CN115572585A - High-temperature-resistant oil-based drilling fluid emulsifier and preparation method thereof - Google Patents
High-temperature-resistant oil-based drilling fluid emulsifier and preparation method thereof Download PDFInfo
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- CN115572585A CN115572585A CN202211231381.5A CN202211231381A CN115572585A CN 115572585 A CN115572585 A CN 115572585A CN 202211231381 A CN202211231381 A CN 202211231381A CN 115572585 A CN115572585 A CN 115572585A
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- drilling fluid
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- emulsifier
- based drilling
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 90
- 238000005553 drilling Methods 0.000 title claims abstract description 86
- 239000012530 fluid Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000013067 intermediate product Substances 0.000 claims description 88
- 238000002156 mixing Methods 0.000 claims description 87
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 68
- 229940117986 sulfobetaine Drugs 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 39
- 239000002002 slurry Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- -1 tetradecyl sulfobetaine Chemical compound 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 24
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 23
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 239000010428 baryte Substances 0.000 claims description 19
- 229910052601 baryte Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 14
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 14
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 13
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 claims description 12
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229940075142 2,5-diaminotoluene Drugs 0.000 claims description 6
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 claims description 6
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 6
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001603 reducing effect Effects 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004945 emulsification Methods 0.000 abstract description 7
- 239000002283 diesel fuel Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 230000001804 emulsifying effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/032—Inorganic additives
Abstract
The invention discloses a high-temperature-resistant oil-based drilling fluid emulsifier and a preparation method thereof. Compared with the prior art, the high-temperature-resistant oil-based drilling fluid emulsifier disclosed by the invention has the advantages that a water-in-oil drilling fluid system taking diesel oil as a continuous phase has good emulsification effect and good high-temperature resistance, the drilling fluid can keep higher demulsification voltage after being treated at high temperature of 160 ℃, and the high-temperature-resistant performance is good.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant oil-based drilling fluid emulsifiers, and particularly relates to a high-temperature-resistant oil-based drilling fluid emulsifier and a preparation method thereof.
Background
The drilling fluid is widely applied to drilling construction, and the oil-based drilling fluid is used in the construction process, has good lubricating property, friction resistance reducing property and the like, and is beneficial to reservoir protection. The emulsifier is the most critical treating agent in the oil-based drilling fluid, and the emulsifying property of the emulsifier is an important index for measuring the temperature resistance and the emulsifying stability of a system. The emulsifier has the action mechanism that an adsorption film with certain strength is formed when the emulsifier is adsorbed on an oil-water interface, so that the interfacial tension of oil and water is reduced, and the external phase viscosity is increased, thereby keeping the emulsion stable.
In the prior art, a problem to be improved in drilling fluid is how to improve the stability of emulsion, especially the stability in high temperature service environment. During drilling, due to the high heat and pressure generated by the drilling friction, the emulsion is always exposed to the undesirable tendency of the emulsification to weaken or even fail completely. Especially when drilling deep hot wells, the high temperatures make the emulsion very susceptible to loss of stability. The emulsifier is an extremely key raw material in a drilling fluid composition system, and the quality and the stability of the emulsifier are extremely key factors for ensuring the balance condition and long-term service reliability of each dispersed phase in the drilling fluid emulsion composition system.
CN107955587A discloses an emulsifier for oil-based drilling fluid, which comprises the following components: organic acid, organic base, sulfonate, stearate, polyamine, chloroacetic acid amide, epichlorohydrin, long-chain alkyl fatty alcohol amide nonionic surfactant, xylene and white oil. The invention has strong emulsifying capacity, can adjust the HLB value of the emulsifier, obtains better lipophilic and hydrophilic capacity and has stronger high-temperature resistance. However, the emulsifier for the oil-based drilling fluid has the advantages of unobvious application effect, poor emulsification effect and easy breakage and failure under high-temperature conditions.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-temperature-resistant oil-based drilling fluid emulsifier and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the drilling fluid emulsifier comprises the following steps:
mixing water, a base agent, modified barite and zinc stearate, and then homogenizing at a high speed to obtain the drilling fluid emulsifier.
