CN116731326A - High-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid and preparation method thereof - Google Patents
High-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid and preparation method thereof Download PDFInfo
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- 239000006260 foam Substances 0.000 title claims abstract description 140
- 239000003381 stabilizer Substances 0.000 title claims abstract description 82
- 238000005553 drilling Methods 0.000 title claims abstract description 67
- 239000012530 fluid Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 115
- 229920002678 cellulose Polymers 0.000 claims abstract description 105
- 239000001913 cellulose Substances 0.000 claims abstract description 105
- 239000000463 material Substances 0.000 claims abstract description 99
- 239000000243 solution Substances 0.000 claims abstract description 93
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000011258 core-shell material Substances 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 56
- 239000006185 dispersion Substances 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000005406 washing Methods 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000004108 freeze drying Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- -1 chloromethyl modified phenolic resin Chemical class 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 241000196324 Embryophyta Species 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007853 buffer solution Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007844 bleaching agent Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 229960002218 sodium chlorite Drugs 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- RKGXJBAAWCGBQA-UHFFFAOYSA-N 4-propan-2-yloxypiperidine Chemical compound CC(C)OC1CCNCC1 RKGXJBAAWCGBQA-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- PXKPKGHXANCVMC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound OS(=O)(=O)C(F)(F)F.CCCCN1CN(C)C=C1 PXKPKGHXANCVMC-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 description 55
- 230000033558 biomineral tissue development Effects 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 20
- 239000004088 foaming agent Substances 0.000 description 19
- 239000011435 rock Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
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- 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 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
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- 239000010902 straw Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- FRZPYEHDSAQGAS-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1 FRZPYEHDSAQGAS-UHFFFAOYSA-M 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
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- 239000002343 natural gas well Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid and a preparation method thereof. The preparation method of the foam stabilizer comprises the following steps: preparing a cellulose material with a core-shell structure by taking nano cellulose fibrils or nano cellulose crystals as cores and taking an organic resin material as a shell; adding the catalyst A into a sodium hydroxide solution, uniformly stirring, and then adding a cellulose material aqueous dispersion liquid with a core-shell structure to obtain a mixed liquid I; adding the catalyst B and a silane coupling agent into water to obtain a mixed solution II; adding the mixed solution II into the mixed solution I, adding a grafting monomer, and reacting to obtain the polymer. Compared with the conventional foam stabilizer, the foam stabilizer has higher foam stabilizing capacity, can have longer half-life period under complex geological conditions, and has excellent temperature resistance and salt resistance.
Description
Technical Field
The invention relates to a high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid and a preparation method thereof, belonging to the technical field of drilling industry.
Background
Geothermal energy is thermal energy stored in the crust of the earth. Geothermal heat originates from the earth's center and is the decay of natural radioactive isotopes (uranium, thorium, potassium) trapped in the magma during earth formation and the energy released during formation. This energy is typically transferred by heating the rock and the fluid in the rock cracks, pores. In recent years, the global energy demand is rapidly increased, new energy industry is rapidly developed, the development and utilization of geothermal energy gradually enter the field of view of people, and many countries begin to use geothermal energy for power generation and heating. Geothermal energy is a clean energy without pollution and has abundant reserves, and in some countries with abundant geothermal resources, the geothermal energy has become an important substitute energy for conventional energy sources such as coal, petroleum and the like, and the properties of green and renewable resources meet the requirement of sustainable development. According to different heat storage mediums, the types of geothermal energy mainly comprise karst fracture type geothermal resources, fracture type geothermal resources and pore type geothermal resources; the temperature range of geothermal resources can be classified into low-temperature geothermal resources (temperature <90 ℃), medium-temperature geothermal resources (temperature 90-150 ℃) and high-temperature geothermal resources (temperature 150-650 ℃). In recent years, along with the decrease of the conventional energy reserves and the improvement of the environmental awareness of people in China, china enters a fast lane for developing geothermal resources. The geothermal resources in China are quite rich, wherein the medium-low temperature geothermal resources are quite large in reserve, the medium-low temperature geothermal resources are almost nationwide, and a quite large development space is provided.
The key technology of geothermal development is geothermal drilling, high-temperature geothermal drilling cost and high risk, and a large amount of uncertainty exists. Compared with the traditional petroleum and natural gas wells, the geothermal well has the following characteristics:
1) The geological condition of the bottom of the well is complex, the temperature of the reservoir is high (from 150 ℃ to 200 ℃ and locally more than 300 ℃);
2) The high-temperature geothermal resource is mostly formed in igneous rock and metamorphic rock, the hardness of the thermal storage rock is higher than that of conventional petroleum drilling, and the abrasive property is high (the quartz content is higher than 50 percent);
3) Fracture height development (fracture width exceeding 1 cm), often with abnormally low pressure formations;
4) The mineralization degree of the stratum fluid is high, and high requirements are put on the pollution resistance of a drilling fluid system.
The complex geological conditions make drilling extremely difficult, firstly, the geothermal reservoir cracks develop, the stratum pressure is low, the drilling fluid is easy to leak by adopting water-based drilling fluid and oil-based drilling fluid, the underground leakage can also cause serious rock carrying difficulty, a series of complex underground accidents such as drilling sticking and burying are caused, the drilling period is prolonged, the geothermal development cost is increased, and the consequence is serious and even the well is scrapped. Secondly, the high-temperature rock mass of the well wall is easy to generate thermal cracking when meeting water, so that accidents such as well wall collapse, drill sticking and the like are caused.
Aiming at the problems existing in geothermal drilling, researchers at home and abroad introduce foam drilling fluid technology into geothermal drilling, compared with water-based/oil-based drilling fluid, the foam drilling fluid has several advantages: the foam fluid has low density and lower hydrostatic column pressure, and the foam fluid has stronger blocking capability when flowing through Kong Hou due to the Jamin effect, and the foam drilling fluid has very low water loss, so that the leakage of the drilling fluid can be effectively reduced; the foam drilling fluid is a mixed system composed of gas and liquid, and is composed of a series of compact and fine bubbles, compared with water-based/oil-based drilling fluid, the foam drilling fluid has higher dynamic shear force, higher viscosity and good rock carrying capacity, has better floating capacity in the drilling process due to lower density, and has the solid particle capacity carried by foam which is ten times that of a liquid medium under the same flow, so that the rock carrying efficiency is improved; the foam drilling fluid system has simple components, generally only comprises a foaming agent and a foam stabilizer, and foam is adsorbed on a drilling tool and a well wall in the drilling process, so that a good lubricating effect is achieved, friction resistance is reduced, circulating pressure drop is reduced, and damage to a reservoir is low. Thus, foamed drilling fluids have become the drilling fluid of choice for currently drilling geothermal wells.
There are many studies on foam drilling fluid drilling at present, but the research on the application of foam drilling fluid in conventional oil and gas drilling is mainly carried out, and few research data on the application of foam drilling fluid in geothermal drilling are provided. The foam belongs to an unstable system in terms of thermodynamics and dynamics, and is subjected to the problems that a foaming agent and a foam stabilizer in foam drilling fluid are easy to thermally degrade and lose effectiveness in a high-temperature environment of a geothermal well, and the like, aiming at the problems, the Chinese patent No. CN113403044A develops a micro-foam foaming system for the drilling fluid, which mainly comprises a main polymer foaming agent and an auxiliary foaming agent, wherein the main foaming agent is an anionic nonionic high polymer surfactant containing a rigid benzene ring structure, and the auxiliary foaming agent is an amino acid zwitterionic surfactant, so that the good foam performance can be maintained in a stratum. Chinese patent CN113122193A prepares a readily soluble low molecular weight high temperature resistant foam stabilizer by improving the surface viscosity of a foam liquid film and adopting a nonionic cellulose ether skeleton structure, a hydrophobic structure and sulfonate groups, and can be applied to low-pressure oil and gas resources. Chinese patent No. CN107523278A relates to a preparation method of foaming stabilizer by using BF 3 The catalytic action of diethyl ether, the reaction of isotridecyl alcohol and epoxy ether to generate alcohol ether, and the reaction product then reacts with chlorosulfonic acid and sodium hydroxide to generate foaming agent, a small amount of foaming stabilizer can generate a large amount of foam, and a novel method is provided for developing high-performance foam drilling fluid.
