CN115885995A - Composition with bactericidal performance and preparation method and application thereof - Google Patents
Composition with bactericidal performance and preparation method and application thereof Download PDFInfo
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- CN115885995A CN115885995A CN202110956855.1A CN202110956855A CN115885995A CN 115885995 A CN115885995 A CN 115885995A CN 202110956855 A CN202110956855 A CN 202110956855A CN 115885995 A CN115885995 A CN 115885995A
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- polyoxyethylene ether
- bactericide
- fatty alcohol
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- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003899 bactericide agent Substances 0.000 claims abstract description 44
- 239000012530 fluid Substances 0.000 claims abstract description 43
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 38
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 38
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- UUIVKBHZENILKB-UHFFFAOYSA-N 2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N UUIVKBHZENILKB-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 9
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003139 biocide Substances 0.000 claims description 5
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 239000003079 shale oil Substances 0.000 claims description 5
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 241000894006 Bacteria Species 0.000 abstract description 29
- 230000001954 sterilising effect Effects 0.000 abstract description 18
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 241000295146 Gallionellaceae Species 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 101100504292 Caenorhabditis elegans gcy-6 gene Proteins 0.000 description 3
- -1 alkyl glycoside Chemical class 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- SMWVIUFPHBFCKQ-UHFFFAOYSA-M 1-(2-phenylethyl)pyridin-1-ium;chloride Chemical compound [Cl-].C=1C=CC=CC=1CC[N+]1=CC=CC=C1 SMWVIUFPHBFCKQ-UHFFFAOYSA-M 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical group OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229960003168 bronopol Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of petrochemical engineering exploitation, and discloses a composition with a bactericidal performance, and a preparation method and application thereof. The composition contains a nonionic bactericide and fatty alcohol-polyoxyethylene ether, wherein the weight ratio of the nonionic bactericide to the fatty alcohol-polyoxyethylene ether is (1-2.5): 1. the preparation method of the composition comprises the following steps: mixing the non-ionic bactericide, the fatty alcohol-polyoxyethylene ether and the auxiliary agent, and adjusting the pH value to 6-8. The fracturing fluid containing the composition can reduce the bacteria content to be within 25/mL within 10-15 minutes, and the composition has the characteristics of small using amount, good sterilization effect and high sterilization speed.
Description
Technical Field
The invention relates to the technical field of petrochemical engineering exploitation, in particular to a composition with a bactericidal performance and a preparation method and application thereof.
Background
Reservoirs such as shale oil, shale gas and compact oil gas have the characteristics of low porosity and low permeability, and ideal yield can be obtained only by volume modification. The hydraulic fracturing fluid system is a new fracturing fluid system developed for the reformation of the compact reservoirs, has wide application in shale oil gas and compact oil gas in China since the successful application in the American hydraulic fracturing, and has wide application prospect.
The water source for preparing the fracturing fluid is generally water of nearby rivers, lakes and the like or water recycled after the water produced by the oil and gas fields is treated. In general, a nearby water source does not undergo sterilization treatment, and therefore, contains a certain amount of bacteria. Even if the water recycled after the oil and gas field produced water treatment meets the requirement of recycled bacteria content, the bacteria can be proliferated in the water storage process. The hydraulic fracturing fluid (also called as a water-reducing and blocking fracturing fluid) system comprises a drag reducer, a glue solution and the like, and the components mainly comprise carbon-containing organic matters, so that nutrition is provided for the growth of bacteria, the bacteria are rapidly bred and propagated in the fracturing fluid, the fracturing fluid is corrupted and deteriorated, and the fracturing fluid is not crosslinked or is not crosslinked fully, and cannot be used for fracturing construction. In addition, bacteria entering the well with the fracturing fluid may be discharged from the oil pipe together with the oil gas in the production process together with the bacteria from the stratum, and enter the ground gathering and transportation system and the subsequent production flow, so that the serious bacterial corrosion problem of the oil pipe, the casing pipe, the gathering and transportation system and the sewage system is caused. The pipeline of the ground gathering and transportation system is corroded and perforated 2 months after the shale gas field is put into operation, and the main reason is that a great amount of bred bacteria exist in the fracturing fluid, so that the serious bacterial corrosion problem occurs.
