CN116925723A - Heterocyclic organosilicon quaternary ammonium salt and active carbon blending bactericide for oil and gas field and preparation method thereof - Google Patents
Heterocyclic organosilicon quaternary ammonium salt and active carbon blending bactericide for oil and gas field and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 59
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 43
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 238000002156 mixing Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 72
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 24
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims abstract description 14
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- DJXNJVFEFSWHLY-UHFFFAOYSA-N quinoline-3-carboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CN=C21 DJXNJVFEFSWHLY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- -1 silicon quaternary ammonium salt Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 37
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 27
- 241000894006 Bacteria Species 0.000 abstract description 21
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 9
- 206010059866 Drug resistance Diseases 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 description 12
- 230000001580 bacterial effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 229930182555 Penicillin Natural products 0.000 description 5
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229940049954 penicillin Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000002147 killing effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- ZXZKYYHTWHJHFT-UHFFFAOYSA-N quinoline-2,8-diol Chemical compound C1=CC(=O)NC2=C1C=CC=C2O ZXZKYYHTWHJHFT-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
-
- 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
- A01N25/08—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 containing solids as carriers or diluents
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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
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The application discloses a heterocyclic organosilicon quaternary ammonium salt and active carbon blending bactericide for oil and gas fields and a preparation method thereof, relates to the technical field of bactericides for oil and gas fields, and solves the technical problem that the expected sterilization efficiency still cannot be achieved after the existing bacteria generate drug resistance, and comprises the following components in parts by weight: absolute ethyl alcohol, active carbon, quinoline-3-carboxylic acid, N, N-dimethylethanolamine, gamma-chloropropyl trimethoxysilane, hypophosphorous acid, sodium iodide and anhydrous dimethyl sulfoxide; the application introduces corresponding heterocyclic structures such as quinoline and the like into the organosilicon quaternary ammonium salt bactericide to form the characteristic of structural diversity, can enhance the sterilizing efficiency, has strong compatibility with active carbon, has obviously stronger sterilizing effect than the traditional sterilizing, has a continuous sterilizing function, and has the advantages of higher sterilizing speed, longer lasting effect, less environmental pollution and less harm to human bodies.
Description
Technical Field
The application relates to the field of oil and gas field chemistry, in particular to the technical field of bactericides for oil and gas fields.
Background
The quaternary ammonium salt cationic surfactant is a bactericide with positive charges on the surface, can adsorb bacteria with negative charges, has good bactericidal effect, and is commonly used for killing bacteria which are easy to cause serious corrosion to equipment, such as Sulfate Reducing Bacteria (SRB) in the production process of oil and gas fields; the organosilicon quaternary ammonium salt is formed by introducing quaternary ammonium salt structure into siloxane, so that the performance of the organosilicon quaternary ammonium salt can be changed. The organosilicon quaternary ammonium salt is positively charged, is a novel cationic surfactant, has the advantages of high temperature resistance, high sterilization speed, lasting sterilization and the like, and can effectively inhibit gram-positive bacteria, gram-negative bacteria, saccharomycetes and fungi; the heterocyclic compound has high efficiency, low toxicity and broad spectrum bioactivity, and has good killing effect on bacteria and fungi. Quinoline is a six-membered heterocyclic compound with a molecular formula of C 9 H 7 N is commonly used for preparing products such as nicotinic acid and hydroxyquinoline medicines, cyanine pigment, photosensitive pigment, rubber accelerator, pesticide 8-hydroxyquinolinone and the like. Proved by researches, the quaternary ammonium salt with a quinoline structure has a certain corrosion inhibition effect; the active carbon has stronger adsorptivity, the micropore diameter of the surface is mostly between 2 and 50nm, and the surface area of each gram of active carbon is 500 to 1500m 2 . Because of the strong adsorptivity of activated carbon, the activated carbon is commonly used for adsorbing impurities in oil extraction sewage.
