CN114907403B - 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 57
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 52
- 150000004714 phosphonium salts Chemical group 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title claims description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 20
- 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
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 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 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001308 synthesis method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 230000001954 sterilising effect Effects 0.000 abstract description 33
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 29
- 239000010865 sewage Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003206 sterilizing agent Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 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
- 239000003921 oil Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002332 oil field water Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000000643 oven drying Methods 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
- 230000006378 damage Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 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 1
- DJIOGHZNVKFYHH-UHFFFAOYSA-N 2-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=N1 DJIOGHZNVKFYHH-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
- 241000282414 Homo sapiens Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 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
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 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
- 238000000605 extraction 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
- 208000014674 injury Diseases 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- 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 Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Dentistry (AREA)
- Water Supply & Treatment (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
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- Materials Engineering (AREA)
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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: 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, diethyl phosphine is slowly added dropwise, stirring reaction is continued after the dropwise addition is completed, and unreacted raw materials are distilled off under reduced pressure; adding a solvent and dibromopropane into the four-neck flask, heating for reflux, and distilling under reduced pressure to obtain a tan viscous liquid, namely a crude product; then adding ethyl acetate into the crude product, heating to dissolve, then cooling to below 10 ℃, precipitating 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 components, no pollution, environmental friendliness, simple synthesis process and small dosage; meanwhile, the sterilizing agent has the advantages of broad-spectrum sterilization and high sterilization efficiency, and the sterilization rate can reach 100% when the using 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 in particular 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% of oil fields in China adopt the mode, and water injection is required to be carried out by about 8-9m per 1 ton of crude oil produced on average 3 . In water flooding development, the water source is mainly reinjected sewage. The reinjection can supplement stratum energy, keep stable production of the oil field and improve recovery ratio; but also can reduce the harm of sewage discharge to human beings and ecological systems, is beneficial to environmental protection, and is widely adopted. However, since many kinds of microorganisms exist in oilfield reinjection water, they cause microbial corrosion of oil extraction equipment during growth, propagation and metabolism. The term "microbial corrosion" refers to micro-organismsCorrosion caused by biological physiology and vital activity, and microorganisms involved in the corrosion are called corrosion microorganisms. Microbial corrosion after oilfield water injection not only worsens water quality and causes corrosion of gathering and water injection pipelines, so that ground equipment and a shaft are damaged, but also the stratum can be blocked, so that water injection pressure is increased and crude oil yield is directly affected.
CN104488874a discloses a compound bactericide for oilfield water injection system, which is characterized in that: the composite bactericide for the oilfield water injection system comprises, by weight, 70-80% of a 45-55% aqueous solution of benzalkonium chloride, 10-20% of a 25-35% ethanol solution of cetylpyridinium bromide, and 10-15% of a 18-22% xylene solution of tetrachloro isophthalonitrile. 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 large content of cetyl pyridine bromide, and the cetyl pyridine has increased toxicity, and can cause secondary pollution after being used, thereby causing environmental injury.
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 solution and B group solution of 2:1 or 1:1: the component A comprises the following components: 20-30 parts of copper sulfate solution, 20-30 parts of copper hydroxide, 10-20 parts of calcium hydroxide and 100-150 parts of distilled water, wherein the components are as follows: 50-70 parts of quicklime, 50-80 parts of distilled water, 10-15 parts of 2-methyl-4-isothiamine, 10-15 parts of dimethyl didecyl ammonium chloride, 1-3 parts of dispersing agent and 5-10 parts of organic solvent. Although the bactericide is low in toxicity, the bactericidal effect is unsatisfactory.
Disclosure of Invention
The invention provides a double quaternary phosphonium salt bactericide and a synthesis method thereof aiming at the defects existing in the prior art. The bactericide has the advantages of wide raw material sources, no inorganic components, no pollution, environmental friendliness, simple synthesis process and small dosage; meanwhile, the sterilizing agent has the advantages of broad-spectrum sterilization and high sterilization efficiency, and the sterilization rate can reach 100% when the using concentration is 10 mg/L.
