CN115197678B - Drilling fluid emulsifier - Google Patents
Drilling fluid emulsifier Download PDFInfo
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- CN115197678B CN115197678B CN202210992753.XA CN202210992753A CN115197678B CN 115197678 B CN115197678 B CN 115197678B CN 202210992753 A CN202210992753 A CN 202210992753A CN 115197678 B CN115197678 B CN 115197678B
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- barite
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- 238000005553 drilling Methods 0.000 title claims abstract description 81
- 239000012530 fluid Substances 0.000 title claims abstract description 79
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 claims abstract description 38
- 239000013067 intermediate product Substances 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 82
- 238000002156 mixing Methods 0.000 claims description 77
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 229940117986 sulfobetaine Drugs 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- -1 tetradecyl sulfobetaine Chemical compound 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 23
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 23
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 22
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000010428 baryte Substances 0.000 claims description 16
- 229910052601 baryte Inorganic materials 0.000 claims description 16
- 238000000034 method 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 14
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 13
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 13
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 13
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 description 15
- 125000000542 sulfonic acid group Chemical group 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 239000004927 clay Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000010410 layer Substances 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
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000994 depressogenic effect 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
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000000080 wetting agent 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Colloid Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a drilling fluid emulsifier and a preparation method thereof. The invention obtains the drilling fluid emulsifier with good stability under high-temperature environment.
Description
Technical Field
The invention relates to the technical field of drilling fluid emulsifiers, in particular to a drilling fluid emulsifier and a preparation method thereof.
Background
The base fluid of the drilling fluid is typically diesel or a less toxic mineral oil. The discontinuous phase in the drilling fluid is mostly brine. After stirring the drilling fluid for a period of time at a certain temperature, an emulsified drilling fluid which can show oil-like properties can be obtained, and a scholars refer to the drilling fluid as an inverse emulsified drilling fluid.
In general, the oil-water ratio of water-in-oil drilling fluids exceeds seventy percent, and is also known in the industry as drilling fluid. The external phase of the drilling fluid is oil, and the inherent property ensures that the drilling fluid has strong inhibition performance, and can be used for stabilizing the well wall, preventing collapse accidents and the like. The drilling fluid has good protection and stability performance for hydrocarbon reservoirs, especially water-sensitive geological reservoirs. Moreover, drilling fluids are generally required to have high temperature resistance and good lubricity at high temperatures, since such drilling fluids are required to be in service in deep well highly deviated wells and the like.
One of the problems in the art of drilling fluids today is how to increase the stability of emulsions, especially in high temperature service environments. During drilling, the emulsion is always subject to the undesirable tendency of the emulsification effect to be impaired or even to complete failure due to the high heat and high pressure generated by the friction of the drilling. Particularly when drilling deep thermal wells, the high temperatures can cause the emulsion to lose stability very easily. The emulsifier is an extremely critical raw material in a drilling fluid composition system, and the quality of the emulsifier and the stability of the emulsifier are extremely critical elements for guaranteeing the equilibrium state and long-term service reliability of each disperse phase in the drilling fluid emulsion composition system.
At present, the research on the high-temperature stability of drilling fluid is still in a development stage, and particularly, the research on the high-temperature stability of an emulsifier in the drilling fluid is greatly insufficient. The problems of the prior art on the emulsifier in the high-temperature service environment are mainly represented by large dosage, poor emulsification effect, poor reliability and stability in the high-temperature service environment, and the like. The reliability and stability of the emulsifier and the drilling fluid are obviously weakened after the emulsifier and the drilling fluid are aged at high temperature, and dangerous phenomena such as aging, thickening and the like often occur. Therefore, the development of an emulsifier for drilling fluid resistant to high-temperature environment has become one of the problems to be solved in the current urgent need.
