CN109371401A - A kind of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter and preparation method thereof - Google Patents
A kind of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter and preparation method thereof Download PDFInfo
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- CN109371401A CN109371401A CN201811568716.6A CN201811568716A CN109371401A CN 109371401 A CN109371401 A CN 109371401A CN 201811568716 A CN201811568716 A CN 201811568716A CN 109371401 A CN109371401 A CN 109371401A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/163—Sulfonic acids
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Abstract
The invention discloses a kind of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter and preparation method thereof, and the structural formula of the corrosion inhibiter isR represents carbochain number as C in formula11~C17Saturated alkyl, mono alkenyl or diene base, n be 5~15 integer；It is before this using Long carbon chain carboxylic acid and diethylenetriamine as Material synthesis Long carbon chain imidazoline intermediate, then addition reaction is carried out with ethylene oxide under alkaline condition and generate polyoxyethylene ether imidazoline, finally carry out quaternization reaction with 3- chlorine-2-hydroxyl propanesulfonate and be prepared.Active group-OH and-SO is introduced in inhibitor structure of the present invention3 ‑, make it that there is good solubility in water, adsorption activity greatly enhances in metal surface, shows excellent corrosion inhibition；And its biological degradability is good, toxicity is low, belongs to environmentally friendly corrosion inhibiter.Corrosion inhibiter of the present invention may be applied not only to containing CO2And H2The oil field produced aqueous medium of S, and can be applied to CO2To slow down corrosion of the fluid to carbon steel in the high-temperature high-pressure medium of oil displacement system.
Description
Technical field
The invention belongs to fine chemical product technical fields, and in particular to a kind of polyoxyethylene ether imidazoline sulfonate inhibition
The preparation method of agent and the corrosion inhibiter.
Background technique
By CO2Oil reservoir is injected, has not only sealed CO up for safekeeping2, oil gas field recovery ratio can also be increased substantially, CO is reached2Emission reduction and
The two-win purpose of oil reservoir Efficient Development.With the CO that shows loving care for2The Efforts To Develop of displacement of reservoir oil engineering at home and abroad, CO2To injected system, underground
The etching problem of the mild steel equipment such as tubing string, production system pipe network is more and more prominent.Oil gas field is inhibited using inhibiter technology
In generally existing CO2Corrosion has that invest low, dosage few and without changing the advantages such as existing equipment and process flow, in oil gas
Tanaka is used widely.Test discovery, imidazoline and its derivative compatibility is good, and thermal stability is high, and toxicity is low, and energy scale inhibition kills
Bacterium, and inhibit CO well with having after other additive compounds2The effect of corrosion belongs to environmentally friendly corrosion inhibiter.
The application of most of imidazolines all carries out in aqueous solution, and conventional imidazoline is general water-soluble poor, because
Its quaternized imidazoline quaternary ammonium salt that is converted into is to improve the water-soluble Major Technology of imidazoline corrosion inhibitor by this.Often at present
Quaternizing agent is mostly benzyl chloride, sodium chloroacetate, dithyl sulfate, sulfamic acid etc., due to the polarity of its quaternary ammonium salt
Level is not sufficient to ensure that entire imidazoline molecule is preferably water-soluble, thus its stability is poor, and it is existing that long term storage easily leads to layering
As.
Summary of the invention
The object of the present invention is to provide one kind to have good water solubility, and performance is stablized, for containing CO2And H2The oil of S
Field produces aqueous medium or CO2Corrosion caused by high-temperature high-pressure medium in oil displacement system has the polyoxy of very strong rejection ability
Vinethene imidazoline sulfonate corrosion inhibiter, and a kind of preparation method is provided for the corrosion inhibiter.
For above-mentioned purpose, the structural formula of polyoxyethylene ether imidazoline sulfonate of the present invention is as follows:
R represents carbochain number as C in formula11~C17Saturated alkyl, carbochain number be C11~C17Mono alkenyl, carbochain number be C11
~C17Diene base in any one, n be 5~15 integer.
