CN116396741A - Antibacterial degradable cleanup additive and preparation method thereof - Google Patents
Antibacterial degradable cleanup additive and preparation method thereof Download PDFInfo
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- CN116396741A CN116396741A CN202310377150.3A CN202310377150A CN116396741A CN 116396741 A CN116396741 A CN 116396741A CN 202310377150 A CN202310377150 A CN 202310377150A CN 116396741 A CN116396741 A CN 116396741A
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- emulsifier
- degradable
- cleanup additive
- quaternary ammonium
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- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 35
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 51
- 239000007908 nanoemulsion Substances 0.000 claims abstract description 37
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 compound salt Chemical class 0.000 claims abstract description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 17
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 17
- 239000004626 polylactic acid Substances 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 11
- 230000000845 anti-microbial effect Effects 0.000 claims description 11
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 11
- 229920000053 polysorbate 80 Polymers 0.000 claims description 11
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 11
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OWMZFQXVDFSPAB-UHFFFAOYSA-N heptatriacontan-19-yl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCCC([NH+](C)C)CCCCCCCCCCCCCCCCCC OWMZFQXVDFSPAB-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract description 6
- 239000003350 kerosene Substances 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 16
- 230000006872 improvement Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical group C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- 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
-
- 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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
Abstract
The invention provides an antibacterial degradable cleanup additive and a preparation method thereof, and belongs to the technical field of cleanup additives. The material is prepared from the following raw materials in parts by weight: 10-20 parts of nano emulsion, 5-7 parts of quaternary ammonium salt emulsifier, 3-5 parts of sodium polylactic acid, 4-8 parts of polyvinyl alcohol, 2-4 parts of compound salt and 50-70 parts of water. The antibacterial degradable cleanup additive disclosed by the invention is convenient to prepare, simple in raw materials and stable in performance. The mixing and compounding of the quaternary ammonium salt emulsifier and the nano emulsion generate a synergistic effect, so that the arrangement of hydrophobic chains on the surface of the liquid is more compact, and the cleanup additive system has low surface tension (25 ℃ less than or equal to 15 mN/m) and low interfacial tension (25 ℃ less than or equal to 0.8 mN/m) and the interfacial tension between the cleanup additive system and kerosene. The prepared antibacterial degradable cleanup additive has good compatibility with the fracturing fluid, and the self performance of the fracturing fluid is not affected after the compounding.
Description
Technical Field
The invention relates to the technical field of discharge aids, in particular to an antibacterial degradable discharge aid and a preparation method thereof.
Background
Conventional foam drainage gas production mainly utilizes surfactant to foam when meeting water, and then reduces shaft fluid density to realize drainage gas production, but has the following problems in the actual operation process:
1. when serious effusion exists in a gas well or the concentration of the foaming agent added in the gas well is not reasonable, the foaming agent added from the oil sleeve annulus cannot form foam with the effusion at the bottom of the well in time and is taken out of the well, and the foaming agent remained in the well for a long time can deteriorate to block the stratum or the well.
2. After the foaming agent is added into the gas well, a large amount of stable foam can be formed on the ground, the defoaming agent is required to be added for defoaming in time, and if the defoaming agent is not timely, triethylene glycol can be caused to cause flooding.
3. Because the temperature is lower in winter in the north, after the foam discharging agent is added in winter, the gas well is extremely easy to be blocked by freezing a shaft and ground pipelines, and the well opening time rate of the gas well is influenced.
4. When a large amount of foam exists in the ground gas production pipeline, the flow resistance is increased, and the phenomenon that the station is free of transient phenomenon is easy to occur due to the fact that the station belongs to medium-high pressure gas collection.
5. After the foam discharging agent is added, when the foam starts and when the foam stops is difficult to determine, so that the time for adding the foam discharging agent is needed to be advanced and pushed back, and the cost is increased.
6. If the defoaming is not thorough, a large amount of foam enters the pressure vessel, and once the foam is broken, the foam can generate 'bursting force' due to inconsistent internal and external pressure of the foam, so that potential safety hazards exist.