Application number 200510045294.0 is named as a preparation method of the organosilicon quaternary ammonium salt bactericide, and mainly aims at the sterilization problem in public places, and the organosilicon quaternary ammonium salt bactericide comprises the following components in percentage by mole: dimethyl octadecyl tertiary amine: gamma-chloropropyl triethoxysilane: absolute ethyl alcohol=1.0:1.1-1.3:7.0-8.0, the bactericide is mainly suitable for the sterilization problem of public places, but the water quality of oil and gas fields is obviously different from that of common public places, so that the bactericide which has high-efficiency sterilization effect under the sewage environment of the oil and gas fields and meets the requirements of environmental protection and the like needs to be developed; application number 201910475514.5 is named as an oilfield reinjection water composite bactericide and a preparation method, and mainly aims at the sterilization problem of oilfield reinjection water, and the oilfield reinjection water composite bactericide comprises the following components in percentage by weight: n-alkyl bis-quaternary ammonium salt: 30% -40% of dodecyl dimethyl benzyl ammonium chloride: 60% -70%. The bactericide has the advantages of simple preparation method, low production cost, small use amount and high sterilization rate, but still belongs to the traditional oilfield quaternary ammonium salt bactericide, and the expected sterilization efficiency still cannot be achieved after bacteria generate drug resistance.
Disclosure of Invention
The application aims at: the application provides a heterocyclic organosilicon quaternary ammonium salt and active carbon blending bactericide for oil and gas fields and a preparation method thereof, aiming at solving the technical problems that the existing bactericide does not have continuous bactericidal property and still cannot reach expected bactericidal efficiency after bacteria generate drug resistance.
The application adopts the following technical scheme for realizing the purposes: the heterocyclic organosilicon quaternary ammonium salt and activated carbon blended bactericide for the oil and gas field comprises the following components in parts by weight: 1000-1400 parts of absolute ethyl alcohol, 20-30 parts of active carbon, 100-120 parts of quinoline-3-carboxylic acid, 50-70 parts of N, N-dimethylethanolamine, 50-70 parts of gamma-chloropropyl trimethoxysilane, 1-5 parts of hypophosphorous acid, 1-5 parts of sodium iodide and 50-70 parts of anhydrous dimethyl sulfoxide.
The technical scheme of the application is as follows: the reaction of the haloalkylsilane and the long-carbon-chain tertiary amine is SN2 nucleophilic substitution reaction, the organosilicon quaternary ammonium salt with quinoline heterocycle can be synthesized through the reaction, and the heterocyclic organosilicon quaternary ammonium salt is formed by introducing the quinoline heterocycle structure into the organosilicon quaternary ammonium salt, and the compound with the quinoline heterocycle has good performance in the aspect of killing microorganisms, so that the sterilization efficiency can be enhanced, and the problem of drug resistance of corrosive bacteria such as sulfate reducing bacteria, iron oxidizing bacteria and the like in an oil field can be solved; the components in the oilfield sewage are complex, the sterilization effect of the bactericide can be influenced, the formed heterocyclic organosilicon quaternary ammonium salt is compounded with the activated carbon, the heterocyclic organosilicon quaternary ammonium salt can be attached to the activated carbon, a large amount of sulfate reducing bacteria can be adsorbed in the sewage, so that the contact area between bacteria and the bactericide is increased, the sterilization efficiency is improved, in addition, the activated carbon can adsorb impurities in the solution, so that the bactericide dissolved in the sewage can avoid the influence of other impurities in the solution, and the sterilization efficiency is improved. The organic silicon quaternary ammonium salt bactericide is introduced with corresponding quinoline heterocyclic structures to form the characteristic of structural diversity, so that the sterilizing efficiency can be enhanced, the problem of drug resistance of corrosive bacteria such as sulfate reducing bacteria and iron oxidizing bacteria in oil fields is solved, meanwhile, the compatibility of the heterocyclic organic silicon quaternary ammonium salt bactericide and activated carbon is strong, the sterilizing effect of the compound bactericide is obviously stronger than that of the traditional bactericide, and the compound bactericide has a continuous sterilizing function, and has the advantages of higher sterilizing speed, longer effect, less environmental pollution and less harm to human bodies.
Preferably, the blended bactericide comprises the following components in parts by weight: 600 parts of absolute ethyl alcohol, 25 parts of active carbon, 110 parts of quinoline-3-carboxylic acid, 60 parts of N, N-dimethylethanolamine, 60 parts of gamma-chloropropyl trimethoxysilane, 3 parts of hypophosphorous acid, 3 parts of sodium iodide and 60 parts of anhydrous dimethyl sulfoxide.