In structure above, preferably R represents undecyl, 4- undecenyl, tridecyl, pentadecyl, pentadecane
Alkenyl, 8,11- pentadecane dialkylene, 9- hexadecene base, heptadecyl, 8- heptadecene base, in 17 carbon dialkylene of 8,11-
Any one.
Polyoxyethylene ether imidazoline sulfonate corrosion inhibiter of the present invention the preparation method comprises the following steps:
1, using dimethylbenzene as solvent, next time at 140~200 DEG C by Long carbon chain carboxylic acid shown in Formulas I and diethylenetriamines
Stream 4~6h of reaction, when deviating from 85% or more of theoretical dehydrating amount, rotary evaporation removes removal xylene, obtains 1- shown in Formula II
Amine ethyl -2- Long carbon chain base imidazoline intermediate.
2, by 1- amine ethyl -2- Long carbon chain base imidazoline intermediate and alkali obtained in above-mentioned steps 1 in N2It is stirred under protection
It mixes and is warming up to 100~120 DEG C, then pass to ethylene oxide gas, continue constant temperature and stir 30~45min, stop ventilation, separate pure
Change, obtains polyoxyethylene ether imidazoline shown in formula III.
3, polyoxyethylene ether imidazoline obtained in above-mentioned steps 2 and 3- chlorine-2-hydroxyl propanesulfonate are heated to 80~
90 DEG C, the pH of regulation system is 7.5~8.0, then proceedes to 2~3h of reaction, obtains polyoxyethylene ether imidazoline shown in formula IV
Sulfonate corrosion inhibiter, reaction process are as follows:
In above-mentioned steps 1, the molar ratio of the Long carbon chain carboxylic acid and diethylenetriamines is 1:1.05~1:1.20, wherein
The preferred Long carbon chain carboxylic acid is lauric acid, linderic acid, myristic acid, palmitinic acid, 2- gaidic acid, 9,12- 16
Carbon dialkylene, 10- heptadecenoic acid, stearic acid, oleic acid, any one in linoleic acid.
In above-mentioned steps 2, the molar ratio of the 1- amine ethyl -2- Long carbon chain base imidazoline intermediate and ethylene oxide is 1:
5~1:16, the dosage of alkali are the 0.3%~0.7% of ethylene oxide quality, wherein the alkali is any one in NaOH, KOH
Kind.
In above-mentioned steps 3, the molar ratio of the polyoxyethylene ether imidazoline and 3- chlorine-2-hydroxyl propanesulfonate is 1:1.5
~1:2.0.
In above-mentioned steps 3, the pH using any one regulation system in NaOH, KOH is 7.5~8.0.
Compared with prior art, the invention has the benefit that
1, active group-OH and-SO is introduced in polyoxyethylene ether imidazoline sulfonate inhibitor structure of the invention3 -, this
Sample can form the multicenter absorption of multiple groups while absorption in metal surface, and the absorption for greatly improving it in steel surface is living
Property, it shows extremely excellent corrosion inhibition, inhibiting effect can be generated to homogeneous corrosion and local corrosion.
2, corrosion inhibiter of the invention has good water solubility, can be applied not only to containing CO2And H2The oil field extracted water of S
Medium, and can be applied to CO2Slow down the corrosion to carbon steel in the high-temperature high-pressure medium of oil displacement system, corrosion inhibition is excellent.
3, corrosion inhibiter of the invention not only can be used alone, but also can be multiple with fungicide, other anticorrosives and surfactant
With use, with good biological degradability, and toxicity is low, belongs to environmentally friendly corrosion inhibiter.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the polyoxyethylene ether imidazoline sulfonate of embodiment 1.
Fig. 2 is the infrared spectrum of the polyoxyethylene ether imidazoline sulfonate of embodiment 2.
