WO2016064718A1 - Suspensions for enhanced hydrocarbon recovery, and methods of recovering hydrocarbons using the suspensions - Google Patents
Suspensions for enhanced hydrocarbon recovery, and methods of recovering hydrocarbons using the suspensions Download PDFInfo
- Publication number
- WO2016064718A1 WO2016064718A1 PCT/US2015/056185 US2015056185W WO2016064718A1 WO 2016064718 A1 WO2016064718 A1 WO 2016064718A1 US 2015056185 W US2015056185 W US 2015056185W WO 2016064718 A1 WO2016064718 A1 WO 2016064718A1
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- WO
- WIPO (PCT)
- Prior art keywords
- amphiphilic nanoparticles
- hydrophilic
- carbon
- suspension
- amphiphilic
- Prior art date
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 93
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 90
- 239000000725 suspension Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 68
- 238000011084 recovery Methods 0.000 title description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 182
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000000463 material Substances 0.000 claims abstract description 117
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 85
- 125000000524 functional group Chemical group 0.000 claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 239000012530 fluid Substances 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims description 86
- 230000015572 biosynthetic process Effects 0.000 claims description 58
- 239000002243 precursor Substances 0.000 claims description 53
- 239000008346 aqueous phase Substances 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 22
- 230000001965 increasing effect Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 230000003247 decreasing effect Effects 0.000 claims description 9
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 8
- 229910003472 fullerene Inorganic materials 0.000 claims description 8
- 239000002113 nanodiamond Substances 0.000 claims description 8
- 241000234282 Allium Species 0.000 claims description 6
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000005755 formation reaction Methods 0.000 description 52
- 239000012071 phase Substances 0.000 description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000004094 surface-active agent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 125000003277 amino group Chemical group 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 229910052732 germanium Inorganic materials 0.000 description 10
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910052718 tin Inorganic materials 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 8
- -1 diphenyl ester Chemical class 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000011162 core material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 230000001687 destabilization Effects 0.000 description 5
- 230000000368 destabilizing effect Effects 0.000 description 5
- 125000001165 hydrophobic group Chemical group 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 239000012454 non-polar solvent Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Chemical group 0.000 description 3
- 239000011593 sulfur Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 125000000962 organic group Chemical group 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
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- 239000002798 polar solvent Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- IEKMLKYASCBALX-UHFFFAOYSA-N propoxy(tripropyl)silane Chemical compound CCCO[Si](CCC)(CCC)CCC IEKMLKYASCBALX-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
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- 150000004756 silanes Chemical class 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YGHFDTDSFZTYBW-UHFFFAOYSA-N O-silylhydroxylamine Chemical class NO[SiH3] YGHFDTDSFZTYBW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 229910010416 TiO(OH)2 Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- VZLNSPSVSKXECI-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO.CCO VZLNSPSVSKXECI-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- ZDXQHTDPMDIGFJ-UHFFFAOYSA-N ethanolate;lead(2+) Chemical compound CCO[Pb]OCC ZDXQHTDPMDIGFJ-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GGQZVHANTCDJCX-UHFFFAOYSA-N germanium;tetrahydrate Chemical compound O.O.O.O.[Ge] GGQZVHANTCDJCX-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- IOANYFLVSWZRND-UHFFFAOYSA-N hydroxy(tripropyl)silane Chemical compound CCC[Si](O)(CCC)CCC IOANYFLVSWZRND-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VWHIRQNZEXUKAZ-UHFFFAOYSA-N methanolate;nickel(2+) Chemical compound CO[Ni]OC VWHIRQNZEXUKAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- FPADWGFFPCNGDD-UHFFFAOYSA-N tetraethoxystannane Chemical compound [Sn+4].CC[O-].CC[O-].CC[O-].CC[O-] FPADWGFFPCNGDD-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- ZQJYXISBATZORI-UHFFFAOYSA-N tributyl(ethoxy)silane Chemical compound CCCC[Si](CCCC)(CCCC)OCC ZQJYXISBATZORI-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- 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
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/20—Displacing by water
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
Definitions
- NANO-SURFACTANTS FOR ENHANCED HYDROCARBON RECOVERY, AND METHODS OF FORMING AND USING SUCH NANO-SURFACTANTS the disclosure of each of which is hereby incorporated herein in its entirety by this reference.