In addition, various substances capable of stabilizing foam are developed for the problem of foam stability at home and abroad. Such as polyacrylamide,Hydroxyethyl cellulose, hydroxymethyl cellulose, nonionic surfactants, etc., but high-valence cations such as Ca are present in large amounts in geothermal wells 2+ And the like, the structure and the surface activity of the foam stabilizer can be damaged, and when the temperature reaches a certain level, the foam stabilizer is completely thermally degraded. Therefore, aiming at the problem of instability of foam under high-temperature and high-pressure stratum, development of a high-temperature and high-salt resistant foam stabilizer suitable for a geothermal well is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the problems that a foam stabilizer is easy to degrade and lose efficacy in a high-temperature high-salt geothermal stratum and the like, the invention provides a high-temperature-resistant high-salt Pickering foam stabilizer for geothermal well drilling fluid and a preparation method thereof. Firstly, extracting a biomass-based nano cellulose material with high specific surface area and high mechanical strength from plants; secondly, the organic resin material is coated on the biomass-based nano cellulose material, so that the temperature resistance of the biomass-based nano cellulose material is improved; finally, the compound containing perfluorinated carbon chains and thiol groups is grafted on the nano-cellulose-based pickering particles, the carbon chains can effectively resist corrosive environments such as high temperature, strong acid, strong alkali and the like, and the thiol groups have good surface activity and corrosion resistance under the high-temperature and high-salinity environments. Compared with the conventional foam stabilizer, the foam stabilizer has higher foam stabilizing capacity, can have longer half-life period under complex geological conditions, and has excellent temperature resistance and salt resistance.
Term interpretation:
room temperature: has the meaning known in the art, meaning 25.+ -. 5 ℃.
The technical scheme of the invention is as follows:
the preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid comprises the following steps:
(1) Preparing a cellulose material with a core-shell structure by taking nano cellulose fibrils (CNF) or nano cellulose crystals (CNC) as cores and taking an organic resin material as a shell;
(2) Adding the catalyst A into a sodium hydroxide solution, uniformly stirring, and then adding a cellulose material aqueous dispersion liquid with a core-shell structure to obtain a mixed liquid I; adding the catalyst B and a silane coupling agent into water to obtain a mixed solution II; and adding the mixed solution II into the mixed solution I, and then adding a grafting monomer for reaction to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
According to the invention, preferably, the organic resin material in the step (1) is chloromethyl modified phenolic resin or polyphenyl methyl siloxane; the viscosity of the polyphenyl methyl siloxane at 25 ℃ is 50-500 mPa.s; the chloromethyl modified phenolic resin is prepared or obtained commercially by referring to Chinese patent document CN 108102290A.
According to a preferred embodiment of the invention, the mass ratio of nanocellulose filaments (CNF) or nanocellulose crystals (CNC) to organic resin material in step (1) is 1:5-15.
According to a preferred embodiment of the present invention, the nanocellulose filaments (CNF) in step (1) are prepared according to the following method: weighing Na 2 CO 3 And NaHCO 3 Dissolving in deionized water to obtain Na 2 CO 3 -NaHCO 3 A buffer solution; dissolving sodium salt and oxidant into buffer solution, dispersing cellulose into the solution, adding NaClO under stirring, stirring at room temperature for reaction, and regulating pH value of the system to 10-10.5 during the reaction; after the reaction is finished, absolute ethyl alcohol is added to terminate the reaction; removing supernatant, centrifugally washing the obtained solid with deionized water to obtain neutral supernatant, removing supernatant, adding water into the obtained solid for ultrasonic treatment, centrifugally taking supernatant, and freeze-drying the obtained supernatant to obtain nanocellulose fibrils (CNF);
further preferred, the Na described in the preparation of nanocellulose fibrils (CNF) 2 CO 3 And NaHCO 3 The mass ratio of (2) is 5-10:3; the Na is 2 CO 3 -NaHCO 3 Na in buffer solution 2 CO 3 The concentration of (2) is 0.1-0.2mol/L;
further preferred, the sodium salt in the preparation of nanocellulose fibrils (CNF) is sodium bromide, sodium nitrate or sodium fluoride; the mass ratio of the sodium salt to the cellulose is 0.2-0.5:1;
further preferred, the oxidizing agent in the preparation of nanocellulose fibrils (CNF) is 2, 6-tetramethylpiperidine oxide or 4-isopropoxy-piperidine; the mass ratio of the oxidant to the cellulose is 0.01-0.05:1;
Further preferred, the mass of said cellulose and Na in the preparation of nanocellulose fibrils (CNF) 2 CO 3 -NaHCO 3 The volume ratio of the buffer solution is 0.01-0.1 g/1 mL;
further preferably, the mass of the NaClO in the preparation of nanocellulose fibrils (CNF) is 30-70% of the mass of cellulose;
further preferably, the pH of the system is maintained at 10-10.5 in the preparation of nanocellulose fibrils (CNF) using a dilute hydrochloric acid solution with a concentration of 0.1-0.5mol/L and a NaOH solution with a concentration of 0.1-1mol/L;
further preferably, the time of the reaction in the preparation of nanocellulose fibrils (CNF) is between 2 and 8 hours;
further preferred, the ratio of the added volume of the absolute ethanol to the mass of cellulose in the preparation of nanocellulose fibrils (CNF) is 10-30ml:1g;
further preferably, the ratio of the volume of water added to the mass of cellulose at the time of ultrasonic treatment in the preparation of nanocellulose fibrils (CNF) is 10-50mL:1g; the ultrasonic treatment time is 30-60min;
it is further preferred that the temperature of said freeze-drying in the preparation of nanocellulose fibrils (CNF) is between-26 and-16 ℃ and the time of freeze-drying is between 10 and 24 hours.
According to the present invention, the nanocellulose crystal (CNC) in step (1) is prepared according to the following method: adding cellulose into sulfuric acid solution for reaction; centrifuging the suspension obtained by the reaction, and centrifugally washing the obtained solid with water until the pH value of the supernatant is neutral; adding water into the obtained solid for ultrasonic treatment, centrifuging, and freeze-drying the obtained supernatant to obtain nanocellulose crystal (CNC);
Further preferably, the mass fraction of the sulfuric acid solution in the preparation of nanocellulose crystals (CNC) is 50-64%; the mass ratio of the cellulose to the sulfuric acid solution is 1:10-20;
further preferably, the temperature of the reaction in the preparation of nanocellulose crystals (CNC) is 40-80 ℃ and the reaction time is 1-3 hours;
further preferably, the ratio of the volume of water added to the mass of cellulose during ultrasonic treatment in the preparation of nanocellulose crystals (CNC) is 10-50mL:1g; the ultrasonic treatment time is 2-4 hours;
further preferably, the temperature of freeze drying in the preparation of nanocellulose crystal (CNC) is-26 to-16 ℃, and the time of freeze drying is 10-24 hours.
According to the present invention, in the preparation of nanocellulose fibrils (CNF) or nanocellulose crystals (CNC), the cellulose used is cellulose extracted from plants, said plants being corn stalks or wood, the extraction method of which is prior art; preferably, the cellulose is extracted according to the following method: firstly, crushing corn stalk or wood into plant powder with 20-100 meshes, washing with water, and drying at 30-80 ℃ for 36-72h; adding the dried plant powder into alkali solution for treatment, filtering, washing the obtained solid with water until the filtrate is neutral, and drying at 30-80 ℃ for 36-72h to obtain alkali-treated raw materials; dispersing the alkali-treated raw materials in water to obtain a dispersion liquid with the concentration of 0.05-0.3g/mL, heating to 60-100 ℃, adding an acid solution and a bleaching agent every 1-2h for extraction, filtering, washing the obtained solid with deionized water until the filtrate is neutral, washing with acetone, and drying at 40-80 ℃ until the weight is constant to obtain cellulose; the alkali solution is sodium hydroxide solution with the mass fraction of 5-20%; the ratio of the volume of the alkali solution to the mass of the dried plant powder is 10-50 mL/1 g; the temperature of the treatment by using the alkali solution is 60-100 ℃, and the treatment time by using the alkali solution is 1-3h; the acid solution is one of glacial acetic acid, 37% hydrochloric acid solution and 68% nitric acid solution, and the mass ratio of each added acid solution to the alkali-treated raw material is 0.1-1:1; the bleaching agent is one of sulfur dioxide, sodium chlorite and sulfur, and the mass ratio of the bleaching agent added each time to the alkali treated raw material is 0.1-1:1; the extraction time is 3-6h.
