CN111234796A - Surfactant and preparation method thereof - Google Patents
Surfactant and preparation method thereof Download PDFInfo
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- CN111234796A CN111234796A CN202010070278.1A CN202010070278A CN111234796A CN 111234796 A CN111234796 A CN 111234796A CN 202010070278 A CN202010070278 A CN 202010070278A CN 111234796 A CN111234796 A CN 111234796A
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- hydroxyethyl methacrylate
- potassium bromate
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 37
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 35
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004153 Potassium bromate Substances 0.000 claims abstract description 35
- 235000019396 potassium bromate Nutrition 0.000 claims abstract description 35
- 229940094037 potassium bromate Drugs 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 16
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 14
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 14
- 230000002209 hydrophobic effect Effects 0.000 claims description 14
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- -1 alkyl dimethyl allyl ammonium chloride Chemical compound 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical group CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical group [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 6
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 239000004576 sand Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 238000012827 research and development Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LZBIYPIDWSGLOV-UHFFFAOYSA-N dimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC=C LZBIYPIDWSGLOV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
- C09K8/62—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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of oil exploitation, and particularly provides a surfactant which comprises the following components in percentage by mass: 1-8% of hydroxyethyl methacrylate, 3-18% of erucamidopropyl trimethyl ammonium chloride, 1-2% of potassium bromate and the balance of water, so that the problems that in the prior art, the use concentration of a hydrophobic polymer is low in fracturing construction, a certain viscosity is shown after dissolution, a low-concentration proppant can be carried in a fracturing process, but the high-temperature proppant cannot be far met in the existing oilfield fracturing modification process, and the proppant concentration is 700Kg/m3The above requirements are high, so that the research and development of a material are needed to solve the problems of sand carrying and rheological property of the hydrophobic polymer under the low-concentration use condition, and the material has the advantages of simple preparation process, easy obtainment of materials, low cost, wide application and capability of pressing oil fieldsThe cracking production increase has important significance.
Description
Technical Field
The invention belongs to the technical field of oil exploitation, and particularly relates to a surfactant and a preparation method thereof.
Background
The fracturing fluid comprises water-based fracturing fluid, oil-based fracturing fluid, foam fracturing fluid, emulsified fracturing fluid and the like. Compared with the derivatives of vegetable gum and cellulose, the synthetic polymer fracturing fluid has the characteristics of better viscosity-temperature characteristic and high-temperature stability, strong thickening capability, insensitivity to bacteria, good jelly stability, strong sand suspending capability and the like. Meanwhile, hydrophobic groups are introduced into the polymer, and a three-dimensional network structure is formed among macromolecules through hydrophobic association. In a dilute solution, macromolecules mainly exist in an intramolecular association mode, molecular chains curl, the hydrodynamic volume is reduced, but after the polymer concentration is higher than the critical association concentration, the macromolecular chains form a supermolecule dynamic network structure mainly based on intermolecular association through hydrophobic association, the hydrodynamic volume is increased, the solution viscosity is obviously improved, and the hydrophobic polymer fracturing liquid system based on the characteristics is simple to prepare and has good performance, so that the hydrophobic polymer fracturing liquid system is widely applied.
At present, because the international oil price is continuously low and the low permeability oil field has higher requirements on the damage rate, the hydrophobic polymer has lower use concentration in the fracturing construction, and although the hydrophobic polymer shows certain viscosity after being dissolved, the hydrophobic polymer can carry low-concentration proppant in the fracturing process, but the hydrophobic polymer cannot far meet the requirements of 700Kg/m proppant concentration at high temperature in the current oil field fracturing modification process3The above requirements are high, and therefore, it is considered to develop a material to improve the sand-carrying and rheological properties of the hydrophobic polymer under the condition of low concentration use.
Disclosure of Invention
The invention provides a watchThe surfactant and the preparation method thereof aim to overcome the defects that in the prior art, due to the fact that the international oil price is continuously low and the damage rate of a low-permeability oil field is higher, the use concentration of a hydrophobic polymer in fracturing construction is lower, the hydrophobic polymer shows certain viscosity after being dissolved, the surfactant can carry a low-concentration proppant in the fracturing process, but the surfactant cannot far meet the requirements of 700Kg/m proppant concentration at high temperature and at high proppant concentration in the current oil field fracturing modification process3The above requirements are high, and therefore, it is considered to develop a material to improve the problems of sand carrying and rheological properties of the hydrophobic polymer under the condition of low concentration use.