The patent CN111139044A provides a composite emulsifier for drilling fluid and high-temperature-resistant ultra-high density drilling fluid, which consists of a main emulsifier, an auxiliary emulsifier, a wetting agent, a cutting agent, a temperature resistant agent and a pour point depressant.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a drilling fluid emulsifier and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the drilling fluid emulsifier comprises the following steps:
mixing water, a base agent, modified barite and zinc stearate, and 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.
Wherein, zinc stearate has good thermal stability.
The preparation method of the base agent comprises the following steps:
e1, mixing and stirring aqueous solutions of m-pentadecyl phenol, methyl epichlorohydrin and potassium hydroxide to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water for reaction, heating, stirring, decompressing and distilling, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine, heating and stirring for reaction, then distilling under the conditions of heating, decompressing and stirring, and collecting distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone, heating and stirring for reaction, then distilling under the conditions of heating, decompressing 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 suction filtering to obtain filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, and then drying to obtain an intermediate product F;
e7 mixing the intermediate product F, sulfobetaine and potassium bromide and homogenizing to obtain the base agent.
In the technical scheme of the invention, meta-pentadecyl phenol and methyl epoxy chloropropane react 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 acid group functional group is taken as an equivalent negative charge center, so that the equilibrium steady state between the tertiary amino group with strong alkalinity and the strongly acidic sulfonic acid group can be achieved, and the base material has good interfacial activation capability in a larger pH variation range. In a drilling fluid system, the base material exists in a zwitterionic form, has higher surface activation capability, and because the tetradecyl sulfobetaine and the hexadecyl sulfobetaine are added in the preparation of the base material, the tension of the emulsifier at an oil-water interface is further reduced, so that the emulsifier can be fully adsorbed at the drilling fluid interface, the arrangement condition of molecules at the water-oil interface becomes more compact, and the strength of an interface film is enhanced, thereby enhancing the emulsifying capability of the emulsifier. The sulfonic acid group (-SO) is introduced into the basic agent of the emulsifier obtained by the invention 3 H) The film thickness of the hydration layer on the surface of the clay particles in the service environment is increased, and the characteristic can effectively maintain the adsorption position of the drilling fluid under the high-temperature condition, so that the thermal stability of the drilling fluid is improved. Moreover, the introduction of the sulfonic acid group can also increase the negative charge density on the surface of the clay particles so as to improve the zeta potential, further lead to the increase of electrostatic repulsive force between the clay particles, and enhance the electrostatic stability of the drilling fluid at high temperature.
The drilling fluid can be preferentially adsorbed in the stratum by adding a proper amount of potassium bromide in the preparation process of the base agent, so that 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 internal salt structure, so that the emulsifier system does not show a tendency of accepting or releasing protons in a whole pH range. Therefore, the emulsifier can form a complex with high-valence metal ions and keep the activity of the complex, so that the complex has stronger capability of resisting calcium ions and magnesium ions, and can effectively prevent the emulsifier from losing effectiveness such as mineralization under a high-temperature service environment. According to the invention, the modified barite is prepared by a specific method, and the surface of the modified barite is treated by trichloroacetic acid and formic acid to generate the alumina hydrate coating layer with compact structure, so that 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 the organic solvent are improved, the occurrence of 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-pentadecyl phenol, methyl epichlorohydrin and 12-17wt.% potassium hydroxide aqueous solution in a mass ratio of (7-8): 4-5.3): 2.4-3.1, and stirring at 60-65 ℃ for 20-35min at a rotating speed of 40-75rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to the mass ratio of (3-5) (0.7-1.2) (8-10), reacting for 2-3 hours at 75-80 ℃, then distilling at the temperature of 85-90 ℃ under the air pressure of 45-60kPa and the 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) (9-10) (3-4), stirring at 65-70 ℃ for 2-3 hours at the rotating speed of 40-50rpm, then distilling at the temperature of 85-90 ℃ under the air 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) (15-19) (0.1-0.3), stirring at 70-80rpm for 20-25min at 60-65 ℃, then distilling at 85-90 ℃ under the conditions of air pressure of 55-60kPa and 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) (1-2), stirring for 40-50min at a rotating speed of 40-50rpm, carrying out suction filtration under the process conditions of 20-25L/min of exhaust gas, 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 a rotation speed of 60-80rpm for 20-30min, filtering, and drying filter residues at 60-65 ℃ for 130-160min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide into the mixture according to the mass ratio of (4-5) (1.5-2.5) (0.25-4), and homogenizing the mixture 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 in the mass ratio of (1-3) to (1-3).