According to the present invention, the cellulose material of the core-shell structure using nano cellulose fibrils (CNF) as the core in the step (1) is of a single-core structure, and is prepared according to the following method:
adjusting the pH value of the nano cellulose fibril (CNF) aqueous dispersion to 5-8, adding the dimethylbenzene dispersion of the organic resin material, adding an initiator I, and stirring for reaction; after the reaction is finished, filtering, washing, ultrasonic dispersing and freeze drying are carried out to obtain the cellulose material with a core-shell structure and taking nano cellulose fibrils (CNF) as cores; the concentration of the nano cellulose fibril (CNF) water dispersion liquid is 0.05-0.5g/mL; adjusting the pH of the aqueous dispersion of nanocellulose fibrils (CNF) using 0.05mol/L sodium hydroxide solution; the concentration of the xylene dispersion liquid of the organic resin material is 0.05-0.25g/mL; the initiator I is benzoyl peroxide or dicumyl peroxide; the mass of the initiator I is 0.5-3% of the mass of the nano cellulose fibril (CNF); the stirring speed is 2000-5000r/min, and the stirring reaction time is 12-36h; the washing is to use ethanol for 3-5 times; the ultrasonic dispersion is to add the solid obtained by washing into water, and uniformly disperse the solid by ultrasonic to obtain suspension, wherein the ratio of the added mass of the water to the mass of the nano cellulose fibrils (CNF) is 40-60:1; the freeze-drying temperature is-26 to-16 ℃, and the freeze-drying time is 10-24 hours.
According to the present invention, the cellulose material of the core-shell structure using the nanocellulose crystal (CNC) as the core in the step (1) is preferably of a single-core structure or a multi-core structure.
Further preferably, the cellulose material with a single core and shell structure using nanocellulose crystal (CNC) as a core is prepared according to the following method:
adjusting the pH value of the nano cellulose crystal (CNC) aqueous dispersion to 5-8, adding the dimethylbenzene dispersion of the organic resin material, adding an initiator II, stirring uniformly, and carrying out standing reaction; after the reaction is finished, filtering, washing, ultrasonic dispersing and freeze drying are carried out to obtain a cellulose material with a single-core-shell structure taking nano cellulose crystal (CNC) as a core; preferably, the concentration of the nanocellulose crystal (CNC) aqueous dispersion is 0.01-0.1g/mL; adjusting the pH of an aqueous dispersion of nanocellulose crystals (CNC) using 0.05mol/L sodium hydroxide solution; the concentration of the xylene dispersion liquid of the organic resin material is 0.05-0.25g/mL; the initiator II is benzoyl peroxide or dicumyl peroxide, and the mass of the initiator II is 0.5-3% of the mass of the nano cellulose crystal (CNC); the standing reaction time is 12-36h; the washing is to use ethanol for 3-5 times; the ultrasonic dispersion is to add the solid obtained by washing into water, and uniformly disperse the solid by ultrasonic to obtain suspension, wherein the ratio of the added mass of the water to the mass of the nano cellulose crystal (CNC) is 40-60:1; the freeze drying is carried out for 12-36h at the temperature of minus 26 to minus 16 ℃.
Further preferably, the cellulose material with a polynuclear core-shell structure using nanocellulose crystal (CNC) as a core is prepared according to the following method:
(a) Adjusting the pH value of the nano cellulose crystal (CNC) aqueous dispersion to 5-8, adding the dimethylbenzene dispersion of the organic resin material, adding an initiator III, stirring uniformly, and carrying out standing reaction; after the reaction is finished, filtering, washing, ultrasonic dispersing and freeze drying are carried out to obtain the cellulose material with a mononuclear core-shell structure; preferably, the concentration of the nanocellulose crystal (CNC) aqueous dispersion is 0.01-0.1g/mL; adjusting the pH of an aqueous dispersion of nanocellulose crystals (CNC) using 0.05mol/L sodium hydroxide solution; the concentration of the xylene dispersion liquid of the organic resin material is 0.05-0.25g/mL; the initiator III is benzoyl peroxide or dicumyl peroxide, and the mass of the initiator III is 0.5-3% of the mass of the nano cellulose crystal (CNC); the standing reaction time is 12-36h; the washing is to use ethanol for 3-5 times; the ultrasonic dispersion is to add the solid obtained by washing into water, and uniformly disperse the solid by ultrasonic to obtain suspension, wherein the ratio of the added mass of the water to the mass of the nano cellulose crystal (CNC) is 40-60:1; the freeze drying is carried out for 12-36h at the temperature of minus 26 to minus 16 ℃;
(b) Adding the cellulose material with the mononuclear core-shell structure obtained in the step (a) into ionic liquid, adding a dispersing agent and an initiator IV, and stirring for reaction to obtain a reaction liquid; then vacuum drying the reaction liquid to obtain a multi-core-shell structured cellulose material taking nano cellulose crystal (CNC) as a core; preferably, the ionic liquid is one of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF 6), 1-butyl-3-methylimidazolium tetrafluoroborate ([ BMIM ] BF 4) and 1-butyl-3-methylimidazolium triflate ([ BMIM ] [ TfO ]), and the mass ratio of the ionic liquid to the cellulose material with a mononuclear core-shell structure is 3-8:1; the dispersing agent is sodium dodecyl sulfate, polyethylene glycol 200 or polyethylene glycol 400, and the mass of the dispersing agent is 2-5% of the mass of the cellulose material with a mononuclear core-shell structure; the initiator IV is benzoyl peroxide or dicumyl peroxide, and the initiator IV is 0.5-3% of the mass of the cellulose material with a mononuclear core-shell structure; the reaction temperature is 60-90 ℃, and the reaction time is 10-15h; the temperature of the vacuum drying is 40-60 ℃, and the time of the vacuum drying is 12-36h.
According to the invention, the nanocellulose fibrils (CNF) in step (1) have a diameter of 1-100nm and a length of 500-2000nm; the diameter of the nano cellulose crystal (CNC) is 2-20nm, and the length is 100-500nm.
According to a preferred embodiment of the present invention, the catalyst A in step (2) is 2, 6-tetramethylpiperidine-N-oxide (TEMPO), ammonia or potassium hydroxide; the mass ratio of the catalyst A to the cellulose material with the core-shell structure is 0.05-0.5:1.
According to a preferred embodiment of the invention, the mass fraction of the sodium hydroxide solution in step (2) is 5-15%; the ratio of the volume of the sodium hydroxide solution to the mass of the cellulose material of the core-shell structure is 1-5 mL/1 g.
According to the present invention, the concentration of the aqueous dispersion of cellulose material of the core-shell structure in the step (2) is preferably 0.01 to 0.2g/mL, more preferably 0.1 to 0.15g/mL.
According to the invention, preferably, the catalyst B in the step (2) is one of triethylamine, nickel oxide and sodium molybdate; the mass ratio of the catalyst B to the cellulose material with the core-shell structure is 0.3-0.8:1; the concentration of the catalyst B in the mixed solution II is 0.05-0.15g/mL.
According to a preferred embodiment of the present invention, the silane coupling agent in step (2) is γ -methacryloxypropyl trimethoxysilane (KH 570), γ -aminopropyl triethoxysilane (KH 550), γ - (2, 3-glycidoxy) propyl trimethoxysilane (KH 560) or vinyltriethoxysilane (a 151); the mass ratio of the silane coupling agent to the cellulose material with the core-shell structure is 0.05-0.3:1.
