CN118126690A - Carbon nano tube plugging agent, preparation method and application thereof, and well control fluid - Google Patents
Carbon nano tube plugging agent, preparation method and application thereof, and well control fluid Download PDFInfo
- Publication number
- CN118126690A CN118126690A CN202410555819.8A CN202410555819A CN118126690A CN 118126690 A CN118126690 A CN 118126690A CN 202410555819 A CN202410555819 A CN 202410555819A CN 118126690 A CN118126690 A CN 118126690A
- Authority
- CN
- China
- Prior art keywords
- plugging agent
- silicon dioxide
- modified
- amino
- plugging
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012530 fluid Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 89
- 239000002041 carbon nanotube Substances 0.000 title claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 239000002981 blocking agent Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 145
- 239000005543 nano-size silicon particle Substances 0.000 claims description 67
- 235000012239 silicon dioxide Nutrition 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 125000004169 (C1-C6) alkyl group Chemical class 0.000 claims description 20
- 239000012267 brine Substances 0.000 claims description 19
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 19
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical group [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 6
- 239000004280 Sodium formate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 5
- 235000019254 sodium formate Nutrition 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 5
- -1 1-methylamino-2, 3-dihydroxynaphthalene Chemical compound 0.000 description 80
- 238000003756 stirring Methods 0.000 description 43
- 239000007788 liquid Substances 0.000 description 32
- 229910052739 hydrogen Inorganic materials 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000011435 rock Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- RHHDMTSHWRREPK-UHFFFAOYSA-N 1,2-dimethoxynaphthalene Chemical compound C1=CC=CC2=C(OC)C(OC)=CC=C21 RHHDMTSHWRREPK-UHFFFAOYSA-N 0.000 description 11
- XZZRGEPWNYCNGI-UHFFFAOYSA-N 1-bromo-2,3-dimethoxynaphthalene Chemical compound C1=CC=C2C(Br)=C(OC)C(OC)=CC2=C1 XZZRGEPWNYCNGI-UHFFFAOYSA-N 0.000 description 11
- 230000000903 blocking effect Effects 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 9
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 230000033444 hydroxylation Effects 0.000 description 7
- 238000005805 hydroxylation reaction Methods 0.000 description 7
- 239000012280 lithium aluminium hydride Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 229940103091 potassium benzoate Drugs 0.000 description 3
- 235000010235 potassium benzoate Nutrition 0.000 description 3
- 239000004300 potassium benzoate Substances 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- ZHVPTERSBUMMHK-UHFFFAOYSA-N 3-aminonaphthalen-2-ol Chemical compound C1=CC=C2C=C(O)C(N)=CC2=C1 ZHVPTERSBUMMHK-UHFFFAOYSA-N 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical group [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/5045—Compositions based on water or polar solvents containing inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/487—Fluid loss control additives; Additives for reducing or preventing circulation loss
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of oil gas development, and discloses a plugging agent, a preparation method and application thereof. The blocking agent has molecular aggregate hydrodynamic particle size D 10=13.4-15μm,D50=87.5-88.3μm,D90 =207-215 μm in a solvent with density of 1.1-1.3g/mL, and adsorption force of 0.6-0.7mN. The plugging agent has good plugging property for heterogeneous reservoir cores with coexisting nanoscale and microscale apertures, can reduce the filtration loss of well killing fluid in the reservoir, and reduces the damage of the well killing fluid to the reservoir.
Description
Technical Field
The invention relates to the technical field of oil gas development, in particular to a carbon nano tube plugging agent and a preparation method and application thereof. In addition, the invention also relates to a well control fluid containing the carbon nano tube plugging agent.
Background
The permeability of the tight oil and gas reservoir is less than or equal to 0.1mD, the pore throat and the microcrack are unevenly distributed, and the size range is from a few nanometers to hundreds of micrometers. In the development of oil and gas, the main component of the well control fluid used in the completion stage is water and some chemicals, with specific consistency, viscosity and density, which are injected into the well to create a certain pressure to prevent formation gas, oil or water from being ejected from the well uncontrollably. If the plugging effect is not ideal, the plugging is not timely, more liquid enters into the stratum cracks easily, the structural force of the well wall is weakened, the problem of instability of the well wall mechanics is caused, and the problem is caused by the fact that the plugging performance of the well killing liquid is insufficient to a great extent. For a well section in a reservoir with uneven pore gap distribution of a tight oil and gas reservoir, if a conventional micron-level or nano-level plugging agent is adopted to prepare well control fluid, the micron-level plugging agent cannot quickly and effectively plug very small nano-level crack pores due to mismatching of the particle size and shape of the plugging agent with the pore gaps, and cannot efficiently plug relatively large-size micro-level pores; in addition, the conventional rigid plugging agent has unsatisfactory plugging effect due to insufficient adsorption capacity on the well wall. The reasons can finally lead to larger filter loss of the well control fluid in the reservoir, and the reservoir protection effect is poor.
Aiming at the problem that the conventional nano plugging agent can not simultaneously plug the nano-scale and micro-scale coexisting heterogeneous pore, a great deal of research on novel plugging materials is carried out by students at home and abroad, but the current public literature still has no specific product report, and the corresponding brine well control liquid research is not carried out. Development of new products of nanometer plugging agents with strong adsorptivity is needed to develop, so that brine well control liquid with strong plugging property is formed, and the reservoir protection requirement in the development process of tight oil and gas reservoirs is met.
Disclosure of Invention
The invention aims to solve the problem that a conventional nano plugging agent in the prior art cannot simultaneously plug heterogeneous pores and slits coexisting in nano-scale and micron-scale, and provides a carbon nano tube plugging agent, a preparation method and application thereof and a well control fluid. The plugging agent has good plugging performance on heterogeneous reservoir cores with coexisting nanoscale and microscale apertures, has good plugging effect when being applied to brine well control liquid, can reduce the filtration loss of the well control liquid in the reservoir, and reduces the damage of the well control liquid to the reservoir.
In order to achieve the above object, the first aspect of the present invention provides a carbon nanotube plugging agent having a molecular aggregate hydrodynamic particle size D 10=13.4-15μm,D50=87.5-88.3μm,D90 =207 to 215 μm in a solvent having a density of 1.1 to 1.3g/mL and an adsorption force of 0.6 to 0.7mN.
The second aspect of the present invention provides a method for preparing a carbon nanotube plugging agent, the method comprising: under the condition of a dehydrating agent, carrying out a contact reaction I on modified nano silicon dioxide and an aminated carbon nano tube, wherein the modified nano silicon dioxide comprises hydroxylated nano silicon dioxide and a modification group A modified on the hydroxylated nano silicon dioxide, and the structure of the modification group A is shown as a formula (I);
Formula (I) wherein R 1 is absent or C1-C6 alkylene, I is a natural number from 0 to 4, j is a natural number from 0 to 2, R a and R b are each independently hydroxy-substituted C1-C6 alkyl, amino-substituted C1-C6 alkyl, hydroxy or amino.
The third aspect of the present invention provides a carbon nanotube plugging agent prepared by the preparation method provided by the second method.
According to a fourth aspect of the present invention, there is provided the use of a carbon nanotube plugging agent according to the first aspect or a plugging agent according to the third aspect in a brine well control fluid.
In a fifth aspect, the present invention provides a well control fluid, where the well control fluid contains the carbon nanotube plugging agent according to the first aspect or the carbon nanotube plugging agent according to the third aspect, and further contains water and formate.
