CN113150761B - anti-H 2 S corrosion inhibitor and preparation method thereof - Google Patents
anti-H 2 S corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN113150761B CN113150761B CN202110037187.2A CN202110037187A CN113150761B CN 113150761 B CN113150761 B CN 113150761B CN 202110037187 A CN202110037187 A CN 202110037187A CN 113150761 B CN113150761 B CN 113150761B
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- 238000005260 corrosion Methods 0.000 title claims abstract description 99
- 230000007797 corrosion Effects 0.000 title claims abstract description 99
- 239000003112 inhibitor Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims description 14
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001507 metal halide Chemical class 0.000 claims abstract description 21
- 150000005309 metal halides Chemical class 0.000 claims abstract description 21
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 11
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- ANFXTILBDGTSEG-UHFFFAOYSA-N 1-methyl-4,5-dihydroimidazole Chemical compound CN1CCN=C1 ANFXTILBDGTSEG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 8
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ASLICXGLMBICCD-UHFFFAOYSA-N 1-ethyl-4,5-dihydroimidazole Chemical compound CCN1CCN=C1 ASLICXGLMBICCD-UHFFFAOYSA-N 0.000 claims description 7
- SPBJUTVLDJRGSY-UHFFFAOYSA-N 1-heptadecyl-4,5-dihydroimidazole Chemical compound CCCCCCCCCCCCCCCCCN1CCN=C1 SPBJUTVLDJRGSY-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910015475 FeF 2 Inorganic materials 0.000 claims description 5
- -1 ferrous halide Chemical class 0.000 claims description 5
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002184 metal Substances 0.000 abstract description 25
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 150000003839 salts Chemical class 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002608 ionic liquid Substances 0.000 abstract description 8
- 229910001338 liquidmetal Inorganic materials 0.000 abstract description 5
- 239000010953 base metal Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 125000002636 imidazolinyl group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013028 medium composition Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Hair brushIt provides an anti-H 2 The corrosion inhibitor is prepared from imidazoline, brominated alkane and metal halide according to the molar ratio of (2). The invention relates to an anti-H 2 The bisimidazoline-based ionic liquid metal salt corrosion inhibitor in the S corrosion inhibitor has good water solubility, two imidazole rings in molecules can form a net structure, the adsorption capacity on base metal is enhanced, and the metal salt can effectively fill up gaps on an adsorption film, so that the adsorption film is more compact and the binding force is firmer. In addition, the metal salt can be used as a bridge, on one hand, the metal salt is easy to deposit on the metal surface, on the other hand, the high-valence Fe is easy to coordinate and adsorb with imidazoline, the adsorption effect of the corrosion inhibitor on the metal surface is enhanced, and the adsorption capacity of molecules on the matrix metal is also enhanced. Thereby making the metal have better H resistance 2 S corrosion performance.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to an anti-H 2 S corrosion inhibitor and a preparation method thereof.
Background
H 2 S is often present in oil and gas as a component of natural gas or petroleum associated gas, H 2 S has strong corrosivity to steel after being dissolved in water, and can cause rapid overall corrosion and severe local corrosion of the steel, so that pipelines and equipment are corroded and lose efficacy. H 2 S not only causes metal corrosion but also leads toThe hydrogen sulfide stress corrosion cracking, the hydrogen induced cracking and the like seriously affect the production safety of the oil and gas field.
The addition of corrosion inhibitors is the most common for inhibiting H 2 One of the methods of S etching. Currently the most commonly used anti-H 2 The S corrosion inhibitor mainly comprises S and N-containing heterocyclic organic matters, and is compounded with thiourea, derivatives thereof and other small molecules to improve the corrosion inhibition performance, but the heterocyclic organic matters are generally toxic, and a large amount of organic solvents must be compounded to pollute the environment. In recent years, in order to improve the environmental friendliness of the corrosion inhibitor, the imidazoline-based ionic liquid corrosion inhibitor is formed, only corrosion inhibiting molecules are contained, no solvent is contained, the environmental friendliness is greatly improved, but the corrosion inhibiting performance of the substance is poor, and the application of the substance is greatly influenced.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a method for inhibiting high H content in the oil and gas field exploitation and gathering and transportation process 2 H resistance of S medium to corrosion of station equipment 2 S corrosion inhibitor and its preparation method.