The invention discloses a double quaternary phosphonium salt bactericide, which has the following molecular structural formula:
the invention further discloses a synthesis method of the double quaternary phosphonium salt bactericide, which comprises the following specific steps:
(1) 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, diethyl phosphine is slowly added dropwise, stirring reaction is continued after the dropwise addition is completed, and unreacted raw materials are distilled off under reduced pressure;
(2) Adding a solvent and dibromopropane into the four-neck flask, heating for reflux, and distilling under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Then adding ethyl acetate into the crude product, heating to dissolve, then cooling to below 10 ℃, precipitating crystals, filtering, and drying at 60-70 ℃ to obtain the crystals, namely the bactericide.
Preferably, the diethylphosphine and dibromopropane are used in an amount of 1 to 1.6 mole parts, 0.45 to 0.7 mole parts, respectively, based on 1 mole part of 2-cyclohexen-1-one; more preferably, the diethylphosphine and dibromopropane are used in an amount of 1.2 to 1.5 parts by mole and 0.5 to 0.65 parts 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 2-3h.
In the step (2), the solvent is one of ethanol, propanol, butanol and isobutanol, and more preferably ethanol or isobutanol.
In the step (2), the mass of the solvent is 2 to 10 times, more preferably 3 to 6 times the mass of 2-cyclohexen-1-one.
In the step (2), the heating reflux time is 2-4h, preferably 3-4h.
In the step (3), the weight of the ethyl acetate is 2 to 10 times, more preferably 3 to 5 times the weight of the 2-cyclohexen-1-one.
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 phosphorus atoms in molecules is larger, the electronegativity is lower, the strong electronegativity is realized, the ring structure has a hydrophobic effect, the positive charge of the phosphorus atoms is further enhanced, and the positively charged molecules are easier to adsorb due to the negatively charged surfaces of bacteria, so that the permeability of cell walls is changed, components in cells of bacteria leak out and die, and the bactericide molecules can also permeate into the interior of the bacteria, so that the bacterial proteins lose activity to achieve the aim of sterilization; the sterilization function of the molecule is further enhanced by the structure of 2 identical functional groups in the same molecule.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The bactericide has wide raw material sources, simple synthesis process, strong adaptability and small dosage, and can meet the requirements of different sewage sterilization;
(2) The bactericide of the invention does not contain inorganic components, does not produce pollution, and is environment-friendly;
(3) The bactericide of the invention has broad spectrum and has killing effect on SRB, TGB, FB in oily sewage;
(4) The bactericide has the advantages of low concentration and high efficiency, and the sterilizing rate of SRB, TGB, FB can reach 100% when the concentration is 10 mg/L.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Example 1:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 9.0g (0.1 mol) of diethyl phosphine is slowly added dropwise, the reaction is continued to be carried out for 1.5h after the dropwise addition, and unreacted raw materials are distilled off under reduced pressure;
(2) 19.2g of propanol and 9.09g (0.045 mol) of dibromopropane are added into the four-neck flask, the mixture is heated and refluxed for 2.5 hours, and reduced pressure distillation is carried out to obtain a tan viscous liquid, namely a crude product;
(3) Then 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) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 14.45g (0.16 mol) of diethyl phosphine is slowly added dropwise, and after the dropwise addition is finished, the reaction is continued to be carried out for 1.0h, and unreacted raw materials are distilled off under reduced pressure;
(2) 81.44g of butanol and 14.14g (0.07 mol) of dibromopropane are added into the four-neck flask, heated and refluxed for 2.0h, and distilled under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Then adding 96g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃ to precipitate crystals, filtering, and drying at 70 ℃ to obtain crystals, namely the bactericide S 2 。
Example 3:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 9.45g (0.105 mol) of diethyl phosphine is slowly added dropwise, the reaction is continued to be carried out for 2 hours after the dropwise addition is finished, and unreacted raw materials are distilled off under reduced pressure;