7. Part of well stations do not have a defoaming process, but gas well effusion is serious, and drainage is urgently needed.
8. The foam discharging agent is added for a long time, so that calcium scale and magnesium scale are easy to appear, and a reservoir is polluted.
9. The foaming agent and the water are compounded according to a certain proportion to be filled, so that the cost is increased.
10. Once the foam enters the ground instrument, inaccurate data and instrument damage are easily caused.
Disclosure of Invention
The invention aims to provide an antibacterial degradable cleanup additive and a preparation method thereof, wherein the cleanup additive has the advantages of convenient preparation, simple raw materials and stable performance. The mixing and compounding of the quaternary ammonium salt emulsifier and the nano emulsion generate a synergistic effect, so that the arrangement of hydrophobic chains on the surface of the liquid is more compact, and the cleanup additive system has low surface tension (25 ℃ less than or equal to 15 mN/m) and low interfacial tension (25 ℃ less than or equal to 0.8 mN/m) and the interfacial tension between the cleanup additive system and kerosene. The prepared antibacterial degradable cleanup additive has good compatibility with the fracturing fluid, and the self performance of the fracturing fluid is not affected after the compounding.
The technical scheme of the invention is realized as follows:
the invention provides an antibacterial degradable cleanup additive, which comprises the following raw materials: the emulsion comprises nano emulsion, quaternary ammonium salt emulsifier, sodium polylactic acid, polyvinyl alcohol, compound salt and water.
As a further improvement of the invention, the invention is prepared from the following raw materials in parts by weight: 10-20 parts of nano emulsion, 5-7 parts of quaternary ammonium salt emulsifier, 3-5 parts of sodium polylactic acid, 4-8 parts of polyvinyl alcohol, 2-4 parts of compound salt and 50-70 parts of water.
As a further improvement of the present invention, the quaternary ammonium salt emulsifier is at least one selected from octadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, and dioctadecyl trimethyl ammonium bromide.
As a further improvement of the invention, the quaternary ammonium salt emulsifier is a composition of octadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride, and the mass ratio is 3-5:1.
As a further improvement of the present invention, the preparation method of the nanoemulsion is as follows: adding hydrophilic emulsifier and lipophilic emulsifier into oil phase, heating and stirring, dripping distilled water, and emulsifying to obtain nanoemulsion.
As a further improvement of the present invention, the hydrophilic emulsifier is at least one selected from the group consisting of tween-20, tween-40, tween-60, tween-80; the lipophilic emulsifier is at least one selected from span-20, span 40, span-60 and span-80, preferably, the hydrophilic emulsifier is Tween-80, and the lipophilic emulsifier is span-20.
As a further improvement of the invention, the oil phase is at least one selected from n-hexane, cyclohexane, petroleum ether, ethyl acetate, methyl acetate and butyl acetate, and the mass ratio of the hydrophilic emulsifier to the lipophilic emulsifier to the oil phase is 5-7:2:100-120.
As a further improvement of the invention, the heating temperature is 60-70 ℃, the adding amount of distilled water is 3-4 times of the mass of the oil phase, the emulsifying condition is 12000-15000r/min, and the time is 3-5min.
As a further improvement of the invention, the compound salt is a mixture of sodium chloride and potassium chloride, and the mass ratio is 2-4:1.
The invention further provides a preparation method of the antibacterial degradable cleanup additive, which comprises the following steps: adding the compound salt into water, heating to 40-50 ℃, adding the sodium polylactic acid, the polyvinyl alcohol and the quaternary ammonium salt emulsifier, stirring and mixing uniformly, and mixing with the nano emulsion to prepare the antibacterial degradable cleanup additive.