The invention is realized by the following technical scheme:
anti-H 2 S corrosion inhibitor, which comprises the following components in molar ratio: imidazoline, brominated alkanes and metal halides, wherein the molar ratio of the imidazoline to the brominated alkanes to the metal halides is 2.
More preferably, the imidazoline is any one of 1-methylimidazoline, 1-ethylimidazoline and 1-heptadecylimidazoline.
As a further preferable mode, the alkyl bromide is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane and 1, 5-dibromopentane.
Further, the metal halide is ferrous halide.
As a further preferable scheme, the metal halide is FeF 2 、FeCl 2 、FeBr 2 、 FeI 2 Any one of them.
Further, the anti-H 2 Slowing of S corrosionThe etching agent is obtained by the following reaction:
wherein, X is any one of F, cl, br and I.
anti-H 2 The preparation method of the corrosion inhibitor for S corrosion comprises the following steps:
s1, weighing imidazoline, bromoalkane and metal halide according to the molar ratio of 2;
s2, adding bromoalkane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing imidazoline and a condensation reflux device with a drying tube at the upper end of an energy converter of an ultrasonic cleaner, and carrying out ultrasonic treatment on the bromoalkane at normal temperature;
s3, dripping imidazoline into the brominated alkane subjected to ultrasonic treatment, then adopting intermittent ultrasonic wave to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1 hour until white floccule is generated, continuing reaction, and filtering to obtain light yellow solid;
s4, mixing the light yellow solid obtained in the S3 with acetone and metal halide, stirring for 30min at room temperature, and then filtering to remove precipitates in the filtrate; adding dichloromethane into the filtered filtrate to generate green precipitate, filtering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 S corrosion inhibitor.
Preferably, the ultrasonic treatment time in the step S2 is 25-35 min.
Preferably, the dropping time of the imidazoline in the step S3 is controlled within 30 min.
Preferably, the ratio of the working time to the off-time of the intermittent ultrasonic wave is 2: 1.
By adopting the technical scheme, the invention has the following beneficial effects:
the anti-H of the invention 2 The bis-imidazoline based ionic liquid metal salt corrosion inhibitor in the S corrosion inhibitor has good water solubility, and two imidazoline rings in the molecule canThe adsorption film is formed into a net structure, so that the adsorption capacity on the base metal is enhanced, and the metal salt can effectively fill the gaps on the adsorption film, so that the adsorption film is more compact and the binding force is firmer. In addition, the metal salt can be used as a bridge, on one hand, the metal salt is easy to deposit on the metal surface, on the other hand, the high-valence Fe is easy to coordinate and adsorb with imidazolinine, the adsorption effect of the corrosion inhibitor on the metal surface is enhanced, and the adsorption capacity of molecules on the matrix metal is also enhanced. Thereby making the metal have better H resistance 2 S corrosion performance.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, preferred embodiments of the present invention are described in detail below.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
In the examples, the specific conditions are not specified, and the examples are carried out under the conventional conditions or conditions recommended by the manufacturer unless otherwise specified. All starting materials mentioned in the following examples were obtained from published commercial sources unless otherwise specified.
Aiming at the current anti-H 2 The corrosion inhibitor corroded by S is a mono-imidazoline molecule, is in point adsorption, has poor adsorption effect, is added with a large amount of solvent and surfactant, has great environmental hazard and the like, and provides the following solution scheme:
the invention provides an anti-H 2 S corrosion inhibitor, which comprises the following components in molar ratio: imidazoline, brominated alkanes and metal halides, wherein the molar ratio of the imidazoline to the brominated alkanes to the metal halides is 2.
More preferably, the imidazoline is any one of 1-methylimidazoline, 1-ethylimidazoline and 1-heptadecylimidazoline.
In a further preferred embodiment, the alkyl bromide is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, and 1, 5-dibromopentane.
Further, the metal halide is ferrous halide.
As a further preferable scheme, the metal halide is FeF 2 、FeCl 2 、FeBr 2 、 FeI 2 Any one of them.
As a preferred embodiment, anti-H 2 The corrosion inhibitor for S corrosion comprises the following components in percentage by mass: 1-methylimidazoline, 1, 2-dibromoethane and ferrous halide, wherein the molar ratio of the 1-methylimidazoline to the 1, 2-dibromoethane to the ferrous halide is 2.