Preferably, the preparation method of the drilling fluid emulsifier comprises the following steps:
mixing 70-95 parts by weight of water, 40-55 parts by weight of base agent, 5-13 parts by weight of modified barite and 1-3 parts by weight of zinc stearate at 20-30 ℃, and homogenizing at 2000-3000rpm for 12-17min to obtain the drilling fluid emulsifier.
Among them, zinc stearate has excellent thermal stability.
The preparation method of the base agent comprises the following steps:
e1, mixing and stirring m-pentadecylphenol, methyl epichlorohydrin and a potassium hydroxide aqueous solution to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water, reacting, heating, stirring, distilling under reduced pressure, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine, heating, stirring, reacting, distilling under the conditions of heating, reducing pressure and stirring, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone, heating, stirring and reacting, distilling under the conditions of heating, reducing pressure and stirring, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether, stirring for reaction, and then carrying out suction filtration to obtain filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by using absolute ethyl alcohol, and then drying to obtain an intermediate product F;
e7, mixing the intermediate product F, the sulfobetaine and the potassium bromide, and then homogenizing to obtain the base agent.
In the technical scheme of the invention, m-pentadecylphenol reacts with methyl epichlorohydrin to generate glycidyl ether, then the glycidyl ether reacts with isopropylamine to generate tertiary amine, and then the tertiary amine reacts with 1, 3-propane sultone to obtain the base material. In the base material, the sulfonic functional group is used as an equivalent negative charge center, so that a balanced stable state can be achieved between a tertiary amine group with strong basicity and a sulfonic acid group with strong acidity, and the base material has good interface activation capability in a large pH variation range. In a drilling fluid system, the base material exists in a zwitterion form, has higher surface activation capacity, and the tetradecyl sulfobetaine and the hexadecyl sulfobetaine are added in the preparation of the base material, so that the tension of the emulsifier at an oil-water interface is further reduced, the emulsifier can be fully adsorbed at the drilling fluid interface, the arrangement condition of molecules at the oil-water interface is more compact, and the interface membrane has higher surface activation capacityThe strength is thereby increased, thereby enhancing the emulsifying ability of the emulsifier. Sulfonic group (-SO) is introduced into the base agent of the emulsifier obtained by the invention 3 H) The thickness of the hydration film on the surface of the clay particles in the service environment is increased, and the characteristic can effectively keep the adsorption position of the drilling fluid under the high-temperature condition, so that the thermal stability of the drilling fluid is improved. In addition, the introduction of the sulfonic acid group can increase the negative charge density on the surface of the clay particles so as to improve zeta potential, further increase electrostatic repulsion among the clay particles, and enhance the electrostatic stability of the drilling fluid at high temperature.
The proper amount of potassium bromide is added in the preparation process of the base agent, so that the drilling fluid can be preferentially adsorbed in the stratum, the adsorption loss of the emulsifier is reduced, and the use efficiency of the emulsifier is improved. The emulsifier system obtained by the invention has a special inner salt structure, so that the emulsifier system does not show a tendency of accepting or releasing protons in the whole pH range. Therefore, the emulsifier obtained by the invention can generate a complex with high-valence metal ions and keep the activity of the complex, so that the complex has stronger calcium ion and magnesium ion resistance, and can effectively prevent the emulsifier from losing efficacy such as mineralization and the like in a high-temperature service environment. According to the invention, the modified barite is prepared by a specific method, the surface of the modified barite is treated by trichloroacetic acid and formic acid to generate an alumina hydrate coating layer with a compact structure, the isoelectric point of the modified barite coated by the compact alumina hydrate coating layer has a tendency of shifting to a high pH value, the solubility, compatibility and dispersibility of the emulsifier and an organic solvent are improved, the agglomeration phenomenon is prevented, and the emulsification effect is improved.
