CN106609371A - Corrosion inhibitor and preparation method and application thereof - Google Patents
Corrosion inhibitor and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of corrosion inhibition of an oilfield and provides a corrosion inhibitor and a preparation method and application thereof. The corrosion inhibitor comprises, by weight, 25-35% of an amphoteric surfactant, 20-28% of a sulfur-containing organic matter, 15-25% of a nitrogen-containing organic matter, 1-10% of an oxygen scavenger and 2-39% of water. The corrosion inhibitor has the advantages of corrosion inhibition, scale inhibition and bactericidal performances, can effectively solve the corrosion problem of the crude oil gathering and transportation pipe, does not contain phosphorus and chlorine, does not influence the downstream processing device, can inhibit metal corrosion in the oilfield gathering and transportation pipe corrosion inhibition, and eliminates the scale corrosion caused by scaling and the corrosion caused by microorganisms.
Description
Technical field
The present invention relates to a kind of corrosion inhibiter and its preparation method and application.
Background technology
Oilfield exploitation injection water, injection steam after condense generation water or original stratum exist water with
Crude oil is extracted.Substantial amounts of carbon dioxide, hydrogen sulfide and high salt component are dissolved in recovered water, has been made
Obtain crude oil gathering line frequently to bore a hole, it has also become affect oilfield safety production great with economical operation
Hidden danger, adds a small amount of corrosion inhibiter to be a kind of effect is significant, reduce the effective of cost of oil production in oil well
Behave, can significantly slow down the generation for even preventing corrosion.
The starting of foreign study Inhibitor For Oil Well System is relatively early, and early stage mainly uses film-forming corrosion inhibitor.Such inhibition
Agent is mainly inorganic matters (such as chromate, nitrite etc.), it is adaptable to which the environment that recovers the oil is neutral medium
Oil well.Such corrosion inhibiter is functional, not yet there is more preferable succedaneum so far.But such corrosion inhibiter is often
Large usage quantity, poor feasibility, and can cause serious local corrosion on the contrary when inhibiter consumption is not enough,
And such corrosion inhibiter is general all poisonous, because ecological environment problem is increasingly taken seriously, in many environments
It is prohibited from using, therefore the research in recent years to film-forming corrosion inhibitor is less.
1949, the U.S. reported the anti-CO of organic nitrogen-containing imidazoline and its derivative2Delay in the oil field of corrosion
Erosion agent.Afterwards, the corrosion inhibiter based on imidazoline and its derivative obtains substantial amounts of research and application.
Domestic end of the seventies in last century HUST cooperates with Department of Well Works, Sichuan Petroleum Administration
7701 composite corrosion inhibitors are developed, China just solves acidifying corrosion inhibitor for oil well technical barrier.Due to each
The operating mode in oil field is different, and the factor for affecting corrosion inhibiter is also differed, so having generally still without working out
The corrosion inhibitor for oil field of the suitability.
The corrosion inhibitor for oil field for using both at home and abroad at present is mostly adsorption corrosion inhibitor, and main inhibition ingredient is that have
Machine thing, such as chain organic amine and its derivant, imidazoline and its salt, quaternary ammonium salts, rosin derivative,
Sulfonate, imines acetogenin and alkynol class etc..Wherein, propiolic alcohol, organic amine, imidazoline
And its corrosion mitigating effect of the Organic substance such as derivatives class, quaternary ammonium salts is preferable.
CN10266074A oil field extracted water corrosion inhibiter contains imidazoline group and phosphonyl group, by weight
Gauge, adds in the reactor diethylenetriamine 350-450 parts, and Oleic acid 650-750 part, catalyst is miscellaneous
Polyacid 15-25 part, azeotropic agent dimethylbenzene 950-1100 parts are heated with stirring to 150 DEG C, keep reaction temperature
Spend for 140-220 DEG C, flow back 5-8 hours, obtains oleic imidazolinone.Under normal temperature condition, in reactor
Middle addition oleic imidazolinone 350-450 parts, hydrochloric 20-30 part, formaldehyde 55-65 parts, stirring
0.5-4h, adds in the reactor aqueous isopropanol 65-75 parts of phosphorous acid, after stirring 1-2h, uses salt
Acid for adjusting pH is 6, obtains the oil field extracted water corrosion inhibiter finished product that concentration is 90%.