At present, the hydraulic fracturing fluid is mainly prepared on the basis of polyacrylamide or other compounds of polyacrylamide. The bactericide commonly used in oil and gas fields is cationic, such as THPS, quaternary ammonium salt and the like. The cationic bactericide and the anionic polymer fracturing fluid can generate a crosslinking reaction, so that the molecular structure of the polymer is changed, and precipitates are generated, thereby not only reducing the fracturing effect, but also causing damage to the stratum. Therefore, the development of novel efficient fracturing fluid bactericides is necessary to ensure the safety of the production of the whole-flow pipeline equipment.
CN105076201B discloses a compound oilfield flooding bactericide, which is prepared from the following raw materials in parts by weight: 25-35 parts of glycosyl gemini quaternary ammonium salt, 2-5 parts of alkyl glycoside, 10-15 parts of quaternary phosphonium salt, 4-10 parts of isothiazolinone and 5-10 parts of dithiocyano-methane. The invention has strong sterilization effect, can effectively remove sulfate reducing bacteria, iron bacteria and saprophytic bacteria in the injected water, and avoids corrosion and blockage of bacteria to pipeline equipment.
"development and performance evaluation of fracturing fluid bactericide GCY-6" (chemical industry of petroleum and natural gas, 2010, vol.39, no. 6, page 510-513) develops a novel composite bactericide GCY-6, and the synthesis method is as follows: adding a certain amount of water into a three-neck flask, selecting long-chain tertiary amine with phenoxy as a reaction monomer, calculating a good molar ratio, feeding under continuous stirring, then heating to 60-70 ℃, and adding an alkylating agent. The formula adopts benzyl chloride as an alkylating agent, the feeding speed is controlled to prevent temperature from suddenly rising when the alkylating agent is added, the temperature of the whole system is raised to 110-120 ℃, the temperature is kept constant for reaction for 2 hours, then the temperature is reduced to about 50 ℃, the metered water is added, the stirring is uniform, and the pH value is adjusted to 6-8. The infrared analysis shows that the synthesized GCY bactericide is a quaternary ammonium salt compound. Then the quaternary ammonium salt compound is supplemented with other sterilization components such as glutaraldehyde and the like and surfactant in a certain proportion to compound a novel bactericide GCY-6.
However, the two bactericides contain cationic bactericidal components which can react with anionic polyacrylamide in the hydraulic fracturing fluid to degrade the anionic polyacrylamide, thereby affecting the oil displacement effect.
CN107047603A discloses a bactericide which is good in sterilization effect and does not influence the polymer oil displacement effect, and a preparation method and application thereof. The bactericide comprises the following components in percentage by mass: 5-8% of bronopol, 10-15% of sodium dichloroisocyanurate, 1-4% of dithiocyano-methane, 20-35% of glutaraldehyde, 2-4% of a dispersant and the balance of water. Through the synergistic effect of the components, sulfate reducing bacteria, iron bacteria and saprophytic bacteria in the produced water of the oil field are removed on the premise of not reducing the viscosity of the oil displacing polymer. However, the invention only mentions that the dosage is 50-200ppm, the sterilization rate is more than 99 percent, and the sterilization speed is not mentioned. In fact, the rate of tertiary oil recovery injection of flooding polymer is much lower than the rate of fracturing fluid during the fracturing process. In addition, if the bacteria content is large (e.g. 10) 6 one/mL) in time, the sterilization rate reaches 99%, and the content of bacteria still alive after sterilization still reaches 100/mL, which still causes corrosion problems. Therefore, the bactericide has low sterilization speed and high bacteria content after sterilization, and can not meet the requirement of the fracturing hydraulic fracturing cycle.