Preferably, the preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a potassium hydroxide aqueous solution with the concentration of 12-17wt.% according to the mass ratio of (7-8) to (4-5.3) to (2.4-3.1), and stirring at the rotating speed of 40-75rpm at the temperature of 60-65 ℃ for 20-35min to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of (3-5) to (0.7-1.2) to (8-10), reacting at 75-80 ℃ for 2-3h, distilling at 85-90 ℃ under the conditions of a pressure of 45-60kPa and a stirring speed of 80-95rpm, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to the mass ratio of (1-3) to (9-10) to (3-4), stirring at the rotating speed of 40-50rpm for 2-3h at 65-70 ℃, then distilling at the temperature of 85-90 ℃, the pressure of 50-60kPa and the stirring speed of 60-80rpm, and collecting distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to the mass ratio of (0.9-1.3) to (15-19) to (0.1-0.3), stirring at 70-80rpm for 20-25min at 60-65 ℃, then distilling at the temperature of 85-90 ℃, the air pressure of 55-60kPa and the stirring speed of 70-80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether according to the mass ratio of (8-9) to (1-2), stirring at the rotating speed of 40-50rpm for 40-50min, carrying out suction filtration under the process conditions of 20-25L/min of exhaust gas volume, 550-600mmHG of vacuum degree and 120-125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 60-80rpm for 20-30min, filtering, and drying filter residues at the temperature of 60-65 ℃ for 130-160min to obtain an intermediate product F;
e7, adding the intermediate product F, the sulfobetaine and the potassium bromide according to the mass ratio of (4-5): (1.5-2.5): (0.25-4), mixing, and homogenizing at the rotating speed of 2500-3000rpm for 10-15min to obtain the base agent.
The sulfobetaine is at least one of tetradecyl sulfobetaine and hexadecyl sulfobetaine.
Preferably, the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to the mass ratio of (1-3) to (1-3).
More preferably, the sulfobetaine is a mixture of tetradecyl sulfobetaine, hexadecyl sulfobetaine 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing and sieving barite to obtain barite powder;
b2, mixing the barite powder and absolute ethyl alcohol, and then homogenizing to obtain slurry;
b3, putting the slurry into a planetary ball mill, and ball-milling by using small alumina balls as a ball-milling medium to obtain ball-milled slurry;
b4, filtering the slurry subjected to ball milling and drying to obtain superfine powder;
and B5, mixing the superfine powder, reaction acid and water, heating, stirring, reacting, filtering, washing filter residues with water, and drying to obtain the modified barite.
Preferably, the preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 300-400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and then homogenizing at the rotating speed of 1500-2000rpm for 12-16min to obtain slurry with the concentration of 50-55 wt%;
b3, putting the slurry into a planetary ball mill, and ball-milling for 3-4h by using alumina balls with the diameter of 5-6mm as a ball-milling medium according to the process parameters of a ball-to-material ratio of (18-20): 1 and a rotation speed of 700-800rpm to obtain ball-milled slurry;
b4, filtering the slurry subjected to ball milling, and drying at 85-90 ℃ for 5-6h to obtain superfine powder;
b5, mixing the superfine powder, the reaction acid and water according to a mass ratio of 1 (3-4) to 2-4, stirring and reacting at 85-90 ℃ at a rotating speed of 40-50rpm for 5-6h, filtering, washing the filter residue with water at 45-50 ℃ for 30-40min, wherein the mass ratio of the filter residue to the water is 1 (23-28), and drying at 85-90 ℃ for 4-6h to obtain the modified barite.
The reaction acid is at least one of trichloroacetic acid and formic acid.
According to the invention, trichloroacetic acid and formic acid are compounded to modify the surface of the barite, so that the stability of the obtained emulsifier is further improved, and the stability is presumed to be related to the difference of acidity of the two reaction acids, and the acidity difference enables the structure of the alumina coating layer to be more compact, so that the equivalent sites of the modified barite are further shifted to high pH.
Preferably, the reaction acid is a mixture of trichloroacetic acid and formic acid in a mass ratio of (1-3) to (1-3).
More preferably, the reaction acid is a mixture of trichloroacetic acid and formic acid in a mass ratio of 1.