Therefore, the invention provides a surfactant which comprises the following components in percentage by mass: 1-8% of hydroxyethyl methacrylate, 3-18% of erucamide propyl trimethyl ammonium chloride, 1-2% of potassium bromate and the balance of water.
The preparation method of the hydroxyethyl methacrylate comprises the following steps: firstly, adding a catalyst into 2-methacrylic acid, stirring and heating to 85 ℃, introducing ethylene oxide gas into the heated solution under the protection of nitrogen for reaction, then adding a polymerization inhibitor into the solution, and keeping the temperature of 80 ℃ for full reaction until the reaction is completed; then, cooling the product after complete reaction to 60 ℃, adding hydroquinone, stirring and dissolving, filtering insoluble substances in the dissolved solution, then carrying out reduced pressure distillation on the dissolved solution, collecting fractions at 86-89 ℃ under the condition of 0.60-0.68KPa, and finally purifying the collected fractions to obtain a finished product of hydroxyethyl methacrylate; the mass ratio of the 2-methacrylic acid to the catalyst to the polymerization inhibitor to the hydroquinone is 30-60: 0.05-0.15: 0.1-0.3: 3-6.
Washing the finished product of hydroxyethyl methacrylate with an aqueous solution of sodium hydroxide, standing, layering, washing the upper solution with an aqueous solution of saturated sodium chloride, extracting the washed solution with n-hexane, and distilling the extracted solution under reduced pressure for 2-3 times to-0.2 KPa; and finally, drying the distilled solution by adopting anhydrous sodium sulfate.
The catalyst is chromium chloride.
The polymerization inhibitor is tert-butyl hydroquinone.
The introduction rate of the ethylene oxide gas is 60-80 g/h.
The use concentration of the surfactant in the fracturing fluid is 0.01-5 wt%.
Use of a surfactant to improve the rheological properties of a hydrophobic polymer.
The hydrophobic polymer is prepared from the following components in percentage by mass: the mass ratio of the hydroxymethyl acrylamide to the hydrophobic propenyl monomer is (3-10) to 1; the hydrophobic allyl monomer is one or more of long-carbon-chain alkyl dimethyl allyl ammonium chloride, stearyl methacrylate, methoxy polyethylene glycol methacrylate, stearyl acrylate and mono-long-chain alkyl maleate sodium salt.
A preparation method of a surfactant comprises the following steps: firstly, under the condition of continuously stirring at 500 revolutions per minute, sequentially adding part of 1-2 mass percent potassium bromate solution, 1-8 mass percent hydroxyethyl methacrylate and the rest 1-2 mass percent potassium bromate solution into 3-18 mass percent erucamide propyl trimethyl ammonium chloride, and uniformly stirring the above solutions to obtain a surfactant solution; the mass ratio of the part of potassium bromate solution with the mass percentage of 1-2% to the rest of potassium bromate solution with the mass percentage of 1-2% is 1: 1.
The invention has the beneficial effects that: the surfactant and the preparation method thereof provided by the invention comprise the following components in percentage by mass: 1-8% of hydroxyethyl methacrylate, 3-18% of erucamide propyl trimethyl ammonium chloride, 1-2% of potassium bromate and the balance of water; compared with the prior art, the surfactant can generate a complex network structure with the hydrophobic polymer fracturing fluid under low concentration, increase the hydrodynamic volume and obviously improve the rheological property of the hydrophobic polymer, thereby solving the problems of low viscosity, poor temperature resistance and the like of the hydrophobic polymer fracturing fluid in the construction process; the surfactant can generate non-chemical crosslinking with hydrophobic polymers, form a three-dimensional space network structure through the bridging action of the surface of the surfactant, and can improve the fracturing application without chemical crosslinkingThe concentration of the carried sand can reach 750Kg/m3. After the surfactant forms a complex network structure, a certain residual network structure still exists after the structure is damaged in the later stage of fracturing, the surfactant still has a certain sand carrying capacity, and the surfactant and acrylate are compounded according to a certain proportion to achieve new balance again in a short time, so that the recycling is realized; the invention has the advantages of simple preparation process, easily obtained materials, lower cost and wide application, and has important significance for increasing the yield of the oil field fracturing.