The preparation method of the heterocyclic organosilicon quaternary ammonium salt and activated carbon blending bactericide for the oil and gas field comprises the following steps:
step 1, adding 500-700 parts of absolute ethyl alcohol into 100-120 parts of quinoline-3-carboxylic acid according to parts by weight, refluxing by using a condenser tube, adding 50-70 parts of N, N-dimethylethanolamine when the temperature is increased to 50-60 ℃, adding 1-5 parts of hypophosphorous acid as a catalyst for reaction, then quickly heating to 70-90 ℃, reacting for 8-10 hours, and cooling to obtain a mixture A;
step 2, adding 500-700 parts of absolute ethyl alcohol into the mixture A obtained in the step 1 according to parts by weight, refluxing by using a condenser tube, adding 50-70 parts of absolute dimethyl sulfoxide, heating to 70-90 ℃ under the protection of nitrogen, adding 1-5 parts of sodium iodide and 50-70 parts of gamma-chloropropyl trimethoxysilane, taking sodium iodide as a reaction catalyst, taking absolute dimethyl sulfoxide as a cosolvent, obtaining a mixture B after full reaction, and purifying by using 500-700 parts of acetone to obtain the heterocyclic organic silicon quaternary ammonium salt;
and step 3, mixing the heterocyclic organosilicon quaternary ammonium salt with 20-30 parts of active carbon to obtain the blending bactericide.
Further, the structural formula of the heterocyclic organosilicon quaternary ammonium salt in the step 2 is as follows:
further, in the step 1, 600 parts of absolute ethyl alcohol is added into 110 parts of quinoline-3-carboxylic acid according to parts by weight, reflux is carried out by using a condenser tube, 60 parts of N, N-dimethylethanolamine is added when the temperature is raised to 55 ℃,3 parts of hypophosphorous acid is added as a catalyst for reaction, the temperature is raised to 80 ℃ rapidly, the reaction is carried out for 9 hours, and the mixture A is obtained after cooling.
Further, in step 2, 600 parts of absolute ethyl alcohol is added into the mixture A obtained in step 1 according to parts by weight, reflux is carried out by using a condenser tube, 3 parts of absolute dimethyl sulfoxide is added, the temperature is raised to 80 ℃ under the protection of nitrogen, 3 parts of sodium iodide and 60 parts of gamma-chloropropyl trimethoxysilane are added, wherein the absolute dimethyl sulfoxide is used as a cosolvent, sodium iodide is used as a reaction catalyst, a mixture B is obtained after full reaction, and 700 parts of acetone is used for purification, so that the heterocyclic organic silicon quaternary ammonium salt is obtained.
The beneficial effects of the application are as follows:
1. the organic silicon quaternary ammonium salt bactericide is introduced with corresponding quinoline heterocyclic structures to form the characteristic of structural diversity, so that the sterilization efficiency can be enhanced, and the problem of drug resistance of corrosive bacteria such as sulfate reducing bacteria, iron oxidizing bacteria and the like in an oil field is solved;
2. meanwhile, the compatibility of the heterocyclic organosilicon quaternary ammonium salt and the activated carbon is strong, the sterilization effect of the compound bactericide is obviously better than that of the traditional bactericide, and the compound bactericide has a continuous sterilization function, and has the advantages of higher sterilization speed, less environmental pollution and less harm to human bodies;
3. the heterocyclic organosilicon quaternary ammonium salt is compounded with the activated carbon, the heterocyclic organosilicon quaternary ammonium salt can be attached to the activated carbon, a large amount of sulfate reducing bacteria can be adsorbed in the sewage, so that the contact area of the bacteria and the bactericide is increased, and the sterilization efficiency is improved, in addition, the activated carbon can adsorb impurities in the solution, so that the bactericide dissolved in the sewage can avoid the influence of other impurities in the solution, and the sterilization efficiency is improved
4. In the synthesis of the mixture B, the reaction of tertiary amine and gamma-chloropropyl silane belongs to typical SN2 nucleophilic substitution reaction, the steric hindrance is large, the contact of an attack reagent and carbon atoms with partial positive charges in C-X bonds is relatively difficult, and the reaction rate is low, so that sodium iodide is used as a catalyst for SN2 quaternization reaction;
5. the mixed bactericide of the heterocyclic organosilicon quaternary ammonium salt and the active carbon for the oil field has the sterilization rate of 100 percent after more than 30 minutes when the filling amount of the bactericide is 35 mg/L.
