CN114907403A - Double-quaternary phosphonium salt bactericide and synthetic method thereof - Google Patents
Double-quaternary phosphonium salt bactericide and synthetic 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 50
- 150000004714 phosphonium salts Chemical group 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001308 synthesis method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000855 fungicidal effect Effects 0.000 claims 2
- 239000000417 fungicide Substances 0.000 claims 2
- 230000001954 sterilising effect Effects 0.000 abstract description 33
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 30
- 239000010865 sewage Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 241000894006 Bacteria Species 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 5
- 244000005700 microbiome Species 0.000 description 4
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 241000295146 Gallionellaceae Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002332 oil field water Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- JSTFROSQSCXFPA-UHFFFAOYSA-N 2-methyl-3h-1,2-thiazole Chemical compound CN1CC=CS1 JSTFROSQSCXFPA-UHFFFAOYSA-N 0.000 description 1
- 108010077805 Bacterial Proteins Proteins 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5435—Cycloaliphatic phosphonium compounds
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of sewage treatment, and particularly relates to a double-quaternary phosphonium salt bactericide and a synthesis method thereof. The synthesis method comprises the following steps: adding 2-cyclohexene-1-ketone into a four-neck flask under the protection of nitrogen, slowly dropwise adding diethyl phosphine, continuously stirring for reaction after dropwise adding is finished, and distilling under reduced pressure to remove unreacted raw materials; adding a solvent and dibromopropane into the four-neck flask, heating and refluxing, and carrying out reduced pressure distillation to obtain a brown viscous liquid, namely a crude product; and adding ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 60 ℃ to obtain the crystals, namely the bactericide. The bactericide has the advantages of wide raw material sources, no inorganic component, no pollution, environmental friendliness, simple synthesis process and small using amount; meanwhile, the bactericidal composition has the advantages of broad-spectrum sterilization and high sterilization efficiency, and the sterilization rate can reach 100% when the use concentration is 10 mg/L.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, relates to an oilfield sewage bactericide and a preparation method thereof, and particularly relates to a double-quaternary phosphonium salt bactericide and a synthesis method thereof.
Background
Water injection is the main mode of oil field development at present, 86.3 percent of oil fields in China adopt the mode, and the water injection is about 8-9m for producing 1 ton of crude oil on average 3 . In water injection development, the water source is mainly the reinjection of sewage. The reinjection can supplement stratum energy, keep the stable yield of the oil field and improve the recovery ratio; but also can reduce the harm of the discharged sewage to human and ecological systems, is beneficial to protecting the environment, and is widely adopted. However, because of the presence of a wide variety of microorganisms in oilfield reinjection water, they can cause microbial corrosion of oil production equipment during growth, propagation, and metabolism. The microbial corrosion refers to corrosion caused by physiological and vital activities of microorganisms, and microorganisms involved in corrosion are referred to as "corrosive microorganisms". The microbial corrosion after the water injection of the oil field not only deteriorates the water quality, causes the corrosion of gathering and transportation and water injection pipelines, damages ground equipment and a shaft, but also blocks the stratum, causes the water injection pressure to rise and directly influences the yield of crude oil.
CN104488874A discloses a compound bactericide for an oilfield flooding system, which is characterized in that: the composite bactericide for the oilfield water injection system comprises, by weight, 70-80% of an aqueous solution containing 45-55% of benzalkonium chloride, 10-20% of an ethanol solution containing 25-35% of cetylpyridinium bromide and 10-15% of a xylene solution containing 18-22% of tetrachloroisophthalonitrile. The compound bactericide for the oilfield water injection system has extremely strong bactericidal effect, can effectively remove sulfate reducing bacteria, iron bacteria and saprophytic bacteria in sewage, avoids corrosion and blockage of bacteria to pipeline equipment, and has the advantages of simple components, convenience in preparation, rapidness, high efficiency, low cost, high bactericidal rate, low use amount, small side effect and the like. However, the bactericide contains a large amount of cetylpyridinium bromide, and the cetylpyridinium bromide has increased toxicity, and causes secondary pollution and environmental damage after being used.
