CN113563539A - Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof - Google Patents
Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof Download PDFInfo
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- 230000036571 hydration Effects 0.000 title claims abstract description 57
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 57
- 238000005553 drilling Methods 0.000 title claims abstract description 54
- 239000012530 fluid Substances 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001868 water Inorganic materials 0.000 title claims abstract description 48
- 239000003112 inhibitor Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229920002545 silicone oil Polymers 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- -1 methyl hydrogen Chemical compound 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000440 bentonite Substances 0.000 claims description 14
- 229910000278 bentonite Inorganic materials 0.000 claims description 14
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 claims description 7
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 5
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- AVWKSSYTZYDQFG-UHFFFAOYSA-M dimethyl-octadecyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC=C AVWKSSYTZYDQFG-UHFFFAOYSA-M 0.000 claims description 4
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical group [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 0.000 claims description 2
- 239000011995 wilkinson's catalyst Substances 0.000 claims description 2
- 239000011435 rock Substances 0.000 abstract description 8
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000003517 fume Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a water-based drilling fluid surface hydration inhibitor, which comprises the following steps: 1) mixing and dissolving a polyether monomer containing an unsaturated bond, a hydrophilic monomer, a cationic monomer and a temperature-resistant monomer with a rigid group in tetrahydrofuran to obtain a mixed solution A; 2) slowly adding a proper amount of methyl hydrogen-containing silicone oil into the mixed solution A, and stirring the mixed solution A at a low speed to obtain a mixed solution B; the low-speed stirring rotating speed is 1000 r/min; 3) adding a proper amount of catalyst into the mixed solution B in an inert atmosphere, reacting at 40-50 ℃, and keeping stirring during the reaction; 4) and removing the solvent tetrahydrofuran after the reaction is finished to obtain the surface hydration inhibitor. The invention also provides a water-based drilling fluid surface hydration inhibitor prepared based on the preparation method and application thereof. The water-based drilling fluid surface hydration inhibitor provided by the invention is high temperature resistant and is beneficial to inhibiting the hydration of the shale component of the drilling well wall rock.
Description
Technical Field
The invention relates to the technical field of petroleum drilling, in particular to a water-based drilling fluid surface hydration inhibitor and application thereof.
Background
About 75% of the formations traversed during drilling are shale, and about 90% of the borehole wall instability problems occur in shale formations. Shale borehole wall stabilization has long been a worldwide problem troubling oil and gas well engineering. Through years of efforts of scholars and engineering technicians at home and abroad, although great progress is made in the aspects of understanding of borehole wall instability mechanism, evaluation method of shale instability, research and development of shale inhibitors, formulation of anti-collapse drilling fluid technical countermeasures and the like, the problem of borehole wall instability of complex shale stratum is still not solved.
The main components of the shale stratum are various clay minerals, and various clays can absorb water and expand, but different clay minerals have different hydration and expansion degrees due to different structures. The hydration and expansion of clay are restricted by three forces, namely surface hydration, osmotic hydration and capillary action. The surface hydration is caused by the hydration of water molecules and exchangeable cations adsorbed on the surface of a clay crystal, is the first stage of the hydration of the clay, and causes small swelling capacity but very large swelling pressure, so that the swelling pressure is a factor which is not negligible in borehole wall instability.
The shale inhibitor can reduce the hydration degree of the shale, is an important additive used for stabilizing well walls in drilling fluid, and can also be used in fracturing fluid and acidizing fluid. The traditional shale inhibitors such as inorganic salts, organic salts, polymeric alcohols, asphalt and the like are still widely applied, and the novel amine inhibitors have more and more outstanding application effects in high-performance water-based drilling fluids and are researched and applied more and more. Shale inhibitors of the plant extract, nanomaterial, etc. type have also attracted attention from researchers. The hydrophilicity of the shale surface is an important reason for its surface hydration. At present, most shale inhibitors cannot solve the problem of hydrophilicity of the shale surface, inhibit the hydration property of the shale surface to be weak, and form an effective hydrophobic layer on the rock surface difficultly, so that the borehole wall instability of a part of complex shale formations is still serious. In addition, the shale inhibitor has poor temperature resistance, is easy to decompose and lose efficacy under high temperature conditions, and is difficult to effectively act on high-temperature deep strata.