Drawings
FIG. 1 is a graph of the final results of SRB concentration in the non-bactericide group (control group) according to the present application;
FIG. 2 is a graph showing the final result of SRB concentration after 30 minutes of the bactericide described in example 1 is added to the original bacterial liquid;
FIG. 3 is a graph showing the final result of SRB concentration after 30 minutes of the bactericide described in example 2 is added to the original bacterial liquid;
FIG. 4 is a graph showing the final result of SRB concentration after 30 minutes of the bactericide described in example 3 is added to the original bacterial liquid;
FIG. 5 is a graph showing the final result of SRB concentration after 30 minutes of the bactericide described in example 4 is added to the original bacterial liquid;
FIG. 6 is a graph showing the final result of SRB concentration after 30 minutes of the bactericide described in example 5 is added to the stock solution according to the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
100g of quinoline-3-carboxylic acid is placed in a three-neck flask, 500mL of absolute ethyl alcohol is added, reflux is carried out by a condensing tube, 50g of N, N-dimethylethanolamine is added when the temperature is raised to 50 ℃, 1g of hypophosphorous acid is added as a catalyst for reaction, then the temperature is quickly raised to 70 ℃, the reaction is carried out for 8 hours, and the mixture A is obtained after cooling. Placing the mixture A into a three-neck flask, adding 500mL of absolute ethyl alcohol, refluxing by using a condenser tube, adding 50g of absolute dimethyl sulfoxide, heating to 70 ℃ under the protection of nitrogen, adding 1g of sodium iodide and 50g of gamma-chloropropyl trimethoxysilane, wherein the sodium iodide is used as a catalyst for reaction, obtaining a mixture B after full reaction, purifying by using 500mL of acetone to obtain the heterocyclic organosilicon quaternary ammonium salt, and finally uniformly mixing the obtained organosilicon quaternary ammonium salt with 20g of active carbon. The bacterial concentration was 0 after 30 minutes and the sterilization rate was 100% by adding 35mg/L to oilfield sewage having an SRB concentration of 2500000/mL.
Example 2
110g of quinoline-3-carboxylic acid is placed in a three-neck flask, 500mL of absolute ethyl alcohol is added, reflux is carried out by a condensing tube, 70g of N, N-dimethylethanolamine is added when the temperature is increased to 50 ℃, 2g of hypophosphorous acid is added as a catalyst for reaction, the temperature is rapidly increased to 90 ℃ to react for 9 hours, and the mixture A is obtained after cooling. Placing the mixture A into a three-neck flask, adding 500mL of absolute ethyl alcohol, refluxing by a condensing tube, adding 60g of absolute dimethyl sulfoxide, heating to 70 ℃ under the protection of nitrogen, adding 2g of sodium iodide and 70g of gamma-chloropropyl trimethoxysilane, wherein the sodium iodide is used as a catalyst for reaction, obtaining a mixture B after full reaction, purifying by 600mL of acetone to obtain the heterocyclic organosilicon quaternary ammonium salt, and finally uniformly mixing the obtained organosilicon quaternary ammonium salt with 25g of active carbon. The bacterial concentration was 0 after 30 minutes and the sterilization rate was 100% by adding 35mg/L to oilfield sewage having an SRB concentration of 2500000/mL.
Example 3
110g of quinoline-3-carboxylic acid is placed in a three-neck flask, 600mL of absolute ethyl alcohol is added, reflux is carried out by a condensing tube, 60g of N, N-dimethylethanolamine is added when the temperature is raised to 55 ℃, 3g of hypophosphorous acid is added as a catalyst for reaction, then the temperature is quickly raised to 180 ℃ for reaction for 9 hours, and the mixture A is obtained after cooling. Placing the mixture A in a three-neck flask, adding 600mL of absolute ethyl alcohol, refluxing by a condensing tube, adding 60g of absolute dimethyl sulfoxide, heating to 80 ℃ under the protection of nitrogen, adding 3g of sodium iodide and 60g of gamma-chloropropyl trimethoxysilane, wherein sodium iodide is used as a catalyst for reaction, obtaining a mixture B after full reaction, purifying by 600mL of acetone to obtain the heterocyclic organosilicon quaternary ammonium salt, and finally uniformly mixing the obtained organosilicon quaternary ammonium salt with 30g of active carbon. The bacterial concentration was 0 after 30 minutes and the sterilization rate was 100% by adding 35mg/L to oilfield sewage having an SRB concentration of 2500000/mL.