Through the technical scheme, the plugging agent provided by the invention has molecular aggregate hydrodynamic particle size D 10=13.4-14.6μm,D50=87.5-88.3μm,D90 =207-215 mu m in a solvent with density of 1.1-1.3g/mL and adsorption force of 0.6-0.7mN, so that the plugging agent has better plugging property on heterogeneous reservoir cores coexisting with nanoscale and microscale apertures, and has better plugging effect when being applied to brine well control fluid. When the method is applied to well control liquid, the well control liquid can be adsorbed and gathered on the outer wall of the inlet of the rock aperture to form a plugging layer along with injection of the well control liquid, a better filtration reducing effect is achieved in a reservoir, and damage of the well control liquid to the reservoir can be reduced.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 1-methylamino-2, 3-dihydroxynaphthalene prepared in preparation example 1-1;
FIG. 2 is an infrared spectrum of 1-methylamino-2, 3-dihydroxynaphthalene prepared in preparation example 1-1;
FIG. 3 is an infrared spectrum of the modified carbon nanotube prepared in preparation example 3-1;
FIG. 4 is a 10 μm scanning electron microscope image of the blocking agent prepared in example 1-1;
FIG. 5 is a graph of the energy spectrum at the red mark in FIG. 3;
FIG. 6 is a graph of energy spectra at the green mark in FIG. 3;
FIG. 7 is a 20 μm scanning electron microscope image of the blocking agent prepared in example 1-1;
FIG. 8 is a graph of energy spectra at the marker of FIG. 7;
FIG. 9 is a 50 μm scanning electron microscope image of the blocking agent prepared in example 1-1;
FIG. 10 is a graph of energy spectra at the label of FIG. 9;
FIG. 11 is a pictorial view of a processed rock laminate;
FIG. 12 is a graphical representation of a completed fluid from example 2-1 after testing of a completed rock formation.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a carbon nanotube plugging agent having a molecular aggregate hydrodynamic particle size D 10=13.4-15μm,D50=87.5-88.3μm,D90 =207 to 215 μm in a solvent having a density of 1.1 to 1.3g/mL, and having an adsorption force of 0.6 to 0.7mN.
Specifically, D 10 may be specifically 13.4 μm, 13.6 μm, 13.8 μm, 14 μm, 14.2 μm, 14.4 μm, 14.6 μm, 14.8 μm, 15 μm, or any value between any two of the above values; d 50 may be, in particular, 87.5 μm, 87.7 μm, 87.9 μm, 88.1 μm, 88.3 μm, or any value between any two of the above values; d 90 may be specifically 207 μm, 209 μm, 211 μm, 213 μm, 215 μm, or any value between any two of the above values; the blocking agent may specifically have an adsorption force of 0.6mN, 0.62mN, 0.64mN, 0.66mN, 0.68mN, 0.7mN, or any value between any two of the above values.
In the invention, the hydrodynamic particle size of a molecular aggregate refers to the apparent diameter of the molecular aggregate formed by aggregation of modified nano silicon dioxide in an aqueous solution, and the testing method comprises the following steps: wet testing is carried out by adopting a Fritsch 22 type laser particle size analyzer and referring to a liquid medium dispersion and measurement method in a particle size analysis laser diffraction method of standard GB/T19077-2016; d 10、D50 and D 90 represent particle sizes corresponding to the cumulative particle size distribution numbers of the samples reaching 10%, 50% and 90%, respectively (the percentages of all particle sizes before or after the particle size are manually added); its physical meaning means that the number of particles having a particle size smaller than the particle size is 10%, 50% and 90% of the number of all particles.
In the invention, the method for testing the adsorption force comprises the following steps: 5. Mu.l of the sample was dropped onto a glass slide (available from Santa Classification Co., ltd., product model 7101) at room temperature (25.+ -. 5 ℃ C.), and the maximum action weight (in mg) at the time of peeling the sample from the glass slide was measured by using a K100 type mechanical tensiometer, and the data of the maximum action weight test was multiplied by the gravitational acceleration of 9.80665N/kg (m/s 2), to obtain the result of the adsorption force.
The inventor finds that the molecular aggregate hydrodynamic particle size D 10=13.4-14.6μm,D50=87.5-88.3μm,D90 = 207-215 mu m and the adsorption force of 0.6-0.7mN of the plugging agent in a solvent with the density of 1.1-1.3g/mL have better plugging property on heterogeneous reservoir cores coexisting with nanoscale and microscale pore gaps, and still have better plugging effect in application to brine well control fluid in the research process. When the method is applied to well control liquid, the well control liquid can be adsorbed and gathered on the outer wall of the inlet of the rock aperture to form a plugging layer along with injection of the well control liquid, a better filtration reducing effect is achieved in a reservoir, and damage of the well control liquid to the reservoir can be reduced.
Preferably, the nano plugging agent contains modified carbon nanotubes, wherein the modified carbon nanotubes comprise aminated carbon nanotubes and modified nano silicon dioxide loaded on the aminated carbon nanotubes, and the modified nano silicon dioxide comprises nano silicon dioxide particles and naphthalene ring structures modified on the nano silicon dioxide particles. Through interaction among three structures of the aminated carbon nanotube, the nano silicon dioxide and the naphthalene ring structure, the plugging agent has relatively proper molecular aggregate hydrodynamic particle size and adsorption capacity, has relatively good plugging performance for heterogeneous reservoir cores coexisting with nanoscale and microscale pores, can be adsorbed and gathered on the outer wall of an inlet of the rock pores along with injection of the well killing liquid to form a plugging layer, plays a role in reducing the filter loss of the well killing liquid in the reservoir, and reduces damage of the well killing liquid to the reservoir.
According to the present invention, the naphthalene ring structure is attached to the nanosilicon dioxide by chemical bonds.
The naphthalene ring structure can be connected with the nano silicon dioxide by any feasible chemical bond, preferably, the nano blocking agent contains a modified carbon nano tube, the modified carbon nano tube comprises an aminated carbon nano tube and modified nano silicon dioxide loaded on the aminated carbon nano tube, the modified nano silicon dioxide comprises nano silicon dioxide particles and a modification group A modified on the nano silicon dioxide particles, the structure of the modification group A is shown as a formula (I),
Formula (I).
According to the invention, the modifying group A and the nanosilica are linked via-O-and-R 1 -NH-.
The inventor surprisingly found in the research process that by modifying the modified nano silicon dioxide with the modification group A shown in the formula (I) on the aminated carbon nano tube, the plugging agent has better plugging property against heterogeneous reservoir cores coexisting with microscale pores through interaction among three structures, and can be adsorbed and accumulated on the outer wall of an inlet of the rock pores along with injection of the well killing liquid to form a plugging layer, so that the effect of reducing the filtration loss of the well killing liquid in the reservoir is achieved, and the damage of the well killing liquid to the reservoir is further reduced.
According to the present invention, in the above structure, the attachment position of each group is not located, meaning that the group may be attached to any one of the attachable positions of the benzene ring structure. -O-and-R 1 -NH-may be ortho-substituents or non-ortho-substituents, preferably ortho-substituents, R b and-O-, R 1 -NH-are attached to the same benzene ring structure and R a is attached to another benzene ring structure.
Preferably, R 1 is absent or is a C1-C6 alkylene group, i is a natural number from 0 to 4, specifically may be 0, 1,2,3, 4,j is a natural number from 0 to 2, specifically may be 0, 1,2, R a and R b are each independently a hydroxy-substituted C1-C6 alkyl group, an amino-substituted C1-C6 alkyl group, a hydroxy group or an amino group. By the above limitation, the blocking performance of the blocking agent can be further improved. From the viewpoint of further improving the blocking performance of the blocking agent, it is further preferable that R 1 is absent or C1-C2 alkylene, i is 0, j is a natural number of 0 to 1, and R b is amino-substituted C1-C4 alkyl or hydroxy.
According to the invention, the C1-C6 alkyl group may be a straight-chain alkyl group without branching, such as methyl, ethyl, propyl, butyl, pentyl, hexyl; it may also be a branched linear alkyl group such as isopropyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, etc. Branched alkyl groups which are free of branching are preferred.
Amino-substituted C1-C6 alkyl refers to a group obtained by amino substitution of at least one hydrogen on a C1-C6 alkyl, and hydroxy-substituted C1-C6 alkyl refers to a group obtained by hydroxy substitution of at least one hydrogen on a C1-C6 alkyl; amino groups in the amino-substituted C1-C6 alkyl groups can replace hydrogen on carbon at the terminal position of the alkyl groups, can replace hydrogen on carbon at other positions, can also replace hydrogen on carbon at the terminal position of the alkyl groups and hydrogen on carbon at other positions at the same time, and are preferably replaced by hydrogen on carbon at the terminal position of the alkyl groups; the hydroxyl group in the hydroxyl-substituted C1-C6 alkyl group may be substituted for the hydrogen on the terminal carbon of the alkyl group, may be substituted for the hydrogen on the other terminal carbon, may be substituted for both the hydrogen on the terminal carbon of the alkyl group and the hydrogen on the other terminal carbon, and is preferably substituted for the hydrogen on the terminal carbon of the alkyl group.