《Corrosion of the N80 tubing and casings in oil field mining liquid and abrasion synergism research》(petroleum works
Build, 33 (2)：26-30, in April, 2007) voluntarily have developed it is a kind of with modified imidazole quinoline derivant,
Component, compounding alkynol compound, thiourea, surfactant and solvent are wanted based on organic thiophosphate
Corrosion inhibiter, the medicament has good protective effect, is suitable for containing to N80, J55, X70 steel
CO2、Cl-With micro H2The oil field mining liquid corrosive environment of S.NYS-9 corrosion inhibiter is to N80 oil bushing steels
With good protective effect, the mass fraction for adding corrosion inhibiter is 100 × 10-6When, corrosion inhibition rate can reach
More than 82%.
From in terms of document above and patented technology, these corrosion inhibiter itself or contain P elements, or containing chlorine unit
Element, corrosion inhibiter also employs chloride compound in preparation process, so that corrosion inhibiter contains
Chlorine element.And if the corrosion inhibiter containing P elements is remained in crude oil, will fill into Downstream processing with crude oil
Put, cause catalyst poisoning during crude refining, and containing the inhibition of chlorine element especially organochlorine
If agent is remained in crude oil, the corrosion of secondary operations device will be caused during crude refining.
The content of the invention
It is an object of the invention to provide one kind is substantially free of the elements such as chlorine, phosphorus, and with inhibition, scale inhibition
With the novel corrosion inhibitor of bactericidal property.
To realize object defined above, according to the first aspect of the invention, the invention provides a kind of corrosion inhibiter,
The corrosion inhibiter contains：Amphoteric surfactant 25-35 weight %, sulfurous organic compound 20-28 weight %,
Itrogenous organic substance 15-25 weight %, oxygen scavenger 1-10 weight % and water 2-39 weight %.
According to the second aspect of the invention, the invention provides a kind of prepare corrosion inhibiter of the present invention
Method, the method includes：Under anaerobic atmosphere, by water, amphoteric surfactant, sulfurous organic compound,
Itrogenous organic substance and selectable organic solvent mix, and are subsequently adding oxygen scavenger.
According to the third aspect of the invention we, the invention provides corrosion inhibiter of the present invention is in oil field gathering and transportation
Application in pipeline corrosion protection.
The corrosion inhibiter of the present invention has inhibition, scale inhibition and bactericidal property simultaneously, can be with effectively solving crude oil collection
The etching problem of defeated pipeline, and corrosion inhibiter is phosphorous, chlorine element, on downstream process units without impact.
The corrosion inhibiter of the present invention, when in for oil field gathering and transportation pipeline anti-corrosion, can suppress the corrosion of metal itself,
Eliminate again and corrode caused by underdeposit corrosion and microorganism caused by fouling.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
It is an object of the invention to provide no matter a kind of corrosion inhibiter for being substantially free of phosphorus, chlorine, thus, emphasize
Whether illustrate, each in the corrosion inhibiter of the present invention constitutes in this body structure not phosphorous, chlorine, can not keep away
Exempt from not contain chlorine, P elements containing chlorine, phospha prime element and this body structure also within the scope of the invention.
Meanwhile, present invention explanation, the corrosion inhibiter of the present invention contains：Amphoteric surfactant, sulfur-bearing are organic
Thing, itrogenous organic substance, oxygen scavenger, then those skilled in the art read the technical scheme of the application and easily know
Know, without cross concept in four kinds of materials.
As it was previously stated, the invention provides a kind of corrosion inhibiter, the corrosion inhibiter contains：Amphoteric surfactant
25-35 weight %, sulfurous organic compound 20-28 weight %, itrogenous organic substance 15-25 weight %, oxygen scavenger
1-10 weight % and water 2-39 weight %.