The invention has the following beneficial effects: the antibacterial degradable cleanup additive disclosed by the invention is convenient to prepare, simple in raw materials and stable in performance. The mixing and compounding of the quaternary ammonium salt emulsifier and the nano emulsion generate a synergistic effect, so that the arrangement of hydrophobic chains on the surface of the liquid is more compact, and the cleanup additive system has low surface tension (25 ℃ less than or equal to 15 mN/m) and low interfacial tension (25 ℃ less than or equal to 0.8 mN/m) and the interfacial tension between the cleanup additive system and kerosene. The prepared antibacterial degradable cleanup additive has good compatibility with the fracturing fluid, and the self performance of the fracturing fluid is not affected after the compounding.
The octadecyl trimethyl ammonium bromide and the dioctadecyl dimethyl ammonium chloride have synergistic effect, can obviously improve the surface performance and the antibacterial effect, can be dissociated into positively charged long-chain cations in acidic and alkaline solutions, has high sterilization efficiency, broad-spectrum antibacterial effect and low toxicity, is not influenced by the change of pH value and hardness, has stronger stripping and separating effect on a mucus layer, has good dispersing and sterilizing performances and has a certain slow release effect.
The nano emulsion prepared by the invention is used as a surfactant carrier, successfully prepares an excellent drainage assisting agent which has low surface tension, anti-adsorption characteristic and long-term stability, has remarkable anti-adsorption performance, has a synergistic effect between a hydrophilic emulsifier Tween-80 and a lipophilic emulsifier span-20, wherein Tween-80 is a hydrophilic emulsifier, is an oil-in-water type emulsifier, span-20 is a lipophilic emulsifier, is a water-in-oil type emulsifier, forms an extremely small nano emulsion in emulsion containing oil and water under the synergistic effect, keeps stable, and further reduces the surface tension of the drainage assisting agent under the synergistic effect of the two.
The quaternary ammonium salt emulsifier not only can reduce the surface tension of the cleanup additive, but also has a good antibacterial effect, and under the synergistic effect of the compound salt, the compound salt can improve the emulsifying effect and simultaneously dehydrate and die bacterial cells, so that the cleanup additive has good antibacterial and bacteriostatic properties.
The sodium polylactic acid and the polyvinyl alcohol added in the invention improve the surface property of the cleanup additive, and simultaneously improve the degradability of the cleanup additive, and the prepared cleanup additive has good degradability.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The present embodiment provides an antimicrobial degradable drainage aid.
The raw materials comprise the following components in parts by weight: 10 parts of nanoemulsion, 5 parts of quaternary ammonium salt emulsifier, 3 parts of sodium polylactic acid, 4 parts of polyvinyl alcohol, 2 parts of compound salt and 50 parts of water.
The quaternary ammonium salt emulsifier is a composition of octadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride, and the mass ratio is 3:1.
The compound salt is a mixture of sodium chloride and potassium chloride, and the mass ratio is 2:1.
The preparation method of the nano emulsion comprises the following steps: adding 5 parts by weight of Tween-80 and 2 parts by weight of span-20 into 100 parts by weight of n-hexane, heating to 60 ℃, stirring, dropwise adding distilled water to 3 times of the mass of the n-hexane, and emulsifying for 3min with 12000r/min to obtain the nano emulsion.
The preparation method comprises the following steps: adding the compound salt into water, heating to 40 ℃, adding the sodium polylactic acid, the polyvinyl alcohol and the quaternary ammonium salt emulsifier, stirring and mixing uniformly, and mixing with the nano emulsion to prepare the antibacterial degradable cleanup additive.
Example 2
The present embodiment provides an antimicrobial degradable drainage aid.
The raw materials comprise the following components in parts by weight: 20 parts of nanoemulsion, 7 parts of quaternary ammonium salt emulsifier, 5 parts of sodium polylactic acid, 8 parts of polyvinyl alcohol, 4 parts of compound salt and 70 parts of water.
The quaternary ammonium salt emulsifier is a composition of octadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride, and the mass ratio is 5:1.
The compound salt is a mixture of sodium chloride and potassium chloride, and the mass ratio is 4:1.