The invention also provides the anti-H 2 The preparation method of the corrosion inhibitor for S corrosion comprises the following steps:
s1, weighing imidazoline, bromoalkane and metal halide according to the molar ratio of 2;
s2, adding bromoalkane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing imidazoline and a condensation reflux device with a drying tube at the upper end of an energy converter of an ultrasonic cleaner, and carrying out ultrasonic treatment on the bromoalkane at normal temperature;
s3, dripping imidazoline into the brominated alkane subjected to ultrasonic treatment, then adopting intermittent ultrasonic wave to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1 hour until white floccules are generated, continuing reaction, and filtering to obtain a light yellow solid;
s4, mixing the light yellow solid obtained in the S3 with acetone and metal halide, stirring for 30min at room temperature, and then filtering to remove precipitates in the filtrate; adding dichloromethane into the filtered filtrate to generate green precipitate, filtering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 And S corrosion inhibitor.
Preferably, the ultrasonic treatment time in the step S2 is 25 to 35min.
Preferably, the dropping time of the imidazoline in the step S3 is controlled within 30 min.
Preferably, the ratio of the working time to the off-time of the intermittent ultrasonic wave is 2: 1.
The reaction principle achieved by the present invention, namely the H resistance, is illustrated below by a specific embodiment 2 The corrosion inhibitor for S corrosion is obtained by the following reaction:
wherein, X is any one of F, cl, br and I.
Each imidazoline group selected by the invention contains N and can form chemical adsorption with metal. The carbon chains among the bisimidazoline groups can form a net structure on the surface of the metal, so that the adsorption effect of the corrosion inhibitor is enhanced, and the bonding strength of the corrosion inhibitor film is increased. The metal salt can effectively fill up the gaps on the adsorption film, so that the adsorption film is more compact and the binding force is firmer.
The present invention will be described in further detail with reference to examples and comparative examples.
It should be noted that:
the corrosion rate of the corrosion inhibitor in the following examples is determined by the following method: medium composition: cl - ： 60701.52mg/L、Ca 2+ :19720mg/L、Mg 2+ ：1949.6mg/L、Na + :13104.17mg/L; test temperature: 25 ℃; test time: 96 hours; test materials: l245NS steel.
Polishing L245NS steel, cleaning with petroleum ether, acetone and ethanol, drying, weighing, placing prepared sample in autoclave, adding 100ppm corrosion inhibitor, stirring, hanging weighed L245NS steel in autoclave, sealing, and sealing with high purity N 2 After deoxygenation for 4H, the temperature is raised to 25 ℃, and high-purity H is introduced 2 S and maintain H 2 The S pressure is 0.1MPa, and high-purity CO is introduced 2 And maintain CO 2 The pressure is 0.28MPa, and high-purity N is introduced 2 Pressurizing until the total pressure is stabilized at 2MPa. And (4) taking out the sample after the sample is stabilized for 96 hours under the condition, removing a corrosion product film on the surface of the sample, weighing after drying, and calculating the corrosion rate.
Example 1:
resistance to H as described in the present embodiment 2 The corrosion inhibitor for S corrosion is prepared from 1-methylimidazoline, 1, 2-dibromoethane and FeF 2 Prepared according to the molar ratio of 2.
The anti-H 2 The preparation method of the corrosion inhibitor for S corrosion comprises the following steps:
s1, weighing 1-methylimidazoline, 1, 2-dibromoethane and FeF according to the molar ratio of 2 2 ；
S2, adding 1, 2-dibromoethane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing 1-methylimidazoline and a condensation reflux device with a drying tube at the upper end of an energy converter of an ultrasonic cleaner, and carrying out ultrasonic treatment on the 1, 2-dibromoethane for 30min at normal temperature;
s3, dropwise adding 1-methylimidazoline into the 1, 2-dibromoethane subjected to ultrasonic treatment, then adopting intermittent ultrasonic waves with the working time to outage time ratio of 2:1 to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1h until white floccules are generated, continuing reaction, and filtering to obtain light yellow solid;
s4, mixing the faint yellow solid obtained in the S3 with acetone and FeF 2 Mixing, stirring at room temperature for 30min, and filtering to remove precipitate; adding dichloromethane into the filtered filtrate to generate green precipitate, filtering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 And S corrosion inhibitor.