- Embodiments of the disclosure relate generally to methods and systems of forming a stabilized emulsion and extracting a hydrocarbon material from a subterranean formation.
- Water flooding is a conventional process of enhancing the extraction of hydrocarbon materials (e.g., crude oil, natural gas, etc.) from subterranean formations.
- an aqueous fluid e.g., water, brine, etc.
- injection wells to sweep a hydrocarbon material contained within interstitial spaces (e.g., pores, cracks, fractures, channels, etc.) of the subterranean formation toward production wells offset from the injection wells.
- One or more additives may be added to the aqueous fluid to assist in the extraction and subsequent processing of the hydrocarbon material.
- a surfactant solid particles (e.g., colloids), or both are added to the aqueous fluid.
- the surfactant and/or the solid particles can adhere to or gather at interfaces between a hydrocarbon material and an aqueous material to form a stabilized emulsion of one of the hydrocarbon material and the aqueous material dispersed in the other of the hydrocarbon material and the aqueous material.
- Surfactants may decrease the surface tension between the hydrocarbon phase and the water phase, such as, for example, in an emulsion of a hydrocarbon phase dispersed within an aqueous phase.
- Stabilization by the surfactant, the solid particles, or both lowers the interfacial tension between the hydrocarbon and water and reduces the energy of the system, preventing the dispersed material (e.g., the hydrocarbon material, or the aqueous material) from coalescing, and maintaining the one material dispersed as units (e.g., droplets) throughout the other material. Reducing the surface tension increases the permeability and the flowability of the hydrocarbon material. As a consequence, the hydrocarbon material may be more easily transported through and extracted from the subterranean formation as compared to water flooding processes that do not employ the addition of a surfactant and/or solid particles.
- the effectiveness of the emulsion is determined in large part by the ability of the emulsion to remain stable and ensure mixing of the two phases.
- surfactants are usually limited by the cost of the chemicals and their adsorption and loss onto the rock of the hydrocarbon-containing formation.
- the affectivity of various surfactants can be detrimentally reduced in the presence of dissolved salts (e.g., such as various salts typically present within a subterranean formation).
- surfactants can have a tendency to adhere to surfaces of the subterranean formation, requiring the economically undesirable addition of more surfactant to the injected aqueous fluid to account for such losses.
- Solid particles can be difficult to remove from the stabilized emulsion during subsequent processing, preventing the hydrocarbon material and the aqueous material thereof from coalescing into distinct, immiscible components, and greatly inhibiting the separate collection of the hydrocarbon material.
- the surfactants are often functional or stable only within particular temperature ranges and may lose functionality at elevated temperatures or various conditions encountered within a subterranean formation.
- Embodiments disclosed herein include methods of recovering hydrocarbon material from a subterranean formation or from a bituminous sand, as well as related stabilized emulsions.
- a method of recovering a hydrocarbon material comprises combining amphophilic nanoparticles comprising a carbon core, at least one hydrophilic group, and at least one hydrophobic group with a carrier fluid to form a suspension, contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension to form an emulsion stabilized by the amphiphilic nanoparticles, and removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
- a method of removing a hydrocarbon from a subterranean formation comprises forming at least one hydrophilic group on a surface of a carbon-containing material comprising at least one of a carbon nanotube, a fullerene, a carbon nanodiamond, graphene, and graphene oxide, mixing the carbon- containing material with a carrier fluid to form a suspension, introducing the suspension into a subterranean formation and contacting hydrocarbons within the subterranean formation with the carrier fluid suspension to form an emulsion stabilized by the carbon-containing material, and transporting the emulsion to a surface of the subterranean formation.
- a suspension for removing hydrocarbons from a subterranean formation comprises a plurality of carbon-containing amphiphilic nanoparticles, the amphiphilic nanoparticles comprising hydrophobic functional groups on a surface of the carbon-containing material, and hydrophilic functional groups on another surface of the carbon-containing material.
- the suspension further comprises a carrier fluid carrier fluid.