Drawings
The present invention will be described in further detail below with reference to the accompanying drawings.
FIG. 1 is a diagram of the mechanism of action of a hydrophobic polymer and a surfactant;
FIG. 2 is a schematic diagram of the network structure formed by the surfactant and the new network structure formed by the action of the surfactant with the acrylate;
FIG. 3 shows the product of example 5 at 110 ℃ for 170s-1Rheology curve after 1h of shear at shear rate.
FIG. 4 shows the product of example 5 after 10 recycles at 110 ℃ for 170s-1Rheology curve after 1h of shear at shear rate.
FIG. 5 shows the product of example 4 at 110 ℃ for 170s-1Rheology curve after 1h of shear at shear rate.
Detailed Description
Example 1:
the surfactant comprises the following components in percentage by mass: 1-8% of hydroxyethyl methacrylate, 3-18% of erucamide propyl trimethyl ammonium chloride, 1-2% of potassium bromate and the balance of water.
Example 2:
as shown in fig. 1 and 2, the surfactant comprises the following components in percentage by mass: 1-8% of hydroxyethyl methacrylate, 3-18% of erucamide propyl trimethyl ammonium chloride, 1-2% of potassium bromate and the balance of water.
The preparation method of the hydroxyethyl methacrylate comprises the following steps: firstly, adding a catalyst into 2-methacrylic acid, stirring and heating to 85 ℃, introducing ethylene oxide gas into the heated solution under the protection of nitrogen for reaction, then adding a polymerization inhibitor into the solution, and keeping the temperature of 80 ℃ for full reaction until the reaction is completed; then, cooling the product after complete reaction to 60 ℃, adding hydroquinone, stirring and dissolving, filtering insoluble substances in the dissolved solution, then carrying out reduced pressure distillation on the dissolved solution, collecting fractions at 86-89 ℃ under the condition of 0.60-0.68KPa, and finally purifying the collected fractions to obtain a finished product of hydroxyethyl methacrylate; the mass ratio of the 2-methacrylic acid to the catalyst to the polymerization inhibitor to the hydroquinone is 30-60: 0.05-0.15: 0.1-0.3: 3-6.
Washing the finished product of hydroxyethyl methacrylate with an aqueous solution of sodium hydroxide, standing, layering, washing the upper solution with an aqueous solution of saturated sodium chloride, extracting the washed solution with n-hexane, and distilling the extracted solution under reduced pressure for 2-3 times to-0.2 KPa; and finally, drying the distilled solution by adopting anhydrous sodium sulfate. The purity of the obtained sample is more than 98%.
The catalyst is chromium chloride.
The polymerization inhibitor is tert-butyl hydroquinone.
The introduction rate of the ethylene oxide gas is 60-80 g/h.
The use concentration of the surfactant in the fracturing fluid is 0.01-5 wt%.
Use of a surfactant to improve the rheological properties of a hydrophobic polymer.
The hydrophobic polymer is prepared from the following components in percentage by mass: the mass ratio of the hydroxymethyl acrylamide to the hydrophobic propenyl monomer is (3-10) to 1; the hydrophobic allyl monomer is one or more of long-carbon-chain alkyl dimethyl allyl ammonium chloride, stearyl methacrylate, methoxy polyethylene glycol methacrylate, stearyl acrylate and mono-long-chain alkyl maleate sodium salt.
A preparation method of a surfactant comprises the following steps: firstly, under the condition of continuously stirring at 500 revolutions per minute, sequentially adding part of 1-2 mass percent potassium bromate solution, 1-8 mass percent hydroxyethyl methacrylate and the rest 1-2 mass percent potassium bromate solution into 3-18 mass percent erucamide propyl trimethyl ammonium chloride, and uniformly stirring the above solutions to obtain a surfactant solution; the mass ratio of the part of potassium bromate solution with the mass percentage of 1-2% to the rest of potassium bromate solution with the mass percentage of 1-2% is 1: 1.