The anti-H obtained in this example 2 The corrosion inhibitor of S corrosion has good water solubility in a test medium, and the corrosion rate is 0.096mm/a.
Example 2:
resistance to H as described in the present embodiment 2 The corrosion inhibitor for S corrosion is prepared from 1-ethylimidazoline, 1, 4-dibromobutane and FeCl 2 Prepared according to the molar ratio of 2.
The anti-H 2 The preparation method of the S corrosion inhibitor comprises the following steps:
s1, weighing 1-ethylimidazoline, 1, 4-dibromobutane and FeCl according to the molar ratio of 2 2 ；
S2, adding 1, 4-dibromobutane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing 1-ethylimidazoline and a condensation reflux device with a drying tube at the upper end of an energy converter of an ultrasonic cleaner, and carrying out ultrasonic treatment on the 1, 4-dibromobutane for 30min at normal temperature;
s3, slowly dripping 1-ethylimidazoline into the 1, 4-dibromobutane after ultrasonic treatment, then adopting intermittent ultrasonic waves with the working time to stop time ratio of 2:1 to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1 hour until white floccules are generated, continuing reaction and filtering to obtain light yellow solid;
s4, mixing the light yellow solid obtained in the step S3 with acetone and FeCl 2 Mixing, stirring at room temperature for 30min, and filtering to remove precipitate; adding dichloromethane into the filtered filtrate to generate green precipitate, filtering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 And S corrosion inhibitor.
The anti-H obtained in this example 2 The S corrosion inhibitor has good water solubility in a test medium, and the corrosion rate is 0.092mm/a.
Example 3:
resistance to H as described in the present embodiment 2 The corrosion inhibitor for S corrosion is prepared from 1-heptadecyl imidazoline, 1, 3-dibromopropane and FeBr 2 Prepared according to the molar ratio of 2.
The anti-H 2 The preparation method of the corrosion inhibitor for S corrosion comprises the following steps:
s1, weighing 1-heptadecyl imidazoline, 1, 3-dibromopropane and FeBr according to the molar ratio of 2 2 ；
S2, adding 1, 3-dibromopropane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing 1-heptadecyl imidazoline and a condensation reflux device with a drying tube at the upper end of a transducer of an ultrasonic cleaner, and carrying out ultrasonic treatment on the 1, 3-dibromopropane for 30min at normal temperature;
s3, dropwise adding 1-heptadecyl imidazoline into the 1, 3-dibromopropane subjected to ultrasonic treatment, then adopting intermittent ultrasonic waves with the working time to outage time ratio of 2:1 to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1h until white floccules are generated, continuing reaction, and filtering to obtain light yellow solid;
s4, mixing the light yellow solid obtained in the S3 with acetone and FeBr 2 Mixing, stirring at room temperature for 30min, and filtering to remove precipitate; adding dichloromethane into the filtered filtrate to generate green precipitate, filtering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 S corrosion inhibitor.
The anti-H obtained in this example 2 The S corrosion inhibitor has good water solubility in a test medium, and the corrosion rate is 0.086mm/a.
And (3) comparison test:
the corrosion inhibitor is the bisimidazoline based ionic liquid corrosion inhibitor, the addition amount is 100ppm, the water solubility in a test medium is good, and the corrosion rate is 0.116mm/a.
The above examples show that bisimidazoline based ionic liquids and FeX 2 Has better synergistic effect, and the bisimidazoline-based ionic liquid metal salt corrosion inhibitor compounded by the two has a good H-component corrosion inhibition effect 2 The S corrosion has good inhibition effect.
anti-H of the invention 2 The bisimidazoline-based ionic liquid metal salt corrosion inhibitor in the S corrosion inhibitor has good water solubility, two imidazole rings in molecules can form a net structure, the adsorption capacity on base metal is enhanced, and the metal salt can effectively fill up gaps on an adsorption film, so that the adsorption film is more compact and the binding force is firmer. In addition, the metal salt can be used as a bridge, on one hand, the metal salt is easy to deposit on the metal surface, on the other hand, the high-valence Fe is easy to coordinate and adsorb with imidazoline, the adsorption effect of the corrosion inhibitor on the metal surface is enhanced, and the adsorption capacity of molecules on the matrix metal is also enhanced. Thereby making the metal have better H resistance 2 S corrosion performance.
