CN116731075A - Bactericide for fracturing, synthetic method and application - Google Patents
Bactericide for fracturing, synthetic method and application Download PDFInfo
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- CN116731075A CN116731075A CN202310608679.1A CN202310608679A CN116731075A CN 116731075 A CN116731075 A CN 116731075A CN 202310608679 A CN202310608679 A CN 202310608679A CN 116731075 A CN116731075 A CN 116731075A
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- bactericide
- fracturing
- phosphine
- dodecylprimary
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 76
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 62
- 238000010189 synthetic method Methods 0.000 title claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 28
- 230000001954 sterilising effect Effects 0.000 claims abstract description 27
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 23
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001308 synthesis method Methods 0.000 claims abstract description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 230000000855 fungicidal effect Effects 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 18
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 abstract description 10
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 17
- 241000894006 Bacteria Species 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 150000004714 phosphonium salts Chemical group 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000010779 crude oil Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003129 oil well Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 102000053602 DNA Human genes 0.000 description 3
- 108020004414 DNA Proteins 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000002147 killing effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241001052560 Thallis Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000003206 sterilizing agent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000295146 Gallionellaceae Species 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001938 Vegetable gum Polymers 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000009096 changqing Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NRDHIACOBGNXHY-UHFFFAOYSA-N ethoxyethane;dihydrochloride Chemical compound Cl.Cl.CCOCC NRDHIACOBGNXHY-UHFFFAOYSA-N 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002699 waste material 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
-
- 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
- A01N57/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus as a ring member
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/605—Compositions for stimulating production by acting on the underground formation containing biocides
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of oilfield sewage treatment, and particularly relates to a bactericide for fracturing and a synthesis method and application thereof. The synthesis method comprises the following steps: adding isopropanol, dodecyl primary phosphine and dichlorodiethyl ether into a four-necked flask, stirring, adjusting pH to 7-8, reacting for 0.5-2h, and heating and refluxing to obtain a mixed solution; adding distilled water into the mixed solution, sufficiently oscillating, separating the solution, discarding the water phase, and taking the oil phase as an aqueous emulsion; transferring the emulsion to a four-neck flask by using isopropanol, adding 1, 3-dibromopropane, and heating and refluxing; and (5) distilling under reduced pressure, recrystallizing to obtain an off-white solid, and drying to obtain the product of the bactericide for fracturing. The bactericide for fracturing has a good bactericidal effect, and the 72-hour viscosity retention rate of guanidine gum base fluid prepared by 10mg/L bactericide reaches more than 99%; meanwhile, the bactericide for fracturing has the advantages of broad-spectrum sterilization, small dosage and the like.
Description
Technical Field
The invention belongs to the technical field of oilfield sewage treatment, and particularly relates to a bactericide for fracturing and a synthesis method and application thereof.
Background
Fracturing is a conventional technological measure for artificially cracking stratum, improving the flowing environment of oil in underground and increasing the yield of an oil well, and can play an important role in improving the flowing condition of the bottom of the oil well, slowing down the interlayer and improving the oil layer utilization condition. Fracturing has been rapidly developed and widely used as a primary stimulation and injection enhancement measure for hydrocarbon reservoirs.
The fracturing needs to consume a large amount of fresh water, influences local water resources, meanwhile, the water content of the produced liquid of the oil well is higher and higher at present, the produced liquid cannot be discharged outwards, only the stratum can be refilled, and a large amount of energy waste is caused. With the remarkable improvement of domestic environmental protection requirements, the preparation of fracturing fluid after the treatment of produced water gradually becomes a trend.
However, the produced water contains a large amount of bacteria, and the vegetable gum thickener used in the fracturing fluid is easy to grow bacteria and spoil, so that the viscosity of the gum fluid is reduced. Bacteria not only destroy the gel by reducing the polymer molecular weight, but also cause formation damage as the water-based fracturing fluid is injected into the reservoir. Particularly, under the conditions of poor water quality and high air temperature, the propagation speed of bacteria is extremely high. Therefore, in the process of preparing the liquid, the bactericide is required to kill bacteria in the high molecular water solution, so that the glue solution is ensured not to be spoiled after preparation and before construction, and the bacteria breeding in the water-based liquid injected into the oil layer is inhibited.
The most commonly used bactericide in the current oil field is dodecyl dimethyl benzyl ammonium chloride (1227), the variety is single, and the long-term use of the bactericide can lead to the generation of certain drug resistance of bacteria, so that the use effect of the bactericide is obviously reduced.