More preferably, the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine 1:1.
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 with absolute ethyl alcohol, and homogenizing to obtain slurry;
b3, putting the slurry into a planetary ball mill, and adopting alumina balls as a ball milling medium to obtain ball-milled slurry after ball milling;
b4, filtering the ball-milled slurry and drying to obtain ultrafine powder;
and B5, mixing the superfine powder, the reaction acid and the water, heating, stirring and reacting, filtering, washing filter residues with the 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 with a 300-400 mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at a rotating speed of 1500-2000rpm for 12-16min to obtain slurry with a concentration of 50-55 wt%;
putting the slurry into a planetary ball mill, adopting alumina balls with the diameter of 5-6mm as a ball milling medium, and performing ball milling for 3-4 hours by using technological parameters with the ball-to-material ratio of (18-20): 1 and the rotation speed of 700-800rpm to obtain ball-milled slurry;
b4, filtering the ball-milled slurry, and drying at 85-90 ℃ for 5-6 hours to obtain superfine powder;
and B5, mixing the superfine powder, the reaction acid and the water according to the mass ratio of 1 (3-4) (2-4), stirring at the temperature of 85-90 ℃ at the rotating speed of 40-50rpm for reacting for 5-6 hours, filtering, washing filter residues with water at the temperature of 45-50 ℃ for 30-40 minutes, wherein the mass ratio of the filter residues to the water is 1 (23-28), and drying at the temperature of 85-90 ℃ for 4-6 hours to obtain the modified barite.
The reaction acid is at least one of trichloroacetic acid and formic acid.
According to the invention, the surface of the barite is modified by compounding trichloroacetic acid and formic acid, so that the stability of the obtained emulsifier is further improved, the difference of the acidity strength of the two reaction acids is presumed to be related, and the difference of the acidity enables the structure of the alumina coating to be more compact, so that the equipotential point of the modified barite is further shifted to high pH value.
Preferably, the reaction acid is a mixture of trichloroacetic acid and formic acid in the mass ratio of (1-3).
More preferably, the reaction acid is a mixture of trichloroacetic acid and formic acid in a mass ratio of 1:1.
The invention has the beneficial effects that:
1. the invention provides a drilling fluid emulsifier and a preparation method thereof, wherein the base material and modified barite prepared by the specific method are used as raw materials, so that the emulsifier with extremely strong resistance to high-temperature aging is obtained, and the emulsifier can be applied to preparation of drilling fluid.
2. The base agent is prepared from raw materials such as m-pentadecyl phenol, methyl epichlorohydrin and the like, and can be used for the drilling fluid emulsifier and the preparation method thereof.
3. The modified barite is prepared by modifying barite powder with trichloroacetic acid and formic acid, and can be used as the drilling fluid emulsifier and the preparation method thereof.
Detailed Description
The above summary of the invention is described in further detail below in connection with the detailed description, but it should not be construed that the scope of the above subject matter of the invention is limited to the examples described below.
Introduction of some of the raw materials in this application:
barite, particle size: 150 mesh, qing nan mineral product processing plant in Ming county.
M-pentadecyl phenol, CAS:501-24-6.