Disclosure of Invention
The invention aims to solve the problems that the sterilizing speed of a bactericide is low and the fracturing effect is reduced by the cross-linking reaction of the bactericide and fracturing fluid components in the prior art, and provides a composition with sterilizing performance and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a composition with bactericidal performance, which contains a nonionic bactericide and fatty alcohol-polyoxyethylene ether, wherein the weight ratio of the nonionic bactericide to the fatty alcohol-polyoxyethylene ether is 1-2.5:1.
in a second aspect, the present invention provides a process for preparing the composition described above, which process comprises: mixing the non-ionic bactericide, fatty alcohol-polyoxyethylene ether, an auxiliary agent, a defoaming agent, a pH regulator, a solvent and an optional stabilizer, and then regulating the pH to 6-8 by using the pH regulator.
In a third aspect, the invention provides a fracturing fluid, wherein the bactericide in the fracturing fluid comprises the composition.
The fourth aspect of the invention provides an application of the fracturing fluid in shale oil, shale gas and compact oil and gas exploitation.
Through the technical scheme, the invention has the following technical effects:
(1) The bactericide of the invention has the characteristics of small usage amount, good sterilization effect and high sterilization speed.
(2) The bactericide has a certain corrosion inhibition effect and can inhibit corrosion and perforation of the pipeline.
(3) The bactericide can be completely compatible with the fracturing fluid, does not cause adverse reactions such as flocculation and the like, and does not influence the fracturing effect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composition with bactericidal performance, which contains a nonionic bactericide and fatty alcohol-polyoxyethylene ether, wherein the weight ratio of the nonionic bactericide to the fatty alcohol-polyoxyethylene ether is (1-2.5): 1, preferably 1.3-2:1.
according to the invention, preferably, the fatty alcohol-polyoxyethylene ether has a structural formula shown in formula (1),
R-O-[CH 2 -CH 2 -O] n -H formula (1)
Therein, 9<n is less than or equal to 20, R is C 12 -C 18 Alkyl group of (1).
According to the present invention, the type of the nonionic bactericide is not particularly limited, and may be a nonionic bactericide commonly used in the art. Preferably, the nonionic bactericide is at least one of 2,2-dibromo-3-nitrilopropionamide (DBNPA), glutaraldehyde, isothiazolinone, and dodecyl betaine.
According to the invention, the composition preferably further comprises an auxiliary agent selected from the group consisting of monohydric alcohols, dihydric alcohols, polyhydric alcohols, C 3 -C 9 Saturated ketone of (1), C 3 -C 6 At least one of an amide of (a), a nonionic silicone defoamer, a pH adjuster, and water.
According to the invention, preferably, the weight ratio of the auxiliary agent to the fatty alcohol-polyoxyethylene ether is 1-12:1, preferably 4 to 7.5:1.
according to the invention, preferably, the monoalcohol is C 1 -C 4 A monohydric alcohol of (a); more preferably, said C 1 -C 4 The monohydric alcohol of (a) is at least one of ethanol, methanol and propanol.
According to the invention, preferably, the diol is C 2 -C 4 The dihydric alcohol of (1); more preferably, C is 2 -C 4 The diol of (b) is ethylene glycol.
According to the invention, preferably, the polyol is polyethylene glycol and/or C 3 -C 5 The trihydric alcohol of (2). More preferably, said C 3 -C 5 The triol of (a) is glycerol.
According to the present invention, the molecular weight of the polyethylene glycol is not particularly limited, and the polyethylene glycol has an average molecular weight of 200 to 600, and more preferably, the polyethylene glycol is polyethylene glycol-200 and/or polyethylene glycol-400.
According to the invention, preferably, C is 3 -C 9 The saturated ketone of (a) is acetone.
According to the invention, preferably, C is 3 -C 6 The amide of (a) is N, N-dimethylformamide.
According to the invention, the nonionic silicone defoamer is preferably provided by federal fine chemical limited in the Guangdong under the types B-257 and B-520.
According to the present invention, the kind of the pH adjuster is not particularly limited, and preferably, the pH adjuster is hydrochloric acid, naOH, naHCO 3 And Na 2 CO 3 At least one of (1).