CN200810023393.2 discloses a water-insoluble quaternary phosphonium salt type bactericide and a preparation method thereof, which is prepared by taking silica gel inorganic materials as carriers and grafting amino-quaternary phosphonium salt or quaternary ammonium-quaternary phosphonium salt functional groups with sterilization function on the surfaces. The water-insoluble quaternary phosphonium salt type bactericide provided by the invention has excellent bactericidal activity, not only has the long-acting property of the quaternary phosphonium salt type bactericidal polymer, but also has the efficient, rapid and broad-spectrum bactericidal effect. And the raw materials are widely available, the cost is low, and the synthesis process is simple. The bactericide is insoluble in water, can be reused after being activated and regenerated after the sterilization rate is reduced, and can be widely applied to sterilization and disinfection of various industrial and civil water and other fluid media and preparation of antibacterial materials. However, when the bactericide is used as an antibacterial material, the application range of the bactericide is limited by taking a silica gel inorganic material as a carrier.
Disclosure of Invention
The invention provides a bactericide for fracturing and a synthesis method and application thereof aiming at the defects of the prior art. The bactericide for fracturing has a good bactericidal effect, and the 72-hour viscosity retention rate of guanidine gum base fluid prepared by 10mg/L bactericide reaches more than 99%; meanwhile, the bactericide for fracturing has the advantages of broad-spectrum sterilization, small dosage and the like, and has the effect of killing SRB, TGB, FB in the produced liquid of the oil field.
The invention discloses a bactericide for fracturing, which has the following molecular structural formula:
the invention further discloses a synthesis method of the bactericide for fracturing, which comprises the following specific steps:
(1) Adding isopropanol, dodecyl primary phosphine and dichlorodiethyl ether into a four-neck flask, stirring, simultaneously dropwise adding 5wt% sodium hydroxide solution to adjust the pH value to 7-8, reacting for 0.5-2h, heating and refluxing to obtain a mixed solution, supplementing the sodium hydroxide solution in the reaction process, and maintaining the pH value to 7-8;
(2) Adding distilled water into the mixed solution, sufficiently oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) Transferring the emulsion to a four-neck flask by using isopropanol, adding 1, 3-dibromopropane, and heating and refluxing;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 105-108 ℃ for 6-8h to obtain the product bactericide for fracturing.
In the present invention, preferably, the dichlorodiethyl ether and 1, 3-dibromopropane are used in an amount of 1 to 1.5 mol parts and 0.45 to 0.6 mol parts, respectively, based on 1 mol part of dodecylprimary phosphine; preferably, the dichlorodiethyl ether and 1, 3-dibromopropane are used in an amount of 1.2 to 1.5 mole parts and 0.48 to 0.55 mole parts, respectively, based on 1 mole part of dodecylprimary phosphine.
Preferably, in the step (1), the weight ratio of the isopropyl alcohol to the dodecylprimary phosphine is 20-30:1, a step of; more preferably, the weight ratio of isopropyl alcohol to dodecylprimary phosphine is 20-25:1.
preferably, in the step (1), the reflux reaction time is 6-12h; more preferably, the reflux reaction time is 8 to 10 hours.
In the present invention, preferably, in the step (2), the weight ratio of the distilled water to the dodecylprimary phosphine is 20-30:1.
in the present invention, preferably, in the step (3), the weight ratio of isopropyl alcohol to dodecylprimary phosphine is 40-60:1, a step of; more preferably, the weight ratio of isopropyl alcohol to dodecylprimary phosphine is 50-60:1.
preferably, in the step (3), the reflux reaction time is 24-48h; more preferably, the reflux reaction time is 30 to 38 hours.
The reaction equation for synthesizing the bactericide for fracturing is as follows:
the invention discloses an application of the bactericide for fracturing in oil reservoir fracturing sterilization.
The bactericide for fracturing is double quaternary phosphonium salt similar to morpholine structure, has larger phosphorus atom radius and lower electronegativity, so the quaternary phosphonium salt has strong positive electricity. The surface of the bacteria is negatively charged, and the quaternary phosphonium salt is easily adsorbed to bacterial thalli, can form hydrogen bonds with the bases of deoxyribonucleic acid (DNA) in proteins in the bacterial thalli, is adsorbed on cells of the bacteria, and damages the DNA structure of the bacteria, so that the bacteria lose replicative capacity and die. Meanwhile, the quaternary phosphonium salt can change the permeability of the cell wall, so that the components in the cells of the bacteria leak out to die. The prepared fracturing fluid water contains a small amount of crude oil, part of bacteria are hidden in the crude oil, and common bactericides are difficult to kill the crude oil. The dodecyl in the molecule of the invention has lipophilicity, and the quaternary phosphonium salt molecule can enter the interior of crude oil to act with bacteria in the interior of crude oil, thereby expanding the sterilizing sweep volume. The sterilization function of the molecule is further enhanced by the structure of 2 identical quaternary phosphonium salt functional groups in the same molecule.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The bactericide for fracturing has a good bactericidal effect, the 72-hour viscosity retention rate of the guanidine gum base fluid prepared by 10mg/L bactericide reaches more than 99%, and the bactericidal rate of SRB, TGB, FB reaches 100%;
(2) The bactericide for fracturing has broad spectrum, has a killing effect on SRB, TGB, FB in oil field produced liquid, and has the advantage of low dosage.
