CN112358861A - Corrosion inhibition bactericide for shale gas field - Google Patents
Corrosion inhibition bactericide for shale gas field Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 76
- 230000007797 corrosion Effects 0.000 title claims abstract description 76
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 60
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 53
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 47
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000004094 surface-active agent Substances 0.000 claims abstract description 69
- 239000002608 ionic liquid Substances 0.000 claims abstract description 47
- 150000003863 ammonium salts Chemical group 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000002401 inhibitory effect Effects 0.000 claims description 12
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 claims description 8
- KKNKZPUCTZEWNF-UHFFFAOYSA-N 1-butyl-3-tetradecyl-2h-imidazole Chemical compound CCCCCCCCCCCCCCN1CN(CCCC)C=C1 KKNKZPUCTZEWNF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- WZVZUMWEVCNDAN-UHFFFAOYSA-N 1-butyl-3-decyl-2H-imidazole Chemical compound CCCCCCCCCCN1CN(CCCC)C=C1 WZVZUMWEVCNDAN-UHFFFAOYSA-N 0.000 claims description 3
- SKTNYXGVOFRMEQ-UHFFFAOYSA-N 1-butyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(CCCC)C=C1 SKTNYXGVOFRMEQ-UHFFFAOYSA-N 0.000 claims description 3
- CYJHQFPXAZQBSN-UHFFFAOYSA-N 1-butyl-3-dodecyl-2h-imidazole Chemical compound CCCCCCCCCCCCN1CN(CCCC)C=C1 CYJHQFPXAZQBSN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 14
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 14
- 238000011161 development Methods 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 34
- 230000000694 effects Effects 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- -1 urea compound Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/10—Quaternary compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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Abstract
The invention relates to the technical field of shale gas field development, in particular to a corrosion inhibition bactericide for a shale gas field, which comprises the following components in percentage by mass: 10-30% of quinoline type biquaternary ammonium salt, 5-20% of urotropine, 1-5% of Gemini type surfactant, 10-20% of ionic liquid and 30-64% of water; the corrosion inhibition bactericide has simple components, good compatibility of the components, and a corrosion inhibition rate of 0.006-0.007mm/a, enhances the corrosion inhibition performance, and has a bactericidal rate of 100% under the consumption of 150ppm of the corrosion inhibition bactericide, thereby enhancing the bactericidal performance; the components are cooperated with each other, so that the corrosion inhibition performance and the sterilization performance are good.
Description
Technical Field
The invention relates to the technical field of shale gas field development, in particular to a corrosion inhibition bactericide for a shale gas field.
Background
Shale gas is a natural gas resource which is stored in a shale layer and can be exploited, and the formation and enrichment of the shale gas have unique characteristics and are often distributed in shale hydrocarbon source rock strata with large thickness and wide distribution in a basin. Compared with the conventional natural gas, the shale gas development has the advantages of long mining life and long production period, most of produced shale gas has wide distribution range and large thickness and generally contains gas, so that the shale gas well can produce gas at a stable rate for a long time. The produced liquid is often accompanied with residual acid and CO in the development process of shale gas field2And HS and other corrosive substances which have strong corrosivity to the underground pipe column and the ground gathering and transportation system. Meanwhile, in the shale gas development process, the injection of water, drilling fluid, fracturing fluid and the like can bring bacteria into the production system. Most of the bacteria are sulfate reducing bacteria, and from the production of shale gas, bacterial corrosion can occur in most shale gas fields, so that huge economic loss is caused, and the living environment of human beings is threatened. Therefore, for shale gas field oil gas gathering and transportation pipelines with bacteria propagation, corrosion inhibitors and bactericides are required to be added respectively, the corrosion inhibitors mainly take adsorption and corrosion inhibition as main components, quaternary ammonium salts and derivatives thereof are used as main components, the effects of sterilization are generally not achieved, bactericides are required to be added additionally, and the compatibility of the existing corrosion inhibitors and bactericides is poor. Based on this, patent CN 104003528A provides a novel bactericidal corrosion inhibitor, which comprises the following components: calculated by 100% of the composition, 1-30% of biquaternary ammonium salt of quinoline and alkyl tertiary ammonium, 1-30% of biquaternary ammonium salt of alkyl tertiary ammonium, 1-15% of organic urea compound, 1-10% of organic amine compound, 1-20% of alkyl quaternary ammonium salt, 1-10% of glutaraldehyde, 1-10% of alkynol, 1-10% of higher fatty amide derivative, 1-10% of alkylphenol polyoxyethylene polyoxypropylene ether and the balance of water; the synthesized biquaternary ammonium salt has bactericidal propertyThe corrosion inhibitor has corrosion inhibition performance, and the corrosion inhibitor and the auxiliary agent are mixed under the synergistic effect of the two, so that the requirements of controlling bacteria and controlling corrosion can be met, but the formula has complex components, and the components are not uniformly mixed, so that the corrosion inhibition performance and the sterilization performance are influenced.