When R 1 is absent, the naphthalene ring structure and the secondary amino group are directly linked, and the C1-C6 methylene group may be methylene, ethylene, propylene, butylene, isopentylene, hexylene, 1-methylethylene, 1-methylpropylene, 1-methylbutylene, 1-methylpentylene, 1-ethylmethylene, or the like.
As a specific embodiment of the invention, R 1 is methylene, j is 0 or 1, and R b is hydroxy. The inventor finds that the modified carbon nano tube with the structure has better plugging effect as a plugging agent in the research process.
That is, the structural formula of the modifying group is shown as formula (II) or formula (III).
Formula (II)/(Formula (III).
Preferably, the mass ratio of the aminated carbon nano tube, the nano silicon dioxide particles and the modifying group A is 0.015-0.04:1:0.6-1. Under the above conditions, the plugging agent has better plugging performance.
Preferably, the particle size of the nano silicon dioxide in the modified nano silicon dioxide is 3-20nm, the diameter of the carbon nano tube in the modified carbon nano tube is 8-15nm, and the length is less than or equal to 50 mu m. The plugging agent obtained under the conditions has better plugging performance.
The second aspect of the present invention provides a method for preparing a carbon nanotube plugging agent, the method comprising: in the presence of dehydration, carrying out a contact reaction I on modified nano silicon dioxide and an aminated carbon nano tube, wherein the modified nano silicon dioxide comprises hydroxylated nano silicon dioxide and a modification group A modified on the hydroxylated nano silicon dioxide, and the structure of the modification group A is shown as a formula (I);
Formula (I) wherein R 1 is absent or C1-C6 alkylene, I is a natural number from 0 to 4, j is a natural number from 0 to 2, R a and R b are each independently hydroxy-substituted C1-C6 alkyl, amino-substituted C1-C6 alkyl, hydroxy or amino.
According to the invention, the dehydrating agent used for dehydration may be a sulfuric acid solution having a concentration of 90-98%. The aminated carbon nanotubes are commercially available or can be prepared by existing methods. The aminated carbon nanotubes employed in the examples of the present invention are commercially available.
According to the invention, in the actual use process, the product of the contact reaction I can be separated and purified to obtain the modified carbon nano tube; the product of the contact reaction I can also be directly separated without purification to obtain a composition of the modified carbon nano tube, the aminated carbon nano tube and the modified silicon dioxide. The separation may be carried out by solid-liquid separation techniques conventional in the art, such as filtration, centrifugation, etc. The manner of purifying the modified carbon nanotubes may be any feasible manner. Preferably, in the actual use process, the product of the contact reaction I is not subjected to purification treatment, the performance of the obtained plugging agent is not affected, the production cost can be greatly reduced, and the production steps are simplified.
By the method, the nano silicon dioxide modified by the modification group A can be loaded on the aminated carbon nano tube, so that the prepared plugging agent has good plugging property for heterogeneous reservoir cores with coexisting nanoscale and microscale pores, and can reduce the fluid loss of well killing fluid in the reservoir and reduce the damage of the well killing fluid to the reservoir.
Preferably, the conditions of the contact reaction I include: the temperature is 70-90deg.C, specifically 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, or any value between the two values; the time is 18-30h, and can be specifically 18h, 20h, 22h, 24h, 26h, 28h, 30h, or any value between the two values. The plugging agent prepared under the reaction conditions has better plugging performance.
Preferably, the mass ratio of the modified nano silicon dioxide to the aminated carbon nano tube is 50-100:1, and can be specifically 50:1, 60:1, 70:1, 80:1, 90:1 or any value between the two values. The inventor finds that the mass ratio of the reaction raw materials is controlled within the range in the research process, so that the prepared plugging agent has better plugging performance, and meanwhile, the production cost can be ensured.
Preferably, the diameter of the aminated carbon nano tube is 8-15nm, the length is less than or equal to 50 mu m, and the amino content is 0.4-0.5 mass%. The plugging agent prepared from the aminated carbon nanotubes under the above conditions has better plugging performance.
The modified nanosilica may be prepared in any feasible manner. In order to further improve the blocking performance of the prepared blocking agent, preferably, the preparation method of the modified nano-silica comprises the following steps: and (3) carrying out a contact reaction II on the hydroxylated nano silicon dioxide and the amino hydroxynaphthalene in the presence of a solvent.
According to the invention, the solution may be water. The hydroxylated nano silicon dioxide can be obtained commercially or by preparation. As a specific embodiment of the present invention, the method for preparing the hydroxylated modified nano silicon dioxide comprises: and (3) carrying out a contact reaction III on the nano silicon dioxide and concentrated sulfuric acid.
Preferably, the conditions of the contact reaction III include: the temperature is 120-150deg.C, specifically 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, or any value between the two values; the time is 10-12h, and can be specifically 10h, 10.5h, 11h, 11.5h, 12h, or any value between the two values.
Preferably, the mass of the nano-silica is 0.08-0.12g relative to 1mL of concentrated sulfuric acid.
Preferably, the particle size of the nano silicon dioxide is 3-20nm, and the specific surface area is 350-410m 2/g.
Preferably, the conditions of the contact reaction II include a temperature of 40-80 ℃, specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, or any value between the two values; the time is 4-6h, and can be specifically 4h, 4.5h, 5h, 5.5h, 6h, or any value between the two values. Under the reaction conditions, the hydroxylated nano silicon dioxide and the amino hydroxynaphthalene have better reaction effect, so that the prepared plugging agent has better plugging performance.
Preferably, the mass ratio of the hydroxylated nano silicon dioxide to the amino hydroxynaphthalene is 1:0.6-1, and specifically can be 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, or any value between any two values of the above. The inventor finds that the mass ratio of the nano silicon dioxide modified by hydroxylation to the amino hydroxynaphthalene is controlled within the range in the research process, so that the reaction raw materials have better reaction effect, and the plugging effect of the plugging agent prepared later is improved.
According to the invention, the structural formula of the amino hydroxynaphthalene is shown as a formula (IV),
Formula (IV).
Preferably, R 1 is absent or is C1-C6 alkylene, i is a natural number from 0 to 4, j is a natural number from 0 to 2, R a and R b are each independently hydroxy-substituted C1-C6 alkyl, amino-substituted C1-C6 alkyl, hydroxy or amino. The modification group A is limited to the structure, so that the plugging performance of the prepared plugging agent can be further improved. From the viewpoint of being able to further improve the blocking performance of the blocking agent produced, it is further preferred that R 1 is absent or C1-C2 alkylene, i is 0, j is a natural number of 0 to 1, and R b is an amino-substituted C1-C6 alkyl group or hydroxyl group. More preferably, R 1 is methylene, j is 1 and R b is hydroxy.
According to the invention, the C1-C6 alkyl group may be a straight-chain alkyl group without branching, such as methyl, ethyl, propyl, butyl, pentyl, hexyl; it may also be a branched linear alkyl group such as isopropyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, etc. Branched alkyl groups which are free of branching are preferred.
Amino-substituted C1-C6 alkyl refers to a group obtained by amino substitution of at least one hydrogen on a C1-C6 alkyl, and hydroxy-substituted C1-C6 alkyl refers to a group obtained by hydroxy substitution of at least one hydrogen on a C1-C6 alkyl; amino groups in the amino-substituted C1-C6 alkyl groups can replace hydrogen on carbon at the terminal position of the alkyl groups, can replace hydrogen on carbon at other positions, can also replace hydrogen on carbon at the terminal position of the alkyl groups and hydrogen on carbon at other positions at the same time, and are preferably replaced by hydrogen on carbon at the terminal position of the alkyl groups; the hydroxyl group in the hydroxyl-substituted C1-C6 alkyl group may be substituted for the hydrogen on the terminal carbon of the alkyl group, may be substituted for the hydrogen on the other terminal carbon, may be substituted for both the hydrogen on the terminal carbon of the alkyl group and the hydrogen on the other terminal carbon, and is preferably substituted for the hydrogen on the terminal carbon of the alkyl group.