Detailed Description
The invention will be described in further detail below with reference to specific examples and with reference to the data. It should be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1:
(1) Adding 80.8g of isopropanol, 20mmol of dodecylprimary phosphine and 20mmol of diethyl ether dichloride into a four-necked flask, stirring, simultaneously dropwise adding 5wt% of sodium hydroxide solution to adjust the pH to 7-8, reacting for 0.5h, heating and refluxing for 6h to obtain a mixed solution, supplementing the sodium hydroxide solution in the reaction process, and maintaining the pH to 7-8;
(2) Adding 80.8g distilled water into the mixed solution, fully oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) The emulsion was transferred to a four-necked flask with 161.6g of isopropyl alcohol, 9mmol of 1, 3-dibromopropane was added thereto, and the mixture was heated under reflux for 24 hours;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 105 ℃ for 6 hours to obtain the product of the bactericide A for fracturing.
Example 2:
(1) 121.2g of isopropanol, 20mmol of dodecylprimary phosphine and 30mmol of diethyl ether are added into a four-necked flask, stirring is carried out, 5wt% of sodium hydroxide solution is added dropwise to adjust the pH value to 7-8, after the reaction is carried out for 1h, heating reflux is carried out for 12h to obtain a mixed solution, the sodium hydroxide solution is supplemented in the reaction process, and the pH value is maintained to 7-8;
(2) Adding 121.2g of distilled water into the mixed solution, fully oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) The emulsion was transferred to a four-necked flask with 242.4g of isopropyl alcohol, 12 mmoles of 1, 3-dibromopropane were added thereto, and heated under reflux for 48 hours;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 108 ℃ for 7 hours to obtain the product of the bactericide B for fracturing.
Example 3:
(1) Adding 100.4g of isopropanol, 20mmol of dodecylprimary phosphine and 25mmol of diethyl ether into a four-necked flask, stirring, simultaneously dropwise adding 5wt% of sodium hydroxide solution to adjust the pH to 7-8, reacting for 2h, heating and refluxing for 8h to obtain a mixed solution, supplementing the sodium hydroxide solution in the reaction process, and maintaining the pH to 7-8;
(2) Adding 100g of distilled water into the mixed solution, fully oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, and taking the oil phase as an aqueous emulsion;
(3) The emulsion was transferred to a four-necked flask with 187.6g of isopropyl alcohol, 9.6 mmols of 1, 3-dibromopropane was added thereto, and the mixture was heated under reflux for 28 hours;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 106 ℃ for 7 hours to obtain the product bactericide C for fracturing.
Example 4:
(1) 110.2g of isopropanol, 20mmol of dodecylprimary phosphine and 28mmol of diethyl ether are added into a four-necked flask, stirring is carried out, 5wt% of sodium hydroxide solution is added dropwise to adjust the pH to 7-8, after the reaction is carried out for 1.5h, heating reflux is carried out for 11h to obtain a mixed solution, the sodium hydroxide solution is supplemented in the reaction process, and the pH is maintained to 7-8;
(2) Adding 101.5g of distilled water into the mixed solution, fully oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) The emulsion was transferred to a four-necked flask with 220.3g of isopropyl alcohol, 11 mmole of 1, 3-dibromopropane was added thereto, and the mixture was heated under reflux for 36 hours;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 107 ℃ for 8 hours to obtain the product bactericide D for fracturing.
Example 5:
(1) 105.6g of isopropanol, 20mmol of dodecylprimary phosphine and 22mmol of diethyl ether are added into a four-necked flask, stirring is carried out, 5wt% of sodium hydroxide solution is added dropwise to adjust the pH to 7-8, after the reaction is carried out for 1.2h, heating and refluxing are carried out for 9h to obtain a mixed solution, the sodium hydroxide solution is supplemented in the reaction process, and the pH is maintained to 7-8;
(2) Adding 101.2g of distilled water into the mixed solution, fully oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) 200g of isopropanol is used for transferring the emulsion to a four-necked flask, 9.8mmol of 1, 3-dibromopropane is added, and the mixture is heated and refluxed for 32 hours;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 106 ℃ for 6 hours to obtain the product bactericide E for fracturing.