Disclosure of Invention
Aiming at solving the technical problems of weak hydration performance of the surface of shale, difficulty in forming an effective hydrophobic layer, poor temperature resistance and the like, the invention provides a modified silicone oil type water-based drilling fluid surface hydration inhibitor.
The invention provides modified silicone oil which can effectively form a film on the surface of shale and form an effective hydrophobic layer on the surface of the shale, so that the wettability of the clay surface is changed from hydrophilic to hydrophobic, the free energy of the rock surface is reduced, and the adsorption of water molecules on the surface of clay minerals is greatly prevented or weakened, thereby playing a role in inhibiting the hydration of the clay surface.
The invention firstly provides a preparation method of a water-based drilling fluid surface hydration inhibitor, which comprises the following steps:
1) mixing and dissolving a polyether monomer containing an unsaturated bond, a hydrophilic monomer, a cationic monomer and a temperature-resistant monomer with a rigid group in tetrahydrofuran to obtain a mixed solution A;
2) slowly adding a proper amount of methyl hydrogen-containing silicone oil into the mixed solution A, and stirring the mixed solution A at a low speed to obtain a mixed solution B; the low-speed stirring rotating speed is 1000 r/min;
3) adding a proper amount of catalyst into the mixed solution B in an inert atmosphere, reacting at 40-50 ℃, and keeping stirring during the reaction;
4) removing the solvent tetrahydrofuran after the reaction is finished to obtain the surface hydration inhibitor;
wherein,
the polyether monomer is one of Allyl Polyoxyethylene Ether (APEG) or methyl allyl polyoxyethylene ether (TPEG);
the hydrophilic monomer is selected from one of acrylamide, acrylic acid and methacrylic acid, or two or more of acrylamide, acrylic acid and methacrylic acid which are mixed in any proportion;
the cationic monomer is one of dimethyl diallyl ammonium chloride (DMDAAC), methyl-acryloyloxyethyl trimethyl ammonium chloride (DMC) or octadecyl dimethyl allyl ammonium chloride;
the temperature-resistant monomer with the rigid group is one or more of 2-acrylamide-2-methyl propane sulfonic Acid (AMPS), Sodium Styrene Sulfonate (SSS) and styrene (St);
the catalyst is Wilkinson's catalyst triphenylphosphine rhodium chloride.
In one embodiment according to the invention, the stirring and the reaction temperature are kept constant for a reaction time of 4 to 6 hours.
In one embodiment according to the present invention, the mass ratio of the polyether monomer, the hydrophilic monomer, the cationic monomer, the temperature-resistant monomer and the catalyst is 100-: 50-60: 30-40: 50-60: 1.
in one embodiment of the invention, the volume ratio of methyl hydrogen-containing silicone oil to mixed liquor A is 1-2: 2-3.
In one embodiment according to the invention, the inert atmosphere is achieved by passing nitrogen into the reaction vessel; preferably, the nitrogen is dry and anhydrous.
In one embodiment according to the invention, the solvent tetrahydrofuran is removed by a rotary evaporator or nitrogen blower.
The invention also provides the water-based drilling fluid surface hydration inhibitor prepared by the preparation method.
The water-based drilling fluid surface hydration inhibitor is white viscous liquid.
The invention further provides a water-based drilling fluid which contains the water-based drilling fluid surface hydration inhibitor.