When R 1 is absent, the direct connection between the naphthalene ring structure and the secondary amino group may be methylene, ethylene, propylene, butylene, isopentylene, hexylene, 1-methylpolylene, 1-methylethylene, 1-methylpropylene, 1-methylbutylene, 1-methylpentylene, 1-ethylmethylene, and the like.
As a relatively preferred embodiment of the present invention, the amino hydroxynaphthalene is methylamino dihydroxynaphthalene.
According to the invention, the amino hydroxynaphthalene may be obtained commercially or may be prepared. Preferably, the preparation method of the amino hydroxynaphthalene comprises the following steps: under the hydrolysis condition, alkylamide dihydroxy naphthalene and alkali are mixed for reaction.
The base is preferably sodium hydroxide and/or potassium hydroxide.
Preferably, the conditions of the hydrolysis conditions include: the temperature is 60-80deg.C, specifically 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, or any value between the two values; the time is 10-12h, and can be specifically 10h, 10.5h, 11h, 11.5h, 12h, or any value between the two values.
Preferably, the mass ratio of the alkylamide dihydroxy naphthalene to the base is 2-4:1.
According to the invention, the alkylamido dihydroxy naphthalenes are commercially available or can be prepared. Preferably, the preparation method of the alkylamide dihydroxy naphthalene comprises the following steps: and (3) carrying out a contact reaction IV on alkylamide dimethoxy naphthalene and alkyl lithium.
Preferably, the alkyl lithium is a C1-C6 alkyl lithium, more preferably butyl lithium, and even more preferably n-butyl lithium.
Preferably, the molar ratio of the alkylamidodimethoxynaphthalene to the alkyllithium is 1:1.5-3.
Preferably, the contact reaction IV of the alkyl lithium and the alkylamidodimethoxynaphthalene is carried out in an organic solvent I. The conditions for the contact reaction IV include: the temperature is 0-5 ℃ and the time is 1-3h. The organic solvent I is chloroform.
The alkylamidodimethoxynaphthalene may be commercially available or may be prepared in any of the available ways. Preferably, the preparation method of the alkylamide dimethoxy naphthalene comprises the following steps: in the presence of an organic solvent II, carrying out a contact reaction V on alkylamino dimethoxy naphthalene and formic acid.
Preferably, the organic solvent II is ethanol, and the conditions of the contact reaction V include: the temperature is 50-70 ℃ and the time is 2-3h.
Preferably, the molar ratio of the alkylamino dimethoxy naphthalene to the formic acid is 1:2-4.
The alkylamino dimethoxy naphthalene may be obtained commercially or may be prepared in any feasible manner, and preferably, the preparation method of the alkylamino dimethoxy naphthalene comprises: in the presence of an organic solvent III, carrying out a contact reaction VI on the alkyl nitrile dimethoxy naphthalene and a reducing agent.
Preferably, the organic solvent III is diethyl ether, the reducing agent is lithium aluminum tetrahydroide, and the conditions of the contact reaction VI include: the temperature is 20-40 ℃ and the time is 2-5h.
Preferably, the molar ratio of the alkyl nitrile dimethoxy naphthalene to the reducing agent is 1:2.5-3.5.
The alkylnitrile dimethoxy naphthalene may be obtained commercially or may be prepared in any feasible manner, and preferably, the preparation method of the alkylnitrile dimethoxy naphthalene includes: in the presence of an organic solvent IV, halogenated dimethoxy naphthalene and copper cyanide are subjected to a contact reaction VII.
Preferably, the organic solvent IV is N-methyl pyrrolidone, and the halogenated dimethoxy naphthalene is bromodimethoxy naphthalene. The conditions for the contact reaction VII include: the temperature is 180-200 ℃ and the time is 7-9h.
Preferably, the molar ratio of the halogenated dimethoxy naphthalene to the copper cyanide is 1:1-1.2.
The third method of the present invention provides a plugging agent prepared by the above preparation method, and the plugging agent has all the advantages of the above preparation method, and is not described herein.
According to a fourth aspect of the present invention there is provided a plugging agent as provided in the first aspect or the use of a plugging agent as provided in the third aspect in a brine kill fluid. Can effectively improve the adsorption force of the brine well killing liquid and has better plugging effect. In a fifth aspect, the present invention provides a well control fluid, which comprises the plugging agent according to the first aspect or the plugging agent according to the third aspect, and further comprises water and formate.
The well control fluid provided by the invention has all the advantages of the plugging agent and the preparation method, and is not described in detail herein.
Preferably, the molecular aggregate hydrodynamic particle size D 10 = 13.4-15 μm of the plugging agent in the well control fluid, which may specifically be 13.4 μm, 13.6 μm, 13.8 μm, 14 μm, 14.2 μm, 14.4 μm, 14.6 μm, 14.8 μm, 15 μm, or any value in between; d 50 =87.5-88.3 μm, which may be 87.5 μm, 87.7 μm, 87.9 μm, 88.1 μm, 88.3 μm, or any value between the two values; d 90 =207-215 μm, which may specifically be 207 μm, 209 μm, 211 μm, 213 μm, 215 μm, or any value between the two values; the absorption force of the well killing liquid is 0.6-0.7mN, specifically can be 0.6mN, 0.62mN, 0.64mN, 0.66mN, 0.68mN, 0.7mN or any value between the two values. The inventor finds that the well killing liquid has better plugging performance on heterogeneous reservoir cores with coexisting nanoscale and microscale pores and gaps.
Preferably, the plugging rate of the well control fluid is 90% or more, and more preferably 90 to 96%.
Preferably, the blocking agent is present in an amount of 0.1 to 0.3g and the formate is present in an amount of 15 to 220g relative to 100mL of water. The well control liquid under the conditions has better plugging effect and higher adsorption force and plugging performance.
Preferably, the formate is potassium formate and/or sodium formate.
According to a particularly preferred embodiment of the present invention, there is provided a method for preparing a plugging agent comprising:
S1 preparation of methylamino dihydroxynaphthalene:
S1-1, in the presence of N-methyl pyrrolidone, reacting halogenated dimethoxy naphthalene and lithium aluminum hydride for 7-9 hours at the temperature of 180-200 ℃ according to the mol ratio of 1:1-1.2 to obtain carbonitrile dimethoxy naphthalene;
S1-2, in the presence of diethyl ether, reacting formonitrile dimethoxy naphthalene and copper cyanide for 2-5 hours at the temperature of 20-40 ℃ according to the mol ratio of 1:2-3 to obtain methylamino dimethoxy naphthalene;
S1-3, in the presence of ethanol, reacting formic acid and methylamino dimethoxy naphthalene at a molar ratio of 1:2-4 for 2-3 hours at a temperature of 50-70 ℃ to obtain formamido dimethoxy naphthalene;
S1-4, in the presence of anhydrous chloroform, reacting alkyl lithium and formamido dimethoxy naphthalene in a molar ratio of 1:1.5-3 at a temperature of 0-5 ℃ for 1-3 hours to obtain formamido dihydroxy naphthalene;
s1-5, reacting formamido dihydroxynaphthalene, alkali and water at the temperature of 60-80 ℃ for 2-4 hours to obtain methylamino dihydroxynaphthalene;
preparation of hydroxylated nanosilica: reacting nano silicon dioxide with 70-980wt% concentrated sulfuric acid at 120-150 ℃ for 10-12h to obtain hydroxylated nano silicon dioxide;
S2, reacting the hydroxylated nano silicon dioxide and methylamino dihydroxy naphthalene in water for 4-6 hours (the temperature is 40-80 ℃), so as to obtain multifunctional nano silicon dioxide (methylamino dihydroxy naphthalene modified nano silicon dioxide);
s3, reacting the multifunctional nano silicon dioxide and the aminated carbon nano tube in the mass ratio of 10:0.1-0.2 in 98wt% concentrated sulfuric acid at 70-90 ℃ for 18-30h, neutralizing with sodium hydroxide to pH=7, continuing stirring, and cooling to normal temperature to obtain the plugging agent.