- FIG. 1 A through FIG. 1C are simplified schematics of an amphiphilic nanoparticle in accordance with embodiments of the disclosure
- FIG. 2 is a simplified flow diagram depicting a method of extracting hydrocarbons from a subterranean formation, in accordance with embodiments of the disclosure; and FIG. 3 is a simplified flow diagram depicting a method of recovering hydrocarbons from bituminous sand, in accordance with embodiments of the disclosure.
- amphiphilic nanoparticle means and includes a particle having an average particle width or diameter of less than about 1 ,000 nm.
- amphiphilic nanoparticle means and includes a nanoparticle exhibiting both hydrophilic and hydrophobic properties (e.g., similar to a Janus nanoparticle).
- the amphiphilic nanoparticle may include a two-dimensional structure with one side of the structure exhibiting hydrophobic characteristics and another, opposite side of the structure exhibiting hydrophilic characteristics.
- an amphiphilic nanoparticle may include both hydrophilic and hydrophobic functional groups.
- the amphiphilic nanoparticle may be formed of a hydrophobic core material and at least one side or portion of the hydrophobic core material may be functionalized with hydrophilic functional groups.
- Surfactants including such amphiphilic nanoparticles may have a higher surface area and may be stable at higher temperatures and salt concentrations than conventional particle surfactants used to stabilize emulsions.
- functional groups on the amphiphilic nanoparticles may be formulated to interact with various media of different subterranean environments.
- the amphiphilic nanoparticles may gather at, adhere to, and/or adsorb onto minerals within a subterranean formation, may adsorb to interfaces of a hydrocarbon material and an aqueous material, or both.
- the amphiphilic nanoparticles may form a stabilized emulsion (e.g., a Pickering emulsion) comprising units of one of the hydrocarbon material and the aqueous material.
- emulsion refers to suspensions of droplets of one immiscible fluid dispersed in another fluid. The emulsion may reduce the interfacial tension between a continuous phase and a dispersed phase.
- Decreasing interfacial tension between, for example, a dispersed hydrocarbon phase and a continuous aqueous phase may increase the hydrocarbon (e.g., oil) mobility and recovery from a subterranean formation or from a slurry of a bituminous sand including the hydrocarbon.
- hydrocarbon e.g., oil
- the amphiphilic nanoparticles may be formulated to remain at an interface between a polar phase and a nonpolar phase, between a hydrophilic phase and a hydrophobic phase, and/or between a hydrocarbon phase and an aqueous phase, such as at an interface between a gas phase and an aqueous phase, an interface between a liquid hydrocarbon phase and an aqueous phase, or an interface between a solid phase and at least one of an aqueous phase and a hydrocarbon phase.
- the amphiphilic nanoparticles may stabilize an emulsion of the hydrocarbon phase within the aqueous phase or an emulsion of the aqueous phase within the hydrocarbon phase.
- Stabilizing the emulsion may prevent the emulsion from coalescing once the emulsion interface is formed.
- One side (e.g., the hydrophilic side) of the amphiphilic nanoparticles may be formulated to be attracted to the aqueous phase while the other side (e.g., the hydrophobic side) of the amphiphilic nanoparticles may be formulated to be attracted to the hydrocarbon phase.
- amphiphilic nanoparticles formed by the methods described herein may have a higher surface area than conventional surfactants.
- the functionalized surfaces of the amphiphilic nanoparticles may be formulated to interact with the interface between the hydrocarbon phase and the aqueous phase or with solid surfaces (e.g., minerals) within the subterranean formation, thereby forming a stable emulsion of a continuous aqueous or hydrocarbon phase and a dispersed phase of the other of the hydrocarbon and aqueous phase.
- the stability of the emulsion may be controlled by one or more of controlling the solubility of the amphiphilic nanoparticles within the aqueous phase, controlling the pH of the emulsion and/or the aqueous phase, and controlling the surface charge of the amphiphilic nanoparticles.
- the amphiphilic nanoparticle 100 may include a base portion.
- the amphiphilic nanoparticle 100 may include a hydrophilic portion 102 and a hydrophobic portion 104.