Preferably, the drilling fluid comprises 4 percent of bentonite-based slurry and 2 percent of water-based drilling fluid surface hydration inhibitor in volume fraction;
preferably, the bentonite-based slurry is prepared by a method comprising the following steps:
under the condition of high-speed stirring, dissolving the drilling fluid test slurry prepared by bentonite and sodium carbonate in water, stirring at high speed for 20min, and maintaining in a closed manner at 25 ℃ for 24h to obtain the drilling fluid test slurry, wherein the ratio of the bentonite to the sodium carbonate is mL: g: g, the proportion of water, bentonite and sodium carbonate is 500: 20: 1.
the invention utilizes the principle of hydrosilylation reaction to synthesize the surface hydration inhibitor modified silicone oil for the water-based drilling fluid. In view of the above problems, the present invention addresses the shortcomings of the conventional surface hydration inhibitors from three aspects. The methyl hydrogen-containing silicone oil is selected as a main body, has good hydrophobic effect and is easy to modify. And polyether monomers and hydrophilic monomers containing unsaturated bonds are introduced, so that the defect of difficult dispersion in the water-based drilling fluid due to over-strong hydrophobicity is overcome. Meanwhile, the cationic monomer is introduced, so that the adsorption effect of the cationic monomer on the shale formation is improved, and the retention effect of the hydration inhibitor on the surface of the shale is improved. And finally, introducing a temperature-resistant monomer with a rigid group to improve the temperature-resistant effect of the temperature-resistant monomer on the deep stratum.
The technical scheme of the invention has the following beneficial effects:
the water-based drilling fluid surface hydration inhibitor provided by the invention has good borehole wall stability, and can form a compact hydrophobic film on the borehole wall, so that water molecules can be prevented from entering the borehole wall, and a good surface hydration inhibition effect is achieved.
Meanwhile, the surface hydration inhibitor for the water-based drilling fluid provided by the invention has a strong adsorption effect, and due to the introduction of the cationic monomer, the binding force between the well wall and the stratum is improved, and the adsorption effect of the hydrophobic membrane is improved.
On the other hand, the surface hydration inhibitor of the water-based drilling fluid provided by the invention has high temperature resistance. The material does not decompose in a high-temperature environment, has excellent temperature resistance and can resist high temperature of 180 ℃.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Example 1: water-based drilling fluid surface hydration inhibitor 1#
1) Adding 10g of methyl allyl polyoxyethylene ether, 4g of acrylamide, 1g of acrylic acid, 3g of dimethyl diallyl ammonium chloride, 3g of 2-acrylamido-2-methylpropanesulfonic acid and 2g of sodium p-styrenesulfonate into 100ml of tetrahydrofuran, and uniformly stirring and mixing to obtain a mixed solution A;
2) placing the mixed solution A on a low-speed stirrer, keeping the stirring rotating speed at 1000r/min, and slowly adding 50ml of methyl hydrogen-containing silicone oil to obtain mixed solution B;
3) and transferring the mixed solution B into a three-neck flask with a double-row vacuum system in a fume hood, deoxidizing by using nitrogen, keeping stirring and heating to 45 ℃, adding 0.1g of catalyst triphenylphosphine rhodium chloride, and keeping anhydrous ventilation and introducing nitrogen in the whole reaction process.
4) The stirring and reaction temperature were kept constant and the reaction time was 5 hours.
5) And after the reaction is finished, moving the mixed solution to a rotary evaporator, and carrying out rotary evaporation to separate the tetrahydrofuran to obtain a reaction product.
The final product was a white viscous liquid.
Example 2: water-based drilling fluid surface hydration inhibitor 2#
1. Adding 12g of allyl polyoxyethylene ether, 4g of acrylamide, 2g of methacrylic acid, 4g of methyl-acryloyloxyethyl trimethyl ammonium chloride and 6g of sodium p-styrene sulfonate into 75ml of tetrahydrofuran, and uniformly stirring and mixing to obtain a mixed solution A;
2. placing the mixed solution A on a low-speed stirrer, keeping the stirring rotating speed at 1000r/min, and slowly adding 50ml of methyl hydrogen-containing silicone oil to obtain mixed solution B;
3. and transferring the mixed solution B into a three-neck flask with a double-row vacuum system in a fume hood, deoxidizing by using nitrogen, keeping stirring and heating to 50 ℃, adding 0.1g of catalyst triphenylphosphine rhodium chloride, and keeping anhydrous ventilation and introducing nitrogen in the whole reaction process.