Fig. 3 is the infrared spectrum of the polyoxyethylene ether imidazoline sulfonate of embodiment 3.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
1, by 56.52g (0.20mol) 9- octadecenoic acid (Formulas I -1), 24.68g (0.24mol) diethylenetriamines and
30mL dimethylbenzene is added in 250mL reactor, heating stirring, slowly persistently overheating, in 160~195 DEG C of back flow reaction 5h, abjection
Water 6.22g (reasonable by the 86.39% of dehydrating amount), rotary evaporation remove removal xylene, obtain brown color dope 1- amine ethyl-
2- (17 alkenyl of 8-) imidazoline intermediate (Formula II -1).
2,1- amine ethyl -2- (17 alkenyl of the 8-) imidazoline intermediate for obtaining 69.96g (0.20mol) step 1 and
0.65g sodium hydroxide is added in reaction flask, is vacuumized after draining air, N2The lower stirring of protection is warming up to slow at 110~120 DEG C
Slowly it is passed through 108.62g (2.47mol) ethylene oxide gas, keeps the temperature 38min after adding again, stopped ventilation, use 98% ice vinegar
Acid is neutralized product, obtains brown liquid 1- polyoxyethylene ether ethylamine -2- (17 alkenyl of 8-) imidazoline (formula
III-1)。
3,175.61g (0.20mol) step 2 is obtained into polyoxyethylene ether imidazoline and the chloro- 2- of 76.69g (0.39mol) 3-
Hydroxypropionate sodium is added in reaction flask, and 85~90 DEG C are heated in water-bath, and the NaOH for the use of mass fraction being 10% is water-soluble
The pH of liquid regulation system is 7.8, the reaction was continued 2.6h, obtains rufous liquid 1,1- polyoxyethylene ether ethylamine-(2- hydroxyl
Propane sulfonic acid base) -2- (17 alkenyl of 8-) imidazoline inhibitor (formula IV -1).
Embodiment 2
1, by 58.39g (0.21mol) octadecanoid acid (Formulas I -2), 22.73g (0.22mol) diethylenetriamines and
30mL dimethylbenzene is added in 250mL reactor, heating stirring, slowly persistently overheating, in 155~190 DEG C of back flow reaction 4.5h, takes off
Water yield 6.48g (reasonable by the 87.70% of dehydrating amount), rotary evaporation remove removal xylene, obtain brown color dope 1- amine second
Base -2- heptadecyl imidazole quinoline intermediate (Formula II -2).
2, the 1- amine ethyl -2- heptadecyl imidazole quinoline intermediate and 0.86g obtained 72.18g (0.21mol) step 1
Sodium hydroxide is added in reaction flask, is vacuumized after draining air, N2Protection lower stirring is slowly led to when being warming up to 105~115 DEG C
Enter 131.92g (3.00mol) ethylene oxide gas, keep the temperature 42min after adding again, stops ventilation, use 98% glacial acetic acid pair
Product is neutralized, and obtains brown liquid 1- polyoxyethylene ether ethylamine -2- heptadecyl imidazole quinoline (formula III -2).
3, by 180.56g (0.21mol) step 2 obtain 1- polyoxyethylene ether ethylamine -2- heptadecyl imidazole quinoline and
73.71g (0.38mol) 3- chlorine-2-hydroxyl propanesulfonate is added in reaction flask, and 82~87 DEG C are heated in water-bath, uses matter
Measuring the pH of KOH aqueous solution regulation system that score is 10% is 7.6, the reaction was continued 2.5h, obtains rufous liquid 1,1- polyoxy
Vinyl ether ethylamine-(2- hydroxy-propanesulfonic acid base) -2- heptadecyl imidazole quinoline corrosion inhibiter (formula IV -2).