Disclosure of Invention
Aiming at the problems of complex components and poor compatibility of the existing bactericidal corrosion inhibitor, the invention provides the corrosion-inhibiting bactericide for the shale gas field, which has the advantages of simple components, good compatibility, uniform mixing of the components and enhanced corrosion inhibition performance and bactericidal performance.
The invention provides a corrosion inhibition bactericide for a shale gas field, which comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 10-30%
5-20% of urotropin
1 to 5 percent of Gemini type surfactant
10 to 20 percent of ionic liquid
30-64% of water.
Preferably, the corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 20%
15 percent of urotropin
Gemini type surfactant 3%
Ionic liquid surfactant 15%
And 47% of water.
The quinoline type biquaternary ammonium salt is prepared by the following steps: adding 20-50% quinoline into a three-necked bottle by taking 40-80% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 8-30% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 4-6h to obtain the quinoline.
Preferably, the quinoline type biquaternary ammonium salt is prepared by the following steps: adding 32% quinoline into a three-necked bottle by using 53% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 15% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 4-6h to obtain the quinoline. The quinoline type biquaternary ammonium salt has the dual-purpose effect of one agent, and has the corrosion inhibition effect and the sterilization effect.
The Gemini surfactant is a sulfonic acid type anion Gemini surfactant. The Gemini type surfactant has certain corrosion inhibition performance, can be compounded with other components to enhance the corrosion inhibition performance, has strong penetrability and excellent surface activity, can uniformly mix the components in the compounding process, and realizes clarification and brightness of the obtained corrosion inhibition bactericide.
The ionic liquid surfactant is one of N-butyl-3-octyl imidazole surface active ionic liquid, N-butyl-3-decyl imidazole surface active ionic liquid, N-butyl-3-dodecyl imidazole surface active ionic liquid or N-butyl-3-tetradecyl imidazole surface active ionic liquid; preferably, the ionic liquid surfactant is N-butyl-3-tetradecyl imidazole surface active ionic liquid. The ionic liquid surfactant has certain bactericidal performance, and can enhance the bactericidal performance after being compounded with other components.
The preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(5) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(6) adding water, heating to 50-70 deg.C and stirring;
(7) adding ionic liquid surfactant to react for 2-3 h;
(8) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibiting bactericide.
The beneficial effect of the invention is that,
(1) the quinoline type biquaternary ammonium salt provided by the application has a dual-purpose effect, has a corrosion inhibition effect and a sterilization effect; the Gemini type surfactant has certain corrosion inhibition performance, can be compounded with other components to enhance the corrosion inhibition performance, has strong penetrability and excellent surface activity, can uniformly mix the components in the compounding process, and realizes clarification and brightness of the obtained corrosion inhibition bactericide; the ionic liquid surfactant has certain bactericidal performance, and can enhance the bactericidal performance after being compounded with other components; the components in the formula have synergistic effect, so that the corrosion inhibition performance and the sterilization performance are improved;
(2) the components are simple, and the compatibility of each component is good, so that the corrosion inhibition performance and the sterilization performance are good; the corrosion inhibition rate is 0.006-0.007mm/a, which is far less than the industrial standard, the corrosion inhibition performance is enhanced, the sterilization rate reaches 100% under the consumption of 150ppm corrosion inhibition bactericide, and the sterilization performance is enhanced.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 20%
15 percent of urotropin
Gemini type surfactant 3%
15 percent of ionic liquid
47% of water;
wherein,
the quinoline type biquaternary ammonium salt is prepared by the following steps: adding 32% quinoline into a three-necked bottle by using 53% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 15% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 6 hours to obtain the quinoline-containing aqueous solution;
the Gemini surfactant is a sulfonic acid type anion Gemini surfactant;
the ionic liquid surfactant is N-butyl-3-tetradecyl imidazole surfactant ionic liquid;
the preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(1) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(2) adding water, heating to 50 deg.C and stirring;
(3) adding ionic liquid surfactant to react for 3 h;
(4) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibition bactericide S1.
