CN114456795A - Hydrophobic association polyacrylamide suspension emulsion for fracturing and preparation method thereof - Google Patents
Hydrophobic association polyacrylamide suspension emulsion for fracturing and preparation method thereof Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 44
- 239000000839 emulsion Substances 0.000 title claims abstract description 36
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 25
- 239000000725 suspension Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 3
- -1 polyoxyethylene octylphenol Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000004548 suspo-emulsion Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 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 description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000693 micelle Substances 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 claims description 2
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical group CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 claims description 2
- BKWMQCLROIZNLX-UHFFFAOYSA-N n-hexadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCNC(=O)C=C BKWMQCLROIZNLX-UHFFFAOYSA-N 0.000 claims description 2
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 claims description 2
- DBLNSVZHOZOZQX-UHFFFAOYSA-N n-tetradecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCNC(=O)C=C DBLNSVZHOZOZQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229920002114 octoxynol-9 Polymers 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- RWOLOMHZCCTUSS-UHFFFAOYSA-N C(CCCCCCCCCCC)[Na].C(C=C)(=O)N Chemical compound C(CCCCCCCCCCC)[Na].C(C=C)(=O)N RWOLOMHZCCTUSS-UHFFFAOYSA-N 0.000 claims 1
- DWIODGYJZKPUEW-UHFFFAOYSA-N C(CCCCCCCCCCCCC)[Na].C(C=C)(=O)N Chemical compound C(CCCCCCCCCCCCC)[Na].C(C=C)(=O)N DWIODGYJZKPUEW-UHFFFAOYSA-N 0.000 claims 1
- UFDGMAPVTDSQOG-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)[Na].C(C=C)(=O)N Chemical compound C(CCCCCCCCCCCCCCCCC)[Na].C(C=C)(=O)N UFDGMAPVTDSQOG-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000012530 fluid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000008719 thickening Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical class CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JFUJGRUREOMMMW-UHFFFAOYSA-M C(CCCCCCCCCCC)S(=O)(=O)O.[Na+].C(=O)(C=C)[NH-] Chemical compound C(CCCCCCCCCCC)S(=O)(=O)O.[Na+].C(=O)(C=C)[NH-] JFUJGRUREOMMMW-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
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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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric 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
- C09K8/62—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
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention relates to a hydrophobic association polyacrylamide suspension emulsion for fracturing and a preparation method thereof, wherein the hydrophobic association polyacrylamide suspension emulsion comprises the following components of an organic hydrocarbon solvent, clay, a high-molecular stabilizer, an emulsifier, a phase transfer agent and hydrophobic association polyacrylamide powder; the preparation method comprises the steps of placing the organic hydrocarbon solvent in a reaction kettle with mechanical stirring; sequentially adding clay, a high-molecular stabilizer and a small-molecular emulsifier into a reaction kettle; adding a phase transfer agent; adding hydrophobic association polyacrylamide powder and continuously stirring. The emulsion has a longer stable period, and is beneficial to reducing the field operation cost.
Description
Technical Field
The invention belongs to the field of petroleum development, and particularly relates to a hydrophobically associating polyacrylamide suspension emulsion for fracturing and a preparation method thereof.
Background
Currently, the petroleum industry is used as a super user of polyacrylamide products in China. The yield of polyacrylamide in China is improved year by year, and more than 70-80% of the yield is applied to the field of oil field development. The polyacrylamide for oil and gas in the market mainly exists in three forms of powder, reversed phase water-in-oil emulsion and water-in-water emulsion. However, when the traditional powdery polyacrylamide product is applied to an oilfield field, the traditional powdery polyacrylamide product needs to be fully swelled in advance, so that the problem caused by uneven liquid in the fracturing construction period is prevented. Therefore, the traditional polyacrylamide construction period is long, the fracturing fluid preparation procedures are multiple, the strength is high, and the fracturing of large-scale oil field wells cannot be completely met. The traditional inverse emulsion is used for synthesizing emulsion polyacrylamide, the friction resistance of the system in the construction process is small, the requirements of the on-site continuous blending process are met, the gel breaking and the flowback are easy, but the flowback liquid can only be used as a front liquid for application, and the salt tolerance of the system is poor. The water-in-water emulsion has the defects of low effective content, low molecular weight, no salt tolerance and the like. In addition, different polymerization processes are adopted, the molecular weight of the polymer is greatly influenced, and the molecular weight has great influence on thickening, drag reduction and viscoelasticity of the product in the application process of the product as the fracturing fluid.