- Surfaces of the base portion may be modified with functional groups to impart desired physical and chemical properties to the surface of the amphiphilic nanoparticle 100.
- the hydrophilic portion 102 may include at least one hydrophilic functional group on a surface of the base portion and the hydrophobic portion 104 may include at least one hydrophobic group on a surface of the base portion.
- the hydrophobic portion 104 may be formed of the base portion and the hydrophilic portion 102 may include at least one hydrophilic functional group on a surface of the hydrophobic base portion.
- the base portion may include any material that may be chemically modified with functional groups to form the hydrophilic portion 102 and the hydrophobic portion 104.
- the base portion includes a silica base.
- the base portion includes a metal or a metal oxide.
- the base portion may include a metal such as iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, cobalt, oxides thereof, and combinations thereof.
- the base portion may include a carbon-based material, such as at least one of carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNTs), multi- walled carbon nanotubes (MWCNTs), and combinations thereof), carbon
- the base portion may include silica, a metal such as one of iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, cobalt, carbon nanotubes, carbon nanodiamonds, graphene, graphene oxide, fullerenes, bucky onions, and combinations thereof.
- the amphiphilic nanoparticle 100 may be formed from a plurality of hydrophilic precursors and a plurality of hydrophobic precursors.
- hydrophilic precursor includes materials having at least one atom of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt, and at least one hydrophilic functional group.
- hydrophobic precursor includes materials having at least one atom of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt, and at least one hydrophobic functional group.
- a plurality of hydrophilic precursors may react to form a nanoparticle including a base of at least one of carbon, silica, a metal, and a metal oxide with one or more hydrophilic functional groups attached to the surface thereof.
- the hydrophilic functional groups of the hydrophilic portion 102 may be formed from the hydrophilic functional group of the hydrophilic precursor.
- the surface of the base portion may be chemically modified to form amphophilic nanoparticles 100 including a hydrophobic portion 104 in addition to the hydrophilic portion 102.
- the hydrophobic portion 104 may be formed from hydrophobic groups attached to the surface of the base portion.
- the hydrophobic groups may include nonpolar groups, such as, for example, alkyl chains.
- the base portion is formed of carbon (e.g., carbon nanotubes, carbon nanodiamonds, graphite, graphene, graphene oxide, fullerenes, bucky onions, etc.)
- the hydrophobic portion 104 may be comprised of the base portion and the hydrophilic portion 102 may be formed on at least some surfaces of the hydrophobic base portion.
- the hydrophilic portion 102 may be soluble in an aqueous phase, whereas the hydrophobic portion 104 may be soluble in an organic phase.
- the amphophilic nanoparticle 100 may be formed of various shapes.
- the shape of the amphiphilic nanoparticle 100 may be controlled by growing the amphiphilic nanoparticles 100 in the presence of a structure-directing agent.
- structure-directing agents include polymers such as a polypyrrole (e.g., polyvinylpyrrolidone (PVP)), an oxidized polypyrrole, a diphenyl ester, and cetyltrimethylammonium bromide (CTAB).
- PVP polyvinylpyrrolidone
- CTAB cetyltrimethylammonium bromide
- the amphiphilic nanoparticle 100 may include a tubular-shaped base with a solid hydrophilic portion 102 and a hollow-tubular shaped hydrophobic portion 104.
- Amphiphilic nanoparticles 100 formed from SWCNTs and MWCNTs may be tubular- shaped as shown in FIG. 1A.
- the amphiphilic nanoparticle 100 may be generally spherical in shape with a hydrophilic portion 102 on one side and a hydrophobic portion 104 on an opposite side.
- Amphiphilic nanoparticles 100 formed from carbon nanodiamonds, fullerenes, and bucky onions may exhibit the spherical shape shown in FIG. I B.
- the amphiphilic nanoparticle 100 may have a platelet shape.
- One side of the platelet may be a hydrophilic portion 102 and the other side of the platelet may be a hydrophilic portion 104.
- the amphiphilic nanoparticles 100 may have the platelet shape as shown in FIG. 1 C.
- the hydrophilic portion 102 of the amphiphilic nanoparticles 100 is formed before forming the hydrophobic portion 104.