Methyl 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:
the drilling fluid emulsifier was obtained by mixing 90 parts by weight of water, 50 parts by weight of a base agent, 8 parts by weight of barite and 2 parts by weight of zinc stearate at 22℃and homogenizing at 2500rpm for 15 minutes.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecyl phenol, methyl epichlorohydrin and 15wt.% potassium hydroxide aqueous solution at a mass ratio of 8:5:3, and stirring at 65 ℃ for 30min at a rotating speed of 60rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5:1:3, reacting for 2 hours at 80 ℃, then distilling at 90 ℃ under the conditions of 50kPa of air pressure and 90rpm of stirring speed, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2:9:4, stirring at 70 ℃ for 2 hours at a rotating speed of 40rpm, then distilling at a temperature of 90 ℃ and a gas pressure of 60kPa at a stirring speed of 80rpm, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17:0.2, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃ under the conditions of air pressure of 60kPa and stirring speed of 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether in a mass ratio of 9:2, stirring at a rotating speed of 50rpm for 50min, and carrying out suction filtration under the process conditions of 23L/min of exhaust gas, 600mmHG of vacuum degree and 125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, stirring at 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide in a mass ratio of 5:2:0.34, mixing, and homogenizing for 10min at a rotating speed of 3000rpm to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in a mass ratio of 1:1.
Example 1
The preparation method of the drilling fluid emulsifier comprises the following steps:
the drilling fluid emulsifier was obtained by mixing 90 parts by weight of water, 50 parts by weight of a base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22℃and homogenizing at 2500rpm for 15 minutes.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecyl phenol, methyl epichlorohydrin and 15wt.% potassium hydroxide aqueous solution at a mass ratio of 8:5:3, and stirring at 65 ℃ for 30min at a rotating speed of 60rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5:1:3, reacting for 2 hours at 80 ℃, then distilling at 90 ℃ under the conditions of 50kPa of air pressure and 90rpm of stirring speed, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2:9:4, stirring at 70 ℃ for 2 hours at a rotating speed of 40rpm, then distilling at a temperature of 90 ℃ and a gas pressure of 60kPa at a stirring speed of 80rpm, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17:0.2, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃ under the conditions of air pressure of 60kPa and stirring speed of 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether in a mass ratio of 9:2, stirring at a rotating speed of 50rpm for 50min, and carrying out suction filtration under the process conditions of 23L/min of exhaust gas, 600mmHG of vacuum degree and 125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, stirring at 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide in a mass ratio of 5:2:0.34, mixing, and homogenizing for 10min at a rotating speed of 3000rpm to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in a mass ratio of 1:1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the crushed barite with a 400-mesh sieve to obtain barite powder;
b2, putting the barite powder into a planetary ball mill, adopting alumina balls with the diameter of 6mm as a ball milling medium, and performing ball milling for 3 hours by using technological parameters with the ball-material ratio of 20:1 and the rotation speed of 800rpm to obtain powder after ball milling;
b3, drying the ball-milled powder for 5 hours at 90 ℃ to obtain ultrafine powder;
b4, mixing the superfine powder, the reaction acid and the water according to a mass ratio of 1:3:2, stirring at 90 ℃ at a rotating speed of 40rpm for reaction for 5 hours, filtering, washing filter residues with water at 50 ℃ for 30 minutes, wherein the mass ratio of the filter residues to the water is 1:25, and drying at 90 ℃ for 4 hours to obtain the modified barite; the reaction acid is trichloroacetic acid.
Example 2
The preparation method of the drilling fluid emulsifier comprises the following steps:
the drilling fluid emulsifier was obtained by mixing 90 parts by weight of water, 50 parts by weight of a base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22℃and homogenizing at 2500rpm for 15 minutes.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecyl phenol, methyl epichlorohydrin and 15wt.% potassium hydroxide aqueous solution at a mass ratio of 8:5:3, and stirring at 65 ℃ for 30min at a rotating speed of 60rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5:1:3, reacting for 2 hours at 80 ℃, then distilling at 90 ℃ under the conditions of 50kPa of air pressure and 90rpm of stirring speed, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2:9:4, stirring at 70 ℃ for 2 hours at a rotating speed of 40rpm, then distilling at a temperature of 90 ℃ and a gas pressure of 60kPa at a stirring speed of 80rpm, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17:0.2, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃ under the conditions of air pressure of 60kPa and stirring speed of 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether in a mass ratio of 9:2, stirring at a rotating speed of 50rpm for 50min, and carrying out suction filtration under the process conditions of 23L/min of exhaust gas, 600mmHG of vacuum degree and 125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, stirring at 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide in a mass ratio of 5:2:0.34, mixing, and homogenizing for 10min at a rotating speed of 3000rpm to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in a mass ratio of 1:1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the crushed barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
putting the slurry into a planetary ball mill, adopting alumina pellets with the diameter of 6mm as a ball milling medium, and performing ball milling for 3 hours by using the technological parameters of a ball-material ratio of 20:1 and a rotation speed of 800rpm to obtain slurry after ball milling;
and B4, filtering the ball-milled slurry and drying the slurry at 90 ℃ for 5 hours to obtain the modified barite.