Example 4
120g of quinoline-3-carboxylic acid is placed in a three-neck flask, 700mL of absolute ethyl alcohol is added, reflux is carried out by a condensing tube, 50g of N, N-dimethylethanolamine is added when the temperature is raised to 60 ℃, 4g of hypophosphorous acid is added as a catalyst for reaction, the temperature is quickly raised to 80 ℃ to react for 10 hours, and the mixture A is obtained after cooling. Placing the mixture A in a three-neck flask, adding 700mL of absolute ethyl alcohol, refluxing by a condensing tube, adding 60g of absolute dimethyl sulfoxide, heating to 80 ℃ under the protection of nitrogen, adding 4g of sodium iodide and 50g of gamma-chloropropyl trimethoxysilane, wherein sodium iodide is used as a catalyst for reaction, obtaining a mixture B after full reaction, purifying by 600mL of acetone to obtain the heterocyclic organosilicon quaternary ammonium salt, and finally uniformly mixing the obtained organosilicon quaternary ammonium salt with 25g of active carbon. The bacterial concentration was 0 after 30 minutes and the sterilization rate was 100% by adding 35mg/L to oilfield sewage having an SRB concentration of 2500000/mL.
Example 5
120g of quinoline-3-carboxylic acid is placed in a three-neck flask, 700mL of absolute ethyl alcohol is added, reflux is carried out by a condensing tube, 70g of N, N-dimethylethanolamine is added when the temperature is raised to 60 ℃, 5g of hypophosphorous acid is added as a catalyst for reaction, then the temperature is quickly raised to 90 ℃, the reaction is carried out for 10 hours, and the mixture A is obtained after cooling. Placing the mixture A in a three-neck flask, adding 700mL of absolute ethyl alcohol, refluxing by using a condenser tube, adding 70g of absolute dimethyl sulfoxide, heating to 90 ℃ under the protection of nitrogen, adding 5g of sodium iodide and 70g of gamma-chloropropyl trimethoxysilane, wherein the sodium iodide is used as a catalyst for reaction, obtaining a mixture B after full reaction, purifying by using 700mL of acetone to obtain the heterocyclic organosilicon quaternary ammonium salt, and finally uniformly mixing the obtained organosilicon quaternary ammonium salt with 30g of active carbon. The bacterial concentration was 0 after 30 minutes and the sterilization rate was 100% by adding 35mg/L to oilfield sewage having an SRB concentration of 2500000/mL.
Sterilization test
The blended bactericides prepared in examples 1 to 5 were used for measuring the sterilization rate, and the measurement results are shown in table 1.
In Table 1, the number 1 bottle to the number 10 bottle are penicillin bottles filled with 9 milliliters of SRB culture solution, and nutrient substances required for SRB growth are contained in the penicillin bottles. Grade 0-9 is the dilution grade. Taking 1mL of the sample to be tested (blending bactericide) of the examples 1-5 into a No. 1 bottle respectively, namely, 0 grade; taking a new injector, and taking 1mL from the No. 1 bottle into the No. 2 bottle, namely, the level 1; taking a new injector, and taking 1mL from a No. 2 bottle into a No. 3 bottle, namely, the grade 2; and so on until 1mL is taken from bottle 9 in bottle 10, namely grade 9. The first step of the dilution of the trace was completed at this point. In the second step, the diluted penicillin bottles are placed at a constant temperature of 35 ℃ for 14 days for reproduction. After stabilization for 14 days, the results were observed. The SRB concentration was measured directly without the addition of the bactericide (control group) as the initial concentration. Examples 1-5 require the addition of a biocide for 30 minutes before this is done. "+" represents positive flask (black), "-" with table negative flask (colorless), and the results are shown in table 1.
TABLE 1 sterilizing Rate of the Mixed sterilizing Agents prepared in examples 1 to 5
As shown in Table 1, the SRB concentration in the group (control group) to which no bactericide was added was 2500000/ml, and after 30 minutes of bactericide was added in examples 1 to 5, the SRB concentration was measured, all the test bottles were kept at a constant temperature of 35℃after the SRB measurement was completed, and the color was observed after 14 days, so that it was confirmed that all the penicillin bottles were negative, and that no SRB survived in the penicillin bottles after the bactericide addition, and that the bactericide was 100%.