Example 2
The corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 30%
Urotropin 7%
Gemini type surfactant 5%
20 percent of ionic liquid
37% of water;
wherein,
the quinoline type biquaternary ammonium salt is prepared by the following steps: adding 20% quinoline into a three-necked bottle by taking 70% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 10% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 6 hours to obtain the quinoline-containing organic compound;
the Gemini surfactant is a sulfonic acid type anion Gemini surfactant;
the ionic liquid surfactant is N-butyl-3-decyl imidazole surfactant ionic liquid;
the preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(1) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(2) adding water, heating to 40 deg.C and stirring;
(3) adding ionic liquid surfactant to react for 3 h;
(4) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibition bactericide S2.
Example 3
The corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 30%
Urotropin 10%
1 percent of Gemini type surfactant
10 percent of ionic liquid
49% of water;
wherein,
the quinoline type biquaternary ammonium salt is prepared by the following steps: adding 32% quinoline into a three-necked bottle by using 53% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 15% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 6 hours to obtain the quinoline-containing aqueous solution;
the Gemini surfactant is a sulfonic acid type anion Gemini surfactant;
the ionic liquid surfactant is N-butyl-3-octyl imidazole surface active ionic liquid;
the preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(1) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(2) adding water, heating to 50 deg.C and stirring;
(3) adding ionic liquid surfactant to react for 3 h;
(4) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibition bactericide S3.
Comparative example 1
The corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 20%
15 percent of urotropin
Gemini type surfactant 3%
62% of water;
wherein,
the quinoline type biquaternary ammonium salt is prepared by the following steps: adding 32% quinoline into a three-necked bottle by using 53% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 15% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 6 hours to obtain the quinoline-containing aqueous solution;
the Gemini surfactant is a sulfonic acid type anion Gemini surfactant;
the ionic liquid surfactant is N-butyl-3-tetradecyl imidazole surfactant ionic liquid;
the preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(1) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(2) adding water, heating to 50 deg.C and stirring;
(3) adding ionic liquid surfactant to react for 3 h;
(4) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibition bactericide D1.
Comparative example 2
The corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 20%
15 percent of urotropin
15 percent of ionic liquid
50% of water;
wherein,
the quinoline type biquaternary ammonium salt is prepared by the following steps: adding 32% quinoline into a three-necked bottle by using 53% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 15% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 6 hours to obtain the quinoline-containing aqueous solution;
the Gemini surfactant is a sulfonic acid type anion Gemini surfactant;
the ionic liquid surfactant is N-butyl-3-tetradecyl imidazole surfactant ionic liquid;
the preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(1) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(2) adding water, heating to 50 deg.C and stirring;
(3) adding ionic liquid surfactant to react for 3 h;
(4) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibition bactericide D2.
Comparative example 3
The corrosion inhibition bactericide for the shale gas field comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 20%
15 percent of urotropin
Gemini type surfactant 3%
15 percent of ionic liquid
47% of water;
wherein,
the quinoline type biquaternary ammonium salt is N-benzyl-R-quinoline quaternary ammonium chloride;
the Gemini surfactant is a sulfonic acid type anion Gemini surfactant;
the ionic liquid surfactant is N-butyl-3-tetradecyl imidazole surfactant ionic liquid;
the preparation method of the corrosion inhibition bactericide for the shale gas field comprises the following steps:
(5) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(6) adding water, heating to 50 deg.C and stirring;
(7) adding ionic liquid surfactant to react for 3 h;
(8) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibition bactericide D3.
Test examples
1. Evaluation of Corrosion inhibition Performance
The corrosion inhibition performance of S1-S3 and D1-D3 corrosion inhibition bactericides is evaluated, the detection is based on a method of 'Q/SY 126-2014' standard of China oil and gas group company, water is simulated on site, and CO is introduced2The corrosion inhibition performance is verified under the condition of gas, and the result is shown in table 1.