Embodiment 3
1, by 59.95g (0.30mol) dodecanoic acid (Formulas I -3), 32.69g (0.32mol) diethylenetriamines and 30mL
Dimethylbenzene is added in 250mL reactor, heating stirring, slowly persistently overheating, in 147~180 DEG C of back flow reaction 5.5h, deviates from water
It measures 9.52g (reasonable by the 88.36% of dehydrating amount), rotary evaporation removes removal xylene, obtains brown color dope 1- amine ethyl -2-
Undecyl imidazole quinoline intermediate (Formula II -3).
2, brown color dope 1- amine ethyl -2- undecyl imidazole is obtained by what 80.05g (0.30mol) step 1 obtained
Quinoline intermediate and 0.43g sodium hydroxide are added in reaction flask, are vacuumized after draining air, N2The lower stirring of protection is warming up to 100
It is slowly introducing 121.58 (2.76mol) ethylene oxide gas at~110 DEG C, keeps the temperature 35min after adding again, stops ventilation, uses
98% glacial acetic acid is neutralized product, obtains brown liquid 1- polyoxyethylene ether ethylamine -2- undecyl miaow
Oxazoline (formula III -3).
3, by 238.06g (0.30mol) step 2 obtain 1- polyoxyethylene ether ethylamine -2- undecyl imidazole quinoline and
89.43g (0.46mol) 3- chlorine-2-hydroxyl propanesulfonate is added in reaction flask, and 85~90 DEG C are heated in water-bath, uses matter
Measuring the pH of NaOH aqueous solution regulation system that score is 10% is 7.9, the reaction was continued 2.2h, obtains rufous liquid 1,1- polyoxy
Vinyl ether ethylamine-(2- hydroxy-propanesulfonic acid base) -2- undecyl imidazole quinoline corrosion inhibiter (formula IV -3).
Embodiment 4
1, by 53.68g (0.21mol) gaidic acid (Formulas I -4), 26.03g (0.25mol) diethylenetriamines and
30mL dimethylbenzene is added in 250mL reactor, heating stirring, slowly persistently overheating, in 165 DEG C~200 DEG C back flow reaction 4.8h,
Deviate from water 6.64g (reasonable by the 87.42% of dehydrating amount), rotary evaporation removes removal xylene, obtains brown color dope 1- amine
Ethyl -2- pentadecane alkenyl imidazoline intermediate (Formula II -4).
2, by 67.85g (0.21mol) step 1 obtain obtain 1- amine ethyl -2- pentadecane alkenyl imidazoline intermediate and
0.96g sodium hydroxide is added in reaction flask, is vacuumized after draining air, N2The lower stirring of protection is warming up to slow at 102~112 DEG C
Slowly it is passed through 138.57g (3.15mol) ethylene oxide gas, keeps the temperature 45min after adding again, stopped ventilation, use 98% ice vinegar
Acid is neutralized product, obtains brown liquid 1- polyoxyethylene ether ethylamine -2- pentadecane alkenyl imidazoline (formula
III-4)。
3,179.25g (0.21mol) step 2 is obtained into 1- polyoxyethylene ether ethylamine -2- pentadecane alkenyl imidazoline
It is added in reaction flask with 72.42g (0.37mol) 3- chlorine-2-hydroxyl propanesulfonate, 80~85 DEG C is heated in water-bath, used
The pH for the NaOH aqueous solution regulation system that mass fraction is 10% is 7.5, the reaction was continued 2.4h, obtains rufous liquid 1, and 1- is poly-
Ethylene oxide ether ethylamine-(2- hydroxy-propanesulfonic acid base) -2- pentadecane alkenyl imidazoline corrosion inhibiter (formula IV -4).
Embodiment 5
In the present embodiment, with equimolar 9,9- octadecenoic acid in 12- octadecadienoic acid alternative embodiment 1 is other
Step is same as Example 1, obtains following 1,1- polyoxyethylene ether ethylamine-(2- hydroxy-propanesulfonic acid the base) -2- of structural formula
(8,11- ten seven carbon dialkylene) imidazoline inhibitor, yield 73%.