According to corrosion inhibiter of the present invention, preferably in the corrosion inhibiter also containing can be miscible with water have
Machine solvent, preferably by weight, the content of organic solvent is 1-5 weight %.
According to corrosion inhibiter of the present invention, optional wider range of the species of the organic solvent, for
The present invention, the preferably organic solvent are one or more in alcohol, Methanamide and the acetone of C1-C4,
The organic solvent specifically preferred according to the invention is ethanol.
According to corrosion inhibiter of the present invention, preferably the amphoteric surfactant is glycine betaine, more preferably
For carboxybetaine and/or sulfobetaines, wherein, sulfobetaines are preferably azochlorosulfonate propyl lycine, example
Such as it is dodecyl azochlorosulfonate propyl lycine, myristyl azochlorosulfonate propyl lycine, cetyl sulfopropyl Radix Betae
One kind or many in alkali, octadecyl azochlorosulfonate propyl lycine and dodecyl dimethyl azochlorosulfonate propyl lycine
Kind.More preferably described amphoteric surfactant is dodecyl dimethyl azochlorosulfonate propyl lycine and cocoyl two
One or more in methyl betaine.
Wherein, it is known that in addition to azochlorosulfonate propyl lycine, remaining glycine betaine in building-up process due to needing
Chlorine-containing compound is used, therefore inevitably containing chlorine element impurity, (impurity content is less than 3.7 weights
Amount %), but amount of the chlorine element brought into by it in corrosion inhibiter is seldom, is negligible substantially.
According to corrosion inhibiter of the present invention, preferably the sulfurous organic compound is that thiourea and/or thiourea are derivative
Thing, wherein, the thiourea derivative is, for example, methylthiourea, dimethyl sulfourea, ethyl thiourea, diethyl
One or more in base thiourea, n-pro-pyl thiourea, allylthiourea, phenylthiourea and tolylthiourea,
For the present invention, preferably the sulfurous organic compound be Allyl thiourea, diethyl thiourea, methylthiourea,
One or more in n-pro-pyl thiourea and tolylthiourea.
According to corrosion inhibiter of the present invention, preferably the itrogenous organic substance is hydroxyquinoline and/or hydroxyl
Quinoline, wherein, the 8-hydroxyquinoline derivative is, for example, 2- cxine sulphates, 4- hydroxyquinoline
One or more in salt and oxinate, for the present invention, the preferably itrogenous organic substance is
One or more in 8-hydroxyquinoline, 8-hydroxyquinoline aluminum, 2- hydroxyquinoline and copper 8-quinolinolate.
According to corrosion inhibiter of the present invention, the species of the oxygen scavenger can be the conventional choosing of this area
Select, for the present invention, preferably the oxygen scavenger is hydrazine, diethyl hydroxylamine, arabo-ascorbic acid, carbonic acid
One or more in hydrazine, acetone oxime, DMKO and aldoxime.
In the present invention, as long as the corrosion inhibiter is above-mentioned composition is capable of achieving the purpose of the present invention, the present invention
To its preparation method without particular/special requirement, for the present invention, the preparation process of the preferably corrosion inhibiter includes：
Under anaerobic atmosphere, by water, amphoteric surfactant, sulfurous organic compound, itrogenous organic substance and can
The organic solvent mixing of selection, is subsequently adding oxygen scavenger.
In the present invention, the implementation of the anaerobic atmosphere has various, for example can be to the raw material that used
Water, amphoteric surfactant, sulfurous organic compound, itrogenous organic substance and selectable organic solvent are removed
Oxygen, and under an inert atmosphere mixed the raw material after deoxygenation.
As it was previously stated, the invention provides corrosion inhibiter of the present invention is in oil field gathering and transportation pipeline anti-corrosion
Using.