According to the invention, the pH of the composition can be selected within a wide range, preferably the pH of the composition is 6 to 8, more preferably 6.5 to 7.5. Limiting the pH of the composition to the above range ensures that the addition of the fracturing fluid biocide does not affect the properties of the fracturing fluid.
According to a particularly preferred embodiment of the invention, the composition comprises: the pesticide comprises fatty alcohol-polyoxyethylene ether, a nonionic bactericide, polyethylene glycol-400, acetone, water, methanol, ethanol and a pH regulator, wherein the weight ratio of the fatty alcohol-polyoxyethylene ether to the nonionic bactericide to the polyethylene glycol-400 to the acetone to the water to the methanol to the ethanol is 1:1.8-2:1-1.2:0.3-0.35:2-2.3:0.26-0.3:0.15-0.25. Wherein the nonionic bactericide is 2,2-dibromo-3-nitrilopropionamide and isothiazolinone, and the weight ratio of 2,2-dibromo-3-nitrilopropionamide to isothiazolinone is 1:1-1.125.
In a second aspect, the present invention provides a process for preparing the composition described above, which process comprises: mixing the non-ionic bactericide, the fatty alcohol-polyoxyethylene ether and the auxiliary agent, and adjusting the pH value to 6-8.
In a third aspect, the invention provides a fracturing fluid, wherein the bactericide in the fracturing fluid comprises the composition.
According to the invention, the concentration of the composition in the fracturing fluid is preferably between 50 and 300ppm, preferably between 100 and 200ppm.
In the present invention, "ppm" means a concentration by weight.
The fourth aspect of the invention provides an application of the fracturing fluid in shale oil, shale gas and compact oil and gas exploitation.
In the present invention, the composition has a better inhibiting effect on Sulfate Reducing Bacteria (SRB), saprophytic bacteria (TGB) and Iron Bacteria (IB), and therefore, the invention also relates to the application of the composition in inhibiting Sulfate Reducing Bacteria (SRB), saprophytic bacteria (TGB) and Iron Bacteria (IB).
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
polyethylene glycol-200 is polyethylene glycol with average molecular weight of 200
Polyethylene glycol-400 is polyethylene glycol with average molecular weight of 400;
the polymerization degree of the fatty alcohol-polyoxyethylene ether is that n is 9-20, R is C 12 -C 18 An alkyl group;
the nonionic organic silicon defoamer is produced by Federal Fine chemical Co., ltd in Guangdong;
the rest is a commercial product.
Example 1
2g of DBNPA,0.5g of glutaraldehyde, 4g of polyethylene glycol-200, 1.5g of fatty alcohol-polyoxyethylene ether and 6g of water are added into a reaction kettle, and the mixture is heated and stirred for 6 hours at the temperature of 50 ℃; when the temperature is reduced to 25 ℃, 0.3g of glycerol is added, the mixture is stirred for 1 hour, 0.3g of nonionic organic silicon defoamer (model B-257) is slowly added, the mixture is continuously stirred for 0.5 hour, a proper amount of dilute hydrochloric acid solution is added, and the pH value is adjusted to be 7, so that the composition with the bactericidal performance is obtained.
Example 2
Adding 1.5g of DBNPA,1.4g of dodecyl betaine, 3g of N, N-dimethylformamide, 0.6g of ethylene glycol, 1.2g of fatty alcohol-polyoxyethylene ether, 4g of water and 2g of ethanol into a reaction kettle, and heating and stirring at 55 ℃ for 5 hours; when the temperature is reduced to 25 ℃, 0.25g of fatty alcohol-polyoxyethylene ether is added, the mixture is stirred for 1.5h, 0.35g of nonionic organic silicon defoamer (model B-520) is slowly added, the mixture is continuously stirred for 1h, a proper amount of dilute NaOH solution is added, and the pH value is adjusted to 7.3, so that the composition with the bactericidal performance is obtained.