Preferably according to the invention, the grafting monomer in step (2) is 1H, 2H-perfluorododecanethiol or 1H, 2H-perfluorodecyl thiol; the mass ratio of the grafting monomer to the cellulose material with the core-shell structure is 5-20:1.
Preferably according to the present invention, the temperature of the reaction in step (2) is 70-90 ℃; the reaction time is 12-36h.
According to the invention, the reaction in the step (2) further comprises a post-treatment step, which is specifically as follows: filtering the obtained reaction liquid, washing the solid obtained by filtering by absolute ethyl alcohol, and then freeze-drying at the temperature of minus 26 ℃ to minus 16 ℃ for 12-36 hours to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
The invention also provides a high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid, which is prepared by adopting the preparation method.
According to the invention, the application of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid is used for stabilizing foam in the geothermal well drilling process.
The invention has the technical characteristics and beneficial effects that:
1. the high-temperature-resistant high-salt Pickering foam stabilizer takes the nano-cellulose material extracted from plants as a core, and the nano-cellulose material has high specific surface area and high mechanical strength, and compared with the surfactant foam stabilizer, the melting point and the temperature resistance of the nano-cellulose material are obviously improved.
2. The high-temperature-resistant high-salt foam stabilizer provided by the invention takes the self-made nano cellulose material as an inner core and takes the organic resin material as an outer shell, so that the inorganic-organic core-shell type nano particle foam stabilizer is formed, the nano cellulose increases the temperature resistance of solid particles through the wrapping effect of the organic resin material, and the strong guarantee is provided for the foam stabilizing capability of a high-temperature stratum.
3. The high-temperature-resistant high-salt foam stabilizer starts from a molecular structure, researches the interaction of all groups among molecules, introduces a plurality of compounds containing perfluorinated carbon chains and mercaptan groups to be grafted on nanocellulose-based solid particles, can effectively resist complex environments such as high temperature, strong acid, strong alkali and the like, and can keep good surface activity and corrosion resistance under the high-temperature and high-salinity environments due to the mercaptan groups. The nanocellulose-based foam stabilizer improves foam stabilizing capability under complex conditions (high temperature and high salt), and provides a new thought for geothermal well development and exploitation.
4. The high-temperature-resistant high-salt foam stabilizer does not influence the performance of drilling fluid, and has the advantages of simple preparation process and convenient production operation.
Drawings
Fig. 1 is an SEM image of nanocellulose fibrils prepared in example 3.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. The raw materials used in the examples are all conventional raw materials and are commercially available; the methods are prior art unless specified otherwise. All other examples of modifications and alterations will be apparent to those skilled in the art based on the examples herein, and are intended to be within the scope of the invention.
Chloromethyl modified phenolic resin was prepared according to example 1 of chinese patent document CN108102290 a.
Example 1
The preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid comprises the following steps:
(1) Extraction of cellulose
Firstly, crushing corn straw into powder with 80 meshes by using a plant crusher, cleaning the powder by using deionized water, and drying the powder in a baking oven with the temperature of 40 ℃ for 48 hours to obtain corn straw powder; weighing 20g of dried corn stalk powder, adding the corn stalk powder into 300mL of 20% sodium hydroxide aqueous solution by mass fraction, stirring at 70 ℃ for 2 hours, filtering, washing the obtained solid by deionized water until the filtrate is neutral, and drying in a 40 ℃ oven for 40 hours to obtain alkali-treated powder; and (3) placing 10g of alkali-treated powder into 100mL of deionized water, dispersing uniformly, heating to 80 ℃, adding 2.1g of glacial acetic acid and 3g of sodium chlorite for extraction every 1h, adding 3 times of glacial acetic acid and sodium chlorite for extraction for 3h, obtaining a pure white solid, filtering, washing the obtained solid with deionized water until the filtrate is neutral, washing with acetone, and drying at 40 ℃ until the weight is constant, thus obtaining cellulose.
(2) Preparation of nanocellulose Crystal (CNC)
Mixing cellulose prepared in the step (1) with a sulfuric acid solution with the mass fraction of 60% according to the mass ratio of 1:10, and reacting for 2 hours at 60 ℃ to obtain a suspension; centrifuging the obtained suspension at 10000r/min for 15min, removing supernatant, and centrifuging and washing the obtained solid with water until the pH value of the supernatant is neutral; then adding water to the obtained solid, wherein the ratio of the volume of added water to the mass of cellulose is 20 mL/1 g; centrifuging after ultrasonic treatment for 2 hours, and taking supernatant, and freeze-drying the obtained supernatant at-26 ℃ for 12 hours to obtain nanocellulose crystal (CNC) for further use.
(3) Preparation of cellulose material with CNC (computerized numerical control) as core and single-core and core-shell structure
Dispersing 5g of nanocellulose crystals (CNC) in 100mL of water, and adjusting the pH value of the obtained nanocellulose crystal dispersion liquid to 7 by using 0.05mol/L sodium hydroxide solution; 50g of chloromethyl modified phenolic resin is dispersed in 500mL of dimethylbenzene, and is added into the nano cellulose crystal dispersion liquid after being uniformly stirred; adding 0.05g of dicumyl peroxide, stirring uniformly at the rotating speed of 3000r/min, and standing at room temperature for reaction for 24 hours; after the reaction is completed, filtering, and washing the solid product obtained by filtering with ethanol for 3 times; the solid product obtained by washing is redispersed in 250g of water, uniformly dispersed by ultrasonic, and then freeze-dried (the temperature is-20 ℃ C., the time is 24 hours), so as to obtain the cellulose material with a single-core and core-shell structure, wherein the nano cellulose crystal (CNC) is used as a core, and the cellulose material is further used.
(4) Surface grafting of nano material
Firstly, weighing 2g of cellulose material with a single core-shell structure and taking nano cellulose crystal (CNC) as a core, adding the cellulose material into 20mL of deionized water, and uniformly stirring to obtain cellulose material dispersion liquid with a core-shell structure; secondly, weighing 0.2g of TEMPO (2, 6-tetramethyl piperidine-N-oxide), adding into 5mL of 10% sodium hydroxide aqueous solution by mass fraction, stirring for 2 hours at a rotating speed of 1000r/min, and adding the obtained solution into cellulose material dispersion liquid with a core-shell structure to obtain a mixed liquid I; 1g of triethylamine and 0.2g of silane coupling agent KH570 are weighed and added into 10mL of deionized water, and evenly stirred to obtain a mixed solution II, and then the mixed solution II is added into the mixed solution I; finally, 20g of 1H, 2H-perfluorododecanethiol is added, and stirring reaction is carried out for 24 hours at 80 ℃ and the rotating speed of 3000 r/min; and then filtering the obtained reaction liquid, washing the solid obtained by filtering by absolute ethyl alcohol, and freeze-drying for 12 hours at the temperature of minus 26 ℃ to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
The foam stabilizer prepared in this example was tested for foaming volume and half-life as follows:
the concentration of the foaming agent in the aqueous solution of the test sample is 5g/L, the foaming agent is sodium dodecyl sulfate, and the concentration of the foam stabilizer is 1g/L.
Foam volume and half-life of the foam stabilizer solution: the evaluation method of the foam stabilizer is tested according to the industry standard Waring Blender method for evaluating the foam stabilizer, and comprises the following specific steps: 200mL of water is placed in a slurry cup, 1g of sodium dodecyl sulfate as a foaming agent and 0.2g of foam stabilizer are added, the mixture is continuously stirred on a high-frequency high-speed stirrer at a stirring speed of 11000r/min for 5min, foam is immediately poured into a glass measuring cylinder after stirring is stopped, the reading is the foaming volume, timing is started, and the time for separating 100mL of liquid is half-life.
Foaming volume and half-life of solutions at different temperatures: the foam stabilizer solution was measured at room temperature (25 ℃) and four additional aqueous solutions containing 5g/L of the foaming agent and 1g/L of the foam stabilizer sample were each heated in a rolling oven at 50 ℃, 100 ℃, 150 ℃, 200 ℃ for 6 hours, and after 6 hours, the foam was rapidly poured into a glass measuring cylinder immediately after stopping stirring, the reading was the foaming volume, and the time was counted, and the time taken for separating 100mL of the liquid was the half-life period.