Embodiment 6
In the present embodiment, with the dodecanoic acid in equimolar tetradecanoic acid alternative embodiment 3, other steps and embodiment 1
It is identical, obtain following 1,1- polyoxyethylene ether ethylamine-(2- hydroxy-propanesulfonic acid the base) -2- tridecyl imidazoline of structural formula
Corrosion inhibiter, yield 68%.
Since the map that Examples 1 to 6 obtains is essentially identical, using VERTEX70 type Fourier infrared spectrograph to implementation
Polyoxyethylene ether imidazoline sulfonate made from example 1~3 carries out molecular structure characterization, and infrared spectrum is as shown in Figures 1 to 3.
The analysis of Fig. 1 principal character peak: 2922cm-1And 2854cm-1Place is-CH2Asymmetry and symmetrical stretching vibration inhale
Receive peak, 1645cm-1Place is the C=N stretching vibration peak of typical imidazoline ring, illustrates to contain imidazoline in synthesis of product molecules
Ring；By 1101cm-1The stretching vibration peak of the C-O-C at place can determine whether to contain polyether chain in synthesis of product molecules；In addition, 1248cm-1
The SO at place3 -Stretching vibration peak deducibility synthetic product in contain sulfonate；In conclusion explanation successfully synthesizes target production
Object.
The analysis of Fig. 2 principal character peak: 2922cm-1And 2855cm-1- the CH at place2Asymmetry and symmetrical stretching vibration inhale
Receive peak, 1643cm-1The C=N stretching vibration peak of the imidazoline ring at place, 1100cm-1The stretching vibration peak of the C-O-C at place, 1248cm-1The SO at place3 -Stretching vibration peak, explanation successfully synthesize target product.
The analysis of Fig. 3 principal character peak: 2922cm-1And 2855cm-1- the CH at place2Asymmetry and symmetrical stretching vibration inhale
Receive peak, 1644cm-1The C=N stretching vibration peak of the imidazoline ring at place, 1100cm-1The stretching vibration peak of the C-O-C at place, 1248cm-1The SO at place3 -Stretching vibration peak, explanation successfully synthesize target product.
In order to prove beneficial effects of the present invention, inventor is referring to " oil field water process corrosion inhibiting and descaling agent technical specification "
Requirement in (Q/SY 126-2014) standard in Appendix B has rated the corrosion inhibiter of Examples 1 to 6 preparation containing only CO respectively2
The live water of simulation in the corrosion inhibition of Q235A steel disc, wherein temperature is 50 DEG C ± 2 DEG C, experimental period 72h, test solution amount
For 1120mL, corrosion inhibiter mass concentration is 50mg/L, and experimental result is shown in Table 1.
Corrosion inhibition under 1 polyoxyethylene ether imidazoline sulfonate corrosion inhibiter static state of table
As shown in Table 1, containing only CO2In-site modeling water in, with the embodiment of the present invention 1~6 prepare corrosion inhibiter pair
The uniform corrosion rate of Q235A steel disc is far below the uniform corrosion rate of blank solution, and corrosion inhibition is all satisfied index request.
In order to further prove the high temperature and pressure performance of corrosion inhibiter of the present invention, inventor is " oil field produced referring to professional standard
Water process corrosion inhibiter performance indicator and evaluation method " (SY/T 5273-2014), it the use of salinity is 2.9 × 104Mg/L's
Certain oil field stratum water simulates CO2(temperature is 60 DEG C to Drainage process condition, CO2Partial pressure is 6.0MPa), test inhibition of the present invention
To the corrosion inhibition of N80 steel when agent mass concentration is 100mg/L, time 72h, experimental result is shown in Table 2.