The plugging agent prepared by the method has good plugging performance on heterogeneous reservoir cores coexisting with nanoscale and microscale pores, can be adsorbed and gathered on the outer wall of an inlet of the rock pores along with injection of the well control fluid to form a plugging layer, plays a role in reducing the filtration loss of the well control fluid in the reservoir, and reduces the damage of the well control fluid to the reservoir. The adsorption force of the aqueous potassium benzoate solution is increased by 48.78-60.97% compared with the adsorption force of the aqueous potassium benzoate solution with the same density when the aqueous potassium benzoate solution is used in well control fluid.
The present invention will be described in detail by examples. The nano silicon dioxide is purchased from Jiangsu Xianfeng nano material technology Co., ltd, the grain diameter is 3-20nm, the specific surface area is 350-410m 2·g-1, and the apparent density is 30-60g/L; the aminated carbon nano tube is purchased from Jiangsu Xianfeng nano material technology Co., ltd, has the diameter of 8-15nm, the length of less than or equal to 50 mu m, the amino content of 0.45 weight percent and the specific surface area of more than 60m 2·g-1; 1-bromo-2, 3-dimethoxynaphthalene was purchased from Shanghai Kaijin chemical Co., ltd (CAS number: 222555-02-4), and the remaining reagents were obtained by commercial purchase.
In the following examples, the molecular aggregate hydrodynamic diameter was tested as follows: wet testing was performed using a Fritsch 22 laser particle size analyzer, with reference to the liquid medium dispersion and measurement method in the standard GB/T19077-2016 "particle size analysis laser diffraction method".
The adsorption force is tested by adopting a K100 type mechanical tensiometer, and the specific steps of the test at room temperature (25+/-5 ℃) are as follows: ① Opening an instrument and software, and selecting an adsorption force test operation unit; ② The adhesion fitting was fixed to the balance lock and 5 μl of sample was added using a pipette; ③ Placing the glass slide on an experiment table, pressing an OK key, testing the adhesion strength of a liquid drop product and the glass slide, and measuring the maximum action weight (in mg) when the sample and the glass slide are peeled off; ④ After the test, the result of the adsorption force was obtained by multiplying the test data (maximum action weight) by the gravitational acceleration of 9.80665N/kg (m/s 2).
PREPARATION EXAMPLE 1-1
(1) 25ML of N-methylpyrrolidone was added to the flask, 2.67g of 1-bromo-2, 3-dimethoxynaphthalene and 0.64g of copper cyanide (the molar ratio of 1-bromo-2, 3-dimethoxynaphthalene to copper cyanide: 1:1.1) were added with stirring, and the mixture was heated to 190℃to react for 8 hours to obtain 1-carbonitrile-2, 3-dimethoxynaphthalene; the reaction equation is as follows:
；
(2) 50mL of diethyl ether was added to the beaker, 2.13g of 1-carbonitrile-2, 3-dimethoxynaphthalene and 0.95g of lithium aluminum hydride (the molar ratio of 1-carbonitrile-2, 3-dimethoxynaphthalene to lithium aluminum hydride is 1:2.5) were added under stirring, and the mixture was reacted at 20℃for 5 hours to give 1-methylamino-2, 3-dimethoxynaphthalene; the reaction equation is as follows:
；
(3) Adding 50mL of ethanol into a beaker, adding 0.92g of formic acid under stirring, adding 2.17g of 1-methylamino-2, 3-dimethoxy naphthalene (the molar ratio of 1-methylamino-2, 3-dimethoxy naphthalene to formic acid is 1:2) after stirring uniformly, and reacting for 2 hours at 50 ℃ to generate 1-formamido-2, 3-dimethoxy naphthalene; the reaction equation is as follows:
；
(4) 50mL of anhydrous chloroform is added into a beaker, the solution is cooled to 0 ℃ by an ice water bath, 0.96g of n-butyllithium is slowly added, after the n-butyllithium is completely dispersed, 2.43g of 1-formamido-2, 3-dimethoxy naphthalene (the mol ratio of the 1-formamido-2, 3-dimethoxy naphthalene to the n-butyllithium is 1:1.5) is added, and the solution is kept at 0 ℃ for 3 hours to react to generate 1-formamido-2, 3-dihydroxy naphthalene; the reaction equation is as follows:
；
(5) 2.15g of 1-formamido-2, 3-dimethoxy naphthalene and 0.5g of sodium hydroxide are hydrolyzed in 50mL of water at 60 ℃ for 2 hours, and the reaction product is recrystallized by ethanol to obtain 1-methylamino-2, 3-dihydroxy naphthalene; the reaction equation is as follows:
；
subjecting the recrystallized product to nuclear magnetic resonance (oxford PULSAR HFC, uk) (see fig. 1) and infrared (shimadzu corporation IRPRESTIGE-21) spectral characterization analysis (see fig. 2);
In FIG. 1, 5 absorption peaks.delta.5.38 ppm correspond to-CH 2 -in the 1-methylamino-2, 3-dihydroxynaphthalene molecule, 6.90ppm correspond to-NH 2 -in the 1-methylamino-2, 3-dihydroxynaphthalene molecule, 7.3ppm and 7.8ppm correspond to naphthalene rings in the 1-methylamino-2, 3-dihydroxynaphthalene molecule, and 8.73ppm correspond to-OH in the 1-methylamino-2, 3-dihydroxynaphthalene molecule. As can be seen from FIG. 1, 1-bromo-2, 3-dimethoxynaphthalene is taken as an original raw material, and a target product 1-methylamino-2, 3-dihydroxynaphthalene can be obtained through multi-step reaction.
As shown in FIG. 2, the telescopic vibration absorption peak of the-OH hydroxyl group at 3670cm -1, the characteristic double absorption peak of the-NH 2 functional group at 3370cm -1、3460cm-1, the bending vibration absorption peak of the naphthalene ring carbon hydrogen bond at 2070cm -1, the telescopic vibration absorption peak of the naphthalene ring at 1640cm -1, and the shear vibration absorption peak of the-CH 2 -at 1460cm -1 are shown. As can be seen from FIG. 2, the target product 1-methylamino-2, 3-dihydroxynaphthalene can be obtained by taking 1-bromo-2, 3-dimethoxynaphthalene as an original raw material and performing multi-step reaction.
The above figures 1 and 2 both demonstrate that 1-methylamino-2, 3-dihydroxynaphthalene can be synthesized by a multi-step reaction using 1-bromo-2, 3-dimethoxynaphthalene as a starting material.
PREPARATION EXAMPLES 1-2
(1) 20ML of N-methylpyrrolidone was added to the flask, 2.67g of 1-bromo-2, 3-dimethoxynaphthalene and 0.69g of copper cyanide (the molar ratio of 1-bromo-2, 3-dimethoxynaphthalene to copper cyanide was 1:1.2) were added thereto with stirring, and the mixture was heated to 180℃to react for 7 hours to obtain 1-carbonitrile-2, 3-dimethoxynaphthalene;
(2) 50mL of diethyl ether is added into a beaker, 2.13g of 1-carbonitrile-2, 3-dimethoxy naphthalene and 1.14g of lithium aluminum hydride (the mol ratio of the 1-carbonitrile-2, 3-dimethoxy naphthalene to the lithium aluminum hydride is 1:3) are added under stirring, and the mixture is reacted for 4 hours at the temperature of 30 ℃ to obtain 1-methylamino-2, 3-dimethoxy naphthalene;
(3) 50mL of ethanol is added into a beaker, 1.38g of formic acid is added under the stirring state, after the stirring is uniform, 2.17g of 1-methylamino-2, 3-dimethoxy naphthalene (the mol ratio of 1-methylamino-2, 3-dimethoxy naphthalene to formic acid is 1:3) is added, the stirring is continued, and the reaction is carried out for 2.5 hours at 60 ℃ to generate 1-formamido-2, 3-dimethoxy naphthalene;
(4) 50mL of anhydrous chloroform is added into a beaker, the solution is cooled to 2 ℃ by an ice water bath, 1.28g of n-butyllithium is slowly added, after the n-butyllithium is completely dispersed, 2.43g of 1-formamido-2, 3-dimethoxy naphthalene (the mol ratio of the 1-formamido-2, 3-dimethoxy naphthalene to the n-butyllithium is 1:2) is added, and the solution is kept at 2 ℃ for 2 hours to react to generate 1-formamido-2, 3-dihydroxy naphthalene;
(5) 2.15g of 1-carboxamide-2, 3-dimethoxynaphthalene and 0.8g of sodium hydroxide were hydrolyzed in 50mL of water at 70℃for 3 hours, and the reaction product was recrystallized from ethanol to give 1-methylamino-2, 3-dihydroxynaphthalene.