Because the corrosion inhibiter of the present invention has inhibition, scale inhibition and bactericidal property simultaneously, can be former with effectively solving
The etching problem of oily gathering line, and corrosion inhibiter is substantially free of phosphorus, chlorine element, to downstream process units
Without impact.The corrosion inhibiter of the present invention, when in for oil field gathering and transportation pipeline anti-corrosion, can suppress metal sheet
The corrosion of body, eliminates and corrode caused by underdeposit corrosion and microorganism caused by fouling again.
During specifically used, preferably the consumption of the corrosion inhibiter is 30-100mg/L.
, according to the invention it is preferred to the oil field extracted water for flowing through oil field gathering and transportation pipeline is sodium bicarbonate
(NaHCO3) water type, magnesium chloride (MgCl2) water type and calcium chloride (CaCl2) water type water in
One or more.
Below by embodiment for whole process is described in detail, but the claim model of the present invention
Enclose and be not restricted by the embodiments.Meanwhile, embodiment has been merely given as realizing the partial condition of this purpose,
But it is not meant to that must being fulfilled for these conditions can just reach this purpose.
In the present invention, the performance of corrosion inhibiter is according to test method《SY/T 5273-2014 oil field extracted waters
Use corrosion inhibiter method of evaluating performance》The uniform corrosion inhibition rates of 4.8 dynamics and the assay method of spot corrosion corrosion inhibition rates enter
Row is determined, wherein, the test condition of corrosion rate：Test temperature (70 ± 1) DEG C, test material is Q235
Carbon steel, test piece linear velocity 0.4m/s, test period 48h.
Embodiment 1
(carbon dioxide saturation, total salinity is 214977.3mg/L to oil field extracted water water quality, and water type is chlorine
Change calcium (CaCl2) water type, oxygen content is 0.3mg/L, and 1) remaining property be shown in Table, and test method is《SY/T
5273-2014 oil field extracted waters corrosion inhibiter method of evaluating performance》The uniform corrosion inhibition rates of 4.8 dynamics and points
The measure of erosion corrosion inhibition rate, the dynamic uniform corrosion rate for measuring carbon steel when not adding corrosion inhibiter is 0.545mm/a,
Pitting penetration is 0.027mm.
Table 1
Using the composite corrosion inhibitor of commercially available corrosion inhibiter 7701, add after corrosion inhibiter that (consumption of corrosion inhibiter is
100mg/L), the dynamic uniform corrosion rate of carbon steel is 0.251mm/a, and the uniform corrosion inhibition rate of dynamic is
54.1%；Pitting penetration is 0.011mm, and spot corrosion corrosion inhibition rate is 59.3%.
Add (consumption of corrosion inhibiter is 100mg/L) after the corrosion inhibiter of the present invention, the dynamic of carbon steel is uniform
Corrosion rate is 0.045mm/a, and the uniform corrosion inhibition rate of dynamic is 91.7%；Pitting penetration is 0.002mm,
Spot corrosion corrosion inhibition rate is 92.6%.
Wherein, the composition of corrosion inhibiter：35 weight % dodecyl dimethyl azochlorosulfonate propyl lycines, 28 weights
Amount % Allyl thioureas, 25 weight %8- hydroxyquinoline, 3 weight % hydrazines, 9 weight % water.
Embodiment 2
Oil field extracted water water quality is same with embodiment 1；
Add (consumption of corrosion inhibiter is 60mg/L) after corrosion inhibiter, the dynamic uniform corrosion rate of carbon steel is
0.075mm/a, the uniform corrosion inhibition rate of dynamic is 86.2%；Pitting penetration is 0.003mm, spot corrosion corrosion inhibition rate
For 88.9%.
Wherein, the composition of corrosion inhibiter：25 weight % cocoyl dimethyl betaines, 28 weight % diethyl
Thiourea, 25 weight %8- hydroxyquinoline aluminums, 3 weight % aldoxime, 19 weight % water.