2 polyoxyethylene ether imidazoline sulfonate corrosion inhibiter of table is in CO2Corrosion inhibition under the conditions of Drainage process
As shown in Table 2, in simulation CO2Under the conditions of Drainage process, the corrosion inhibiter prepared with the embodiment of the present invention 1~6 is to N80
The uniform corrosion rate of steel disc is far below the uniform corrosion rate of blank solution, and the corrosion inhibition rate relative to blank solution reaches
90% or more, it is good slow to illustrate that polyoxyethylene ether imidazoline sulfonate corrosion inhibiter of the invention has in high-temperature high-pressure medium
Corrosion energy.
Claims (9)
1. a kind of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter, it is characterised in that the structural formula of the corrosion inhibiter is as follows:
R represents carbochain number as C in formula11~C17Saturated alkyl, carbochain number be C11~C17Mono alkenyl, carbochain number be C11~C17
Diene base in any one, n be 5~15 integer.
2. polyoxyethylene ether imidazoline sulfonate corrosion inhibiter according to claim 1, it is characterised in that: the R is represented
Undecyl, 4- undecenyl, tridecyl, pentadecyl, pentadecane alkenyl, 8,11- pentadecane dialkylene, 16 carbon of 9-
Alkenyl, heptadecyl, 8- heptadecene base, any one in 17 carbon dialkylene of 8,11-.
3. a kind of preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter described in claim 1, it is characterised in that:
(1) using dimethylbenzene as solvent, Long carbon chain carboxylic acid shown in Formulas I and diethylenetriamines are flowed back at 140~200 DEG C anti-
4~6h is answered, when deviating from 85% or more of theoretical dehydrating amount, rotary evaporation removes removal xylene, obtains 1- amine second shown in Formula II
Base -2- Long carbon chain base imidazoline intermediate；
(2) the 1- amine ethyl -2- Long carbon chain base imidazoline intermediate and alkali obtained above-mentioned steps (1) is in N2The lower stirring of protection rises
Temperature then passes to ethylene oxide gas to 100~120 DEG C, continues constant temperature and stirs 30~45min, stops ventilation, isolate and purify,
Obtain polyoxyethylene ether imidazoline shown in formula III；
(3) polyoxyethylene ether imidazoline and 3- chlorine-2-hydroxyl propanesulfonate that above-mentioned steps (2) obtain are heated to 80~90
DEG C, the pH of regulation system is 7.5~8.0, then proceedes to 2~3h of reaction, obtains polyoxyethylene ether imidazoline sulphur shown in formula IV
Hydrochlorate corrosion inhibiter.
4. the preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter according to claim 3, it is characterised in that: step
Suddenly in (1), the molar ratio of the Long carbon chain carboxylic acid and diethylenetriamines is 1:1.05~1:1.20.
5. the preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter according to claim 4, it is characterised in that: institute
The Long carbon chain carboxylic acid stated is lauric acid, linderic acid, myristic acid, palmitinic acid, 2- gaidic acid, 16 carbon two of 9,12-
Alkenyl, 10- heptadecenoic acid, stearic acid, oleic acid, any one in linoleic acid.
6. the preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter according to claim 3, it is characterised in that: step
Suddenly in (2), the molar ratio of the 1- amine ethyl -2- Long carbon chain base imidazoline intermediate and ethylene oxide is 1:5~1:16, alkali
Dosage is the 0.3%~0.7% of ethylene oxide quality.
7. the preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter, feature according to claim 3 or 6 exist
In: the alkali is any one in NaOH, KOH.
8. the preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter according to claim 3, it is characterised in that: step
Suddenly in (3), the molar ratio of the polyoxyethylene ether imidazoline and 3- chlorine-2-hydroxyl propanesulfonate is 1:1.5~1:2.0.
9. the preparation method of polyoxyethylene ether imidazoline sulfonate corrosion inhibiter according to claim 3, it is characterised in that: step
It suddenly is 7.5~8.0 with the pH of any one regulation system in NaOH, KOH in (3).
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| CN114106805A (en) * | 2021-10-28 | 2022-03-01 | 西安石油大学 | Corrosion inhibition type foaming agent and preparation method thereof |
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