Preparation examples 1 to 3
(1) 18ML of N-methylpyrrolidone was added to the flask, 2.67g of 1-bromo-2, 3-dimethoxynaphthalene and 0.58g of copper cyanide (the molar ratio of 1-bromo-2, 3-dimethoxynaphthalene to copper cyanide: 1:1) were added with stirring, and the mixture was heated to 200℃to react for 9 hours to obtain 1-carbonitrile-2, 3-dimethoxynaphthalene;
(2) 50mL of diethyl ether was added to the beaker, 2.13g of 1-carbonitrile-2, 3-dimethoxynaphthalene and 1.33g of lithium aluminum hydride (the molar ratio of 1-carbonitrile-2, 3-dimethoxynaphthalene to lithium aluminum hydride is 1:3.5) were added under stirring, and the mixture was reacted at 40℃for 2 hours to obtain 1-methylamino-2, 3-dimethoxynaphthalene;
(3) 50mL of ethanol is added into a beaker, 1.52g of formic acid is added under the stirring state, after the stirring is uniform, 2.17g of 1-methylamino-2, 3-dimethoxy naphthalene (the mol ratio of 1-methylamino-2, 3-dimethoxy naphthalene to formic acid is 1:4) is added, the stirring is continued, and the reaction is carried out for 3 hours at 70 ℃ to generate 1-formamido-2, 3-dimethoxy naphthalene;
(4) 50mL of anhydrous chloroform is added into a beaker, the solution is cooled to 5 ℃ by ice water bath, 1.92g of n-butyllithium is slowly added, after the n-butyllithium is completely dispersed, 2.43g of 1-formamido-2, 3-dimethoxy naphthalene (the mol ratio of 1-formamido-2, 3-dimethoxy naphthalene to n-butyllithium is 1:3) is added, and the solution is kept at 5 ℃ for reaction for 1 hour to generate 1-formamido-2, 3-dihydroxy naphthalene;
(5) 2.15g of 1-carboxamide-2, 3-dimethoxynaphthalene and 1g of potassium hydroxide were hydrolyzed in 50mL of water at 80℃for 4 hours, and the reaction product was recrystallized from ethanol to give 1-methylamino-2, 3-dihydroxynaphthalene.
PREPARATION EXAMPLE 2-1
1G of nano silicon dioxide is reacted in 100mL of 98wt% concentrated sulfuric acid for 10 hours at 120 ℃ for hydroxylation modification, and nano silicon dioxide # 1 modified by hydroxylation is obtained. The reaction schematic equation is as follows:
；
the number of hydroxyl groups modified on the nano silicon dioxide is not the actual number, and is only schematic.
PREPARATION EXAMPLE 2-2
10G of nano silicon dioxide is reacted in 100mL of 70wt% concentrated sulfuric acid for 12 hours at 130 ℃ for hydroxylation modification, and nano silicon dioxide # 2 modified by hydroxylation is obtained.
PREPARATION EXAMPLES 2-3
5G of nano silicon dioxide is reacted in 100mL of 85wt% concentrated sulfuric acid for 10 hours at 150 ℃ for hydroxylation modification, and the nano silicon dioxide 3# with hydroxylation modification is obtained.
PREPARATION EXAMPLE 3-1
10G of the hydroxylated modified silicon dioxide 1# prepared in preparation example 2-1 and 6g of the 1-methylamino-2, 3-dihydroxynaphthalene prepared in preparation example 1-1 are reacted in 50mL of water at 40 ℃ for 6h to obtain multifunctional nano silicon dioxide A. The reaction schematic equation is as follows:
Among them, since it is difficult to measure the exact amount of hydroxyl groups on the surface of the nanosilica and the amount of 1-methylamino-2, 3-dihydroxynaphthalene reacted therewith, the number of hydroxyl groups on the surface of the nanosilica in the reaction formula and the amount of 1-methylamino-2, 3-dihydroxynaphthalene reacted therewith are not actual numbers, and thus are only schematically illustrated.
The product is purified by filtration, washing, crystallization and the like, and the obtained pure product is subjected to infrared spectrum characterization analysis (see figure 3).
Comparing FIG. 3 with FIG. 2, it can be seen that, compared with the infrared spectrum of 1-methylamino-2, 3-dihydroxynaphthalene, the original double absorption peak of amino group is changed into a single absorption peak of secondary amino group at -1 cm from 3390cm, si-O-C absorption peak appears at -1 cm 3240cm, symmetrical and asymmetrical telescopic absorption peaks of Si-O-C appear at 1341cm -1、1025cm-1, and the absorption peaks of other functional groups are basically unchanged. The above results show that when the hydroxylated nano silicon dioxide and 1-methylamino-2, 3-dihydroxynaphthalene are subjected to grafting reaction under the reaction conditions set by the invention, new functional groups can be generated.
PREPARATION EXAMPLE 3-2
10G of the hydroxylated modified silicon dioxide 2# prepared in preparation example 2-2 and 8g of the 1-methylamino-2, 3-dihydroxynaphthalene prepared in preparation example 1-2 are reacted in 50mL of water at 60 ℃ for 5 hours to obtain multifunctional nano silicon dioxide B.
PREPARATION EXAMPLES 3-3
10G of the hydroxylated modified silicon dioxide 3# prepared in preparation examples 2 to 3 and 10g of the 1-methylamino-2, 3-dihydroxynaphthalene prepared in preparation examples 1 to 3 are reacted in 50mL of water at 80 ℃ for 4 hours to obtain multifunctional nano silicon dioxide C.
PREPARATION EXAMPLES 3 to 4
10G of the hydroxylated modified silicon dioxide 2# was reacted with 6.7g of 3-amino-2-hydroxynaphthalene (CAS number: 5417-63-0) in 50mL of water at 60℃for 5 hours to give multifunctional nanosilica D.
Example 1-1
10G of multifunctional nano silicon dioxide A and 0.1g of aminated carbon nano tube are reacted for 24 hours at 80 ℃ in 10mL of 98% concentrated sulfuric acid, the product is neutralized to pH=7 by sodium hydroxide, stirring is continued, and the temperature is reduced to normal temperature, so as to obtain the plugging agent No. 1. The reaction schematic equation is as follows:
The scanning electron microscope (FEI COMPANY Quanta) prepared in this example is shown in fig. 4, 7 and 9, fig. 7 and 9 are enlarged views of different magnifications of fig. 5, the energy spectrum analysis is shown in fig. 5, 6, 8 and 10, fig. 5 is the energy spectrum of the red mark portion of fig. 4, fig. 6 is the energy spectrum of the green mark portion of fig. 4, fig. 8 is the energy spectrum of the mark portion of fig. 7, fig. 10 is the energy spectrum of the mark portion of fig. 9, it can be seen from fig. 4, 7 and 9 that the carbon nanotubes have micro particles thereon, and the energy spectrum analysis is performed on the carbon nanotubes, and the positions are found to contain C, H, O and Si elements at the same time, which indicates that the modified nano silica is loaded on the carbon nanotubes.