CN 113519555A discloses a water-based low-toxicity bactericide and a production method thereof, wherein the bactericide comprises the following components in parts by weight of a group A solution and a group B solution in a ratio of 2: 1 or 1: the component A comprises: 20-30 parts of copper sulfate solution, 20-30 parts of copper hydroxide, 10-20 parts of calcium hydroxide and 150 parts of distilled water, wherein the component B comprises the following components: 50-70 parts of quicklime, 50-80 parts of distilled water, 10-15 parts of 2-methyl-4-isothiazoline, 10-15 parts of dimethyl didecyl ammonium chloride, 1-3 parts of a dispersing agent and 5-10 parts of an organic solvent. Although the bactericide has low toxicity, the bactericidal effect is not satisfactory.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a double quaternary phosphonium salt bactericide and a synthesis method thereof. The bactericide has the advantages of wide raw material sources, no inorganic component, no pollution, environmental friendliness, simple synthesis process and small using amount; meanwhile, the bactericidal composition has the advantages of broad-spectrum sterilization and high sterilization efficiency, and the sterilization rate can reach 100% when the use concentration is 10 mg/L.
The invention discloses a double quaternary phosphonium salt bactericide, which has the following molecular structural formula:
the invention also discloses a synthesis method of the double quaternary phosphonium salt bactericide, which comprises the following specific steps:
(1) adding 2-cyclohexene-1-ketone into a four-neck flask under the protection of nitrogen, slowly dropwise adding diethyl phosphine, continuously stirring for reaction after dropwise adding is finished, and distilling under reduced pressure to remove unreacted raw materials;
(2) adding a solvent and dibromopropane into the four-neck flask, heating and refluxing, and carrying out reduced pressure distillation to obtain a brown viscous liquid, namely a crude product;
(3) and adding ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 60-70 ℃ to obtain the crystals, namely the bactericide.
Preferably, the diethylphosphine and dibromopropane are used in amounts of 1 to 1.6 parts by mole and 0.45 to 0.7 part by mole, respectively, based on 1 part by mole of 2-cyclohexen-1-one; more preferably, the diethylphosphine and dibromopropane are used in amounts of 1.2 to 1.5 parts by mole and 0.5 to 0.65 part by mole, respectively, based on 1 part by mole of 2-cyclohexen-1-one.
In the step (1), the stirring reaction time is 1-4h, preferably 2-3 h.
In the step (2), the solvent is one of ethanol, propanol, butanol and isobutanol, and is more preferably ethanol or isobutanol.
In the step (2), the mass of the solvent is 2-10 times of that of the 2-cyclohexene-1-ketone, and more preferably 3-6 times.
In the step (2), the heating reflux time is 2-4h, preferably 3-4 h.
In the step (3), the weight of the ethyl acetate is 2-10 times of that of the 2-cyclohexene-1-ketone, and more preferably 3-5 times.
The reaction equation for synthesizing the double quaternary phosphonium salt bactericide is as follows:
the double quaternary phosphonium salt bactericide has stronger bactericidal activity, the radius of a phosphorus atom in a molecule is larger, the electronegativity is lower, the electronegativity is stronger, a ring structure has a hydrophobic effect, the positive charge of the phosphorus atom is further enhanced, and the molecule with the positive charge is easier to adsorb due to the negative charge on the surface of bacteria, so that the permeability of a cell wall is changed, components in a bacterial cell leak out and die, and the bactericide molecule can also permeate into the bacteria, so that the activity of bacterial protein is lost, and the purpose of sterilization is achieved; the 2 same functional group structures in the same molecule further enhance the sterilization function of the molecule.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the bactericide has the advantages of wide raw material sources, simple synthesis process, strong adaptability and small using amount, and can meet the requirements of different sewage sterilization;
(2) the bactericide of the invention does not contain inorganic components, does not generate pollution and is environment-friendly;
(3) the bactericide has broad spectrum and has killing effect on SRB, TGB and FB in the oil-containing sewage;
(4) the bactericide has the advantages of low concentration and high efficiency, and the sterilization rate of SRB, TGB and FB can reach 100% when the using concentration is 10 mg/L.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Example 1:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 9.0g (0.1mol) of diethyl phosphine, continuously stirring and reacting for 1.5h after the dropwise adding is finished, and distilling off unreacted raw materials under reduced pressure;
(2) adding 19.2g of propanol and 9.09g (0.045mol) of dibromopropane into the four-neck flask, heating and refluxing for 2.5h, and distilling under reduced pressure to obtain a yellow brown viscous liquid, namely a crude product;