4. The stirring and reaction temperature were kept constant and the reaction time was 4 hours.
5. And after the reaction is finished, moving the mixed solution to a rotary evaporator, and carrying out rotary evaporation to separate the tetrahydrofuran to obtain a reaction product.
The final product was a white viscous liquid.
Example 3: surface hydration inhibitor 3# for water-base drilling fluid
1. Adding 12g of methyl allyl polyoxyethylene ether, 3g of acrylic acid, 3g of acrylamide, 3g of octadecyl dimethyl allyl ammonium chloride, 3g of sodium p-styrene sulfonate and 2g of styrene into 100ml of tetrahydrofuran, and uniformly stirring and mixing to obtain a mixed solution A;
2. placing the mixed solution A on a low-speed stirrer, keeping the stirring rotating speed at 1000r/min, and slowly adding 50ml of methyl hydrogen-containing silicone oil to obtain mixed solution B;
3. and transferring the mixed solution B into a three-neck flask with a double-row vacuum system in a fume hood, deoxidizing by using nitrogen, keeping stirring and heating to 40 ℃, adding 0.1g of catalyst triphenylphosphine rhodium chloride, and keeping anhydrous ventilation and introducing nitrogen in the whole reaction process.
4. The stirring and reaction temperature were kept constant and the reaction time was 6 hours.
5. And after the reaction is finished, moving the mixed solution to a rotary evaporator, and carrying out rotary evaporation to separate the tetrahydrofuran to obtain a reaction product.
The final product was a white viscous liquid.
Example 4: surface hydration inhibitor 4# for water-base drilling fluid
1. Adding 11g of allyl polyoxyethylene ether, 3g of acrylamide, 3g of acrylic acid, 3.5g of octadecyl dimethyl allyl ammonium chloride and 5g of sodium p-styrene sulfonate into 75ml of tetrahydrofuran, and uniformly stirring and mixing to obtain a mixed solution A;
2. placing the mixed solution A on a low-speed stirrer, keeping the stirring rotating speed at 1000r/min, and slowly adding 50ml of methyl hydrogen-containing silicone oil to obtain mixed solution B;
3. and transferring the mixed solution B into a three-neck flask with a double-row vacuum system in a fume hood, deoxidizing by using nitrogen, keeping stirring and heating to 50 ℃, adding 0.1g of catalyst triphenylphosphine rhodium chloride, and keeping anhydrous ventilation and introducing nitrogen in the whole reaction process.
4. The stirring and reaction temperature were kept constant and the reaction time was 4 hours.
5. And after the reaction is finished, moving the mixed solution to a rotary evaporator, and carrying out rotary evaporation to separate the tetrahydrofuran to obtain a reaction product.
The final product was a white viscous liquid.
Example 5: surface hydration inhibitor 5# for water-base drilling fluid
1. Adding 12g of methyl allyl polyoxyethylene ether, 5g of acrylamide, 3.5g of methyl-acryloyloxyethyl trimethyl ammonium chloride and 5g of 2-acrylamido-2-methylpropanesulfonic acid into 100ml of tetrahydrofuran, and uniformly stirring and mixing to obtain a mixed solution A;
2. placing the mixed solution A on a low-speed stirrer, keeping the stirring rotating speed at 1000r/min, and slowly adding 50ml of methyl hydrogen-containing silicone oil to obtain mixed solution B;
3. and transferring the mixed solution B into a three-neck flask with a double-row vacuum system in a fume hood, deoxidizing by using nitrogen, keeping stirring and heating to 50 ℃, adding 0.1g of catalyst triphenylphosphine rhodium chloride, and keeping anhydrous ventilation and introducing nitrogen in the whole reaction process.
4. The stirring and reaction temperature were kept constant and the reaction time was 4 hours.
5. And after the reaction is finished, moving the mixed solution to a rotary evaporator, and carrying out rotary evaporation to separate the tetrahydrofuran to obtain a reaction product.
The final product was a white viscous liquid.