Example 3
Adding 1.6g of dodecyl betaine, 0.8g of glutaraldehyde, 1.8g of polyethylene glycol-400, 0.5g of glycerol, 1.6g of fatty alcohol-polyoxyethylene ether and 5.6g of ethanol into a reaction kettle, and heating and stirring at 45 ℃ for 5.5 hours; when the temperature is reduced to 30 ℃, 0.22g of fatty alcohol-polyoxyethylene ether is added, the mixture is stirred for 1.5h, 0.4g of ethanol is slowly added, the stirring is continued for 0.6h, and a proper amount of diluted NaHCO is added 3 Adjusting the pH value of the solution to 7.5 to obtain the composition with the bactericidal performance.
Example 4
Adding 1.8g of isothiazolinone, 0.8g of glutaraldehyde, 2.2g of glycol, 2g of fatty alcohol-polyoxyethylene ether and 6g of water into a reaction kettle, and heating and stirring at 55 ℃ for 4 hours; when the temperature is reduced to 20 ℃,0.2g of fatty alcohol-polyoxyethylene ether and 1.2g of glycerol are added, the mixture is stirred for 0.8h, 0.3g of nonionic organic silicon defoamer (model B-257) is slowly added, the mixture is continuously stirred for 0.6h, a proper amount of dilute NaOH solution is added, and the pH value is adjusted to 6.5, so that the composition with the bactericidal performance is obtained.
Example 5
Adding 3g of DBNPA,3g of ethylene glycol, 0.8g of N, N-dimethylformamide, 1.8g of fatty alcohol-polyoxyethylene ether and 5.5g of ethanol into a reaction kettle, and heating and stirring at 50 ℃ for 6 hours; when the temperature is reduced to 25 ℃, adding 3g of glycerol, stirring for 1.2h, slowly adding 0.3g of ethanol, continuing stirring for 1h, adding a proper amount of diluted NaHCO 3 Adjusting the pH value of the solution to 6.8 to obtain the composition with the bactericidal performance.
Example 6
Adding 1.6g of DBNPA,1.8g of isothiazolinone, 2g of polyethylene glycol-400, 0.6g of acetone, 1.5g of fatty alcohol-polyoxyethylene ether, 4g of water and 0.5g of methanol into a reaction kettle, and heating and stirring for 5 hours at 65 ℃; when the temperature is reduced to 35 ℃, 0.3g of fatty alcohol-polyoxyethylene ether is added, the mixture is stirred for 1.5h, 0.35g of ethanol is slowly added, the mixture is continuously stirred for 1h, a proper amount of dilute NaOH solution is added, and the pH value is adjusted to 6.5, so that the composition with the sterilization performance is obtained.
Example 7
Adding 0.8g of DBNPA,1.2g of isothiazolinone, 0.2g of polyethylene glycol-400, 0.6g of acetone, 1.7g of fatty alcohol-polyoxyethylene ether, 1.5g of water and 0.5g of methanol into a reaction kettle, and heating and stirring at 65 ℃ for 5 hours; when the temperature is reduced to 35 ℃, 0.3g of fatty alcohol-polyoxyethylene ether is added, stirring is carried out for 1.5h, 0.1g of ethanol is slowly added, stirring is carried out for 1h, a proper amount of dilute NaOH solution is added, and the pH value is adjusted to 6.5, so as to obtain the composition with the sterilization performance.
Example 8
Adding 1.6g of dodecyl betaine, 0.8g of glutaraldehyde, 1.8g of polyethylene glycol-400, 3.2g of glycerol, 0.77g of fatty alcohol-polyoxyethylene ether and 6g of ethanol into a reaction kettle, and heating and stirring at 45 ℃ for 5.5 hours; when the temperature is reduced to 30 ℃,0.2g of fatty alcohol-polyoxyethylene ether is added, the mixture is stirred for 1.5h, 0.6g of ethanol is slowly added, the mixture is continuously stirred for 0.6h, and a proper amount of diluted NaHCO is added 3 Adjusting the pH value of the solution to 7.5 to obtain the composition with the bactericidal performance.