Examples 1 to 2
10G of multifunctional nano silicon dioxide B and 0.125g of aminated carbon nano tube are reacted for 30 hours at 70 ℃ in 10mL of 98% concentrated sulfuric acid, the product is neutralized to pH=7 by sodium hydroxide, stirring is continued, and the temperature is reduced to normal temperature, so as to obtain plugging agent No. 2.
Examples 1 to 3
10G of multifunctional nano silicon dioxide C and 0.2g of aminated carbon nano tube are reacted for 18 hours at 90 ℃ in 10mL of 98% concentrated sulfuric acid, the product is neutralized to pH=7 by sodium hydroxide, stirring is continued, and the temperature is reduced to normal temperature, so as to obtain the plugging agent 3#.
Examples 1 to 4
10G of multifunctional nano silicon dioxide D and 0.125g of aminated carbon nano tube are reacted for 30 hours at 70 ℃ in 10mL of 98% concentrated sulfuric acid, the product is neutralized to pH=7 by sodium hydroxide, stirring is continued, and the temperature is reduced to normal temperature, so as to obtain plugging agent No. 4.
Example 2-1
Taking proper clear water, adding 19.9wt% of potassium formate (with the density of 1.1 g/mL) based on 100% of water by mass ratio, completely dissolving under stirring, and adding 0.3wt% of plugging agent 1# to stir uniformly to obtain brine well control fluid 1#.
Example 2-2
Taking proper clear water, adding 46.1wt% of potassium formate (with the density of 1.2 g/mL) based on 100% of water by mass ratio, completely dissolving under stirring, and adding 0.2wt% of plugging agent 2# to stir uniformly to obtain brine well control liquid 2#.
Examples 2 to 3
Taking proper clear water, adding 75.5wt% sodium formate (with the density of 1.3 g/mL) into the clear water according to the mass ratio of 100%, completely dissolving the clear water under the stirring condition, and adding 0.1wt% plugging agent 3# into the clear water, and uniformly stirring the clear water to obtain the brine well control fluid 3#.
Examples 2 to 4
Taking proper clear water, adding 46.1wt% of potassium formate (with the density of 1.2 g/mL) based on 100% of water by mass ratio, completely dissolving under stirring, and adding 0.2wt% of plugging agent 4# to stir uniformly to obtain brine well control fluid 4#.
Examples 2 to 5
Taking proper clear water, adding 29.9wt% of potassium formate (with the density of 1.15 g/mL) based on 100% of water by mass ratio, completely dissolving under stirring, and adding 0.3wt% of plugging agent 1# to stir uniformly to obtain brine well control liquid 5#.
Examples 2 to 6
Taking proper clear water, adding 57.9wt% sodium formate (density is 1.25 g/mL) based on 100% of water mass ratio, completely dissolving under stirring, adding 0.1wt% plugging agent 3# and uniformly stirring to obtain brine well control fluid 6#.
Comparative example 2-1
Taking a proper amount of clear water, adding 19.9wt% of potassium formate (with the density of 1.1 g/mL) based on 100% of the mass of the water, and completely dissolving under the stirring condition to obtain the comparison completion fluid 1.
Comparative examples 2 to 2
Taking a proper amount of clear water, adding 46.1wt% of potassium formate (with the density of 1.2 g/mL) based on 100% of the mass of the water, and completely dissolving under the stirring condition to obtain the comparison completion fluid 2.
Comparative examples 2 to 3
Taking a proper amount of clear water, adding 46.1wt% of potassium formate (the density is 1.2 g/mL) based on 100% of the mass of the water, completely dissolving under the stirring condition, and then adding 0.2wt% of nano silicon dioxide, and uniformly stirring to obtain the comparison completion fluid 3.
Comparative examples 2 to 4
Taking a proper amount of clear water, adding 46.1wt% of potassium formate (with the density of 1.2 g/mL) based on 100% of the mass of the water, completely dissolving under the stirring condition, and then adding 0.2wt% of multifunctional nano silicon dioxide B, and uniformly stirring to obtain a comparison completion fluid 4.
Comparative examples 2 to 5
Taking a proper amount of clear water, adding 46.1wt% of potassium formate (with the density of 1.2 g/mL) based on 100% of the mass of the water, completely dissolving under the stirring condition, and then adding 0.2wt% of the aminated carbon nano tube, and uniformly stirring to obtain the comparison completion fluid 5.
Comparative examples 2 to 6
Taking a proper amount of clear water, adding 46.1wt% of potassium formate (the density is 1.2 g/mL) based on 100% of the mass of the water, completely dissolving under the stirring condition, adding 0.2wt% of multifunctional nano silicon dioxide B, adding 0.2wt% of amino carbon nano tubes, and uniformly stirring to obtain a comparison completion fluid 6.
Comparative examples 2 to 7
Taking a proper amount of clear water, adding 75.5wt% of sodium formate (the density is 1.3 g/mL) based on 100% of the mass of the water, completely dissolving under the stirring condition, and then adding 0.3wt% of the aminated carbon nano tube, and uniformly stirring to obtain the comparison completion fluid 7.
Test example 1-1 molecular aggregate hydrodynamic particle size test
The hydrodynamic particle size of the molecular aggregate refers to the apparent particle size of the molecular aggregate formed by aggregation of the blocking agent in formate solutions of different densities, and the test method is as follows: wet testing was performed using a Fritsch 22 laser particle size analyzer, with reference to the liquid medium dispersion and measurement method in the standard GB/T19077-2016 "particle size analysis laser diffraction method", the data obtained from the test being recorded in table 1; d10, D50 and D90 represent the particle sizes corresponding to the cumulative particle size distribution numbers of the samples reaching 10%, 50% and 90%, respectively (the percentages of all the particle sizes before or after the particle size are manually added); its physical meaning means that the number of particles having a particle size smaller than the particle size is 10%, 50% and 90% of the number of all particles.
Test example 2 adsorption force test
A5. Mu.l sample of completion fluid was dropped onto the slide glass at room temperature (25.+ -. 5 ℃ C.), and the maximum action weight (in mg) at the time of peeling the sample from the slide glass was measured by a K100 type mechanical tensiometer, and the maximum action weight test data was multiplied by the gravitational acceleration of 9.80665N/kg (m/s 2) to obtain the adsorption force result, which is shown in Table 1.
Test example 3 blocking Rate test
The method comprises the steps of adopting a natural rock plate (permeability is 0.001mD-1mD, aperture size is 0.01-200 mu m) with the same compact reservoir rock core to process a fixed size, placing the natural rock plate on a sample cylinder bottom plate of a GGS71-B high-temperature high-pressure filtration instrument, adding a sealing ring to complete sealing, connecting a pipeline with a nitrogen steel cylinder and the high-temperature high-pressure filtration instrument, opening a pressurizing valve to enable the pressure in the sample cylinder of the high-temperature high-pressure filtration instrument to be 10MPa, completing a sealing test by observing the pressure drop condition of a pressure gauge, and enabling the high-temperature high-pressure filtration instrument to have good sealing performance if no pressure drop exists. And placing a completion fluid sample (with the volume of V1) in the sample cylinder at the temperature of 25 ℃, pressurizing to 10MPa, opening a pressure relief valve at the bottom of the sample cylinder, collecting the sample filtrate, and closing the pressure relief valve when the sample filtrate sample volume is 10min, wherein the sample filtrate sample volume is V 2.
The plugging rate is calculated as shown in the formula (2):
Φ=,%
phi-the blocking rate,%;
V 1 -sample volume, mL;
V 2 -filtrate volume, mL.
The test results are shown in Table 1.
Taking the completion fluid prepared in the example 2-1 as an example, the natural rock plate is shown in fig. 11 before testing, and the rock plate is shown in fig. 12 after testing, which illustrates that the completion fluid provided by the invention can form a compact plugging layer on the surface of the rock plate.