Embodiment 3
Oil field extracted water water quality is same with embodiment 1；
Add (consumption of corrosion inhibiter is 30mg/L) after corrosion inhibiter, the dynamic uniform corrosion rate of carbon steel is
0.120mm/a, the uniform corrosion inhibition rate of dynamic is 78.0%；Pitting penetration is 0.005mm, spot corrosion corrosion inhibition rate
For 81.5%.Wherein, the composition of corrosion inhibiter：25 weight % cocoyl dimethyl betaines, 20 weight %
Methylthiourea, 15 weight %8- hydroxyquinoline, 1 weight % carbonic acid hydrazine, 39 weight % water.
Embodiment 4
Oil field extracted water water quality is same with embodiment 1；
Add (consumption of corrosion inhibiter is 100mg/L), the dynamic uniform corrosion rate of carbon steel after corrosion inhibiter
For 0.068mm/a, the uniform corrosion inhibition rate of dynamic is 87.5%；Pitting penetration is 0.003mm, spot corrosion inhibition
Rate is 88.9%.
Wherein, the composition of corrosion inhibiter：30 weight % dodecyl dimethyl azochlorosulfonate propyl lycines, 25 weights
Amount % n-pro-pyl thiourea, 20 weight %2- hydroxyquinoline, 2 weight % diethyl hydroxylamines, 23 weight % water.
Embodiment 5
(carbon dioxide saturation, total salinity 3228mg/L, water type is NaHCO to oil field extracted water water quality3,
Oxygen content is 0.7mg/L, and 2) remaining property be shown in Table, and the dynamic uniform corrosion rate of carbon steel is 0.227mm/
A, pitting penetration is 0.018mm.
Table 2
Using the composite corrosion inhibitor of commercially available corrosion inhibiter 7701, add after corrosion inhibiter that (consumption of corrosion inhibiter is
100mg/L), the dynamic uniform corrosion rate of carbon steel is 0.126mm/a, and the uniform corrosion inhibition rate of dynamic is
44.5%；Pitting penetration is 0.009mm, and spot corrosion corrosion inhibition rate is 50.0%；
Add (consumption of corrosion inhibiter is 60mg/L), the dynamic homogeneous corrosion of carbon steel after corrosion inhibiter of the present invention
Speed is 0.036mm/a, and the uniform corrosion inhibition rate of dynamic is 84.1%；Pitting penetration is 0.003mm, spot corrosion
Corrosion inhibition rate is 83.3%；
Wherein, the composition of corrosion inhibiter：30 weight % cocoyl dimethyl betaines, 25 weight % diethyl
Thiourea, 20 weight %8- hydroxyquinoline, 7 weight % hydrazines and 18 weight % water.
Embodiment 6
According to the consumption of embodiment 5, except for the difference that, corrosion inhibiter is consisted of：30 weight % cocoyl two
Methyl betaine, 25 weight % diethyl thioureas, 20 weight %8- hydroxyquinoline, 7 weight % hydrazines,
13 weight % water, 5% ethanol, the dynamic uniform corrosion rate of carbon steel is 0.024mm/a, and dynamic is uniform slow
Erosion rate is 86.3%；Pitting penetration is 0.002mm, and spot corrosion corrosion inhibition rate is 88.9%.
Embodiment 7
According to the consumption of embodiment 5, except for the difference that, corrosion inhibiter is consisted of：30 weight % cocoyl two
Methyl betaine, 25 weight % tolylthioureas, 20 weight %8- copper quinolinates, 7 weight % are different anti-
Bad hematic acid, 18 weight % water, the dynamic uniform corrosion rate of carbon steel is 0.033mm/a, and dynamic is uniform slow
Erosion rate is 85.5%；Pitting penetration is 0.002mm, and spot corrosion corrosion inhibition rate is 88.9%.
Comparative example 1
According to the consumption of embodiment 5, except for the difference that, corrosion inhibiter is consisted of：25 weight % diethyl sulfides
Urea, 20 weight %8- hydroxyquinoline, 7 weight % hydrazines and 48 weight % water, the dynamic of carbon steel is uniform rotten
Erosion speed is 0.157mm/a, and the uniform corrosion inhibition rate of dynamic is 30.8%；Pitting penetration is 0.012mm, point
Erosion corrosion inhibition rate is 33.3%.