With the exploration of deeper formations, it is necessary to prepare higher temperature, higher density additives to improve the high temperature resistance of the emulsifier.
Further, the invention discloses a high-temperature-resistant oil-based drilling fluid emulsifier and a preparation method thereof.
A preparation method of a high-temperature-resistant oil-based drilling fluid emulsifier comprises the following steps: mixing 70-95 parts of water, 40-55 parts of base agent, 5-13 parts of modified barite, 1-3 parts of zinc stearate and 8-12 parts of high temperature resistant additive at 20-30 ℃, and homogenizing at 2000-3000rpm for 12-17min to obtain the high temperature resistant oil-based drilling fluid emulsifier.
The preparation method of the high-temperature resistant additive comprises the following steps:
adding 5-9 parts by weight of N, N-dimethylacrylamide, 2-3 parts by weight of maleic anhydride, 6-8 parts by weight of 1-nonadecene and 7-8 parts by weight of 3- (methacryloyloxy) propyltrimethoxysilane into 50-60 parts by weight of toluene, uniformly mixing, then adding 0.1-0.5 part by weight of benzoyl peroxide, heating to 80-95 ℃ for reacting for 4-6h, then adding 0.5-1 part by weight of 2, 5-diaminotoluene, keeping the temperature of 80-95 ℃ for reacting for 5-10min, after the reaction is finished, carrying out rotary evaporation to remove toluene, washing and drying to obtain the high-temperature resistant additive.
The method takes N, N-dimethylacrylamide, maleic anhydride, 1-nonadecene and 3- (methacryloyloxy) propyl trimethoxy silane as raw materials, takes benzoyl peroxide as an initiator and 2, 5-diaminotoluene as a cross-linking agent to prepare a high-temperature resistant additive through high-temperature polymerization, and molecular chain association is generated among molecules of the N, N-dimethylacrylamide, the maleic anhydride, the 1-nonadecene and the 3- (methacryloyloxy) propyl trimethoxy silane to form a compact network structure; a large number of carboxyl, amide and pyrrolidone groups introduced by grafting are exposed on the polymer chain. And (3) forming hydrogen bonds by-NH 2 and-C-O in the high-temperature resistant additive and Al-OH and Si-OH groups on the surface of the clay to form intercalation adsorption. Secondly, maleic anhydride has active chemical properties, is easy to react with amino and other active groups, 2, 5-diaminotoluene is easy to react with C = O, and has good bridging capacity for other additives in the drilling fluid to form a three-dimensional network polymer structure. The high-temperature resistant additive can improve the stability of the emulsifier, has a compact net structure, prevents oil from passing through, and has high-temperature performance, so that high-temperature chain scission decomposition is prevented.
The invention has the beneficial effects that:
compared with the prior art, the high-temperature-resistant oil-based drilling fluid emulsifier disclosed by the invention has the advantages that a water-in-oil drilling fluid system taking diesel oil as a continuous phase has good emulsification effect and good high-temperature resistance, the drilling fluid can keep higher demulsification voltage after being treated at a high temperature of 160 ℃, and the high-temperature-resistant oil-based drilling fluid emulsifier has good high-temperature resistance.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
barite, particle size: 150 mesh, ling shou county Qing nan mineral processing factory.
M-pentadecylphenol, CAS:501-24-6.
Epichlorohydrin, CAS:598-09-4.
Ethylbenzene, CAS:100-41-4.
Isopropylamine, CAS:75-31-0.
1, 3-propane sultone, CAS:1120-71-4.
Petroleum ether, CAS:92062-35-6.
Trichloroacetic acid, CAS:76-03-9.
Formic acid, CAS:64-18-6.