Example 3
The preparation method of the drilling fluid emulsifier comprises the following steps:
the drilling fluid emulsifier was obtained by mixing 90 parts by weight of water, 50 parts by weight of a base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22℃and homogenizing at 2500rpm for 15 minutes.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecyl phenol, methyl epichlorohydrin and 15wt.% potassium hydroxide aqueous solution at a mass ratio of 8:5:3, and stirring at 65 ℃ for 30min at a rotating speed of 60rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5:1:3, reacting for 2 hours at 80 ℃, then distilling at 90 ℃ under the conditions of 50kPa of air pressure and 90rpm of stirring speed, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2:9:4, stirring at 70 ℃ for 2 hours at a rotating speed of 40rpm, then distilling at a temperature of 90 ℃ and a gas pressure of 60kPa at a stirring speed of 80rpm, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17:0.2, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃ under the conditions of air pressure of 60kPa and stirring speed of 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether in a mass ratio of 9:2, stirring at a rotating speed of 50rpm for 50min, and carrying out suction filtration under the process conditions of 23L/min of exhaust gas, 600mmHG of vacuum degree and 125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, stirring at 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide in a mass ratio of 5:2:0.34, mixing, and homogenizing for 10min at a rotating speed of 3000rpm to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in a mass ratio of 1:1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the crushed barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
putting the slurry into a planetary ball mill, adopting alumina pellets with the diameter of 6mm as a ball milling medium, and performing ball milling for 3 hours by using the technological parameters of a ball-material ratio of 20:1 and a rotation speed of 800rpm to obtain slurry after ball milling;
b4, filtering the ball-milled slurry and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, the reaction acid and the water according to a mass ratio of 1:3:2, stirring at 90 ℃ at a rotating speed of 40rpm for reaction for 5 hours, filtering, washing filter residues with water at 50 ℃ for 30 minutes, wherein the mass ratio of the filter residues to the water is 1:25, and drying at 90 ℃ for 4 hours to obtain the modified barite; the reaction acid is trichloroacetic acid.
Example 4
The preparation method of the drilling fluid emulsifier comprises the following steps:
the drilling fluid emulsifier was obtained by mixing 90 parts by weight of water, 50 parts by weight of a base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22℃and homogenizing at 2500rpm for 15 minutes.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecyl phenol, methyl epichlorohydrin and 15wt.% potassium hydroxide aqueous solution at a mass ratio of 8:5:3, and stirring at 65 ℃ for 30min at a rotating speed of 60rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5:1:3, reacting for 2 hours at 80 ℃, then distilling at 90 ℃ under the conditions of 50kPa of air pressure and 90rpm of stirring speed, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2:9:4, stirring at 70 ℃ for 2 hours at a rotating speed of 40rpm, then distilling at a temperature of 90 ℃ and a gas pressure of 60kPa at a stirring speed of 80rpm, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17:0.2, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃ under the conditions of air pressure of 60kPa and stirring speed of 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether in a mass ratio of 9:2, stirring at a rotating speed of 50rpm for 50min, and carrying out suction filtration under the process conditions of 23L/min of exhaust gas, 600mmHG of vacuum degree and 125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, stirring at 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide in a mass ratio of 5:2:0.34, mixing, and homogenizing for 10min at a rotating speed of 3000rpm to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in a mass ratio of 1:1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the crushed barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
putting the slurry into a planetary ball mill, adopting alumina pellets with the diameter of 6mm as a ball milling medium, and performing ball milling for 3 hours by using the technological parameters of a ball-material ratio of 20:1 and a rotation speed of 800rpm to obtain slurry after ball milling;
b4, filtering the ball-milled slurry and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, the reaction acid and the water according to a mass ratio of 1:3:2, stirring at 90 ℃ at a rotating speed of 40rpm for reaction for 5 hours, filtering, washing filter residues with water at 50 ℃ for 30 minutes, wherein the mass ratio of the filter residues to the water is 1:25, and drying at 90 ℃ for 4 hours to obtain the modified barite; the reaction acid is formic acid.