- the hydrophilic portion 102 is formed by hydrolyzing the hydrophilic precursor.
- the hydrophilic precursor may include an organosilane having the general formula, R cetSiX(4 -n ), where X is a hydrolyzable group, such as an alkoxy, acyloxy, amine, or halide group, and R n includes a hydrophilic functional group.
- hydrolyzable group means and includes a group that can be at least partially depolymerized to lower molecular weight units by hydrolysis (i.e., the cleavage of a chemical bond by the reaction with water).
- the hydrolyzable group may be reactive with an aqueous material, such as water.
- a carbon-containing material that forms the base portion may include one or more exposed functional groups such as a hydroxyl group, a carboxyl group, a carbonyl group, an amino group, a thiol group, a phosphate group, an azo group, or another hydrophilic or polar functional group.
- carbon nanotubes may include one or more hydrophilic functional groups on at least one of the outside or the inside (e.g., an inner wall or an outer wall) of the carbon nanotube.
- at least one side of graphite platelets, graphene platelets or graphene oxide platelets may be functionalized with at least one type of hydrophilic functional group.
- a carbon-containing material may be functionalized by oxidation with concentrated nitric acid, sulfuric acid, and combinations thereof.
- the oxidation may form carboxyl groups on exposed surfaces of the carbon-containing material, such as on sidewalls of carbon nanotubes or on exposed surfaces of a graphene plate.
- the exposed carboxyl groups may form reaction sites for further functionalizing the carbon-containing material.
- the exposed carboxyl groups may be exposed to an amine (primary amine (RNH 2 ), a secondary amine (RR'NH), or a tertiary amine (RR'R"N), where R, R', and R" include a hydrocarbon group, such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, each of which may include one or more hydrogen atoms substituted with one or more halides, hydroxyl groups, amine groups, or
- amine functionalized nanotubes a compound including a hydroxyl group and at least one of NH 2 , NHR, and NRR' where R and R' include the same groups described above with respect to amines.
- the amine groups attached to the carbon-containing base may form hydrophilic groups attached to the hydrophobic carbon-containing base.
- exposed hydroxyl groups of a carbon-containing core may react with other hydrophilic precursors including terminal hydroxyl groups in a condensation reaction to attach the hydrophilic portion 102 to the carbon-containing material.
- the terminal hydroxyl groups of a carbon- containing material may react with materials such as a hydroxylamine (e.g., HO- NRR', where R and R' include a hydrocarbon group as described above and include at least one hydrogen substituted with at least one of a halide, a hydroxyl group, an amine group, and a sulfur-containing compound) in a condensation reaction.
- a hydroxylamine e.g., HO- NRR', where R and R' include a hydrocarbon group as described above and include at least one hydrogen substituted with at least one of a halide, a hydroxyl group, an amine group, and a sulfur-containing compound
- the hydrophilic precursor may include oxysilanes, orthosilicates, aminosilanes, silanols, epoxy silanes, metal oxides, hydroxides, metal hydroxides, or combinations thereof.
- oxysilane means and includes materials including a silicon atom bonded to at least one oxygen atom (e.g., -Si ⁇ OR, where R is a hydrocarbon material or hydrogen).
- orthosilicate means and includes materials including a silicon atom bonded to four oxygen atoms (e.g., Si(OR)4, where R is a hydrocarbon material or hydrogen).
- the hydrophilic precursor may include orthosilicates, such as, for example, tetramethyl orthosilicate, tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate, trimethylmethoxysilane, triethylethoxysilane, or tripropylpropoxysilane.
- TEOS tetraethyl orthosilicate
- the hydrolysis of trimethylmethoxysilane, triethylethoxysilane, or tripropylpropoxysilane may form a silanol such as trimethylsilanol, triethylsilanol, or tripropyl silanol, respectively.
- the hydrophilic precursor includes ethyoxysilanes such as trimethoxysilane, triethoxysilane, or tributyl(ethoxy)silane.
- the hydrophilic precursor includes metal hydroxides and metal salts.