Example 9
The preparation of a composition having fungicidal properties was carried out in accordance with the procedure of example 5, except that DBNPA was replaced with chlorophenol.
Comparative example 1
Tetrakis (hydroxymethyl) phosphonium sulfate (THPS) was used directly in place of the composition of example 1 having biocidal properties.
Comparative example 2
By direct use of N-benzylmethylpyridinium chloride (C) 13 H 16 ClN) alternative example 1 composition with fungicidal properties.
Comparative example 3
The preparation of the composition was carried out according to the method of example 1, except that the fatty alcohol-polyoxyethylene ether was replaced with glutaraldehyde.
Comparative example 4
The preparation of a composition was conducted in accordance with the procedure of example 5, except that the amount of the fatty alcohol polyoxyethylene ether added was 2.2g and the amount of DBNPA added was 1.9g.
Comparative example 5
The preparation of the composition was carried out according to the method of example 5, except that DBNPA was replaced with cationic bactericide imidazoline.
Comparative example 6
The preparation of the composition was carried out as in example 5, except that no fatty alcohol polyoxyethylene ether was added.
Test example 1
The compositions prepared in the above examples and comparative examples were tested for bactericidal performance, which was tested with reference to SY/T0532-2012 (oilfield injection water bacteria analysis method abstinence dilution) and SY/T5890-93 (bactericide performance evaluation method). Selecting fracturing fluid containing Sulfate Reducing Bacteria (SRB), saprophytic bacteria (TGB) and Iron Bacteria (IB) as a water sample, and observing the content change of the bacteria in the water sample after the composition is added. Wherein, the compositions of example 1-1, example 3-1 and example 6-1 are tested for bactericidal performance after incubation at 90 ℃ for 1 hour for the compositions of example 1, example 3 and example 6, respectively. Examples 1-2, 3-2 and 6-2 were tested for bactericidal properties after incubation at 90 ℃ for 24 hours for the compositions of example 1, 3 and 6, respectively. All other examples and comparative examples were tested for bactericidal performance after incubation at 90 c for about 12 minutes. The test results are shown in table 1.
TABLE 1
As can be seen from the table, examples 1-6 reduced the bacteria in the fracturing fluid to within 25/mL in 10-15 minutes. The compositions of examples 1, 3 and 6 are stable in 1 hour and 24 hours, can reduce bacteria to be within 25/mL, meet the requirements of the underground environment of the fracturing fluid, and have no influence on the performance of the fracturing fluid. It can be seen from comparative examples 1, 2 and 5 that when the ionic bactericide is added into the fracturing fluid, the reaction such as flocculation and the like of the fracturing fluid can be caused, and the bactericidal effect is poor. Comparative examples 3, 5 and 6 show that the bactericidal effect is significantly reduced when no fatty alcohol-polyoxyethylene ether or non-ionic bactericide is added to the composition. Comparative example 4 the amounts of fatty alcohol polyoxyethylene ether and non-ionic biocide were outside the range of the present invention, and the biocidal effect was poor.
Test example 2
The apparent viscosities of the compositions prepared in the above examples and comparative examples were measured, according to SY/T5764-2007 (general technical requirement for vegetable gum for fracturing), a fracturing fluid containing Sulfate Reducing Bacteria (SRB), saprophytic bacteria (TGB) and Iron Bacteria (IB) was selected as a water sample, and then the change in the apparent viscosity of the fracturing fluid after the composition was added was observed. The test results are shown in table 2.
TABLE 2
As can be seen from table 2: comparative examples 1, 2 and 5 showed a significant drop in apparent viscosity of the fracturing fluid due to the flocculation reaction, and the apparent viscosities of the other examples and comparative examples were not significantly changed.
Test example 3
The corrosion inhibition performance of the compositions prepared in the above examples and comparative examples is tested and evaluated according to SY/T5273-2014 (performance index and evaluation method of corrosion inhibitor for oilfield produced water treatment). The test results are shown in table 3.