The preparation method of the nano emulsion comprises the following steps: adding 7 parts by weight of Tween-80 and 2 parts by weight of span-20 into 120 parts by weight of cyclohexane, heating to 70 ℃, stirring, dripping distilled water to 4 times of the mass of the cyclohexane, and emulsifying for 5min at 15000r/min to obtain the nano emulsion.
The preparation method comprises the following steps: adding the compound salt into water, heating to 50 ℃, adding the sodium polylactic acid, the polyvinyl alcohol and the quaternary ammonium salt emulsifier, stirring and mixing uniformly, and mixing with the nano emulsion to prepare the antibacterial degradable cleanup additive.
Example 3
The present embodiment provides an antimicrobial degradable drainage aid.
The raw materials comprise the following components in parts by weight: 15 parts of nano emulsion, 6 parts of quaternary ammonium salt emulsifier, 4 parts of sodium polylactic acid, 6 parts of polyvinyl alcohol, 3 parts of compound salt and 60 parts of water.
The quaternary ammonium salt emulsifier is a composition of octadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride, and the mass ratio is 4:1.
The compound salt is a mixture of sodium chloride and potassium chloride, and the mass ratio is 3:1.
The preparation method of the nano emulsion comprises the following steps: adding 6 parts by weight of Tween-80 and 2 parts by weight of span-20 into 110 parts by weight of ethyl acetate, heating to 60-70 ℃, stirring, dripping distilled water to 3.54 times of the mass of the ethyl acetate, and emulsifying for 4min at 13500r/min to obtain the nano emulsion.
The preparation method comprises the following steps: adding the compound salt into water, heating to 45 ℃, adding the sodium polylactic acid, the polyvinyl alcohol and the quaternary ammonium salt emulsifier, stirring and mixing uniformly, and mixing with the nano emulsion to prepare the antibacterial degradable cleanup additive.
Example 4
The difference compared to example 3 is that the quaternary ammonium salt emulsifier is a single octadecyl trimethyl ammonium bromide.
Example 5
The difference compared to example 3 is that the quaternary ammonium salt emulsifier is a single dioctadecyl dimethyl ammonium chloride.
Example 6
The difference compared to example 3 is that no tween-80 was added to the nanoemulsion.
The method comprises the following steps:
the preparation method of the nano emulsion comprises the following steps: adding 8 parts by weight of span-20 into 110 parts by weight of ethyl acetate, heating to 60-70 ℃, stirring, dripping distilled water to 3.54 times of the mass of the ethyl acetate, and emulsifying for 4min at 13500r/min to obtain the nano emulsion.
Example 7
In comparison with example 3, the difference is that span-20 was not added to the nanoemulsion.
The method comprises the following steps:
the preparation method of the nano emulsion comprises the following steps: adding 8 parts by weight of Tween-80 into 110 parts by weight of ethyl acetate, heating to 60-70 ℃, stirring, dripping distilled water to 3.54 times of the mass of the ethyl acetate, and emulsifying for 4min at 13500r/min to obtain the nano emulsion.
Comparative example 1
The difference compared to example 3 is that no quaternary ammonium salt emulsifier is added.
The raw materials comprise the following components in parts by weight: 21 parts of nano emulsion, 4 parts of sodium polylactic acid, 6 parts of polyvinyl alcohol, 3 parts of composite salt and 60 parts of water.
Comparative example 2
The difference compared to example 3 is that no nanoemulsion was added.
The raw materials comprise the following components in parts by weight: 21 parts of quaternary ammonium salt emulsifier, 4 parts of sodium polylactic acid, 6 parts of polyvinyl alcohol, 3 parts of compound salt and 60 parts of water.
Comparative example 3
In comparison with example 3, the difference is that no complex salt was added.
The raw materials comprise the following components in parts by weight: 15 parts of nano emulsion, 6 parts of quaternary ammonium salt emulsifier, 4 parts of sodium polylactic acid, 6 parts of polyvinyl alcohol and 60 parts of water.
Test example 1
The antibacterial degradable cleanup additive prepared in examples 1 to 7 and comparative examples 1 to 3 of the present invention was added to the fracturing fluid and kerosene in an amount of 0.1% and the test temperature was 25℃and the results are shown in Table 1.