Example 5
The preparation method of the drilling fluid emulsifier comprises the following steps:
the drilling fluid emulsifier was obtained by mixing 90 parts by weight of water, 50 parts by weight of a base agent, 8 parts by weight of modified barite and 2 parts by weight of zinc stearate at 22℃and homogenizing at 2500rpm for 15 minutes.
The preparation method of the base agent comprises the following steps:
e1, mixing m-pentadecyl phenol, methyl epichlorohydrin and 15wt.% potassium hydroxide aqueous solution at a mass ratio of 8:5:3, and stirring at 65 ℃ for 30min at a rotating speed of 60rpm to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water according to a mass ratio of 5:1:3, reacting for 2 hours at 80 ℃, then distilling at 90 ℃ under the conditions of 50kPa of air pressure and 90rpm of stirring speed, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine according to a mass ratio of 2:9:4, stirring at 70 ℃ for 2 hours at a rotating speed of 40rpm, then distilling at a temperature of 90 ℃ and a gas pressure of 60kPa at a stirring speed of 80rpm, and collecting a distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone according to a mass ratio of 1:17:0.2, stirring at 80rpm for 25min at 65 ℃, then distilling at 90 ℃ under the conditions of air pressure of 60kPa and stirring speed of 80rpm, and collecting distillate to obtain an intermediate product D;
e5, mixing the intermediate product D and petroleum ether in a mass ratio of 9:2, stirring at a rotating speed of 50rpm for 50min, and carrying out suction filtration under the process conditions of 23L/min of exhaust gas, 600mmHG of vacuum degree and 125W of power, and taking filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, stirring at 80rpm for 25min, filtering, and drying filter residues at 65 ℃ for 150min to obtain an intermediate product F;
e7, adding the intermediate product F, sulfobetaine and potassium bromide in a mass ratio of 5:2:0.34, mixing, and homogenizing for 10min at a rotating speed of 3000rpm to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in a mass ratio of 1:1.
The preparation method of the modified barite comprises the following steps:
b1, crushing barite and sieving the crushed barite with a 400-mesh sieve to obtain barite powder;
b2, mixing the barite powder with absolute ethyl alcohol, and homogenizing at 2000rpm for 15min to obtain slurry with the concentration of 55 wt.%;
putting the slurry into a planetary ball mill, adopting alumina pellets with the diameter of 6mm as a ball milling medium, and performing ball milling for 3 hours by using the technological parameters of a ball-material ratio of 20:1 and a rotation speed of 800rpm to obtain slurry after ball milling;
b4, filtering the ball-milled slurry and drying the slurry at 90 ℃ for 5 hours to obtain superfine powder;
b5, mixing the superfine powder, the reaction acid and the water according to a mass ratio of 1:3:2, stirring at 90 ℃ at a rotating speed of 40rpm for reaction for 5 hours, filtering, washing filter residues with water at 50 ℃ for 30 minutes, wherein the mass ratio of the filter residues to the water is 1:25, and drying at 90 ℃ for 4 hours to obtain the modified barite; the reaction acid is a mixture of trichloroacetic acid and formic acid in a mass ratio of 1:1.