Foaming volume and half-life of solutions at different mineralization levels: respectively preparing mineralization degree (mineralization degree is expressed by mg/L or ppm, for example, one liter of water contains 1000 mg of salt, its mineralization degree is 1000 mg/L, i.e. 1000ppm; the solution is prepared by using simulated formation water, and the interior contains Na) + ，Ca 2+ ，Mg 2+ Plasma, wherein Na + ，Ca 2+ ，Mg 2+ The plasma being present in equal proportions, e.g. 1000 mg of salt in one liter of water, na + ，Ca 2+ ，Mg 2+ The plasma was 333.3 mg each. ) Is 1X 10 4 、3×10 4 、5×10 4 、7×10 4 9×10 4 200mL of each of the simulated formation water of ppm was added with 1g of sodium dodecyl sulfate as a foaming agent and 0.2g of a foam stabilizer, each was continuously stirred on a high-frequency high-speed stirrer at a stirring speed of 11000r/min for 5min, immediately after the stirring was stopped, the foam was rapidly poured into a glass measuring cylinder, the reading was the foaming volume, and the timing was started, and the time taken for separating 100mL of the liquid was half-life.
The foaming volume and half-life of the aqueous foaming agent solution (5 g/L) without added foam stabilizer were also tested for comparison.
The specific test results of the blowing agent solutions with and without the addition of the foam stabilizer of this example are shown in tables 1 and 2, and the test results of the blowing agent aqueous solutions without the addition of the foam stabilizer are shown in tables 3 and 4.
TABLE 1 foaming volume and half-life of foam stabilizer added foaming agent solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 401 | 156 |
| 50 | 396 | 154 |
| 100 | 378 | 150 |
| 150 | 353 | 148 |
| 200 | 321 | 140 |
TABLE 2 foaming volume and half-life of foam stabilizer-added foaming agent solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 394 | 152 |
| 3×10 4 | 385 | 150 |
| 5×10 4 | 361 | 147 |
| 7×10 4 | 338 | 143 |
| 9×10 4 | 305 | 135 |
TABLE 3 foaming volume and half-life of solutions without added foam stabilizer at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 457 | 20 |
| 50 | 426 | 17 |
| 100 | 212 | 14 |
| 150 | 153 | 2 |
| 200 | 0 | 0 |
TABLE 4 foaming volume and half-life of solutions without added foam stabilizer at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 437 | 20 |
| 3×10 4 | 419 | 17 |
| 5×10 4 | 187 | 13 |
| 7×10 4 | 129 | 5 |
| 9×10 4 | 58 | 1 |
Example 1 a biomass-based nanocellulose material with high specific surface area and high mechanical strength was first extracted from plants. And secondly, the organic resin material is coated on the biomass-based nanocellulose material, so that the temperature resistance of the biomass-based nanocellulose material is improved. Finally, the compound containing a plurality of perfluorinated carbon chains and thiol groups is grafted on the nanocellulose-based pickering particles, the carbon chains can effectively resist corrosive environments such as high temperature, strong acid, strong alkali and the like, and the thiol groups have good surface activity and corrosion resistance under the high temperature and high salinity environments. The half-life of the foaming agent solution is 156min at normal temperature (25 ℃) and 140min at high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the half life of the foam is 135min, and the obtained foam stabilizer has excellent temperature resistance and salt resistance. The half-life of the foaming agent solution without the foam stabilizer is 20min at normal temperature (25 ℃) and 0min at high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the half life of the foam is 1min, the capability of stabilizing the foam is greatly reduced, and the main reason for the phenomenon is that the surfactant is easy to lose activity under the high temperature condition under the background of the existence of the surfactant, and the capability of stabilizing the foam is sharply reduced; under high salt conditions, the foam is susceptible to losing its ability to stabilize under the influence of high salt.
Example 2
The preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid comprises the following steps:
(1) Extraction of cellulose
Step (1) was performed as in example 1.
(2) Preparation of nanocellulose Crystal (CNC)
Step (2) was performed as in example 1.
(3) Preparation of cellulose material with CNC (computerized numerical control) as core and single-core and core-shell structure
Step (3) was performed as in example 1.
(4) Preparing a cellulose material with a CNC (computer numerical control) core and polynuclear core-shell structure:
adding 5g of a cellulose material with a single-core and shell structure and taking nano cellulose crystals (CNC) as cores into 20g of ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate, adding 0.15g of dispersing agent sodium dodecyl sulfate, adding 0.05g of initiator dicumyl peroxide, stirring at 60 ℃ for reaction for 12 hours, and then vacuum drying the obtained reaction solution at 40 ℃ for 24 hours to obtain the cellulose material with a polynuclear and shell structure and taking nano cellulose crystals (CNC) as cores.
(5) Surface grafting of nano material
Firstly, weighing 2g of cellulose material with a polynuclear core-shell structure and taking nano cellulose crystal (CNC) as a core, adding the cellulose material into 20mL of deionized water, and uniformly stirring to obtain cellulose material dispersion liquid with the core-shell structure; secondly, weighing 0.2g of TEMPO (2, 6-tetramethyl piperidine-N-oxide), adding into 5mL of 10% sodium hydroxide aqueous solution by mass fraction, stirring for 2 hours at a rotating speed of 1000r/min, and adding the obtained solution into cellulose material dispersion liquid with a core-shell structure to obtain a mixed liquid I; 1g of triethylamine and 0.2g of silane coupling agent KH570 are weighed and added into 10mL of deionized water, and evenly stirred to obtain a mixed solution II, and then the mixed solution II is added into the mixed solution I; finally, 20g of 1H, 2H-perfluorododecanethiol is added, and stirring reaction is carried out for 24 hours at 80 ℃ and the rotating speed of 3000 r/min; and then filtering the obtained reaction liquid, washing the solid obtained by filtering by absolute ethyl alcohol, and freeze-drying for 12 hours at the temperature of minus 26 ℃ to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
The foam stabilizer prepared in this example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific test results are shown in tables 5 and 6.
TABLE 5 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 397 | 169 |
| 50 | 375 | 163 |
| 100 | 354 | 157 |
| 150 | 335 | 156 |
| 200 | 304 | 154 |
TABLE 6 foaming volume and half-life of solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 381 | 167 |
| 3×10 4 | 376 | 163 |
| 5×10 4 | 352 | 159 |
| 7×10 4 | 321 | 154 |
| 9×10 4 | 301 | 151 |
The foaming agent solution added with the foam stabilizer of the embodiment has a foaming volume of 397mL and a half-life of 169min at normal temperature (25 ℃), and has a foaming volume of 304mL and a half-life of 154min at high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the lather volume was 301mL and the half-life of the lather was 151min. The foam volume in this example was reduced compared to that in example 1, mainly due to the multi-core shell-knotThe structure has stronger interfacial bonding capability, resulting in a slight decrease in foaming capability. Compared with a single core-shell structure, the multi-core shell structure has the advantages that a plurality of cores can interact, so that the stability of the structure is improved, and therefore, the foam stabilizer has excellent temperature resistance and salt resistance, and the foam stabilizing capability is enhanced.
Example 3
The preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid comprises the following steps:
(1) Extraction of cellulose
Step (1) was performed as in example 1.
(2) Preparation of nanocellulose fibrils (CNF)
Firstly, 7g of sodium carbonate and 3g of sodium bicarbonate are weighed and dissolved in 500mL of deionized water to obtain Na 2 CO 3 -NaHCO 3 A buffer solution; next, 4g of sodium bromide and 0.2g of 2, 6-tetramethylpiperidine oxide were weighed and dissolved in Na 2 CO 3 -NaHCO 3 In a buffer solution, 10g of cellulose was then dispersed into the Na 2 CO 3 -NaHCO 3 Adding 5g of NaClO into the buffer solution under the stirring condition, stirring at room temperature for reacting for 5 hours, and regulating the pH of the system to be between 10 and 10.5 by using 0.1mol/L dilute hydrochloric acid solution and 0.1mol/L NaOH solution in the reaction process; after the reaction is finished, 200mL of absolute ethyl alcohol is added to terminate the reaction, then the reaction is kept stand for 12 hours, the supernatant is removed, the obtained solid is centrifugally washed to be neutral by deionized water, the supernatant is removed, 100mL of water is added to the obtained solid for ultrasonic treatment for 30 minutes, and then the obtained solid is centrifugally treated, and the obtained supernatant is freeze-dried for 12 hours at the temperature of minus 26 ℃ to obtain the nano cellulose fibrils (CNF).
