvent 5%～10%；
Synergist 2%～10%；
Solvent 20%～60%；
Described Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant is that to use dichloroetane or dibromobutane be bridging agent, fatty acid
For hydrophobic group, diethylenetriamine is that the initial feed synthesis of hydrophilic group prepares；Described fatty acid is oleic acid or sinapic acid；
Described Shuangzi pyridine quaternary ammonium salt type surfactant is to use double chloromethylated intermediates or double bromine intermediate same with pyridine or pyridine
It is that thing, triethylamine and benzyl chloride are synthesized.
Corrosion inhibiter the most according to claim 1, it is characterised in that described synergist is molybdic acid sodium salt or ammonium salt, chemical formula
For Na2MoO4·2H2O or (NH4)2MoO4·2H2O。
Corrosion inhibiter the most according to claim 1, it is characterised in that described solvent is dimethylformamide, molecular formula is
HCON(CH3)2。
4. the preparation method of the corrosion inhibiter described in the arbitrary claim of claim 1-3, it is characterised in that its step is as follows,
Reactor is sequentially added into Shuangzi imidazolinyl quaternary ammonium salt cationic surfactant, Shuangzi pyridine quaternary ammonium salt type surfactant, increasing
Effect agent, mutual solvent and solvent, be sufficiently stirred at 50 60 DEG C 1-2 hour, be configured to corrosion inhibiter.
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| CN105884688A (en) * | 2014-12-24 | 2016-08-24 | 秦皇岛胜利化工有限公司 | Preparation method of amphoteric gemini imidazolidine |
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| CN106085399A (en) * | 2016-06-27 | 2016-11-09 | 中国石油集团渤海钻探工程有限公司 | Acidifying compounding Imidazoline corrosion inhibitor and preparation method thereof |
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| CN108913113A (en) * | 2018-06-15 | 2018-11-30 | 吉林石油集团兴业石油化学技术服务有限公司 | A kind of protection is high to contain CO2The oil base oil-gas gathering and transportation corrosion inhibiter and preparation method of well annular space |
| CN109912506A (en) * | 2019-03-22 | 2019-06-21 | 徐州工程学院 | A kind of synthetic method of symmetric form imidazoline Gemini surface active |
| CN110055045B (en) * | 2019-04-26 | 2021-08-20 | 中国石油化工股份有限公司 | Oligomeric cationic quaternary ammonium salt surfactant synergistic oil displacement agent |
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| CN117512600A (en) * | 2023-10-28 | 2024-02-06 | 安徽红太阳新材料有限公司 | High-temperature acidification corrosion inhibitor |
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Effective date of registration: 20210811 Address after: 101400 room 205, cultural service center, building 1, yard 5, qingxiuyuan street, Jingjia Road, Yanqi Town, Huairou District, Beijing Patentee after: Anton Institute of Geological Engineering Technology (Beijing) Co.,Ltd. Address before: 629000 jinjiagou modern logistics base in Western China, Chuanshan District, Suining City, Sichuan Province Patentee before: SICHUAN ANTON OIL & GAS ENGINEERING TECHNOLOGY SERVICE Co.,Ltd. |