Comparative example 1
The preparation method of the drilling fluid emulsifier comprises the following steps:
and mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of barite and 2 parts by weight of zinc stearate at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a potassium hydroxide aqueous solution with the concentration of 15wt.% according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water in a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, the sulfobetaine and the potassium bromide into the mixture according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
Example 1
The preparation method of the drilling fluid emulsifier comprises the following steps:
and mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a 15wt.% potassium hydroxide aqueous solution according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water in a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃, 60kPa and 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, the sulfobetaine and the potassium bromide into the mixture according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 400-mesh sieve to obtain barite powder;
b2, putting the barite powder into a planetary ball mill, and ball-milling for 3 hours by using alumina balls with the diameter of 6mm as ball-milling media according to the technological parameters of the ball-material ratio of 20;
b3, drying the powder subjected to ball milling for 5 hours at 90 ℃ to obtain superfine powder;
b4, mixing the superfine powder, reaction acid and water in a mass ratio of 1; the reaction acid is trichloroacetic acid.
Example 2
The preparation method of the drilling fluid emulsifier comprises the following steps:
and mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a potassium hydroxide aqueous solution with the concentration of 15wt.% according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water in a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃, 60kPa and 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, the sulfobetaine and the potassium bromide into the mixture according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at the rotating speed of 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
b3, putting the slurry into a planetary ball mill, and ball-milling for 3 hours by using alumina balls with the diameter of 6mm as a ball-milling medium according to the process parameters of a ball-material ratio of 20 and a rotation speed of 800rpm to obtain ball-milled slurry;
and B4, filtering the slurry subjected to ball milling, and drying for 5 hours at 90 ℃ to obtain the modified barite.
Example 3
The preparation method of the drilling fluid emulsifier comprises the following steps:
and mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a 15wt.% potassium hydroxide aqueous solution according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding and mixing the intermediate product F, the sulfobetaine and the potassium bromide according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at the rotating speed of 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
b3, putting the slurry into a planetary ball mill, and ball-milling for 3h by using an alumina ball with the diameter of 6mm as a ball-milling medium according to the process parameters of the ball-material ratio of 20;
b4, filtering the slurry subjected to ball milling, and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, reaction acid and water according to a mass ratio of 1; the reaction acid is trichloroacetic acid.
Example 4
The preparation method of the drilling fluid emulsifier comprises the following steps:
and mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a 15wt.% potassium hydroxide aqueous solution according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water in a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding and mixing the intermediate product F, the sulfobetaine and the potassium bromide according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at the rotating speed of 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
b3, putting the slurry into a planetary ball mill, and ball-milling for 3 hours by using alumina balls with the diameter of 6mm as a ball-milling medium according to the process parameters of a ball-material ratio of 20 and a rotation speed of 800rpm to obtain ball-milled slurry;
b4, filtering the slurry subjected to ball milling, and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, reaction acid and water according to a mass ratio of 1; the reaction acid is formic acid.
Example 5
The preparation method of the drilling fluid emulsifier comprises the following steps:
and mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a potassium hydroxide aqueous solution with the concentration of 15wt.% according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃, 60kPa and 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, the sulfobetaine and the potassium bromide into the mixture according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and then homogenizing at the rotating speed of 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
b3, putting the slurry into a planetary ball mill, and ball-milling for 3h by using an alumina ball with the diameter of 6mm as a ball-milling medium according to the process parameters of the ball-material ratio of 20;
b4, filtering the slurry subjected to ball milling, and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, reaction acid and water according to a mass ratio of 1; the reaction acid is a mixture consisting of trichloroacetic acid and formic acid according to a mass ratio of 1.
Test example 1
And (3) demulsification voltage testing: the demulsification voltage of the drilling fluid emulsifier obtained in each example of the invention is tested by referring to SY/T6615-2005 emulsifier evaluation procedure for drilling fluid, and the higher the demulsification voltage is, the better the emulsifying effect of the emulsifier is.
The temperature of the emulsion used for the test was 50 ℃; the increasing speed of the test voltage was 180V/s.
For the drilling fluid emulsifier obtained in each example, 5 parts of different samples are taken for testing, and the test results are averaged.
The test results are shown in table 1.
TABLE 1 demulsification Voltage of drilling fluid emulsifiers
| Breakdown voltage (V) | |
| Comparative example 1 | 854 |
| Example 1 | 1148 |
| Example 2 | 952 |
| Example 3 | 1287 |
| Example 4 | 1211 |
| Example 5 | 1303 |
Test example 2
And (3) emulsion stability test: the emulsion stability of the drilling fluid emulsifier obtained in each example of the invention was tested according to SY/T6615-2005 emulsifier evaluation procedure for drilling fluids.