SRB concentration tests were tested using SY/T0532-2012 oilfield injection water bacterial analysis method by the dilution of trace extinction method standard.
In order to reduce experimental errors, the application carries out three parallel tests on SRB concentration measurement, namely, three times of test on a unified sample, and the comprehensive three times of test results correspond to indexes listed in a table A.3 of SY/T0532-2012 standard, thereby obtaining the SRB concentration. FIG. 1 shows the results of SRB test without bactericide (stock solution), wherein the number of positive bottles was 7 after three repeated tests, corresponding to the values in the A.3 table, the growth index was 300, the bacterial count was 2.5/mL, and the final SRB content was 2.5X10 n . N is the multiple diluted before the index position, and the experimental result shows that the index starts to be calculated only at the 7 th step, so n is taken as 6. The end result is 2500000/mL. While all of figures 2-6 are negative, indicating that there is no SRB.
Claims (6)
1. The heterocyclic organosilicon quaternary ammonium salt and activated carbon blended bactericide for the oil and gas field is characterized by comprising the following components in parts by weight: 1000-1400 parts of absolute ethyl alcohol, 20-30 parts of active carbon, 100-120 parts of quinoline-3-carboxylic acid, 50-70 parts of N, N-dimethylethanolamine, 50-70 parts of gamma-chloropropyl trimethoxysilane, 1-5 parts of hypophosphorous acid, 1-5 parts of sodium iodide and 50-70 parts of anhydrous dimethyl sulfoxide.
2. The heterocyclic organosilicon quaternary ammonium salt and activated carbon blended bactericide for oil and gas fields as described in claim 1, wherein the blended bactericide comprises the following components in parts by weight: 1200 parts of absolute ethyl alcohol, 25 parts of active carbon, 110 parts of quinoline-3-carboxylic acid, 60 parts of N, N-dimethylethanolamine, 60 parts of gamma-chloropropyl trimethoxysilane, 3 parts of hypophosphorous acid, 3 parts of sodium iodide and 60 parts of anhydrous dimethyl sulfoxide.
3. The method for preparing the heterocyclic organosilicon quaternary ammonium salt and activated carbon blending bactericide for oil and gas fields as set forth in claim 1 or 2, characterized by comprising the following steps:
step 1, adding 500-700 parts of absolute ethyl alcohol into 100-120 parts of quinoline-3-carboxylic acid according to parts by weight, refluxing by using a condenser tube, adding 50-70 parts of N, N-dimethylethanolamine when the temperature is increased to 50-60 ℃, adding 1-5 parts of hypophosphorous acid as a catalyst for reaction, then quickly heating to 70-90 ℃, reacting for 8-10 hours, and cooling to obtain a mixture A;
step 2, adding 500-700 parts of absolute ethyl alcohol into the mixture A obtained in the step 1 according to parts by weight, refluxing by using a condenser tube, adding 50-70 parts of absolute dimethyl sulfoxide, heating to 70-90 ℃ under the protection of nitrogen, adding 1-5 parts of sodium iodide and 50-70 parts of gamma-chloropropyl trimethoxysilane, taking sodium iodide as a reaction catalyst, taking absolute dimethyl sulfoxide as a cosolvent, obtaining a mixture B after full reaction, and purifying by using 500-700 parts of acetone to obtain the heterocyclic organic silicon quaternary ammonium salt;
and step 3, mixing the heterocyclic organosilicon quaternary ammonium salt with 20-30 parts of active carbon to obtain the blending bactericide.
4. A process according to claim 3, wherein the heterocyclic silicone quaternary ammonium salt in step 2 has the following structural formula:
5. the preparation method according to claim 3, wherein in step 1, 600 parts of absolute ethyl alcohol is added to 110 parts of quinoline-3-carboxylic acid by weight, reflux is carried out by a condenser, 60 parts of N, N-dimethylethanolamine is added when the temperature is raised to 55 ℃,3 parts of hypophosphorous acid is added as a catalyst for the reaction, the temperature is raised to 80 ℃ rapidly, the reaction is carried out for 9 hours, and the mixture A is obtained after cooling.