TABLE 1 sample and sample Performance test results
As can be seen from Table 1, the aqueous solutions of potassium formate salt of comparative examples 2-1 and 2 were free of solid phase substances and had hydrodynamic diameters of 0. Mu.m; in comparative examples 2 to 3, the adsorption force was only 0.41mN due to the presence of unmodified nanosilicon dioxide, which had a certain self-aggregation effect in potassium formate brine, and the large-size aggregate was smaller, and D 90 was only 35.48 μm; in the comparative examples 2 to 4, the adsorption force is improved due to the presence of the functionalized nano silicon dioxide containing strong adsorption groups in the potassium formate brine, the self-aggregation effect is strong in the potassium formate brine, and the aggregate size is larger than that of the comparative example 2; the aminated carbon nanotubes containing the amino group with strong adsorption groups in comparative examples 2-4 and 2-7 have strong self-aggregation in formate water, and the aggregate size is larger than that of comparative examples 2-3; in comparative examples 2-6, there was a simple mixed functionalized nano silica and aminated carbon nanotube, and since more strongly adsorbed groups amino and hydroxyl were contained, the adsorption force was further increased to 0.56mN, the self-aggregation in potassium formate brine was stronger, the aggregate size was larger, and D 90 reached 132.74 μm. In comparative examples 2-1 to 2-3, the blocking agent of the sphere/tube structure was generated by the chemical reaction of the functionalized nano-silica and the aminated carbon nanotube, the adsorption force was further improved to 0.61-0.66mN by the interaction between the two structures, the aggregate hydrodynamic diameter was significantly wider and larger than the aggregate distribution of comparative example, and aggregates above 200 μm were present.
Thus, the above examples, due to the different aggregate sizes, bring about a change in the blocking rate performance. The formate water of comparative example 2-1 and comparative example 2-2 had no blocking ability, and the blocking ratio was 0. The aggregates of comparative examples 2-3, comparative examples 2-4, comparative examples 2-5 and comparative examples 2-7 become large, have a certain blocking capacity, and the blocking rate is only 5% -20%; comparative examples 2-6 contained simply mixed functionalized nano-silica and aminated carbon nanotubes, and the plugging adaptability was stronger, and the plugging rate was increased to 58%. In comparative examples 2-1 to 2-3, the nano plugging agent forms a uniformly distributed ball/tube structure in the saline solution due to chemical modification, the aggregate size distribution is 0.01-214.58 μm, the adsorption force is strong, and a plugging layer is easily and rapidly formed at a hole seam in the fluid loss process (see figure 12), so that the plugging capability is greatly improved, the plugging rate is more than or equal to 90%, and the plugging agent fully meets the fluid loss requirement of well control fluid in the well completion process of a tight reservoir.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A carbon nanotube plugging agent, characterized in that the plugging agent has a molecular aggregate hydrodynamic particle size D 10=13.4-15μm,D50=87.5-88.3μm,D90 = 207-215.3 μm and an adsorption force of 0.6-0.7mN in a solvent having a density of 1.1-1.3 g/mL.
2. The plugging agent according to claim 1, wherein the plugging agent contains modified carbon nanotubes, wherein the modified carbon nanotubes comprise aminated carbon nanotubes and modified nanosilica supported on the aminated carbon nanotubes, the modified nanosilica comprises nanosilica particles and modifying groups A modified on the nanosilica particles, the modifying groups A have a structure as shown in formula (I),
Formula (I) wherein R 1 is absent or C1-C6 alkylene, I is a natural number from 0 to 4, j is a natural number from 0 to 2, R a and R b are each independently hydroxy-substituted C1-C6 alkyl, amino-substituted C1-C6 alkyl, hydroxy or amino.
3. The blocking agent according to claim 2, wherein R 1 is absent or is C1-C2 alkylene, i is 0, j is a natural number from 0 to 1, R b is amino-substituted C1-C4 alkyl or hydroxy.
4. A blocking agent according to claim 3, wherein R 1 is methylene, j is 0 or 1 and R b is hydroxy.
5. The plugging agent of any one of claims 1-4, wherein the mass ratio of the aminated carbon nanotubes, the nanosilica particles and the modifying group a is 0.015-0.04:1:0.6-1.
6. A method for preparing a carbon nanotube plugging agent, which is characterized by comprising the following steps: under the dehydration condition, carrying out a contact reaction I on the modified nano silicon dioxide and the aminated carbon nano tube; the modified nano silicon dioxide comprises hydroxylated nano silicon dioxide particles and a modification group A modified on the hydroxylated nano silicon dioxide particles, wherein the structure of the modification group A is shown as a formula (I);
Formula (I) wherein R 1 is absent or C1-C6 alkylene, I is a natural number from 0 to 4, j is a natural number from 0 to 2, R a and R b are each independently hydroxy-substituted C1-C6 alkyl, amino-substituted C1-C6 alkyl, hydroxy or amino.
7. The method according to claim 6, wherein the diameter of the aminated carbon nanotube is 8 to 15nm, the length is 50 μm or less, and the amino content is 0.4 to 0.5 mass%.
8. The preparation method according to claim 6 or 7, wherein the mass ratio of the modified nano-silica to the aminated carbon nanotubes is 50-100:1; and/or the number of the groups of groups,
The dehydrating agent adopted in the dehydration is sulfuric acid solution with the concentration of 90-98%, and the conditions of the contact reaction I comprise: the temperature is 70-90 ℃ and the time is 18-30h.
9. The method according to any one of claims 6 to 8, wherein the method for producing the modified nano-silica comprises: and (3) carrying out a contact reaction II on the hydroxylated nano silicon dioxide and the amino hydroxynaphthalene in the presence of a solvent.
10. The process of claim 9, wherein the solvent is water and the contacting reaction II conditions comprise: the temperature is 40-80 ℃ and the time is 4-6h; and/or the number of the groups of groups,
The mass ratio of the hydroxylated nano silicon dioxide to the amino hydroxynaphthalene is 1:0.6-1.
11. A carbon nanotube plugging agent produced by the production process according to any one of claims 6 to 10.
12. Use of the carbon nanotube plugging agent of any one of claims 1 to 5 and 11 in brine well control fluid.
13. A well control fluid comprising the carbon nanotube plugging agent of any one of claims 1 to 5 and 11, water and formate.
14. The well control fluid of claim 13, wherein the plugging agent is present in an amount of 0.1-0.3g and the formate is present in an amount of 15-220g relative to 100mL of water; and/or the number of the groups of groups,
The formate is potassium formate and/or sodium formate.
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| CN112430455A (en) * | 2020-11-23 | 2021-03-02 | 安东石油技术（集团）有限公司 | Nano plugging agent and preparation method and application thereof |
| CN113403050A (en) * | 2021-07-02 | 2021-09-17 | 北京宏勤石油助剂有限公司 | Nano plugging agent and preparation method thereof |
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| CN114350332A (en) * | 2020-08-26 | 2022-04-15 | 中国石油大学(北京) | Bionic and amphiphobic high-efficiency water-based drilling fluid |
| WO2023183609A1 (en) * | 2022-03-25 | 2023-09-28 | Geothermic Solution, Inc. | Geothermal cementing system with high thermal conductivity |
| CN117285920A (en) * | 2022-06-17 | 2023-12-26 | 中国石油化工股份有限公司 | Synthetic fracturing fluid for reservoir protection and preparation method thereof |
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| CN114350332A (en) * | 2020-08-26 | 2022-04-15 | 中国石油大学(北京) | Bionic and amphiphobic high-efficiency water-based drilling fluid |
| CN112430455A (en) * | 2020-11-23 | 2021-03-02 | 安东石油技术（集团）有限公司 | Nano plugging agent and preparation method and application thereof |
| CN113403050A (en) * | 2021-07-02 | 2021-09-17 | 北京宏勤石油助剂有限公司 | Nano plugging agent and preparation method thereof |
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| CN114350331A (en) * | 2022-01-24 | 2022-04-15 | 西南石油大学 | Strong-adsorption salt-resistant plugging agent based on nano-silica and water-based drilling fluid |
| WO2023183609A1 (en) * | 2022-03-25 | 2023-09-28 | Geothermic Solution, Inc. | Geothermal cementing system with high thermal conductivity |
| CN117285920A (en) * | 2022-06-17 | 2023-12-26 | 中国石油化工股份有限公司 | Synthetic fracturing fluid for reservoir protection and preparation method thereof |
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