Compared with the prior art, the surfactant can generate a complex network structure with the hydrophobic polymer fracturing fluid under low concentration, increase the hydrodynamic volume and obviously improve the rheological property of the hydrophobic polymer, thereby solving the problems of low viscosity, poor temperature resistance and the like of the hydrophobic polymer fracturing fluid in the construction process; the surfactant can generate non-chemical crosslinking with hydrophobic polymers, form a three-dimensional space network structure through the bridging action of the surface of the surfactant, and can improve the sand carrying concentration of fracturing construction without chemical crosslinking, and the sand carrying concentration can reach 750Kg/m3. After the surfactant forms a complex network structure, a certain residual network structure still exists after the structure is damaged in the later stage of fracturing, the surfactant still has a certain sand carrying capacity, and the surfactant and acrylate are compounded according to a certain proportion to achieve new balance again in a short time, so that the recycling is realized; the invention has the advantages of simple preparation process, easily obtained materials, lower cost and wide application, and has important significance for increasing the yield of the oil field fracturing.
Example 3:
the surfactant comprises the following components in percentage by mass: 5% of hydroxyethyl methacrylate, 9% of erucamide propyl trimethyl ammonium chloride, 2% of potassium bromate and the balance of water.
The preparation method of the hydroxyethyl methacrylate comprises the following steps: firstly, adding 0.1g of chromium chloride into 50g of 2-methacrylic acid, stirring and heating to 85 ℃, introducing ethylene oxide gas into the heated solution at a rate of 70g/h under the protection of nitrogen for reaction, then adding 0.2g of polymerization inhibitor tert-butylhydroquinone into the solution, and keeping the temperature of 80 ℃ for sufficient reaction until the reaction is completed; then, cooling the product after complete reaction to 60 ℃, adding 5g of hydroquinone, stirring and dissolving, filtering insoluble substances in the dissolved solution, carrying out reduced pressure distillation on the dissolved solution, collecting fractions at 86-89 ℃ under the condition of 0.64KPa, and finally purifying the collected fractions to obtain a finished product of hydroxyethyl methacrylate; then washing the finished product of hydroxyethyl methacrylate with an aqueous solution of sodium hydroxide and then standing, washing the upper solution with an aqueous solution of saturated sodium chloride after standing and layering, extracting the washed solution with n-hexane, and distilling the extracted solution under reduced pressure for 2 times to-0.2 KPa; and finally, drying the distilled solution by adopting anhydrous sodium sulfate. The purity of the obtained sample is more than 98%.
The use concentration of the surfactant in the fracturing fluid is 0.01-5 wt%.
Use of a surfactant to improve the rheological properties of a hydrophobic polymer.
The hydrophobic polymer is prepared from the following components in percentage by mass: the mass ratio of the hydroxymethyl acrylamide to the hydrophobic allyl monomer is 6: 1; the hydrophobic allyl monomer is one or two of long carbon chain alkyl dimethyl allyl ammonium chloride and stearyl methacrylate.
A preparation method of a surfactant comprises the following steps: firstly, under the condition of continuously stirring at 500 revolutions per minute, adding a part of potassium bromate solution with the mass percentage of 2%, 5% of hydroxyethyl methacrylate and the rest of potassium bromate solution with the mass percentage of 2% in sequence into erucamide propyl trimethyl ammonium chloride with the mass percentage of 9%, and uniformly stirring the above solutions to obtain a surfactant solution; the mass ratio of the part of potassium bromate solution with the mass percentage of 2% to the rest of potassium bromate solution with the mass percentage of 2% is 1: 1.
Example 4:
the surfactant comprises the following components in percentage by mass: 1% of hydroxyethyl methacrylate, 3% of erucamide propyl trimethyl ammonium chloride, 1% of potassium bromate and the balance of water.
The preparation method of the hydroxyethyl methacrylate comprises the following steps: firstly, adding 0.05g of chromium chloride into 30g of 2-methacrylic acid, stirring and heating to 85 ℃, introducing ethylene oxide gas into the heated solution at a rate of 60g/h under the protection of nitrogen for reaction, then adding 0.1g of polymerization inhibitor tert-butylhydroquinone into the solution, and keeping the temperature of 80 ℃ for sufficient reaction until the reaction is completed; then, cooling the product after complete reaction to 60 ℃, adding 3g of hydroquinone, stirring and dissolving, filtering insoluble substances in the dissolved solution, carrying out reduced pressure distillation on the dissolved solution, collecting fractions at 86-89 ℃ under the condition of 0.60KPa, and finally purifying the collected fractions to obtain a finished product of hydroxyethyl methacrylate; then washing the finished product of hydroxyethyl methacrylate with an aqueous solution of sodium hydroxide and then standing, washing the upper solution with an aqueous solution of saturated sodium chloride after standing and layering, extracting the washed solution with n-hexane, and distilling the extracted solution under reduced pressure for 3 times to-0.2 KPa; and finally, drying the distilled solution by adopting anhydrous sodium sulfate. The purity of the obtained sample is more than 98%.