(3) Preparation of cellulose material with CNF as core and single core-shell structure
Dispersing 5g of nanocellulose fibrils (CNF) in 50mL of water, and adjusting the pH value of the obtained nanocellulose fibril dispersion liquid to 7 by using 0.05mol/L sodium hydroxide solution; 50g of chloromethyl modified phenolic resin is dispersed in 500mL of dimethylbenzene, and is added into the nano cellulose fibril dispersion liquid after being uniformly stirred; adding 0.05g of dicumyl peroxide, and stirring at the rotating speed of 3000r/min for reaction for 24 hours; filtering, washing the solid product obtained by filtering with ethanol for 3 times; the solid product obtained by washing is redispersed in 250g of water, dispersed evenly by ultrasonic, and then freeze-dried (the temperature is-20 ℃ C., the time is 12 h), so as to obtain the cellulose material with a mononuclear core-shell structure, the nano cellulose fibril (CNF) of which is the core, for further use.
(4) Surface grafting of nano material
Firstly, weighing 2g of cellulose material with a single core and shell structure and taking nano cellulose fibrils (CNF) as cores, adding the cellulose material into 20mL of deionized water, and stirring the mixture uniformly to obtain cellulose material dispersion liquid with a core-shell structure; secondly, weighing 0.2g of TEMPO (2, 6-tetramethyl piperidine-N-oxide), adding into 5mL of 10% sodium hydroxide aqueous solution by mass fraction, stirring for 2 hours at a rotating speed of 1000r/min, and adding the obtained solution into cellulose material dispersion liquid with a core-shell structure to obtain a mixed liquid I; 1g of triethylamine and 0.2g of silane coupling agent KH570 are weighed and added into 10mL of deionized water, and evenly stirred to obtain a mixed solution II, and then the mixed solution II is added into the mixed solution I; finally, 20g of 1H, 2H-perfluorododecanethiol is added, and stirring reaction is carried out for 24 hours at 80 ℃ and the rotating speed of 3000 r/min; and then filtering the obtained reaction liquid, washing the solid obtained by filtering by absolute ethyl alcohol, and freeze-drying for 12 hours at the temperature of minus 26 ℃ to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
The foam stabilizer prepared in this example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific test results are shown in tables 7 and 8.
TABLE 7 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 381 | 187 |
| 50 | 362 | 177 |
| 100 | 346 | 174 |
| 150 | 324 | 169 |
| 200 | 295 | 163 |
TABLE 8 foaming volume and half-life of solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 372 | 185 |
| 3×10 4 | 365 | 176 |
| 5×10 4 | 334 | 171 |
| 7×10 4 | 314 | 168 |
| 9×10 4 | 292 | 161 |
The half-life of the foaming agent solution added with the foam stabilizer of the embodiment is 187min under the condition of normal temperature (25 ℃) and 163min under the condition of high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the half life of the foam was 161min. Compared with the CNC spherical structure of the multi-core shell, the CNC spherical structure of the multi-core shell has the advantages that the shape of the CNC core-shell structure is fibrous, more surface area can be provided at a gas/liquid interface, and the strength of an interface film is increased, so that the stability of foam is improved, and therefore, the foam stabilizer has excellent temperature resistance and salt resistance and stronger foam stabilizing capability.
Comparative example 1
A pick-up foam stabilizer was prepared as described in example 1, except that the organic resin material in step (3) was replaced with chloromethyl modified polystyrene resin.
The foam stabilizer prepared in this comparative example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific test results are shown in tables 9 and 10.
TABLE 9 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 378 | 142 |
| 50 | 371 | 139 |
| 100 | 352 | 138 |
| 150 | 331 | 132 |
| 200 | 315 | 127 |
TABLE 10 foaming volume and half-life of solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 372 | 136 |
| 3×10 4 | 363 | 133 |
| 5×10 4 | 345 | 130 |
| 7×10 4 | 321 | 123 |
| 9×10 4 | 307 | 120 |
Compared with example 1, the organic resin material of this comparative example was adjusted to chloromethyl modified polystyrene resin, the half-life of the solution was 142min at normal temperature (25 ℃) and 127min at high temperature (200 ℃). Mineralization degree of 9×10 4 At ppm, the half life of the foam was 120min. The ability to stabilize the foam in comparative example 1 was reduced compared to the half-life in example 1.
Comparative example 2
A method of preparing pickering stabilizers is described in example 1, except that: the grafting monomer in the step (4) is changed into 2-acrylamide-2-methylpropanesulfonic acid.
The foam stabilizer prepared in this comparative example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific test results are shown in tables 11 and 12.
TABLE 11 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 425 | 117 |
| 50 | 413 | 94 |
| 100 | 386 | 82 |
| 150 | 321 | 76 |
| 200 | 234 | 64 |
TABLE 12 foaming volume and half-life of solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 413 | 78 |
| 3×10 4 | 394 | 75 |
| 5×10 4 | 313 | 69 |
| 7×10 4 | 301 | 64 |
| 9×10 4 | 275 | 46 |
Compared with example 1, the grafting monomer in comparative example 2 is replaced by 2-acrylamide-2-methylpropanesulfonic acid, the half-life of the solution is 117min at normal temperature (25 ℃) and 64min at high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the half life of the foam was 46min. The ability to stabilize the foam in comparative example 1 was reduced compared to the half-life in example 1, which is dominantThe grafting monomer is replaced by 2-acrylamide-2-methylpropanesulfonic acid, so that the grafting monomer does not have perfluorinated carbon chains and mercaptan, and the foam stabilizing capacity is reduced; meanwhile, the foam has no high temperature resistance and salt resistance, so that the half life of the foam is greatly reduced under the high temperature condition and the high salt condition.
Comparative example 3
A method of preparing pickering stabilizers is described in example 1, except that: the alkali treatment concentration in the extraction of the cellulose in the step (1) is changed into 40% sodium hydroxide solution.
The foam stabilizer prepared in this comparative example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific test results are shown in tables 13 and 14.
TABLE 13 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 385 | 142 |
| 50 | 381 | 140 |
| 100 | 361 | 138 |
| 150 | 349 | 136 |
| 200 | 311 | 130 |
TABLE 14 foaming volume and half-life of solutions at different mineralizations
Compared with example 1, the sodium hydroxide concentration in comparative example 3 was adjusted to 40%, the half-life of the solution was 142min at normal temperature (25 ℃) and 130min at high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the half life of the foam was 128min. The main reason for this is that the foam stabilizing ability in comparative example 3 is slightly lowered compared to the half life in example 1, because the concentration of sodium hydroxide is too high, the crystalline structure of cellulose is changed, resulting in lowering of strength and temperature resistance, and lowering of foam stabilizing ability.
Comparative example 4
A method of preparing a pickering stabilizer is described in steps (3) - (4) of example 1, except that: cellulose is replaced by nanosilica (commercially available, between 2-20nm in diameter).
The foam stabilizer prepared in this comparative example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific results are shown in tables 15 and 16.
TABLE 15 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 405 | 79 |
| 50 | 401 | 76 |
| 100 | 381 | 73 |
| 150 | 369 | 70 |
| 200 | 331 | 63 |
TABLE 16 foaming volume and half-life of solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 402 | 76 |
| 3×10 4 | 391 | 75 |
| 5×10 4 | 377 | 67 |
| 7×10 4 | 349 | 64 |
| 9×10 4 | 323 | 60 |
Compared with example 1, the self-made nanocellulose in comparative example 4 was replaced with nanosilica, the half-life of the solution was 79min at normal temperature (25 ℃) and 63min at high temperature (200 ℃); mineralization degree of 9×10 4 At ppm, the half life of the foam was 60min. The main reason for this phenomenon, which is greatly reduced in the ability to stabilize the foam in comparative example 4 compared to the half-life in example 1, is that nanocellulose has a larger aspect ratio than nanosilica, which is more advantageous for the stabilization of the foam.