Example 6 evaluation of the Performance of the surface hydration inhibitors for Water-based drilling fluids prepared in examples 1-5
The modified silicone oils prepared in examples 1 to 5 were subjected to the following characterization and performance evaluation:
1. evaluation of hydrophobic Effect
The modified organic silicon oil surface hydration inhibitor is respectively prepared into aqueous solution with the mass fraction of 1 percent and 2 percent, and the cut original rock core slices (phi 25 multiplied by 3mm) of the Longmaxi outcrop are added into the aqueous solution. And (5) aging for 16h at 180 ℃, and observing the hydrophobic layer condition of the core after drying. And simultaneously measuring the water phase contact angle of the dried core surface.
TABLE 1 relationship table of surface hydration inhibitor concentration and core contact angle
| Concentration of surface hydration inhibitor | Core contact Angle/° |
| 0 | 14.3 |
| 1% example 1 | 101 |
| 2% example 1 | 111 |
| 1% example 2 | 108 |
| 2% example 2 | 113 |
| 1% example 3 | 99 |
| 2% example 3 | 104 |
| 1% example 4 | 105 |
| 2% example 4 | 114 |
| 1% example 5 | 103 |
| 2% example 5 | 109 |
As can be seen from Table 1, after the modified silicone oil surface hydration inhibitor synthesized by the invention is aged at 180 ℃, a layer of hydrophobic material is adsorbed on the surface of the core piece, and a hydrophobic film is formed. As the concentration of the modified silicone oil increases, the shale surface contact angle also increases, but the magnitude of the increase is limited. The increase of the contact angle can reduce the free energy of the shale surface theoretically, reduce the water adsorption capacity of the shale surface and achieve the effect of inhibiting the surface hydration.
2. Compatibility evaluation
Preparing bentonite-based slurry:
400mL of tap water is poured into a high-stirring cup, 16.0g of bentonite for drilling fluid test slurry preparation (SY/T5490-2016) and 0.8g of sodium carbonate (chemical purity) are added under the condition of high-speed stirring, the mixture is stirred at high speed for 20min, and the mixture is sealed and maintained for 24h at the temperature of 25 ℃.
Adding 2% of example products into 4% of bentonite-based slurry prepared, and testing rheological parameters and API (American Petroleum institute) filtration loss of the drilling fluid by referring to the national standard GB/T29170-2012 Petroleum and gas industry drilling fluid laboratory test; and (3) aging for 16h at 180 ℃ by using a roller heating furnace, and measuring rheological parameters, API (American Petroleum institute) filtration loss and high-temperature high-pressure filtration loss of the drilling fluid.
Table 2 effect of example products on rheological properties of drilling fluids
Table 3 effect of the product of the example on fluid loss properties of drilling fluids
As can be seen from Table 2, after the example product is added, compared with base slurry, the rheological parameters of the drilling fluid are not changed adversely before and after aging, which shows that the example product of the invention has excellent temperature resistance and has no adverse effect on the rheological property of the drilling fluid. As can be seen from table 3, there was no significant adverse change in the API fluid loss of the base slurry added to the product of the examples relative to the bentonite base slurry. After high-temperature aging, the high-temperature high-pressure filtration loss of the base slurry added into the product of the example is reduced to a certain extent relative to the base slurry.
Therefore, the modified organic silicone oil surface hydration inhibitor can resist higher temperature and hardly has adverse effect on rheological parameters of drilling fluid.
3. Evaluation of suppression Properties
Shale dispersion experiments at different temperatures were carried out using the Sichuan pine forest shale mudstone samples. The experimental steps are as follows, 50g of shale rock sample with 6-10 meshes is added into 350ml of solution in the embodiment of the 2% modified organic silicon oil surface hydration inhibitor, after the shale rock sample is hot rolled for 16 hours at 180 ℃, the shale rock sample is cleaned by clean water and passes through a standard sieve with 40 meshes, the residue of the sieve is dried for 4 hours at 105 ℃, and then the shale rock sample is weighed to calculate the recovery rate.