In order to take all advantages into consideration, the polyacrylamide suspension emulsion becomes a hotspot for market research and development and use. It can give consideration to the advantages of high molecular weight and high salt resistance of the powder polymer, has high solubility of the inverse emulsion, and can meet the requirement of on-site connection blending.
Chinese patent (CN 201810279436.7-a suspended emulsion type slippery water resistance reducing agent and a preparation method thereof) introduces a preparation method of suspended emulsion, wherein inorganic clay and a small molecular surfactant are used in the system, so that polyacrylamide powder is stably dispersed in white oil, and the suspended emulsion with certain stability can be obtained. (Table 1 shows the layering time for the different cases disclosed in this patent)
However, the stability of the product should be further improved when the product is distributed as a commercial product.
Meanwhile, the conventional polyacrylamide fracturing fluid has poor salt resistance, temperature resistance and shear resistance. In order to solve the above problems, a hydrophobic association system fracturing fluid has appeared. The fracturing fluid is a water-soluble polymer with a small amount of hydrophobic groups on a hydrophilic macromolecular chain, and the unique amphiphilic molecular structure of the fracturing fluid enables the solution to have special thickening and shearing resistant effects.
The literature reports (Ainshun, preparation and application of concentrated associative polymer fracturing thickening agent of oleyl alcohol series, 2016, 33 (1): 107-. It can realize on-site rapid preparation and has good temperature resistance and shear resistance. In addition, the associated non-crosslinked fluid also has the characteristics of sand carrying property, easy gel breaking and flowback, low residue and the like, and is a clean fracturing fluid with good performance. However, the polyacrylamide effective substance of the system is only 25 percent, and the effective content (30 to 50 percent) is lower than that of the conventional polyacrylamide suspension emulsion, so that the competitiveness is weaker.
The literature reports (Qi, Chen, Zhangxi, analysis of mechanism of molecular self-assembly on associative fracturing fluid viscosity recovery, 2017, 34 (3): 111-116) that for an emulsion system, due to the existence of a large amount of activators, the associative action of associative polymers is inhibited to a certain extent, so that the selection of a proper emulsion stabilizing system is also crucial to the performance of the associative polymers.
Disclosure of Invention
In order to achieve the above objects, the present invention provides in a first aspect a multifunctional hydrophobically associating polyacrylamide suspoemulsion for fracturing having a long stabilization period and being advantageous for reducing the cost of on-site operations.
The technical scheme adopted by the invention is as follows: the hydrophobically associating polyacrylamide suspoemulsion comprises the following components by weight:
600 parts of organic hydrocarbon solvent 400-50 parts of clay, 10-30 parts of high molecular stabilizer, 10-20 parts of emulsifier and phase transfer agent and 500 parts of hydrophobic association polyacrylamide powder 300-50 parts by weight;
wherein, the organic hydrocarbon solvent is selected from one or more of gasoline, kerosene, diesel oil or white oil, and white oil is preferred.
The clay is preferably bentonite.
The high molecular stabilizer is one or a mixture of more of methacrylic acid and methacrylic acid multi-carbon alkyl ester copolymer, polyvinylpyrrolidone, copolymer of styrene and maleic anhydride, and copolymer of vinylpyrrolidone and vinyl acetate.
The emulsifier is one selected from Tween-20, Tween-80, op-10 and span-80.
The phase inversion agent is a nonionic surfactant and is selected from one or a mixture of sorbitan monolaurate, polyoxyethylene octylphenol ether, polyoxyethylene octyl phenyl ether and polyoxyethylene sorbitan fatty acid ester.
The hydrophobic association polyacrylamide is prepared by a conventional aqueous solution polymerization or micelle polymerization process. The unsaturated hydrophobic monomers from which the hydrophobically associative polymers are prepared may be anionic, cationic or nonionic and are selected from the group consisting of monovinylic compounds of 8 to 21 carbon atoms.
Preferably, the unsaturated hydrophobic monomer is selected from one or more of N-alkyl substituted acrylamide and its derivatives, long chain alkyl unsaturated quaternary ammonium salts, alkyl (meth) acrylates, acrylamide alkyl sulfonic acids and their sulfonates.
Preferably, the anionic monomer is one or more of sodium acrylamide dodecyl sulfonate, sodium acrylamide tetradecyl sulfonate, sodium acrylamide hexadecyl sulfonate and sodium acrylamide octadecyl sulfonate, the nonionic monomer is N-dodecyl acrylamide, N-tetradecyl acrylamide, N-hexadecyl acrylamide, N-octadecyl acrylamide, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate and octadecyl (meth) acrylate, and the cationic monomer is one or more of allyl dodecyl ammonium chloride, allyl tetradecyl ammonium chloride, allyl hexadecyl ammonium chloride and allyl octadecyl ammonium chloride.