The use concentration of the surfactant in the fracturing fluid is 0.01-5 wt%.
Use of a surfactant to improve the rheological properties of a hydrophobic polymer.
The hydrophobic polymer is prepared from the following components in percentage by mass: the mass ratio of the hydroxymethyl acrylamide to the hydrophobic allyl monomer is 3: 1; the hydrophobic propenyl monomer is one or two of methoxy polyethylene glycol methacrylate and octadecyl acrylate.
A preparation method of a surfactant comprises the following steps: firstly, under the condition of continuously stirring at 500 revolutions per minute, adding a part of potassium bromate solution with the mass percentage of 1%, hydroxyethyl methacrylate with the mass percentage of 1% and the rest of potassium bromate solution with the mass percentage of 1% in sequence into erucamide propyl trimethyl ammonium chloride with the mass percentage of 3%, and uniformly stirring the above solutions to obtain a surfactant solution; the mass ratio of the part of potassium bromate solution with the mass percentage of 1% to the rest of potassium bromate solution with the mass percentage of 1% is 1: 1.
Example 5:
the surfactant comprises the following components in percentage by mass: 8% of hydroxyethyl methacrylate, 18% of erucamide propyl trimethyl ammonium chloride, 1.5% of potassium bromate and the balance of water.
The preparation method of the hydroxyethyl methacrylate comprises the following steps: firstly, adding 0.15g of chromium chloride into 60g of 2-methacrylic acid, stirring and heating to 85 ℃, introducing ethylene oxide gas into the heated solution at a rate of 80g/h under the protection of nitrogen for reaction, then adding 0.3g of polymerization inhibitor tert-butylhydroquinone into the solution, and keeping the temperature of 80 ℃ for sufficient reaction until the reaction is completed; then, cooling the product after complete reaction to 60 ℃, adding 6g of hydroquinone, stirring and dissolving, filtering insoluble substances in the dissolved solution, carrying out reduced pressure distillation on the dissolved solution, collecting fractions at 86-89 ℃ under the condition of 0.68KPa, and finally purifying the collected fractions to obtain a finished product of hydroxyethyl methacrylate; then washing the finished product of hydroxyethyl methacrylate with an aqueous solution of sodium hydroxide and then standing, washing the upper solution with an aqueous solution of saturated sodium chloride after standing and layering, extracting the washed solution with n-hexane, and distilling the extracted solution under reduced pressure for 3 times to-0.2 KPa; and finally, drying the distilled solution by adopting anhydrous sodium sulfate. The purity of the obtained sample is more than 98%.
The use concentration of the surfactant in the fracturing fluid is 0.01-5 wt%.
Use of a surfactant to improve the rheological properties of a hydrophobic polymer.
The hydrophobic polymer is prepared from the following components in percentage by mass: the mass ratio of the hydroxymethyl acrylamide to the hydrophobic allyl monomer is 3: 1; the hydrophobic allyl monomer is maleic acid single long-chain alkyl ester sodium salt.
A preparation method of a surfactant comprises the following steps: firstly, under the condition of continuously stirring at 500 revolutions per minute, sequentially adding part of potassium bromate solution with the mass percent of 1.5%, hydroxyethyl methacrylate with the mass percent of 8% and the rest of potassium bromate solution with the mass percent of 1.5% into erucamide propyl trimethyl ammonium chloride with the mass percent of 18%, and uniformly stirring the above solutions to obtain a surfactant solution; the mass ratio of the part of potassium bromate solution with the mass percentage of 1.5% to the rest of potassium bromate solution with the mass percentage of 1.5% is 1: 1.
The experimental test results are as follows:
as shown in FIG. 3, the experiment was conducted using an MCR301 rheometer to test 0.2% surfactant (8% hydroxyethyl methacrylate, 18% erucamidopropyltrimethylammonium chloride, 1.5% potassium bromate) with 0.3% hydrophobic polymer at 110 ℃ for 170s-1The rheological curve after shearing for 1h at the shearing rate can be seen from figure 3, the surfactant has obvious effect on improving the rheological property of the hydrophobic polymer, and meanwhile, the surfactant can still keep better effect after being repeatedly recycled for 10 times, as shown in figure 4.