6. The preparation method according to claim 5, wherein in step 2, 600 parts of absolute ethyl alcohol is added into the mixture A obtained in step 1, reflux is carried out by a condenser tube, 3 parts of absolute dimethyl sulfoxide is added, the temperature is raised to 80 ℃ under the protection of nitrogen, 3 parts of sodium iodide and 60 parts of gamma-chloropropyl trimethoxysilane are added, wherein the absolute dimethyl sulfoxide is used as a cosolvent, sodium iodide is used as a catalyst for reaction, the mixture B is obtained after full reaction, and 600 parts of acetone is used for purification, so that the heterocyclic organosilicon quaternary ammonium salt is obtained.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902340A (en) * | 1982-05-07 | 1990-02-20 | Ciba-Geigy Corporation | Use of quinoline derivatives for the protection of cultivated plants from herbicides |
| JPH0967320A (en) * | 1995-08-29 | 1997-03-11 | Kao Corp | Production of quartery ammonium salt and liquid bleaching agent composition comprising quaternary ammonium salt |
| CN1146281A (en) * | 1995-09-26 | 1997-04-02 | 中国石油化工总公司石油化工科学研究院 | Quaternary ammonium salt bactericide and preparation method |
| CN1792158A (en) * | 2005-11-30 | 2006-06-28 | 山东大学 | Method for preparing organosilyl quaternary ammonium salt sterilizing agent |
| CN101547907A (en) * | 2006-12-06 | 2009-09-30 | 詹森药业有限公司 | Antibacterial quinoline derivatives |
| CN102786477A (en) * | 2012-08-17 | 2012-11-21 | 上海师范大学 | Hydroxy halogen amine compound containing quaternary ammonium salt functional group and preparation method and application thereof |
| CN104003528A (en) * | 2014-05-29 | 2014-08-27 | 西安石油大学 | Novel bactericidal corrosion inhibitor |
| CN109603782A (en) * | 2019-01-21 | 2019-04-12 | 葛畅 | A kind of preparation method of the absorbent-type deodorant with sterilizing function |
-
2022
- 2022-03-30 CN CN202210323296.5A patent/CN116925723A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902340A (en) * | 1982-05-07 | 1990-02-20 | Ciba-Geigy Corporation | Use of quinoline derivatives for the protection of cultivated plants from herbicides |
| JPH0967320A (en) * | 1995-08-29 | 1997-03-11 | Kao Corp | Production of quartery ammonium salt and liquid bleaching agent composition comprising quaternary ammonium salt |
| CN1146281A (en) * | 1995-09-26 | 1997-04-02 | 中国石油化工总公司石油化工科学研究院 | Quaternary ammonium salt bactericide and preparation method |
| CN1792158A (en) * | 2005-11-30 | 2006-06-28 | 山东大学 | Method for preparing organosilyl quaternary ammonium salt sterilizing agent |
| CN101547907A (en) * | 2006-12-06 | 2009-09-30 | 詹森药业有限公司 | Antibacterial quinoline derivatives |
| CN102786477A (en) * | 2012-08-17 | 2012-11-21 | 上海师范大学 | Hydroxy halogen amine compound containing quaternary ammonium salt functional group and preparation method and application thereof |
| CN104003528A (en) * | 2014-05-29 | 2014-08-27 | 西安石油大学 | Novel bactericidal corrosion inhibitor |
| CN109603782A (en) * | 2019-01-21 | 2019-04-12 | 葛畅 | A kind of preparation method of the absorbent-type deodorant with sterilizing function |
Non-Patent Citations (3)
| Title |
|---|
| XUE, JUAN-QIN; MA, XIAO-NA; YU, LI-HUA; TANG, CHANG-BIN; MA, JING: "Development of a Novel Acidification Corrosion Inhibitor for P110 Steel at High Temperature", SCIENCE OF ADVANCED MATERIALS, vol. 4, no. 1, 31 January 2012 (2012-01-31), pages 61 - 67 * |
| 焦玉超: "季铵盐和卤胺聚合物改性活性炭的制备及其应用", 中国优秀硕博士学位论文全文库, no. 2014, 15 January 2014 (2014-01-15) * |
| 王汐璆: "咪唑啉型Gemini表面活性剂的合成与应用", 中国优秀硕博士学位论文全文库, no. 2020, 15 December 2020 (2020-12-15) * |
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