- the hydrophilic precursor may include metal hydroxides such as an iron hydroxide, titanium hydroxide (e.g., TiO(OH)2, Ti(OH) 4 ), germanium hydroxide, tin hydroxide, lead hydroxide, zirconium hydroxide, ruthenium hydroxide, nickel hydroxide, and cobalt hydroxide.
- the hydrophilic precursor includes a metal salt such as salts of at least one of iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt.
- a hydrophilic precursor including a metal hydroxide may react with an exposed hydroxyl group on a surface of the base of the nanoparticle.
- the hydrophilic precursor includes a metal oxide.
- the hydrophilic precursor may include iron oxide (Fe 2 0 3 , Fe 3 C>4), titanium dioxide, germanium oxide (GeO, Ge0 2 ), tin oxide (SnO, Sn0 2 ), lead oxide (PbO, Pb0 2 , Pb 3 C>4), zirconium oxide, ruthenium oxide (Ru0 2 , R.UO4), nickel oxide (NiO, Ni 2 0 3 ), and cobalt oxide (CoO, ⁇ 3 ⁇ 40 3 , C0 3 O 4 ).
- the hydrophilic precursor may include a metal alkoxide.
- the hydrophilic precursor may include iron ethoxide, titanium isopropoxide, titanium ethoxide, germanium ethoxide, tin ethoxide, lead ethoxide, zirconium ethoxide, and nickel(II) methoxide.
- the hydrophilic precursor may include an aminosilane including at least one amino group.
- the at least one amino group may be in addition to at least two oxysilane groups.
- suitable aminosilanes include (3-aminopropyl)-diethoxy-methylsilane (APDEMS), (3-aminopropyl)- trimethoxysilane (APTMS), (3-aminopropyl)-methyldiethoxysilane, (3-aminopropyl)- triethoxysilane (APTES), 3-aminopropyltriethoxysilane, bis(3-triethoxysilylpropyl) amine, and bis(3-trimethoxysilylproply) amine.
- APDEMS (3-aminopropyl)-diethoxy-methylsilane
- APITMS trimethoxysilane
- APTES triethoxysilane
- 3-aminopropyltriethoxysilane bis(3-tri
- Hydrolysis of the aminooxysilanes may form a hydroxyl terminated hydrophilic portion 102 including amino groups.
- the aminosilanes may be reacted with, for example, an ethylene carbonate to form a hydrophilic portion 102 including exposed hydroxyl groups.
- the hydrophilic precursor may include an epoxy silane.
- epoxy silanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidyloxypropyltriethoxysilane.
- the epoxy silane may be hydrolyzed to form exposed hydroxyl groups on the hydrophilic portion 102.
- the synthesis of the hydrophilic portion 102 of the amphophilic nanoparticles 100 may be carried out in a polar solvent.
- the hydrophilic portion 102 may be soluble in the solvent.
- the solvent may include an alcohol such as methanol, ethanol, propanol, butanol, pentanol, other alcohol, acetone, or combinations thereof.
- the hydrophilic precursor may be soluble in the solvent.
- Additional agents may be added to the reaction solution.
- structure-directing agents such as polyvinylpyrrolidone (PVP)
- PVP polyvinylpyrrolidone
- the pH of the reaction solution may be varied by adding various acids or bases.
- the pH of the solution may be increased by adding sodium bicarbonate, sodium hydroxide, or other base to the solution.
- the pH of the solution may be decreased by adding an acid such as hydrochloric acid, acetic acid, or other acid to the solution.
- the synthesis of the hydrophilic portion 102 may be carried out at room temperature.
- the reaction solution may be heated to increase a reaction rate of formation of the hydrophilic portion 102 of the amphiphilic nanoparticles 100.
- the reaction rate may be increased by microwave irradiation.
- the reaction may proceed for between about one minute and several hours.
- the size of the hydrophilic portion 102 may be increased by increasing the synthesis time of forming the hydrophilic portion 102.
- the reaction may leave one or more exposed hydroxyl groups on the hydrophilic portion 102.
- the hydrophilic portion 102 may include one or more additional functional groups, such as additional hydroxyl groups, a carboxyl group, a carbonyl group, an amino group, a thiol group, and a phosphate group.