TABLE 1
| Group of | Surface tension of fracturing fluid (mN/m) | Kerosene interfacial tension (mN/m) |
| Example 1 | 14.5 | 0.8 |
| Example 2 | 14.2 | 0.7 |
| Example 3 | 13.9 | 0.5 |
| Example 4 | 24.4 | 2.5 |
| Example 5 | 25.2 | 2.8 |
| Example 6 | 28.9 | 3.8 |
| Example 7 | 28.2 | 3.5 |
| Comparative example 1 | 30.2 | 3.3 |
| Comparative example 2 | 32.7 | 4.2 |
| Comparative example 3 | 18.8 | 1.5 |
The antimicrobial degradable drainage aids prepared in examples 1-3 of the present invention provide a tighter alignment of hydrophobic chains on the surface of the liquid, resulting in a drainage aid system with low surface tension and low interfacial tension.
Test example 2
Antibacterial property tests were conducted on the antibacterial degradable discharge aiding agents prepared in examples 1 to 7 and comparative examples 1 to 3 of the present invention, and the results are shown in Table 2.
TABLE 2
The antibacterial degradable cleanup additive prepared in the embodiments 1-3 has good antibacterial and bacteriostatic properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. An antibacterial degradable discharge assisting agent is characterized by comprising the following raw materials: the emulsion comprises nano emulsion, quaternary ammonium salt emulsifier, sodium polylactic acid, polyvinyl alcohol, compound salt and water.
2. The antibacterial degradable cleanup additive according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight: 10-20 parts of nano emulsion, 5-7 parts of quaternary ammonium salt emulsifier, 3-5 parts of sodium polylactic acid, 4-8 parts of polyvinyl alcohol, 2-4 parts of compound salt and 50-70 parts of water.
3. The antimicrobial degradable cleanup additive of claim 1, wherein the quaternary ammonium salt emulsifier is selected from at least one of octadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, and dioctadecyl trimethyl ammonium bromide.
4. The antimicrobial degradable cleanup additive according to claim 3, wherein the quaternary ammonium salt emulsifier is a combination of octadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride in a mass ratio of 3-5:1.
5. The antimicrobial degradable cleanup additive according to claim 1, wherein the nanoemulsion is prepared by the following method: adding hydrophilic emulsifier and lipophilic emulsifier into oil phase, heating and stirring, dripping distilled water, and emulsifying to obtain nanoemulsion.
6. The antimicrobial degradable cleanup of claim 5, wherein the hydrophilic emulsifier is selected from at least one of tween-20, tween-40, tween-60, tween-80; the lipophilic emulsifier is at least one selected from span-20, span 40, span-60 and span-80, preferably, the hydrophilic emulsifier is Tween-80, and the lipophilic emulsifier is span-20.
7. The antimicrobial degradable cleanup according to claim 5, wherein the oil phase is selected from at least one of n-hexane, cyclohexane, petroleum ether, ethyl acetate, methyl acetate, butyl acetate, and the mass ratio of hydrophilic emulsifier, lipophilic emulsifier, and oil phase is 5-7:2:100-120.
8. The antibacterial degradable drainage aid according to claim 5, wherein the heating temperature is 60-70 ℃, the adding amount of distilled water is 3-4 times of the mass of the oil phase, the emulsifying condition is 12000-15000r/min, and the time is 3-5min.
9. The antimicrobial degradable cleanup additive according to claim 1, wherein the compound salt is a mixture of sodium chloride and potassium chloride in a mass ratio of 2-4:1.
10. A method of preparing an antimicrobial degradable drainage aid according to any one of claims 1 to 9, comprising the steps of: adding the compound salt into water, heating to 40-50 ℃, adding the sodium polylactic acid, the polyvinyl alcohol and the quaternary ammonium salt emulsifier, stirring and mixing uniformly, and mixing with the nano emulsion to prepare the antibacterial degradable cleanup additive.
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