Example 6:
(1) 108.8g of isopropanol, 20mmol of dodecylprimary phosphine and 26mmol of diethyl ether are added into a four-necked flask, stirring is carried out, 5wt% of sodium hydroxide solution is added dropwise to adjust the pH value to 7-8, after the reaction is carried out for 1h, heating reflux is carried out for 10h to obtain a mixed solution, the sodium hydroxide solution is supplemented in the reaction process, and the pH value is maintained to 7-8;
(2) Adding 98.5g of distilled water into the mixed solution, fully oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) The emulsion was transferred to a four-necked flask with 230.4g of isopropyl alcohol, 10.2mmol of 1, 3-dibromopropane was added thereto, and the mixture was heated under reflux for 38 hours;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 105 ℃ for 7 hours to obtain the product bactericide F for fracturing.
Example 7: evaluation of viscosity retention of fracturing fluid
The bactericidal effect was evaluated by referring to the method of Q/GRLH 011-2020, surface active class of bactericide for fracturing LH-8004.
Preparing 0.5wt% guanidine gum base liquid with reinjection water treated by a joint station of a victory oil field, dividing the reinjection water into a plurality of parts, adding sterilizing agents with different concentrations into 500ml of each part, and uniformly stirring, wherein a sample without the sterilizing agents is left blank.
All samples are simultaneously put in a constant-temperature water bath at 30 ℃, the viscosity is tested after a blank sample is subjected to a test for 4 hours, the viscosity is tested after a sample is subjected to a test for 72 hours, the viscosity value ratio of the sample to the blank sample is the viscosity retention rate, and the test results are shown in Table 1.
TABLE 1 viscosity-maintaining effect (viscosity-maintaining rate,%)
As can be seen from table 1: the viscosity retention rate of the fracturing fluid bactericide F reaches 95.8% at most, and the viscosity retention rate of 1227 is 51.3% which is obviously lower than that of the fracturing fluid bactericide F, wherein the mass concentration of the fracturing fluid bactericide is 5wt% and the viscosity retention rate of the fracturing fluid bactericide for A, B, C, D, E, F h reaches more than 92%; the viscosity retention rate of the fracturing fluid reaches more than 99% in the mass concentration of 10wt% of the bactericide A, B, C, D, E, F h for fracturing, and the viscosity retention rate of 1227 is 77.8% and is lower than 20% of the bactericide.
Example 8: evaluation of Sterilization Rate
100ml of fracturing flowback fluid of a certain oil well of a Changqing oil field is respectively added into a series of fine-mouth bottles, wherein the fracturing flowback fluid contains 450 SRB (sulfate reducing bacteria), 110 TGB (saprophytic bacteria) and 45 FB (iron bacteria). Adding bactericides with different concentrations, shaking, placing in a 50 ℃ oven, sampling after 1h, detecting residual bacterial content by adopting a three-tube MPN method, calculating sterilization rate, and testing results are shown in tables 2, 3 and 4.
TABLE 2 SRB sterilization results (sterilization rate,%)
TABLE 3 TGB sterilization results (sterilization rate,%)
| Concentration, mg/L | 5 | 10 | 15 |
| A | 97.3 | 100 | 100 |
| B | 99 | 100 | 100 |
| C | 99 | 100 | 100 |
| D | 99.4 | 100 | 100 |
| E | 99.4 | 100 | 100 |
| F | 100 | 100 | 100 |
| 1227 | 59.1 | 77.3 | 94.1 |
Table 4 FB sterilization results (sterilization rate,%)
| Concentration, mg/L | 5 | 10 | 15 |
| A | 98.7 | 100 | 100 |
| B | 99.3 | 100 | 100 |
| C | 99.3 | 100 | 100 |
| D | 100 | 100 | 100 |
| E | 100 | 100 | 100 |
| F | 100 | 100 | 100 |
| 1227 | 59.1 | 95.6 | 98.7 |
As can be seen from table 1: the sterilizing rate of the fracturing bactericide A, B, C, D, E, F for the fracturing reaches more than 93 percent and up to 99.3 percent (E, F) when the using concentration is 5 mg/L; when the using concentration is 10mg/L or above, the sterilization rate of SRB reaches 100 percent; 1227 had a SRB sterilization rate of 33.3% at a use concentration of 5mg/L and 44.4% at a use concentration of 10mg/L, respectively. Compared with the existing bactericide, the bactericide for fracturing has good bactericidal effect on SRB.