- the hydrophilic precursor may be hydrolyzed to form a plurality of hydrophilic precursors with exposed hydroxyl groups.
- the exposed hydroxyl groups of the hydrophilic precursors may react with each other in a condensation reaction, forming the hydrophilic portion 102 including a base material and hydrophilic functional groups on a surface of the base material.
- the exposed functional groups may be the same functional groups as the functional groups of the hydrophilic precursor.
- a surface of the hydrophilic portion 102 may have the general structure as shown below, where R n includes a hydrophilic group, and M is at least one of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt.
- adjacent metal atoms may be directly bonded to each other without intervening oxygen atoms and the carbon based materials may include hydrophilic substitution (e.g., adjacent carbon atoms may be directly bonded to each other or may be connected via a hydrophilic functional group).
- a metal e.g., iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt
- adjacent metal atoms may be directly bonded to each other without intervening oxygen atoms and the carbon based materials may include hydrophilic substitution (e.g., adjacent carbon atoms may be directly bonded to each other or may be connected via a hydrophilic functional group).
- a hydrophobic precursor may be added to the reaction solution including the hydrophilic portion 102.
- An organic solvent in which the hydrophobic precursor is soluble may be added to the reaction mixture.
- the organic solvent is a nonpolar solvent.
- the hydrophobic functional group of the hydrophobic precursor may be soluble in an organic phase whereas the hydrophilic functional group on the surface of the base material may be soluble in an aqueous phase.
- the amphiphilic nanoparticles 100 may be formed by reacting at least some of the exposed hydroxyl groups of the hydrophilic portion 102 with one or more of the hydrophobic precursors.
- the hydrophobic precursor may include one or more exposed hydroxyl groups.
- the hydrophobic precursor is hydrolyzed to create exposed hydroxyl groups on the hydrophobic precursor.
- the hydrophobic portion 104 grows from one end of the hydrophilic portion 102. Without being bound by any theory, it is believed that only a portion of the hydrophilic portion 102 contacts the nonpolar solvent in which the hydrophobic precursors are dissolved because of the insolubility of the hydrophilic portion 102 in the nonpolar solvent.
- the hydroxyl groups of a portion of the hydrophilic portion 102 that contacts the hydrophobic precursor may react with the hydrophobic precursors to form the hydrophobic portion 104 of the amphiphilic nanoparticle 100.
- An exposed surface of the hydrophobic portion 104 may have a general structure as shown below, where R m includes a hydrophobic functional group, and M is at least one of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt.
- M is a metal (e.g., iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt)
- adjacent metal atoms may be directly bonded to each other without intervening oxygen atom.
- the amphiphilic nanoparticle 100 may include one or more exposed hydrophobic, nonpolar organic groups from the hydrophobic precursor, and one or more functional groups (e.g., hydroxyl, carboxyl, carbonyl, amino, thiol, phosphate, a metal, a metal oxide) from the hydrophilic precursor.
- one or more functional groups e.g., hydroxyl, carboxyl, carbonyl, amino, thiol, phosphate, a metal, a metal oxide
- the hydrophobic precursor may include an oxysilane including a nonpolar, organic component.
- the hydrophobic precursor may include at least one central atom such as carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt, one or more hydrocarbon groups bonded to the central atom, and one or more alkoxy groups bonded to the central atom.
- the hydrocarbon group is an alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, and/or octadecyl groups, an alkaryl group such as benzyl groups attached via the aryl portion (e.g., 4-methylphenyl, 4 hydroxymethylphenyl, or
- the alkoxy group is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.
- the hydrophobic precursors may include alkyloxysilanes, such as trialkoxysilanes including trimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane. hexadecyltrimethoxysilane (HDTMOS), methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane,
- alkyloxysilanes such as trialkoxysilanes including trimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane.
- HDTMOS hexadecyltrimethoxysilane
- methyltrimethoxysilane ethyltrimethoxysilane
- octyltrimethoxysilane octyl
- octyltriethoxysilane or other oxysilanes.
- the hydrophobic precursor may include a compound configured to form hydrophobic functional groups on a surface of the amphiphilic nanoparticle 100.