400mL of distilled water is measured and put in a stirring cup, 24g of sodium bentonite for drilling fluid experiments is added, the mixture is stirred at a high speed for 200min, and the mixture is sealed and maintained for 24h for standby. Measuring 140mL of base slurry, adding 6.3g of the drilling fluid emulsifier under the stirring of an electric stirrer at the rotating speed of 1000rpm, slowly adding 210mL of diesel oil, stirring for 40min cumulatively, transferring the emulsion into a 500mL measuring cylinder, standing for 24h, and observing, wherein if no oil is separated out, the emulsifying effect is good;
for each drilling fluid emulsifier obtained, 5 different samples were taken for testing.
The test results are shown in table 2.
TABLE 2 emulsion stability of drilling fluid emulsifiers
In the technical scheme of the invention, m-pentadecylphenol reacts with methyl epichlorohydrin to generate glycidyl ether, then the glycidyl ether reacts with isopropylamine to generate tertiary amine, and then the tertiary amine reacts with 1, 3-propane sultone to obtain the base material. In the base material, the sulfonic functional group is used as an equivalent negative charge center, so that a balanced stable state can be achieved between a tertiary amine group with strong basicity and a sulfonic acid group with strong acidity, and the base material has good interface activation capability in a large pH variation range. In a drilling fluid system, the base material exists in a zwitterion form, so that the surface activation capacity is high, and the tetradecyl sulfobetaine and the hexadecyl sulfobetaine are added in the preparation of the base material, so that the tension of the emulsifier at an oil-water interface is further reduced, the emulsifier can be fully adsorbed at the interface of the drilling fluid, the arrangement condition of molecules at the oil-water interface is more compact, the strength of an interface film is enhanced, and the emulsifying capacity of the emulsifier is enhanced. Sulfonic group (-SO) is introduced into the base agent of the emulsifier obtained by the invention 3 H) The thickness of the hydrated film on the surface of the clay particles in the service environment is increased, and the characteristic can effectively keep the adsorption position of the drilling fluid under the high-temperature condition, so that the thermal stability of the drilling fluid is improved. In addition, the introduction of the sulfonic acid group can increase the negative charge density on the surface of the clay particles, thereby improving zeta potential, further leading the electrostatic repulsion among the clay particles to be increased, and enhancing the electrostatic stability of the drilling fluid at high temperature. The addition of a proper amount of potassium bromide during the preparation of the base agent can enable the drilling fluid to be preferentially adsorbed in the stratum, thereby reducing the adsorption loss of the emulsifierAnd the use efficiency of the emulsifier is improved. The emulsifier system obtained by the invention has a special internal salt structure, so that the emulsifier system does not show the tendency of accepting or releasing protons in the whole pH range. Therefore, the emulsifier obtained by the invention can generate a complex with high-valence metal ions and keep the activity of the complex, so that the complex has stronger calcium ion and magnesium ion resistance, and can effectively prevent the emulsifier from losing efficacy such as mineralization and the like in a high-temperature service environment. The modified barite is prepared by a specific method, the surface of the modified barite is treated by trichloroacetic acid and formic acid to generate an alumina hydrate coating layer with a compact structure, the isoelectric point of the modified barite coated by the compact alumina hydrate coating layer has a tendency of shifting to high pH, the solubility, compatibility and dispersibility of the emulsifier and an organic solvent are improved, the agglomeration phenomenon is prevented, and the emulsification effect is improved.