As shown in FIG. 5, the experiment was conducted using an RS6000 rheometer to test 0.15% surfactant (hydroxyethyl methacrylate 1%, erucamidopropyl trimethyl ammonium chloride 3%, potassium bromate 1%) and 0.15% hydrophobic polymer at 110 ℃ for 170s-1The rheological curve after shearing for 1h at the shear rate can be seen from figure 5, and the surfactant also shows good effect of improving the rheological property of the hydrophobic polymer under the condition of low concentration.
In a word, the concentration of the related auxiliary agent can be adjusted according to actual needs, so that the method is suitable for the needs of reservoir transformation at different temperatures, and the effect is obvious.
The above examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims and any design similar or equivalent to the scope of the invention.
Claims (10)
1. A surfactant characterized by: the composition comprises the following components in percentage by mass: 1-8% of hydroxyethyl methacrylate, 3-18% of erucamide propyl trimethyl ammonium chloride, 1-2% of potassium bromate and the balance of water.
2. The surfactant of claim 1, wherein: the preparation method of the hydroxyethyl methacrylate comprises the following steps: firstly, adding a catalyst into 2-methacrylic acid, stirring and heating to 85 ℃, introducing ethylene oxide gas into the heated solution under the protection of nitrogen for reaction, then adding a polymerization inhibitor into the solution, and keeping the temperature of 80 ℃ for full reaction until the reaction is completed; then, cooling the product after complete reaction to 60 ℃, adding hydroquinone, stirring and dissolving, filtering insoluble substances in the dissolved solution, then carrying out reduced pressure distillation on the dissolved solution, collecting fractions at 86-89 ℃ under the condition of 0.60-0.68KPa, and finally purifying the collected fractions to obtain a finished product of hydroxyethyl methacrylate; the mass ratio of the 2-methacrylic acid to the catalyst to the polymerization inhibitor to the hydroquinone is 30-60: 0.05-0.15: 0.1-0.3: 3-6.
3. The surfactant of claim 2, wherein: washing the finished product of hydroxyethyl methacrylate with an aqueous solution of sodium hydroxide, standing, layering, washing the upper solution with an aqueous solution of saturated sodium chloride, extracting the washed solution with n-hexane, and distilling the extracted solution under reduced pressure for 2-3 times to-0.2 KPa; and finally, drying the distilled solution by adopting anhydrous sodium sulfate.
4. The surfactant of claim 3, wherein: the catalyst is chromium chloride.
5. The surfactant of claim 4, wherein: the polymerization inhibitor is tert-butyl hydroquinone.
6. The surfactant of claim 5, wherein: the introduction rate of the ethylene oxide gas is 60-80 g/h.
7. The surfactant of claim 6, wherein: the use concentration of the surfactant in the fracturing fluid is 0.01-5 wt%.
8. Use of a surfactant according to claim 7 for improving the rheological properties of a hydrophobic polymer.
9. The use of claim 8, wherein: the hydrophobic polymer is prepared from the following components in percentage by mass: the mass ratio of the hydroxymethyl acrylamide to the hydrophobic propenyl monomer is (3-10) to 1; the hydrophobic allyl monomer is one or more of long-carbon-chain alkyl dimethyl allyl ammonium chloride, stearyl methacrylate, methoxy polyethylene glycol methacrylate, stearyl acrylate and mono-long-chain alkyl maleate sodium salt.
10. A preparation method of a surfactant is characterized by comprising the following steps: the method comprises the following steps: firstly, under the condition of continuously stirring at 500 revolutions per minute, sequentially adding part of 1-2 mass percent potassium bromate solution, 1-8 mass percent hydroxyethyl methacrylate and the rest 1-2 mass percent potassium bromate solution into 3-18 mass percent erucamide propyl trimethyl ammonium chloride, and uniformly stirring the above solutions to obtain a surfactant solution; the mass ratio of the part of potassium bromate solution with the mass percentage of 1-2% to the rest of potassium bromate solution with the mass percentage of 1-2% is 1: 1.
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| CN110295036A (en) * | 2019-06-14 | 2019-10-01 | 中国石油天然气股份有限公司 | Slickwater fracturing fluid for medium-high temperature compact reservoir and preparation method thereof |
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