Comparative example 5
The preparation method of the pickering stabilizer is as in example 1, except that: and (3) adding no grafting modifier 1H, 2H-perfluoro dodecanethiol into the nano material in the step (4).
The foam stabilizer prepared in this comparative example was tested for foaming volume and half-life, the specific test method is shown in example 1, and the specific results are shown in tables 17 and 18.
TABLE 17 foaming volume and half-life of solutions at different temperatures
| Temperature/. Degree.C | Foaming volume/mL | Half life/min |
| 25 | 356 | 58 |
| 50 | 336 | 51 |
| 100 | 324 | 40 |
| 150 | 298 | 35 |
| 200 | 257 | 31 |
TABLE 18 foaming volume and half-life of solutions at different mineralizations
| Mineralization degree/ppm | Foaming volume/mL | Half life/min |
| 1×10 4 | 304 | 57 |
| 3×10 4 | 278 | 54 |
| 5×10 4 | 247 | 43 |
| 7×10 4 | 214 | 28 |
| 9×10 4 | 196 | 20 |
Compared with example 1, the half-life of the solution under the condition of normal temperature (25 ℃) is 58min and the half-life under the condition of high temperature (200 ℃) is 31min without adding the grafting modifier in the comparative example 5; mineralization degree of 9×10 4 At ppm, the half life of the foam was 20min. Compared with example 1 The half life period and the capability of stabilizing the foam in the comparative example 5 are obviously reduced, the main reason of the phenomenon is that the nano particles are not subjected to grafting modification, the particles show that the foam stabilizing capability is reduced due to the fact that the perfluoro carbon chains and the thiol groups do not contain temperature-resistant and salt-resistant perfluoro carbon chains, the hydrophobicity of the perfluoro carbon chains can effectively inhibit the cracking and fusion of the foam, the instability and degradation of the foam are prevented, the thiol groups can be used as surface active components, the interfacial property and the surface tension of the solution are effectively improved, a stable gas/liquid interface is formed, and the stability of the foam is enhanced; in the absence of both groups in nanocellulose, the interfacial particle stability is insufficient and the foam stability is reduced; and also does not have good foam stabilizing ability in high temperature, high salinity environments.
Claims (10)
1. The preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid comprises the following steps:
(1) Preparing a cellulose material with a core-shell structure by taking nano cellulose fibrils or nano cellulose crystals as cores and taking an organic resin material as a shell;
(2) Adding the catalyst A into a sodium hydroxide solution, uniformly stirring, and then adding a cellulose material aqueous dispersion liquid with a core-shell structure to obtain a mixed liquid I; adding the catalyst B and a silane coupling agent into water to obtain a mixed solution II; and adding the mixed solution II into the mixed solution I, and then adding a grafting monomer for reaction to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
2. The method for preparing the high-temperature-resistant and high-salt-resistant pick-up foam stabilizer for geothermal well drilling fluid according to claim 1, wherein the organic resin material in the step (1) is chloromethyl modified phenolic resin or polyphenyl methyl siloxane; the viscosity of the polyphenyl methyl siloxane at 25 ℃ is 50-500 mPa.s; the mass ratio of the nano cellulose fibrils or nano cellulose crystals to the organic resin material is 1:5-15.
3. The method for preparing the high-temperature-resistant and high-salt-resistant pick-up foam stabilizer for geothermal well drilling fluid according to claim 1, wherein the nanocellulose fibrils in the step (1) are prepared according to the following method:
weighing Na 2 CO 3 And NaHCO 3 Dissolving in deionized water to obtain Na 2 CO 3 -NaHCO 3 A buffer solution; dissolving sodium salt and oxidant into buffer solution, dispersing cellulose into the solution, adding NaClO under stirring, stirring at room temperature for reaction, and regulating pH value of the system to 10-10.5 during the reaction; after the reaction is finished, absolute ethyl alcohol is added to terminate the reaction; removing supernatant, centrifugally washing the obtained solid with deionized water to obtain neutral supernatant, removing supernatant, adding water into the obtained solid for ultrasonic treatment, centrifugally taking supernatant, and freeze-drying the obtained supernatant to obtain nanocellulose fibrils;
Preferably, the Na described in the preparation of nanocellulose fibrils 2 CO 3 And NaHCO 3 The mass ratio of (2) is 5-10:3; the Na is 2 CO 3 -NaHCO 3 Na in buffer solution 2 CO 3 The concentration of (2) is 0.1-0.2mol/L; the sodium salt is sodium bromide, sodium nitrate or sodium fluoride, and the mass ratio of the sodium salt to the cellulose is 0.2-0.5:1; the oxidant is 2, 6-tetramethyl piperidine oxide or 4-isopropoxy-piperidine, and the mass ratio of the oxidant to cellulose is 0.01-0.05:1; the mass and Na of the cellulose 2 CO 3 -NaHCO 3 The volume ratio of the buffer solution is 0.01-0.1 g/1 mL; the mass of NaClO is 30-70% of the mass of cellulose; the pH of the system is regulated to be 10-10.5 by using a dilute hydrochloric acid solution and a NaOH solution, wherein the concentration of the dilute hydrochloric acid solution is 0.1-0.5mol/L, and the concentration of the NaOH solution is 0.1-1mol/L;
preferably, the time of the reaction in the preparation of nanocellulose fibrils is 2-8 hours; the ratio of the added volume of the absolute ethyl alcohol to the mass of the cellulose is 10-30 mL/1 g; during ultrasonic treatment, the ratio of the volume of added water to the mass of cellulose is 10-50 mL/1 g; the ultrasonic treatment time is 30-60min; the freeze-drying temperature is-26 to-16 ℃, and the freeze-drying time is 10-24 hours.
4. The method for preparing the high-temperature-resistant and high-salt-resistant pick-up foam stabilizer for geothermal well drilling fluid according to claim 1, wherein the nanocellulose crystal in the step (1) is prepared according to the following method: adding cellulose into sulfuric acid solution for reaction; centrifuging the suspension obtained by the reaction, and centrifugally washing the obtained solid with water until the pH value of the supernatant is neutral; adding water into the obtained solid for ultrasonic treatment, centrifuging, and freeze-drying the obtained supernatant to obtain nanocellulose crystals;
Preferably, the mass fraction of the sulfuric acid solution is 50-64%; the mass ratio of the cellulose to the sulfuric acid solution is 1:10-20; the reaction temperature is 40-80 ℃ and the reaction time is 1-3h; during ultrasonic treatment, the ratio of the volume of added water to the mass of cellulose is 10-50 mL/1 g; the ultrasonic treatment time is 2-4 hours; the freeze-drying temperature is-26 to-16 ℃, and the freeze-drying time is 10-24 hours.
5. The method for preparing the high-temperature-resistant high-salt-resistant pick-up foam stabilizer for geothermal well drilling fluid according to claim 3 or 4, wherein the cellulose is extracted from plants, and the plants are corn stalks or wood; the cellulose is extracted according to the following method: firstly, crushing corn stalk or wood into plant powder with 20-100 meshes, washing with water, and drying at 30-80 ℃ for 36-72h; adding the dried plant powder into alkali solution for treatment, filtering, washing the obtained solid with water until the filtrate is neutral, and drying at 30-80 ℃ for 36-72h to obtain alkali-treated raw materials; dispersing the alkali-treated raw materials in water to obtain a dispersion liquid with the concentration of 0.05-0.3g/mL, heating to 60-100 ℃, adding an acid solution and a bleaching agent every 1-2h for extraction, filtering, washing the obtained solid with deionized water until the filtrate is neutral, washing with acetone, and drying at 40-80 ℃ until the weight is constant to obtain cellulose;
Preferably, the alkali solution is sodium hydroxide solution with the mass fraction of 5-20%; the ratio of the volume of the alkaline solution to the mass of the plant powder is 10-50 mL/1 g; the temperature of the treatment by using the alkali solution is 60-100 ℃, and the treatment time by using the alkali solution is 1-3h; the acid solution is one of glacial acetic acid, 37% hydrochloric acid solution and 68% nitric acid solution, and the mass ratio of each added acid solution to the alkali-treated raw material is 0.1-1:1; the bleaching agent is one of sulfur dioxide, sodium chlorite and sulfur; the mass ratio of the bleaching agent added each time to the alkali-treated raw material is 0.1-1:1; the extraction time is 3-6h.