As can be seen from table 2: the sterilization rate of the fracturing bactericide A, B, C, D, E, F reaches more than 97% and up to 100% (F) when the use concentration is 5 mg/L; when the using concentration is 10mg/L or above, the sterilization rate of TGB reaches 100 percent; 1227 exhibits a TGB sterilization rate of 59.1% at a use concentration of 5mg/L and a TGB sterilization rate of 77.3% at a use concentration of 10 mg/L. Compared with the existing bactericide for fracturing, the bactericide disclosed by the invention has a good sterilization effect on TGB.
As can be seen from table 3: the sterilization rate of the bactericide A, B, C, D, E, F reaches more than 98 percent and up to 100 percent (F) when the use concentration is 5 mg/L; the FB sterilization rate reaches 100% when the use concentration is 10mg/L or above; 1227 had a FB sterilization rate of 59.1% at a use concentration of 5mg/L and 95.6% at a use concentration of 10 mg/L. Compared with the existing bactericide for fracturing, the bactericide disclosed by the invention has a good bactericidal effect on FB.
The bactericide for fracturing has good bactericidal effect, the 72-hour viscosity retention rate of guanidine gum base fluid prepared by 10mg/L bactericide reaches more than 99%, and the bactericidal rate of SRB, TGB, FB reaches 100%; the bactericide for fracturing has broad spectrum, has a killing effect on SRB, TGB, FB in oil field produced liquid, and has the advantage of low dosage. Therefore, the bactericide for fracturing has wide application prospect.
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 bactericide for fracturing is characterized by comprising the following steps:
(1) Adding isopropanol, dodecyl primary phosphine and dichlorodiethyl ether into a four-neck flask, stirring, simultaneously dropwise adding 5wt% sodium hydroxide solution to adjust the pH value to 7-8, reacting for 0.5-2h, heating and refluxing to obtain a mixed solution, supplementing the sodium hydroxide solution in the reaction process, and maintaining the pH value to 7-8;
(2) Adding distilled water into the mixed solution, sufficiently oscillating, separating the solution, discarding the water phase, repeating the water washing operation once, discarding the water phase, wherein the oil phase is an aqueous emulsion;
(3) Transferring the emulsion to a four-neck flask by using isopropanol, adding 1, 3-dibromopropane, and heating and refluxing;
(4) And (3) performing reduced pressure distillation by a rotary evaporator to obtain brown viscous solid, recrystallizing by ethyl acetate to obtain white solid, and drying at 105-108 ℃ for 6-8h to obtain the product bactericide for fracturing.
2. The synthetic method according to claim 1, wherein the dichlorodiethyl ether and 1, 3-dibromopropane are used in an amount of 1 to 1.5 mol parts and 0.45 to 0.6 mol parts, respectively, based on 1 mol part of dodecylprimary phosphine.
3. The synthetic method according to claim 2, wherein the dichlorodiethyl ether and 1, 3-dibromopropane are used in an amount of 1.2 to 1.5 mol parts and 0.48 to 0.55 mol parts, respectively, based on 1 mol part of dodecylprimary phosphine.
4. The method of claim 1, wherein in step (1), the weight ratio of isopropyl alcohol to dodecylprimary phosphine is 20-30:1.
5. the method of claim 1, wherein in step (1), the reflux reaction time is 6 to 12 hours.
6. The method according to claim 1, wherein in the step (2), the weight ratio of distilled water to dodecylprimary phosphine is 20-30:1.
7. the method according to claim 1, wherein in the step (3), the weight ratio of isopropyl alcohol to dodecylprimary phosphine is 40-60:1.
8. the method of claim 1, wherein in step (3), the reflux reaction time is 24 to 48 hours.
9. The bactericide for fracturing prepared by the synthesis method according to any one of claims 1 to 8, wherein the molecular structural formula of the bactericide for fracturing is as follows:
10. the use of a fracturing fungicide according to claim 9, characterized in that said use is in the sterilization of oil reservoirs.
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| CN114907403A (en) * | 2022-06-01 | 2022-08-16 | 东营施普瑞石油工程技术有限公司 | Double-quaternary phosphonium salt bactericide and synthetic method thereof |
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| CN114907403A (en) * | 2022-06-01 | 2022-08-16 | 东营施普瑞石油工程技术有限公司 | Double-quaternary phosphonium salt bactericide and synthetic method thereof |
| CN114907403B (en) * | 2022-06-01 | 2023-11-28 | 东营施普瑞石油工程技术有限公司 | Double quaternary phosphonium salt bactericide and synthetic method thereof |
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