Test example 1
Demulsification voltage test: the emulsion breaking voltage of the drilling fluid emulsifier obtained by each example of the invention is tested by referring to SY/T6615-2005 'evaluation program of emulsifier for drilling fluid', and the higher the emulsion breaking voltage is, the better the emulsion effect of the emulsifier is.
The temperature of the emulsion used in the test was 50 ℃; the test voltage was increased at a rate of 180V/s.
For each example of the resulting drilling fluid emulsifier, 5 different samples were tested and the test results averaged.
The test results are shown in Table 1.
TABLE 1 demulsification Voltage of drilling fluid emulsifiers
| Demulsification voltage (V) | |
| Comparative example 1 | 854 |
| Example 1 | 1148 |
| Example 2 | 952 |
| Example 3 | 1287 |
| Example 4 | 1211 |
| Example 5 | 1303 |
Test example 2
Emulsion stability test: the emulsion stability of the emulsion for drilling fluids obtained in each example of the present invention was tested according to SY/T6615-2005 procedure for evaluation of emulsion for drilling fluids.
400mL of distilled water is measured and put into 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 maintained in a sealed mode 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 in an accumulated way, transferring the emulsion into a 500mL measuring cylinder, standing for 24h, observing, and if oil-free precipitation is carried out, indicating that the emulsifying effect is good;
for each example of the resulting drilling fluid emulsifier, 5 different samples were taken and tested.
The test results are shown in Table 2.
TABLE 2 emulsion stability of drilling fluid emulsifiers
| Appearance of solution | |
| Comparative example 1 | With a small amount of oil separating out |
| Example 1 | Oil-free precipitation |
| Example 2 | Oil-free precipitation |
| Example 3 | Oil-free precipitation |
| Example 4 | Oil-free precipitation |
| Example 5 | Oil-free precipitation |
In the technical scheme of the invention, meta-pentadecyl phenol and methyl epoxy chloropropane react 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 acid group functional group is taken as an equivalent negative charge center, so that the equilibrium steady state between the tertiary amino group with strong alkalinity and the strongly acidic sulfonic acid group can be achieved, and the base material has good interfacial activation capability in a larger pH variation range. In a drilling fluid system, the base material exists in a zwitterionic form, has higher surface activation capability, and because the tetradecyl sulfobetaine and the hexadecyl sulfobetaine are added in the preparation of the base material, the tension of the emulsifier at an oil-water interface is further reduced, so that the emulsifier can be fully adsorbed at the drilling fluid interface, the arrangement condition of molecules at the water-oil interface becomes more compact, the strength of an interface film is enhanced, and the emulsion is enhancedEmulsifying capacity of the agent. The sulfonic acid group (-SO) is introduced into the basic agent of the emulsifier obtained by the invention 3 H) The film thickness of the hydration layer on the surface of the clay particles in the service environment is increased, and the characteristic can effectively maintain the adsorption position of the drilling fluid under the high-temperature condition, so that the thermal stability of the drilling fluid is improved. Moreover, the introduction of the sulfonic acid group can also increase the negative charge density on the surface of the clay particles so as to improve the zeta potential, further lead to the increase of electrostatic repulsive force of the clay particles and enhance the electrostatic stability of the drilling fluid at high temperature. The drilling fluid can be preferentially adsorbed in the stratum by adding a proper amount of potassium bromide in the preparation process of the base agent, so that 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 internal salt structure, so that the emulsifier system does not show a tendency of accepting or releasing protons in a whole pH range. Therefore, the emulsifier can form a complex with high-valence metal ions and keep the activity of the complex, so that the complex has stronger capability of resisting calcium ions and magnesium ions, and can effectively prevent the emulsifier from losing effectiveness such as mineralization under a high-temperature service environment. According to the invention, the modified barite is prepared by a specific method, and the surface of the modified barite is treated by trichloroacetic acid and formic acid to generate the alumina hydrate coating layer with compact structure, so that 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 the organic solvent are improved, the occurrence of agglomeration phenomenon is prevented, and the emulsification effect is improved.