6. The preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid according to claim 1, wherein the cellulose material of the core-shell structure taking nano cellulose filaments as cores in the step (1) is of a single-core structure, and the preparation method is characterized in that the cellulose material is prepared according to the following steps:
adjusting the pH value of the nano cellulose fibril aqueous dispersion to 5-8, adding the dimethylbenzene dispersion of the organic resin material, adding an initiator I, and stirring for reaction; after the reaction is finished, filtering, washing, ultrasonic dispersing and freeze drying are carried out to obtain the cellulose material with a core-shell structure taking nano cellulose filaments as cores;
Preferably, the concentration of the nanocellulose fibril aqueous dispersion is 0.05-0.5g/mL; adjusting the pH of the aqueous dispersion of nanocellulose fibrils using 0.05mol/L sodium hydroxide solution; the concentration of the xylene dispersion liquid of the organic resin material is 0.05-0.25g/mL; the initiator I is benzoyl peroxide or dicumyl peroxide; the mass of the initiator I is 0.5-3% of the mass of the nano cellulose fibrils; the stirring speed is 2000-5000r/min, and the stirring reaction time is 12-36h; the washing is to use ethanol for 3-5 times; the ultrasonic dispersion is to add the solid obtained by washing into water, and the ultrasonic dispersion is uniform to obtain suspension, wherein the ratio of the added mass of the water to the mass of the nano cellulose fibrils is 40-60:1; the freeze-drying temperature is-26 to-16 ℃, and the freeze-drying time is 10-24 hours.
7. The method for preparing the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid according to claim 1, wherein the cellulose material of the core-shell structure taking the nanocellulose crystal as the core in the step (1) is of a single-core structure or a multi-core structure;
the cellulose material with a mononuclear core-shell structure and taking nano cellulose crystals as cores is prepared by the following method:
Adjusting the pH value of the nano cellulose crystal aqueous dispersion to 5-8, adding the dimethylbenzene dispersion of the organic resin material, adding an initiator II, stirring uniformly, and carrying out standing reaction; after the reaction is finished, filtering, washing, ultrasonic dispersing and freeze drying are carried out to obtain the cellulose material with a mononuclear core-shell structure taking nano cellulose crystals as cores;
preferably, the concentration of the nano cellulose crystal aqueous dispersion liquid is 0.01-0.1g/mL; adjusting the pH of the aqueous dispersion of nanocellulose crystals by using 0.05mol/L sodium hydroxide solution; the concentration of the xylene dispersion liquid of the organic resin material is 0.05-0.25g/mL; the initiator II is benzoyl peroxide or dicumyl peroxide, and the mass of the initiator II is 0.5-3% of the mass of the nano cellulose crystal; the stirring speed is 2000-5000r/min, and the standing reaction time is 12-36h; the washing is to use ethanol for 3-5 times; the ultrasonic dispersion is to add the solid obtained by washing into water, and the ultrasonic dispersion is uniform to obtain suspension, wherein the ratio of the added mass of the water to the mass of the nano cellulose crystal is 40-60:1; the freeze drying is carried out for 12-36h at the temperature of minus 26 to minus 16 ℃.
8. The preparation method of the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid according to claim 7, wherein the cellulose material with a polynuclear core-shell structure taking nano cellulose crystals as cores is prepared by the following method:
(a) Adjusting the pH value of the nano cellulose crystal aqueous dispersion to 5-8, adding the dimethylbenzene dispersion of the organic resin material, adding an initiator III, stirring uniformly, and carrying out standing reaction; after the reaction is finished, filtering, washing, ultrasonic dispersing and freeze drying are carried out to obtain the cellulose material with a mononuclear core-shell structure; preferably, the concentration of the nano cellulose crystal aqueous dispersion liquid is 0.01-0.1g/mL; adjusting the pH of the aqueous dispersion of nanocellulose crystals by using 0.05mol/L sodium hydroxide solution; the concentration of the xylene dispersion liquid of the organic resin material is 0.05-0.25g/mL; the initiator III is benzoyl peroxide or dicumyl peroxide, and the mass of the initiator III is 0.5-3% of the mass of the nano cellulose crystal; the stirring speed is 2000-5000r/min, and the standing reaction time is 12-36h; the washing is to use ethanol for 3-5 times; the ultrasonic dispersion is to add the solid obtained by washing into water, and the ultrasonic dispersion is uniform to obtain suspension, wherein the ratio of the added mass of the water to the mass of the nano cellulose crystal is 40-60:1; the freeze drying is carried out for 12-36h at the temperature of minus 26 to minus 16 ℃;
(b) Adding the cellulose material with the mononuclear core-shell structure obtained in the step (a) into ionic liquid, adding a dispersing agent and an initiator IV, and stirring for reaction to obtain a reaction liquid; then vacuum drying the reaction liquid to obtain a multi-core-shell structured cellulose material taking nano cellulose crystals as cores; preferably, the ionic liquid is one of 1-butyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole trifluoromethane sulfonate, and the mass ratio of the ionic liquid to the cellulose material with a mononuclear core-shell structure is 3-8:1; the dispersing agent is sodium dodecyl sulfate, polyethylene glycol 200 or polyethylene glycol 400, and the mass of the dispersing agent is 2-5% of the mass of the cellulose material with a mononuclear core-shell structure; the initiator IV is benzoyl peroxide or dicumyl peroxide, and the initiator IV is 0.5-3% of the mass of the cellulose material with a mononuclear core-shell structure; the reaction temperature is 60-90 ℃, and the reaction time is 10-15h; the temperature of the vacuum drying is 40-60 ℃, and the time of the vacuum drying is 12-36h.
9. The method for preparing the high-temperature-resistant and high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid according to claim 1, wherein the catalyst A in the step (2) is 2, 6-tetramethylpiperidine-N-oxide, ammonia water or potassium hydroxide; the mass ratio of the catalyst A to the cellulose material with the core-shell structure is 0.05-0.5:1;
The mass fraction of the sodium hydroxide solution is 5-15%; the ratio of the volume of the sodium hydroxide solution to the mass of the cellulose material of the core-shell structure is 1-5 mL/1 g;
the concentration of the cellulose material aqueous dispersion liquid with the core-shell structure is 0.01-0.2g/mL, preferably 0.1-0.15g/mL;
the catalyst B is one of triethylamine, nickel oxide and sodium molybdate; the mass ratio of the catalyst B to the cellulose material with the core-shell structure is 0.3-0.8:1; the concentration of the catalyst B in the mixed solution II is 0.05-0.15g/mL;
the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or vinyl triethoxy silane; the mass ratio of the silane coupling agent to the cellulose material with the core-shell structure is 0.05-0.3:1;
the grafting monomer is 1H, 2H-perfluorododecanethiol or 1H, 2H-perfluorodecyl thiol; the mass ratio of the grafting monomer to the cellulose material of the core-shell structure is 5-20:1;
the temperature of the reaction is 70-90 ℃; the reaction time is 12-36h;
the reaction also comprises a post-treatment step, which is specifically as follows: filtering the obtained reaction liquid, washing the solid obtained by filtering by absolute ethyl alcohol, and then freeze-drying at the temperature of minus 26 ℃ to minus 16 ℃ for 12-36 hours to obtain the high-temperature-resistant high-salt-resistant Pickering foam stabilizer for the geothermal well drilling fluid.
10. The high-temperature-resistant high-salt-resistant Pickering foam stabilizer for geothermal well drilling fluid is characterized by being prepared by the preparation method of claim 1.
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