Comparative example 2
According to the consumption of embodiment 5, except for the difference that, corrosion inhibiter is consisted of：30 weight % cocoyl two
Methyl betaine, 20 weight %8- hydroxyquinoline, 7 weight % hydrazines and 43 weight % water.Carbon steel it is dynamic
State uniform corrosion rate is 0.132mm/a, and the uniform corrosion inhibition rate of dynamic is 41.9%；Pitting penetration is
0.010mm, spot corrosion corrosion inhibition rate is 44.4%.
Comparative example 3
According to the consumption of embodiment 5, except for the difference that, corrosion inhibiter is consisted of：30 weight % cocoyl two
Methyl betaine, 25 weight % diethyl thioureas, 7 weight % hydrazines and 38 weight % water, carbon steel it is dynamic
State uniform corrosion rate is 0.119mm/a, and the uniform corrosion inhibition rate of dynamic is 47.6%；Pitting penetration is
0.009mm, spot corrosion corrosion inhibition rate is 50.0%.
Comparative example 4
According to the consumption of embodiment 5, except for the difference that, corrosion inhibiter is consisted of：30 weight % cocoyl two
Methyl betaine, 25 weight % diethyl thioureas, 20 weight %8- hydroxyquinoline and 25 weight % water,
The dynamic uniform corrosion rate of carbon steel is 0.142mm/a, and the uniform corrosion inhibition rate of dynamic is 37.4%；Spot corrosion depth
Spend for 0.010mm, spot corrosion corrosion inhibition rate is 44.4%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (9)
1. a kind of corrosion inhibiter, it is characterised in that the corrosion inhibiter contains：Amphoteric surfactant 25-35
Weight %, sulfurous organic compound 20-28 weight %, itrogenous organic substance 15-25 weight %, oxygen scavenger 1-10
Weight % and water 2-39 weight %.
2. corrosion inhibiter according to claim 1, wherein, also containing can be with the corrosion inhibiter
The organic solvent that water dissolves each other, by weight, the content of organic solvent is 1-5 weight %, described organic molten
Agent is ethanol.
3. corrosion inhibiter according to claim 1 and 2, wherein, the amphoteric surfactant is
Glycine betaine, preferably carboxybetaine and/or sulfobetaines, more preferably dodecyl dimethyl sulphur third
One or more in base glycine betaine and cocoyl dimethyl betaine.
4. corrosion inhibiter according to claim 1 and 2, wherein, the sulfurous organic compound is thiourea
And/or thiourea derivative, preferably Allyl thiourea, diethyl thiourea, methylthiourea, n-pro-pyl thiourea
With one or more in tolylthiourea.
5. corrosion inhibiter according to claim 1 and 2, wherein, the itrogenous organic substance is hydroxyl
Quinoline and/or 8-hydroxyquinoline derivative, preferably 8-hydroxyquinoline, 8-hydroxyquinoline aluminum, 2- hydroxyquinoline
With one or more in copper 8-quinolinolate.
6. corrosion inhibiter according to claim 1 and 2, wherein, the oxygen scavenger be hydrazine, two
One kind in ethylhydroxyl amine, arabo-ascorbic acid, carbonic acid hydrazine, acetone oxime, DMKO and aldoxime or
It is various.
7. a kind of method for preparing the corrosion inhibiter in claim 1-6 described in any one, its feature exists
In the method includes：Under anaerobic atmosphere, by water, amphoteric surfactant, sulfurous organic compound, contain
Nitrogen organic and selectable organic solvent mix, and are subsequently adding oxygen scavenger.
8. the corrosion inhibiter in claim 1-6 described in any one in oil field gathering and transportation pipeline anti-corrosion should
With.
9. application according to claim 8, wherein, the consumption of the corrosion inhibiter is 30-100mg/L,
The oil field extracted water for flowing through oil field gathering and transportation pipeline is attached most importance to sodium carbonate water type, chlorination magnesium-water type and calcium chloride water type
Water in one or more.
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