Example 6
The preparation method of the high-temperature-resistant oil-based drilling fluid emulsifier comprises the following steps:
mixing 90 parts by weight of water, 50 parts by weight of base agent, 8 parts by weight of modified barite, 2 parts by weight of zinc stearate and 10 parts by weight of high-temperature resistant additive at 22 ℃, and homogenizing at the rotating speed of 2500rpm for 15min to obtain the drilling fluid emulsifier.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecylphenol, methyl epichlorohydrin and a 15wt.% potassium hydroxide aqueous solution according to a mass ratio of 8;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1;
e5, mixing the intermediate product D and petroleum ether according to a mass ratio of 9;
e6, washing the intermediate product E with absolute ethyl alcohol, stirring at the rotating speed of 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, the sulfobetaine and the potassium bromide into the mixture according to a mass ratio of 5; the sulfobetaine is a mixture consisting of tetradecyl sulfobetaine and hexadecyl sulfobetaine according to a mass ratio of 1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at the rotating speed of 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
b3, putting the slurry into a planetary ball mill, and ball-milling for 3h by using an alumina ball with the diameter of 6mm as a ball-milling medium according to the process parameters of the ball-material ratio of 20;
b4, filtering the slurry subjected to ball milling, and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, reaction acid and water according to a mass ratio of 1; the reaction acid is a mixture consisting of trichloroacetic acid and formic acid according to a mass ratio of 1.
The preparation method of the high-temperature resistant additive comprises the following steps:
adding 7.5 parts by weight of N, N-dimethylacrylamide, 2.4 parts by weight of maleic anhydride, 6.2 parts by weight of 1-nonadecene and 7.5 parts by weight of 3- (methacryloyloxy) propyltrimethoxysilane into 50 parts by weight of toluene, uniformly mixing, then adding 0.26 part by weight of benzoyl peroxide, heating to 80 ℃ for reaction for 4 hours, then adding 0.5 part by weight of 2, 5-diaminotoluene, keeping the temperature at 80 ℃ for reaction for 10 minutes, performing rotary evaporation to remove toluene after the reaction is finished, washing and drying to obtain the high-temperature resistant additive.
Example 7
Essentially the same as example 6, except that: the preparation method of the high-temperature resistant additive comprises the following steps: adding 7.5 parts by weight of N, N-dimethylacrylamide and 2.4 parts by weight of maleic anhydride into 50 parts by weight of toluene, uniformly mixing, then adding 0.26 part by weight of benzoyl peroxide, heating to 80 ℃ for reaction for 4 hours, then adding 0.5 part by weight of 2, 5-diaminotoluene, keeping the temperature of 80 ℃ for reaction for 10 minutes, after the reaction is finished, carrying out rotary evaporation to remove toluene, washing and drying to obtain the high-temperature resistant additive.
Test example 3
And (3) testing the high-temperature resistance:
the high temperature resistance performance tests were performed on the high temperature resistant oil-based drilling fluid emulsifiers prepared in examples 6-7. The high temperature resistant oil-based drilling fluid emulsifier prepared in examples 6-7 was formulated into an emulsion according to the formulation of 5.4.1 emulsion in SY/T6615-2005 emulsifier for drilling fluid evaluation procedure, and the emulsion was placed in a 160 ℃ oven and allowed to stand for 16 hours to test the breaking voltage before and after high temperature.
TABLE 3 high temperature resistance test results for high temperature resistant oil-based drilling fluid emulsifiers
As can be seen from Table 3, the demulsification voltage of the diesel-oil based drilling fluid prepared from the high-temperature-resistant oil-based drilling fluid emulsifier is higher than 1000V at normal temperature, and is higher than 800V after the high-temperature standing treatment at 160 ℃, which indicates that the emulsifier prepared by the invention has high-temperature resistance and emulsification performance.
Claims (9)
1. The preparation method of the high-temperature-resistant oil-based drilling fluid emulsifier is characterized by comprising the following steps of:
mixing water, a base agent, modified barite, zinc stearate and a high-temperature resistant additive, and then homogenizing at a high speed to obtain the high-temperature resistant oil-based drilling fluid emulsifier.
2. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: the preparation method of the high-temperature resistant additive comprises the following steps: adding 5-9 parts by weight of N, N-dimethylacrylamide, 2-3 parts by weight of maleic anhydride, 6-8 parts by weight of 1-nonadecene and 7-8 parts by weight of 3- (methacryloyloxy) propyltrimethoxysilane into 50-60 parts by weight of toluene, uniformly mixing, then adding 0.1-0.5 part by weight of benzoyl peroxide, heating to 80-95 ℃ for reaction for 4-6h, then adding 0.5-1 part by weight of 2, 5-diaminotoluene, keeping the temperature of 80-95 ℃ for reaction for 5-10min, after the reaction is finished, carrying out rotary evaporation to remove toluene, washing and drying to obtain the high-temperature resistant additive.
3. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: the preparation method of the base agent comprises the following steps:
e1, mixing and stirring m-pentadecyl phenol, methyl epichlorohydrin and a potassium hydroxide aqueous solution to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water, reacting, heating, stirring, distilling under reduced pressure, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine, heating, stirring, reacting, distilling under the conditions of heating, reducing pressure and stirring, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone, heating, stirring, reacting, distilling under the conditions of heating, reducing pressure and stirring, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D with petroleum ether, stirring for reaction, and then carrying out suction filtration to obtain filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by using absolute ethyl alcohol, and then drying to obtain an intermediate product F;
e7, mixing the intermediate product F, the sulfobetaine and the potassium bromide, and then homogenizing to obtain the base agent.
4. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: the sulfobetaine is at least one of tetradecyl sulfobetaine and hexadecyl sulfobetaine.
5. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: the preparation method of the modified barite comprises the following steps:
b1, crushing and sieving barite to obtain barite powder;
b2, mixing the barite powder and absolute ethyl alcohol, and then homogenizing to obtain slurry;
b3, putting the slurry into a planetary ball mill, and ball-milling by using small alumina balls as ball-milling media to obtain ball-milled slurry;
b4, filtering the slurry subjected to ball milling and drying to obtain superfine powder;
and B5, mixing the superfine powder, reaction acid and water, heating, stirring, reacting, filtering, washing filter residues with water, and drying to obtain the modified barite.
6. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: and B3, putting the slurry into a planetary ball mill, and ball-milling for 3-4h by using alumina balls with the diameter of 5-6mm as a ball-milling medium according to the technological parameters of the ball-to-material ratio of (18-20): 1 and the rotation speed of 700-800rpm to obtain the ball-milled slurry.
7. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: and in the step B5, mixing the superfine powder and reaction acid according to the mass ratio of 1 (3-4), stirring and reacting for 5-6h at 85-90 ℃ at the rotating speed of 40-50rpm, filtering, washing filter residue for 30-40min by using water at the temperature of 45-50 ℃, wherein the mass ratio of the filter residue to the water is 1 (23-28), and drying for 4-6h at the temperature of 85-90 ℃ to obtain the modified barite.
8. The method of making the high temperature resistant oil-based drilling fluid emulsifier of claim 1, wherein: the reaction acid is at least one of trichloroacetic acid and formic acid.
9. The high-temperature-resistant oil-based drilling fluid emulsifier is characterized in that: the high-temperature-resistant oil-based drilling fluid emulsifier is prepared by the preparation method of any one of claims 1-7.
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| CN102716693A (en) * | 2012-06-26 | 2012-10-10 | 郑州大学 | Cashew base nonionic surfactant and preparation method of cashew base nonionic surfactant |
| CN109097005A (en) * | 2018-08-09 | 2018-12-28 | 李志平 | A kind of oil-based drilling fluid emulsifying agent |
| CN112708403A (en) * | 2020-12-29 | 2021-04-27 | 扬州工业职业技术学院 | Petroleum drilling fluid and preparation method thereof |
-
2022
- 2022-10-08 CN CN202211231381.5A patent/CN115572585A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716693A (en) * | 2012-06-26 | 2012-10-10 | 郑州大学 | Cashew base nonionic surfactant and preparation method of cashew base nonionic surfactant |
| CN109097005A (en) * | 2018-08-09 | 2018-12-28 | 李志平 | A kind of oil-based drilling fluid emulsifying agent |
| CN112708403A (en) * | 2020-12-29 | 2021-04-27 | 扬州工业职业技术学院 | Petroleum drilling fluid and preparation method thereof |
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