(2) Adding 25.55g of ethanol and 9.25g (0.046 mol) of dibromopropane into the four-neck flask, heating and refluxing for 3 hours, and distilling under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Then 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 crystals, namely the bactericide S 3 。
Example 4:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 13.68g (0.152 mol) of diethyl phosphine is slowly added dropwise, and after the dropwise addition is finished, the reaction is continued to be carried out for 4 hours, and unreacted raw materials are distilled off under reduced pressure;
(2) 66.71g of isobutanol and 13.90g (0.069 mol) of dibromopropane are added into the four-neck flask, the mixture is heated and refluxed for 3.5 hours, and reduced pressure distillation is carried out to obtain a tan viscous liquid, namely a crude product;
(3) Adding 70.25g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10deg.C, separating out crystal, filtering, and oven drying at 60deg.C to obtain crystal as bactericide S 4 。
Example 5:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 10.89g (0.121 mol) of diethyl phosphine is slowly added dropwise, and after the dropwise addition is finished, the reaction is continued to be carried out for 2.4 hours, and unreacted raw materials are distilled off under reduced pressure;
(2) Adding 30.15g of ethanol and 10.14g (0.051 mol) of dibromopropane into the four-neck flask, heating and refluxing for 4 hours, and distilling under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Adding 29.18g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10deg.C, separating out crystal, filtering, and oven drying at 62deg.C to obtain crystal as bactericide S 5 。
Example 6:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 13.14g (0.146 mol) of diethyl phosphine is slowly added dropwise, and after the dropwise addition is finished, the reaction is continued to be carried out for 1.5 hours, and unreacted raw materials are distilled off under reduced pressure;
(2) Adding 40.33g of isopropanol and 13.09g (0.065 mol) of dibromopropane into the four-neck flask, heating and refluxing for 3.2h, and distilling under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Then 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 crystals, namely the bactericide S 6 。
Example 7:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 11.61g (0.129 mol) of diethyl phosphine is slowly added dropwise, and after the dropwise addition is finished, the reaction is continued to be carried out for 2.5 hours, and unreacted raw materials are distilled off under reduced pressure;
(2) 32.45g of ethanol and 11.23g (0.056 mol) of dibromopropane are added into the four-neck flask, heated and refluxed for 2.5h, and distilled under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Adding 32.45g of ethyl acetate into the crude product, heating to dissolve, cooling to below 10deg.C, separating out crystal, filtering, and oven drying at 67 deg.C to obtain crystal as bactericide S 7 。
Example 8:
(1) 9.6g (0.1 mol) of 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, 12.42g (0.138 mol) of diethyl phosphine is slowly added dropwise, the reaction is continued to be carried out for 3 hours after the dropwise addition is finished, and unreacted raw materials are distilled off under reduced pressure;
(2) 96g of isobutanol and 12.08g (0.060 mol) of dibromopropane are added into the four-neck flask, heating reflux is carried out for 2.8h, and reduced pressure distillation is carried out, thus obtaining a tan viscous liquid, namely a crude product;
(3) Then 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 crystals, namely the bactericide S 8 。
Example 9: evaluation of Sterilization Rate
500ml of water samples of a joint station of a victory oil field containing SRB (sulfate reducing bacteria), TGB (saprophytic bacteria) and FB (iron bacteria) are respectively added into a series of fine-mouth bottles, bactericides with different concentrations are added, the mixture is uniformly shaken, the mixture is placed in a 50 ℃ oven, sampling is carried out after 1 hour, the content of residual bacteria is detected by adopting a three-tube method MPN, and the sterilization rate is calculated.
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: the bactericide S of the invention 1-8 When the concentration is 5mg/L, the sterilization rate of SRB reaches more than 90 percent, and the highest sterilization rate reaches 98.2 percent (S) 8 ) The method comprises the steps of carrying out a first treatment on the surface of the When the using concentration is 10mg/L or above, the sterilization rate of SRB reaches 100 percent; whereas 2, 3-dichlorophenol and 1227 had a SRB kill rate of 0 and 33.3% respectively at a concentration of 5mg/L and 44.4% and 74.4% respectively at a concentration of 10 mg/L. Compared with the existing bactericides, the bactericide has good bactericidal effect on SRB.