(3) adding 19.2g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 60 ℃ to obtain the crystals, namely the bactericide S 1 。
Example 2:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 14.45g (0.16mol) of diethyl phosphine, continuously stirring and reacting for 1.0h after the dropwise adding is finished, and distilling off unreacted raw materials under reduced pressure;
(2) 81.44g of butanol and 14.14g (0.07mol) of dibromopropane are added into the four-neck flask, heated and refluxed for 2.0 hours, and distilled under reduced pressure to obtain a yellow brown viscous liquid, namely a crude product;
(3) adding 96g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 70 ℃ to obtain the crystals, namely the bactericide S 2 。
Example 3:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 9.45g (0.105mol) of diethyl phosphine, continuously stirring for reacting for 2h after dropwise adding is finished, and distilling under reduced pressure to remove unreacted raw materials;
(2) adding 25.55g of ethanol and 9.25g (0.046mol) of dibromopropane into the four-neck flask, heating and refluxing for 3 hours, and distilling under reduced pressure to obtain a brown viscous liquid, namely a crude product;
(3) adding 23.18g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 65 ℃ to obtain the crystals, namely the bactericide S 3 。
Example 4:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 13.68g (0.152mol) of diethyl phosphine, continuously stirring and reacting for 4 hours after the dropwise adding is finished, and distilling off unreacted raw materials under reduced pressure;
(2) 66.71g of isobutanol and 13.90g (0.069mol) of dibromopropane are added into the four-mouth flask, heated and refluxed for 3.5 hours, and then decompressed and distilled to obtain a yellow brown viscous liquid, namely a crude product;
(3) adding 70.25g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 60 ℃ to obtain the crystals, namely the bactericide S 4 。
Example 5:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 10.89g (0.121mol) of diethyl phosphine, continuously stirring and reacting for 2.4h after the dropwise adding is finished, and distilling off unreacted raw materials under reduced pressure;
(2) adding 30.15g of ethanol and 10.14g (0.051mol) of dibromopropane into the four-neck flask, heating and refluxing for 4 hours, and distilling under reduced pressure to obtain a yellow brown viscous liquid, namely a crude product;
(3) adding 29.18g ethyl acetate into the crude product, heating to dissolve, cooling to below 10 deg.C, separating out crystal, filtering, and oven drying at 62 deg.C to obtain crystal as bactericide S 5 。
Example 6:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 13.14g (0.146mol) of diethyl phosphine, continuously stirring and reacting for 1.5h after the dropwise adding is finished, and distilling off unreacted raw materials under reduced pressure;
(2) adding 40.33g of isopropanol and 13.09g (0.065mol) of dibromopropane into the four-neck flask, heating and refluxing for 3.2h, and distilling under reduced pressure to obtain a brown viscous liquid, namely a crude product;
(3) adding 44.14g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 60 ℃ to obtain the crystals, namely the bactericide S 6 。
Example 7:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 11.61g (0.129mol) of diethyl phosphine, continuously stirring and reacting for 2.5h after the dropwise adding is finished, and distilling off unreacted raw materials under reduced pressure;
(2) adding 32.45g of ethanol and 11.23g (0.056mol) of dibromopropane into the four-neck flask, heating and refluxing for 2.5h, and distilling under reduced pressure to obtain a brown viscous liquid, namely a crude product;
(3) adding 32.45g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 67 ℃ to obtain the crystals, namely the bactericide S 7 。
Example 8:
(1) adding 9.6g (0.1mol) of 2-cyclohexene-1-ketone into a four-neck flask protected by nitrogen, slowly dropwise adding 12.42g (0.138mol) of diethyl phosphine, continuously stirring and reacting for 3h after the dropwise adding is finished, and distilling under reduced pressure to remove unreacted raw materials;
(2) adding 96g of isobutanol and 12.08g (0.060mol) of dibromopropane into the four-mouth flask, heating and refluxing for 2.8h, and carrying out reduced pressure distillation to obtain a brown viscous liquid, namely a crude product;
(3) adding 38.85g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 65 ℃ to obtain the crystals, namely the bactericide S 8 。
Example 9: evaluation of Sterilization Rate
Respectively adding 500ml of water sample of a certain United station of the Shengli oilfield containing SRB (sulfate reducing bacteria), TGB (saprophytic bacteria) and FB (iron bacteria) into a series of narrow-mouth bottles, adding bactericides with different concentrations, shaking uniformly, placing in a 50 ℃ oven, sampling after 1h, detecting the content of residual bacteria by adopting a three-tube method MPN, and calculating the sterilization rate.