A preparation method of a hydrophobically associating polyacrylamide suspension emulsion comprises the following steps:
placing an organic alkane solvent in a reaction kettle with mechanical stirring;
step two, sequentially adding clay, a high-molecular stabilizer and a small-molecular emulsifier into a reaction kettle;
step three, adding a phase transfer agent;
and step four, adding the hydrophobic association polyacrylamide powder, and continuously stirring.
The invention adopts the introduced macromolecular stabilizer as one component of a stabilizing system. The polymer stabilizer is a polymer compound having a relative molecular number of thousands or more and having surface activity. The macromolecular emulsifier has a series of unique properties because of unique structure and adjustable sizes, positions and the like of hydrophilic groups and hydrophobic groups. Firstly, it has good stability and is not easy to migrate and desorb; secondly, the two ends of the polymer stabilizer are provided with hydrocarbon long chains, and the polymer stabilizer and the oil phase can form a directional wedge-shaped interface at the interface layer to form a strong space blocking effect and have a synergistic effect with clay; finally, the longer the hydrocarbon chains at the two ends of the high molecular stabilizer, the larger the range of action with lipophilic molecules, so that the application performance of the suspension emulsion is affected. The stable period is improved to more than 1 month, and the hydrophobic association polyacrylamide suspension emulsion with the effective content of 30-50 percent can meet the use requirements of customers.
Detailed Description
Example 1: preparation of hydrophobically associating polyacrylamide suspension emulsion A
Preparation of the suspoemulsion:
the first step is as follows: accurately weighing 460 parts of No. 5 white oil, adding into a four-neck flask, and selecting a three-blade stirring paddle at the rotating speed of 500 rpm;
the second step is that: weighing 25 parts of organic bentonite, adding into white oil, and stirring for 5 min;
the third step: adding 5 parts of emulsifier, and continuously stirring for 3 min;
the fourth step: adding 15 parts of high molecular stabilizer vinyl pyrrolidone and vinyl acetate copolymer, and stirring at 600 rpm for 3 min;
the fifth step: adding 5 parts of phase transfer agent, and stirring at 600 rpm for 3 min;
and a sixth step: 490 parts of hydrophobically associating polyacrylamide powder is added, and the stirring speed is changed to 900 rpm for 5min after 1300 rpm stirring for 2 min.
Example 2: preparation of hydrophobically associating polyacrylamide suspension emulsion B
Preparation of the suspoemulsion:
the first step is as follows: accurately weighing 540 parts of No. 5 white oil, adding into a four-mouth flask, and selecting a three-blade stirring paddle at the rotating speed of 500 rpm;
the second step is that: 42 parts of organic bentonite is weighed and added into the white oil to be stirred for 5 min;
the third step: adding 5 parts of emulsifier, and continuously stirring for 3 min;
the fourth step: adding 20 parts of high molecular stabilizer vinyl pyrrolidone and vinyl acetate copolymer, and stirring at 600 rpm for 3 min;
the fifth step: adding 5 parts of phase transfer agent, and stirring at 600 rpm for 3 min;
and a sixth step: adding 388 parts of hydrophobically associating polyacrylamide powder, stirring at 1300 rpm for 2min, and then stirring at 900 rpm for 5 min.
The performance of the examples was evaluated as follows:
1. thickening performance of suspension emulsion
Conventional polyacrylamide powder (with the molecular weight of 2600 to 2700 ten thousand tested by a method in partially hydrolyzed polyacrylamide for oil displacement of Q-SY 119-. The performance of the oil field simulated brine (50000 mg/L sodium chloride +8325mg/L calcium chloride +58 mg/ferric chloride) and the clean water are respectively detected, and the results are respectively shown in tables 2 and 3.
And then selecting common polyacrylamide powder of the same batch to prepare a suspension emulsion according to the step 2 of the embodiment case and preparing the hydrophobic association powder into the suspension emulsion. The properties were measured in the same manner and the results are shown in tables 4 and 5, respectively.
As can be seen from the above table, with the increase of the dosage of the emulsion, the viscosity of the suspension emulsion (i) and (iii) prepared from the common polyacrylamide powder with higher molecular weight has no obvious fluctuation in saline water or clear water, increases linearly, and cannot embody the thickening effect. But when the dosage of the suspended emulsion prepared by the hydrophobic association powder in the saline water reaches 1.0 percent and 1.5 percent and the dosage of the suspended emulsion in the clear water reaches 1.4 percent and 1.7 percent, the viscosity rises suddenly, and the intermolecular association thickening effect is fully embodied after the certain association concentration is reached.