As can be seen from table 2: the bactericide S of the invention 1-8 When the concentration is 5mg/L, the sterilization rate of TGB reaches more than 90 percent, and the highest sterilization rate reaches 99.1 percent (S) 8 ) The method comprises the steps of carrying out a first treatment on the surface of the When the using concentration is 10mg/L or above, the sterilization rate of TGB reaches 100 percent; whereas 2, 3-dichlorophenol and 1227 had a sterilization rate of 0 and 9.6% for TGB at a concentration of 5mg/L and 0 and 59.1% for TGB at a concentration of 10mg/L, respectively. Compared with the existing bactericides, the bactericide has good sterilizing effect on TGB.
As can be seen from table 3: the bactericide S of the invention 1-8 The FB sterilization rate reaches more than 90 percent when the using concentration is 5mg/L, and the highest FB sterilization rate reaches 99.3 percent (S) 8 ) The method comprises the steps of carrying out a first treatment on the surface of the The FB sterilization rate reaches 100% when the use concentration is 10mg/L or above; and 2, 3-dichlorophenol and 1227 had a sterilization rate of 0 and 0, respectively, at a use concentration of 5mg/L and 0 and 55.6%, respectively, at a use concentration of 10 mg/L. Compared with the existing bactericides, the bactericidal agent has good bactericidal effect on FB.
In conclusion, the bactericide disclosed by the invention has a killing effect on SRB, TGB, FB in oily sewage, and the sterilizing rate on SRB, TGB, FB in the oily sewage reaches 100% when the using concentration is 10mg/L, so that the bactericide disclosed by the invention has broad spectrum. Compared with the existing bactericides, the bactericide has the advantages of low use concentration and good sterilizing effect, and can be widely applied to sewage sterilization treatment.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The synthesis method of the double quaternary phosphonium salt bactericide is characterized by comprising the following steps:
(1) 2-cyclohexene-1-one is added into a four-neck flask protected by nitrogen, diethyl phosphine is slowly added dropwise, stirring reaction is continued after the dropwise addition is completed, and unreacted raw materials are distilled off under reduced pressure;
(2) Adding a solvent and dibromopropane into the four-neck flask, heating for reflux, and distilling under reduced pressure to obtain a tan viscous liquid, namely a crude product;
(3) Adding ethyl acetate into the crude product, heating to dissolve, cooling to below 10 ℃, precipitating crystals, filtering, and drying at 60-70 ℃ to obtain crystals, namely the bactericide;
the molecular structural formula of the bactericide is as follows:
2. the synthetic method according to claim 1, wherein the diethyl phosphine and dibromopropane are used in an amount of 1 to 1.6 mol parts and 0.45 to 0.7 mol parts, respectively, based on 1mol part of 2-cyclohexen-1-one.
3. The synthetic method according to claim 2, wherein the diethyl phosphine and dibromopropane are used in an amount of 1.2 to 1.5 mol parts and 0.5 to 0.65 mol parts, respectively, based on 1mol part of 2-cyclohexen-1-one.
4. The method of claim 1, wherein in step (1), the stirring reaction time is 1 to 4 hours.
5. The method according to claim 1, wherein in the step (2), the solvent is one of ethanol, propanol, butanol, and isobutanol.
6. The method according to claim 5, wherein in the step (2), the solvent is ethanol or isobutanol.
7. The method according to claim 1, wherein the mass of the solvent is 2 to 10 times the mass of 2-cyclohexen-1-one.
8. The method of claim 1, wherein in step (2), the heating reflux time is 2 to 4 hours.
9. The method according to claim 1, wherein in the step (3), the weight of the ethyl acetate is 2 to 10 times the weight of the 2-cyclohexen-1-one.
10. The bactericide produced by the synthetic method according to any one of claims 1 to 9, characterized by the following molecular structural formula:
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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 |
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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 |
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