TABLE 3
Application test example 1
The composition prepared in example 3 was used in the fracturing process of a newly developed well in a shale gas field by an on-site compounding method, the addition concentration of the composition prepared in example 3 in the fracturing fluid was 200ppm, and the on-site application results are shown in table 4.
TABLE 4
From the results in table 4, it can be seen that the bacterial content in the fracturing fluid and the production flowback fluid after the composition prepared in example 3 was added was effectively controlled, much less than 25/mL. Before the shale gas field is added with a fracturing fluid bactericide, bacterial corrosion perforation is generated after the shale gas field is used for 2 months. Bacterial corrosion perforation also occurred after 2 months of use after addition of the biocide of comparative example 5. After the composition with the bactericidal performance prepared by the invention is added, perforation still does not occur after 12 months of use, which shows that the composition has the bactericidal performance and can inhibit corrosion perforation. After the composition (bactericide) of the invention is injected in the fracturing process, the corrosion perforation frequency is reduced by 96.8%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. The composition with the bactericidal performance is characterized by comprising a nonionic bactericide and fatty alcohol-polyoxyethylene ether, wherein the weight ratio of the nonionic bactericide to the fatty alcohol-polyoxyethylene ether is (1-2.5): 1.
2. the composition according to claim 1, wherein the weight ratio of the nonionic bactericide to the fatty alcohol-polyoxyethylene ether is 1.3-2:1.
3. the composition of claim 1 or 2, wherein the non-ionic biocide is at least one of 2,2-dibromo-3-nitrilopropionamide, glutaraldehyde, isothiazolinone, and dodecyl betaine.
4. The composition according to any one of claims 1 to 3, wherein the composition further comprises an auxiliary selected from the group consisting of monohydric alcohols, dihydric alcohols, polyhydric alcohols, C 3 -C 9 Saturated ketone of (1), C 3 -C 6 At least one of an amide of (a), a nonionic silicone defoamer, a pH adjuster, and water.
5. The composition of claim 4, wherein the weight ratio of the auxiliary agent to the fatty alcohol-polyoxyethylene ether is 1-12:1, preferably 4 to 7.5:1.
6. the composition of claim 4 or 5, wherein the monohydric alcohol is C 1 -C 4 The monohydric alcohol of (a);
and/or, the dihydric alcohol is C 2 -C 4 The dihydric alcohol of (1);
and/or the polyalcohol is polyethylene glycol and/or C 3 -C 5 The trihydric alcohol of (1).
7. The composition of any one of claims 4-6, wherein C is 1 -C 4 The monohydric alcohol of (a) is at least one of ethanol, methanol and propanol;
and/or, said C 2 -C 4 The dihydric alcohol of (a) is ethylene glycol;
and/or, said C 3 -C 5 The trihydric alcohol of (b) is glycerol;
and/or the polyethylene glycol is polyethylene glycol-200 and/or polyethylene glycol-400.
8. The composition of any one of claims 4-7, wherein C is 3 -C 9 The saturated ketone of (a) is acetone;
and/or, said C 3 -C 6 The amide of (A) is N, N-dimethylAnd (3) a formamide.
9. The composition of any one of claims 4-8, wherein the pH adjusting agent is hydrochloric acid, naOH, naHCO 3 And Na 2 CO 3 At least one of (1).
10. A method of preparing the composition of any one of claims 4 to 9, comprising: mixing the non-ionic bactericide, the fatty alcohol-polyoxyethylene ether and the auxiliary agent, and adjusting the pH value to 6-8.
11. A fracturing fluid, wherein the biocide comprises a composition according to any one of claims 1 to 10.
12. Use of the fracturing fluid of claim 11 in shale oil, shale gas and tight oil and gas production.
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| US20170369767A1 (en) * | 2015-11-19 | 2017-12-28 | Sichuan Guangya Polymer Chemical Co., Ltd. | Multi-functional hybrid fracturing fluid system |
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| US20150114638A1 (en) * | 2012-05-12 | 2015-04-30 | Glenn Louis TAYLOR | Compositions and methods for hydraulic fracturing of natural gas and oil |
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