Claims (4)
1. The preparation method of the drilling fluid emulsifier is characterized by comprising the following steps of:
mixing water, a base agent, modified barite and zinc stearate, and then homogenizing at a high speed to obtain the drilling fluid emulsifier;
the preparation method of the base agent comprises the following steps:
e1, mixing and stirring aqueous solutions of m-pentadecyl phenol, methyl epichlorohydrin and potassium hydroxide to obtain an intermediate product A;
e2, mixing the intermediate product A, ethylbenzene and water for reaction, heating, stirring, decompressing and distilling, and collecting distillate to obtain an intermediate product B;
e3, mixing the intermediate product B, absolute ethyl alcohol and isopropylamine, heating and stirring for reaction, then distilling under the conditions of heating, decompressing and stirring, and collecting distillate to obtain an intermediate product C;
e4, mixing the intermediate product C, isopropanol and 1, 3-propane sultone, heating and stirring for reaction, then distilling under the conditions of heating, decompressing 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 suction filtering to obtain filter residues to obtain an intermediate product E;
e6, washing the intermediate product E by absolute ethyl alcohol, and then drying to obtain an intermediate product F;
e7, mixing the intermediate product F, sulfobetaine and potassium bromide and homogenizing to obtain the base agent; the sulfobetaine is a mixture of tetradecyl sulfobetaine and hexadecyl sulfobetaine in the mass ratio of (1-3);
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 with absolute ethyl alcohol, and homogenizing to obtain slurry;
b3, putting the slurry into a planetary ball mill, and adopting alumina balls as a ball milling medium to obtain ball-milled slurry after ball milling;
b4, filtering the ball-milled slurry and drying to obtain ultrafine powder;
b5, mixing the superfine powder, the reaction acid and the water, heating, stirring and reacting, filtering, washing filter residues with the water, and drying to obtain the modified barite; the reaction acid is a mixture of trichloroacetic acid and formic acid.
2. The method for preparing the drilling fluid emulsifier according to claim 1, wherein the method comprises the following steps: and B3, putting the slurry into a planetary ball mill, adopting alumina balls with the diameter of 5-6mm as a ball milling medium, and performing ball milling for 3-4 hours by using the technological parameters of ball-to-material ratio (18-20): 1 and rotation speed of 700-800rpm to obtain the ball-milled slurry.
3. The method for preparing the drilling fluid emulsifier according to claim 1, wherein the method comprises the following steps: and B5, mixing the superfine powder and the reaction acid according to the mass ratio of 1 (3-4), stirring at the temperature of 85-90 ℃ at the rotating speed of 40-50rpm for reacting for 5-6 hours, filtering, washing filter residues with water at the temperature of 45-50 ℃ for 30-40 minutes, wherein the mass ratio of the filter residues to the water is 1 (23-28), and drying at the temperature of 85-90 ℃ for 4-6 hours to obtain the modified barite.
4. Drilling fluid emulsifier, its characterized in that: a process for the preparation of a drilling fluid emulsifier according to any one of claims 1 to 3.
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| WO2019205210A1 (en) * | 2018-04-27 | 2019-10-31 | 中国石油大学(北京) | Lubricant for drilling fluid, preparation method therefor and application thereof |
| US10829679B1 (en) * | 2019-12-02 | 2020-11-10 | Southwest Petroleum University | Micro-nanometer plugging anti-collapse drilling fluid and preparation method and use thereof |
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| CN109097005A (en) * | 2018-08-09 | 2018-12-28 | 李志平 | A kind of oil-based drilling fluid emulsifying agent |
| US10829679B1 (en) * | 2019-12-02 | 2020-11-10 | Southwest Petroleum University | Micro-nanometer plugging anti-collapse drilling fluid and preparation method and use thereof |
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