Table 4 examples rolling recovery experiments
| Formulation of | Rolling recovery% |
| Clean water | 7.0 |
| Clear Water + 2% example 1 | 83.5 |
| Clear Water + 2% example 2 | 84.0 |
| Clear Water + 2% example 3 | 84.8 |
| Clean Water + 2% example 4 | 82.7 |
| Clear Water + 2% example 5 | 85.1 |
As can be seen from Table 4, the modified silicone oil surface hydration inhibitor developed by the present invention can still maintain a higher rolling recovery rate after being aged at 180 ℃ compared with clear water. The rolling recovery rate of the embodiment is more than 80%, which shows that the invention can effectively inhibit surface hydration, play a good shale inhibition effect and improve the well wall stability during well drilling. Meanwhile, the invention also shows that the invention has good temperature resistance effect and good shale hydration inhibition effect after aging at 180 ℃.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a water-based drilling fluid surface hydration inhibitor is characterized by comprising the following steps:
1) mixing and dissolving a polyether monomer containing an unsaturated bond, a hydrophilic monomer, a cationic monomer and a temperature-resistant monomer with a rigid group in tetrahydrofuran to obtain a mixed solution A;
2) slowly adding a proper amount of methyl hydrogen-containing silicone oil into the mixed solution A, and stirring the mixed solution A at a low speed to obtain a mixed solution B; the low-speed stirring rotating speed is 1000 r/min;
3) adding a proper amount of catalyst into the mixed solution B in an inert atmosphere, reacting at 40-50 ℃, and keeping stirring during the reaction;
4) removing the solvent tetrahydrofuran after the reaction is finished to obtain the surface hydration inhibitor;
wherein,
the polyether monomer is one of Allyl Polyoxyethylene Ether (APEG) or methyl allyl polyoxyethylene ether (TPEG);
the hydrophilic monomer is selected from one of acrylamide, acrylic acid and methacrylic acid, or two or more of acrylamide, acrylic acid and methacrylic acid which are mixed in any proportion;
the cationic monomer is one of dimethyl diallyl ammonium chloride (DMDAAC), methyl-acryloyloxyethyl trimethyl ammonium chloride (DMC) or octadecyl dimethyl allyl ammonium chloride;
the temperature-resistant monomer with the rigid group is one or more of 2-acrylamide-2-methyl propane sulfonic Acid (AMPS), Sodium Styrene Sulfonate (SSS) and styrene (St);
the catalyst is Wilkinson's catalyst triphenylphosphine rhodium chloride.
2. The process according to claim 1, wherein the stirring and the reaction temperature are kept constant, and the reaction time is 4 to 6 hours.
3. The method according to claim 1, wherein the mass ratio of the polyether monomer, the hydrophilic monomer, the cationic monomer, the temperature-resistant monomer and the catalyst is 100-120: 50-60: 30-40: 50-60: 1.
4. the method according to claim 1, wherein the volume ratio of methyl hydrogen silicone oil to mixed solution a is 1-2: 2-3.
5. The method of claim 1, wherein the inert atmosphere is achieved by introducing nitrogen into the reaction vessel; preferably, the nitrogen is dry and anhydrous.
6. The process according to claim 1, wherein the solvent tetrahydrofuran is removed by a rotary evaporator or a nitrogen blower.
7. The water-based drilling fluid surface hydration inhibitor prepared by the preparation method of any one of claims 1-6.
8. The water-based drilling fluid surface hydration inhibitor of claim 7 wherein the water-based drilling fluid surface hydration inhibitor is a white viscous liquid.
9. A water-based drilling fluid comprising the water-based drilling fluid surface hydration inhibitor of claim 7 or 8 in the preparation of a drilling fluid.
10. The water-based drilling fluid of claim 9, comprising, in volume fraction, 4% bentonite-based slurry and 2% water-based drilling fluid surface hydration inhibitor;
preferably, the bentonite-based slurry is prepared by a method comprising the following steps:
under the condition of high-speed stirring, dissolving the drilling fluid test slurry prepared by bentonite and sodium carbonate in water, stirring at high speed for 20min, and maintaining in a closed manner at 25 ℃ for 24h to obtain the drilling fluid test slurry, wherein the ratio of the bentonite to the sodium carbonate is mL: g: g, the proportion of water, bentonite and sodium carbonate is 500: 20: 1.
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