Table 1 SRB sterilization results (sterilization rate,%)
| Concentration, mg/L | 5 | 10 | 15 | 20 | 30 |
| S 1 | 91.1 | 100 | 100 | 100 | 100 |
| S 2 | 92.2 | 100 | 100 | 100 | 100 |
| S 3 | 94.4 | 100 | 100 | 100 | 100 |
| S 4 | 95.1 | 100 | 100 | 100 | 100 |
| S 5 | 95.3 | 100 | 100 | 100 | 100 |
| S 6 | 96.9 | 100 | 100 | 100 | 100 |
| S 7 | 97.8 | 100 | 100 | 100 | 100 |
| S 8 | 98.2 | 100 | 100 | 100 | 100 |
| 2, 3-dichlorophenol | 0 | 44.4 | 66.7 | 85.6 | 98.2 |
| 1227 | 33.3 | 74.4 | 85.6 | 94.7 | 100 |
TABLE 2 TGB Sterilization results (Sterilization Rate,%)
TABLE 3 FB Sterilization results (Sterilization Rate,%)
| Concentration, mg/L | 5 | 10 | 15 | 20 | 30 |
| S 1 | 91.1 | 100 | 100 | 100 | 100 |
| S 2 | 93.3 | 100 | 100 | 100 | 100 |
| S 3 | 95.6 | 100 | 100 | 100 | 100 |
| S 4 | 95.6 | 100 | 100 | 100 | 100 |
| S 5 | 97.6 | 100 | 100 | 100 | 100 |
| S 6 | 98.4 | 100 | 100 | 100 | 100 |
| S 7 | 98.7 | 100 | 100 | 100 | 100 |
| S 8 | 99.3 | 100 | 100 | 100 | 100 |
| 2, 3-dichlorophenol | 0 | 0 | 55.6 | 64.4 | 74.4 |
| 1227 | 0 | 55.6 | 64.4 | 77.8 | 83.3 |
As can be seen from table 1: bactericide S of the present invention 1-8 The sterilization rate of the SRB reaches over 90 percent and the highest sterilization rate reaches 98.2 percent when the using concentration is 5mg/L (S) 8 ) (ii) a The sterilization rate of SRB reaches 100% when the using concentration is 10mg/L or more; and 2, 3-dichlorophenol and 1227 have sterilization rates of 0 and 33.3% for SRB at a concentration of 5mg/L and 44.4% and 74.4% for SRB at a concentration of 10mg/L, respectively. Compared with the existing bactericide, the bactericide of the invention has good effect of sterilizing SRB.
As can be seen from table 2: bactericide S of the present invention 1-8 The sterilization rate of TGB reaches more than 90 percent and reaches 99.1 percent at the highest when the use concentration is 5mg/L (S) 8 ) (ii) a The sterilization rate of TGB reaches 100% when the use concentration is 10mg/L or more; and 2, 3-dichlorophenol and 1227 were 0 and 9.6% in TGB bactericidal ratio at 5mg/L and 0 and 59.1% in TGB bactericidal ratio at 10mg/L, respectively. Compared with the existing bactericide, the bactericide of the invention has good effect of sterilizing TGB.