Thus, the invention provides anti-H 2 The corrosion inhibitor for S corrosion is a bisimidazoline-based ionic liquid metal salt corrosion inhibitor, has a compact self-adsorption film and is H-resistant 2 S corrosion resistance is excellent, and the H corrosion resistance is 2 The S corrosion inhibitor is miscible with water at any ratio, has excellent water solubility, and does not need to be addedA synergist.
In addition to this, the anti-H 2 The S corrosion inhibitor is suitable for environments with higher temperature and high H2S partial pressure, and has the advantages of good corrosion resistance effect, small using amount, low cost and environmental friendliness.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions without departing from the spirit of the invention as set forth in the claims appended hereto.
Claims (7)
1. anti-H 2 The S corrosion inhibitor is characterized by comprising the following components in molar ratio: imidazoline, brominated alkanes and metal halides, wherein the molar ratio of the imidazoline to the brominated alkanes to the metal halides is 2;
the imidazoline is any one of 1-methylimidazoline, 1-ethylimidazoline and 1-heptadecyl imidazoline;
the metal halide is ferrous halide;
the preparation method of the corrosion inhibitor comprises the following steps:
s1, weighing imidazoline, bromoalkane and metal halide according to the molar ratio of 2;
s2, adding bromoalkane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing imidazoline and a condensation reflux device with a drying tube at the upper end of an energy converter of an ultrasonic cleaner, and carrying out ultrasonic treatment on the bromoalkane at normal temperature;
s3, dripping imidazoline into the brominated alkane subjected to ultrasonic treatment, then adopting intermittent ultrasonic wave to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1 hour until white floccule is generated, continuing reaction, and filtering to obtain light yellow solid;
s4, mixing the light yellow solid obtained in the S3 with acetone and metal halide, stirring for 30min at room temperature, and then filtering to remove precipitates in the filtrate; adding dichloromethane into the filtered filtrate to generate green precipitateFiltering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 S corrosion inhibitor.
2. An anti-H according to claim 1 2 The corrosion inhibitor for S corrosion is characterized in that: the brominated alkane is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane and 1, 5-dibromopentane.
3. An anti-H according to claim 1 2 The corrosion inhibitor for S corrosion is characterized in that: the metal halide is FeF 2 、FeCl 2 、FeBr 2 、FeI 2 Any one of them.
4. An anti-H according to claim 1 2 The preparation method of the S corrosion inhibitor is characterized by comprising the following steps:
s1, weighing imidazoline, bromoalkane and metal halide according to the molar ratio of 2;
s2, adding bromoalkane into a three-neck round-bottom flask, fixing a constant-pressure dropping funnel containing imidazoline and a condensation reflux device with a drying tube at the upper end of an energy converter of an ultrasonic cleaner, and carrying out ultrasonic treatment on the bromoalkane at normal temperature;
s3, dripping imidazoline into the brominated alkane subjected to ultrasonic treatment, then adopting intermittent ultrasonic wave to enable the clear liquid to become turbid, continuing ultrasonic treatment for 1 hour until white floccules are generated, continuing reaction, and filtering to obtain a light yellow solid;
s4, mixing the light yellow solid obtained in the step S3 with acetone and metal halide, stirring for 30min at room temperature, and filtering to remove precipitates in the filtrate; adding dichloromethane into the filtered filtrate to generate green precipitate, filtering, rotary evaporating to remove acetone and dichloromethane, and vacuum drying to obtain anti-H 2 And S corrosion inhibitor.
5. An anti-H according to claim 4 2 The preparation method of the corrosion inhibitor for S corrosion is characterized by comprising the following steps: the ultrasonic treatment time in the step S2 is 25 to 35min.
6. An anti-H according to claim 4 2 The preparation method of the corrosion inhibitor for S corrosion is characterized by comprising the following steps: the dropping time of the imidazoline in the step S3 is controlled within 30 min.
7. An anti-H according to claim 4 2 The preparation method of the corrosion inhibitor for S corrosion is characterized by comprising the following steps: the ratio of the working time to the stop time of the intermittent ultrasonic wave is 2: 1.
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