TABLE 1 Corrosion inhibition Rate of Corrosion-inhibiting Fungicide at different dosages
2. Evaluation of Sterilization Properties
The bactericidal performance of S1-S3 and D1-D3 corrosion-inhibiting bactericides is evaluated according to an API RP-38 method, and the conditions are as follows: the bacteria and the medicine are contacted for 1h at 37 ℃, the bacteria bottle is an SRB-HX type bacteria bottle, and the initial bacteria amount is 1 multiplied by 106The results are shown in Table 2.
TABLE 2 Sterilization rates of different corrosion-inhibiting bactericides at different dosages
The corrosion inhibitor has the advantages that the components are simple, the compatibility of the components is good, the corrosion inhibition rate is 0.006-0.007mm/a and is far less than the industrial standard, the corrosion inhibition performance is enhanced, the sterilization rate reaches 100% under the condition of using 150ppm of the corrosion inhibitor and the sterilization performance is enhanced. The Gemini type surfactant has certain corrosion inhibition performance, can be compounded with other components to enhance the corrosion inhibition performance, has strong penetrability and excellent surface activity, can uniformly mix the components in the compounding process, and realizes clarification and brightness of the obtained corrosion inhibition bactericide; the ionic liquid surfactant has certain bactericidal performance, and can enhance the bactericidal performance after being compounded with other components; the components in the formula have synergistic effect, so that the corrosion inhibition performance and the sterilization performance are improved.
The present invention has been described in detail by way of preferred embodiments, but the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The corrosion inhibition bactericide for the shale gas field is characterized by comprising the following components in percentage by mass:
quinoline type biquaternary ammonium salt 10-30%
5-20% of urotropin
1 to 5 percent of Gemini type surfactant
10 to 20 percent of ionic liquid
30-64% of water.
2. The corrosion-inhibiting bactericide for the shale gas field according to claim 1, which comprises the following components in percentage by mass:
quinoline type biquaternary ammonium salt 20%
15 percent of urotropin
Gemini type surfactant 3%
Ionic liquid surfactant 15%
And 47% of water.
3. The corrosion-inhibiting bactericide for shale gas fields according to claim 1 or 2, wherein the quinoline-type diquaternary ammonium salt is prepared by the following steps: adding 20-50% quinoline into a three-necked bottle by taking 40-80% of ethanol as a solvent, stirring and heating to 30-50 ℃, adding 8-30% of 1, 6-dichlorohexane into a reaction container in a dropwise manner, and carrying out reflux reaction for 4-6h to obtain the quinoline.
4. The corrosion-inhibiting bactericide for the shale gas field according to any one of claims 1 or 2, wherein the Gemini surfactant is a sulfonic acid type anionic Gemini surfactant.
5. The corrosion-inhibiting bactericide for shale gas fields according to claim 1 or 2, wherein the ionic liquid surfactant is one of N-butyl-3-octylimidazole surfactant ionic liquid, N-butyl-3-decylimidazole surfactant ionic liquid, N-butyl-3-dodecylimidazole surfactant ionic liquid or N-butyl-3-tetradecylimidazole surfactant ionic liquid.
6. The corrosion inhibiting bactericide for shale gas fields according to any one of claims 5, wherein the ionic liquid surfactant is N-butyl-3-tetradecylimidazole surface active ionic liquid.
7. The corrosion inhibiting bactericide for shale gas fields according to any one of claims 1 or 2, which is prepared by the following steps:
(1) adding quinoline type biquaternary ammonium salt and urotropine into a flask;
(2) adding water, heating to 50-70 deg.C and stirring;
(3) adding ionic liquid surfactant to react for 2-3 h;
(4) then adding Gemini type surfactant, and continuously stirring until the system is clear and bright, thus obtaining the corrosion-inhibiting bactericide.
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| WO2023124953A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Bactericidal corrosion inhibitor as well as preparation method therefor and use thereof |
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Effective date of registration: 20220128 Address after: 100000 22 Chaoyangmen North Street, Chaoyang District, Beijing. Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Applicant after: SINOPEC CHONGQING FULING SHALE GAS EXPLORATION AND DEVELOPMENT Co.,Ltd. Applicant after: Binzhou Guangyou Chemical Co.,Ltd. Address before: 408000 No.6 Hefeng Avenue, Fuling District, Chongqing Applicant before: SINOPEC CHONGQING FULING SHALE GAS EXPLORATION AND DEVELOPMENT Co.,Ltd. Applicant before: Binzhou Guangyou Chemical Co.,Ltd. |
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