As can be seen from table 3: bactericide S of the present invention 1-8 The sterilization rate to FB can reach more than 90% when the use concentration is 5mg/LUp to 99.3% (S) 8 ) (ii) a The sterilization rate to FB reaches 100% when the use concentration is 10mg/L or more; and 2, 3-dichlorophenol and 1227 have 0 and 0 sterilization rate to FB at 5mg/L and 0 and 55.6 sterilization rate to FB at 10mg/L, respectively. Compared with the existing bactericide, the bactericide of the invention has good effect of sterilizing FB.
In conclusion, the bactericide has a killing effect on SRB, TGB and FB in the oil-containing sewage, and has a broad-spectrum property, and the sterilization rate of the bactericide on the SRB, TGB and FB in the oil-containing sewage reaches 100% when the use concentration is 10 mg/L. Compared with the existing bactericide, the bactericide of the invention has the advantages of low use concentration and good bactericidal effect, thus being widely applied to sewage sterilization treatment.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The synthesis method of the double quaternary phosphonium salt bactericide is characterized by comprising the following steps of:
(1) adding 2-cyclohexene-1-ketone into a four-neck flask under the protection of nitrogen, slowly dropwise adding diethyl phosphine, continuously stirring for reaction after dropwise adding is finished, and distilling under reduced pressure to remove unreacted raw materials;
(2) adding a solvent and dibromopropane into the four-neck flask, heating and refluxing, and carrying out reduced pressure distillation to obtain a brown viscous liquid, namely a crude product;
(3) and adding ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, separating out crystals, filtering, and drying at 60-70 ℃ to obtain the crystals, namely the bactericide.
2. The synthesis method according to claim 1, wherein the diethylphosphine and dibromopropane are used in an amount of 1 to 1.6 parts by mole and 0.45 to 0.7 part by mole, respectively, based on 1 part by mole of 2-cyclohexen-1-one.
3. The synthesis method according to claim 2, wherein the diethylphosphine and dibromopropane are used in an amount of 1.2 to 1.5 parts by mole and 0.5 to 0.65 part by mole, respectively, based on 1 part by mole of 2-cyclohexen-1-one.
4. The synthesis method of claim 1, wherein in the step (1), the stirring reaction time is 1-4 h.
5. The synthesis method according to claim 1, wherein in the step (2), the solvent is one of ethanol, propanol, butanol and isobutanol.
6. The method of claim 5, wherein in step (2), the solvent is ethanol or isobutanol.
7. The synthesis method according to claim 1, wherein the mass of the solvent is 2-10 times of that of the 2-cyclohexen-1-one.
8. The synthesis method of claim 1, wherein in the step (2), the heating reflux time is 2-4 h.
9. The method of claim 1, wherein in step (3), the weight of ethyl acetate is 2 to 10 times the weight of 2-cyclohexen-1-one.
10. The fungicide prepared by the synthesis method according to any one of claims 1 to 9, characterized in that the molecular structural formula of the fungicide is as follows:
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| CN107347909A (en) * | 2017-05-15 | 2017-11-17 | 北京化工大学 | A kind of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls and preparation method thereof |
| CN114957525A (en) * | 2022-06-01 | 2022-08-30 | 山东科兴化工有限责任公司 | Bactericide for oilfield sewage treatment and synthetic method |
| CN116731075A (en) * | 2023-05-28 | 2023-09-12 | 东营施普瑞石油工程技术有限公司 | Bactericide for fracturing, synthetic method and application |
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| CN114957525A (en) * | 2022-06-01 | 2022-08-30 | 山东科兴化工有限责任公司 | Bactericide for oilfield sewage treatment and synthetic method |
| CN116731075A (en) * | 2023-05-28 | 2023-09-12 | 东营施普瑞石油工程技术有限公司 | Bactericide for fracturing, synthetic method and application |
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| CN116444801A (en) * | 2023-06-20 | 2023-07-18 | 中石化西南石油工程有限公司 | Emulsion breaker and synthesis method thereof |
| CN116444801B (en) * | 2023-06-20 | 2023-10-24 | 中石化西南石油工程有限公司 | Emulsion breaker and synthesis method thereof |
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