2. Associative polymer suspoemulsions made with different stabilizing systems for thickening
According to the prior formulation of the hydrophobic association suspension emulsion in the literature, the same batch of hydrophobic association powder (with the molecular weight of 2300 to 2400 ten thousand) is used, the effective content of the hydrophobic association powder is improved from 25 percent to 35 percent, and the suspension emulsion A is prepared. Then, suspoemulsion B was prepared according to the procedure of example 2. The associative polymer suspoemulsion thickening pairs prepared with the stabilizing system are shown in table 6 below.
As can be seen from Table 6 above, the formulation of the literature results in a decrease in the hydrophobic association effect when formulated in a high effective amount of suspoemulsion, and no viscosity increase occurs when the amount is up to 1.6%, which is not the case with the new formulation.
3. Stability of the suspension emulsion
The stability of the suspoemulsions prepared with the stabilizing system of the present invention is shown in tables 8 and 9 below.
After standing for 4 weeks, the mixture of example 1 and example 2 was layered 3.2mm and 2.1mm, and after stirring, the uniformity was restored without the bottom being hardened by sedimentation. The stable system of the invention can prepare the suspension emulsion with better stability no matter what polyacrylamide is used.
Claims (6)
1. The hydrophobically associating polyacrylamide suspension emulsion for fracturing is characterized in that: comprises the following components in parts by weight:
600 parts of organic hydrocarbon solvent 400-50 parts of clay, 10-30 parts of high molecular stabilizer, 10-20 parts of emulsifier and phase transfer agent and 500 parts of hydrophobic association polyacrylamide powder 300-50 parts by weight;
wherein, the organic hydrocarbon solvent is selected from one or more of gasoline, kerosene, diesel oil or white oil;
the high molecular stabilizer is one or a mixture of more of methacrylic acid and methacrylic acid multi-carbon alkyl ester copolymer, polyvinylpyrrolidone, copolymer of styrene and maleic anhydride, and copolymer of vinylpyrrolidone and vinyl acetate;
the emulsifier is one selected from Tween-20, Tween-80, op-10 and span-80;
the phase inversion agent is a nonionic surfactant and is selected from one or a mixture of sorbitan monolaurate, polyoxyethylene octylphenol ether, polyoxyethylene octyl phenyl ether and polyoxyethylene sorbitan fatty acid ester;
the hydrophobic association polyacrylamide is prepared by a conventional aqueous solution polymerization or micelle polymerization process, and the unsaturated hydrophobic monomer for preparing the hydrophobic association polymer can be anionic, cationic or nonionic and is selected from a monovinyl compound with 8-21 carbon atoms.
2. The hydrophobically associating polyacrylamide suspoemulsion for fracturing as claimed in claim 1, wherein: the organic hydrocarbon solvent is preferably white oil.
3. The hydrophobically associating polyacrylamide suspoemulsion for fracturing as claimed in claim 1, wherein: the clay is preferably bentonite.
4. The hydrophobically associating polyacrylamide suspoemulsion for fracturing as claimed in claim 1, wherein: the unsaturated hydrophobic monomer is selected from one or more of N-alkyl substituted acrylamide and derivatives thereof, long-chain alkyl unsaturated quaternary ammonium salt, alkyl (meth) acrylate, acrylamide alkyl sulfonic acid and sulfonate thereof.
5. The hydrophobically associating polyacrylamide suspoemulsion for fracturing as claimed in claim 1, wherein: the anionic monomer is one or more of acrylamide dodecyl sodium sulfonate, acrylamide tetradecyl sodium sulfonate, acrylamide hexadecyl sodium sulfonate and acrylamide octadecyl sodium sulfonate, the nonionic monomer is N-dodecyl acrylamide, N-tetradecyl acrylamide, N-hexadecyl acrylamide, N-octadecyl acrylamide, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate and octadecyl (meth) acrylate, and the cationic monomer is one or more of allyl dodecyl ammonium chloride, allyl tetradecyl ammonium chloride, allyl hexadecyl ammonium chloride and allyl octadecyl ammonium chloride.
6. A preparation method of hydrophobically associating polyacrylamide suspension emulsion for fracturing comprises the following steps:
1) placing an organic hydrocarbon solvent in a reaction kettle with mechanical stirring;
2) sequentially adding clay, a high-molecular stabilizer and a small-molecular emulsifier into a reaction kettle;
3) adding a phase transfer agent;
4) adding hydrophobic association polyacrylamide powder and continuously stirring.
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