- a hydroxyl group of the alcohol or the hydrophobic precursor may react with an exposed hydroxyl group on the base of the amphiphilic nanoparticle in a condensation reaction to form the hydrophobic portion 104.
- a hydrophobic precursor may react with an exposed hydroxyl group on a carbon-containing material to form the hydrophobic portion 104.
- a hydroxyl group of the hydrophobic precursor may react with exposed hydroxyl groups of the hydrophilic portion 102 in a condensation reaction to form the hydrophobic portion 104.
- the hydrophobic precursor may include an alcohol having the general formula RR'R"- OH, where R, R', and R" may include hydrogen, or an organic group, such as an alkyl group, alkenyl group, alkynyl group, aryl group, etc.
- the alcohol may include one or more hydroxyl groups (e.g., a diol, a triol, etc.).
- the hydrophobic portion 104 may be formed on only one side of the amphiphilic nanoparticle 100 (e.g., an opposite side as the hydrophilic portion 102).
- the hydrophobicity of the hydrophobic portion 104 may be controlled by altering the number of functional groups and the size of the functional groups of the hydrophobic precursor. In some embodiments, the hydrophobicity of the hydrophobic portion 104 is increased by increasing the carbon content of the functional group of the hydrophobic precursor. For example, ethyltrimethoxysilane may be more hydrophobic than methyltrimethoxysilane. Similarly, hexadecyltrimethoxysilane may be more hydrophobic than ethyltrimethoxysilane.
- the hydrophobicity of the amphiphilic nanoparticles 100 may also be increased by increasing a concentration of the hydrophobic functional group relative to a concentration of the hydrophilic functional group in the reaction mixture or by decreasing a reaction time of forming the hydrophilic portion 102 relative to a reaction time of forming the hydrophobic portion 104.
- the hydrophobic portion 104 of the amphiphilic nanoparticle 100 may be the core and the hydrophilic portions 1 02 may be any hydrophilic functional groups attached to the carbon-containing material.
- the amphiphilic nanoparticles 100 may be removed from the reaction solution by centrifugation, ultrafiltration, or combinations thereof.
- the amphiphilic nanoparticles 100 are recovered by flowing the solution through a membrane filter.
- the filter may have a pore size ranging from between about 10 nm and about 1 ,000 nm, such as between about 10 nm and about 100 nm, between about 100 nm and about 200 nm, between about 200 nm and about 400 nm, or between about 400 nm and about 1 ,000 nm.
- the solution is flowed through a filter having a pore size of between about 200 nm and about 400 nm.
- the resulting solid residue may be dried and collected.
- the solid residue may include amphiphilic nanoparticles 100 with a hydrophilic portion 102 and a hydrophobic portion 104.
- the hydrophobic portion 104 may be opposite the hydrophilic portion 102 such that one portion of the amphiphilic nanoparticle 100 is attracted to and soluble in a hydrocarbon phase and another portion of the amphiphilic nanoparticle 100 is attracted to and soluble in an aqueous phase.
- the amphiphilic nanoparticles 100 may have a size distribution ranging from between about 10 nm and about 1,000 nm. In some embodiments, the size distribution may correspond to the size of the filter through which the solution was passed to separate the nanoparticles from the reaction solution.
- the amphiphilic nanoparticles 100 may be monodisperse wherein each of the amphiphilic nanoparticles 100 has substantially the same size, shape, and material composition, or may be polydisperse, wherein the amphiphilic nanoparticles 100 include a range of sizes, shapes, and/or material composition. In some embodiments, each of the amphiphilic nanoparticles 100 has substantially the same size and the same shape as each of the other amphiphilic nanoparticles 100.
- the amphiphilic nanoparticles 100 may stabilize an emulsion at higher temperatures than a typical surfactant. For example, typical surfactants may degrade or otherwise lose functionality at temperatures in excess of about 250°C. However, the amphiphilic nanoparticles 100 described herein may be stable at high temperatures that may be encountered within a subterranean formation. For example, the amphiphilic nanoparticles 100 may be stable at temperatures up to about 500°C. In some embodiments, the amphiphilic nanoparticles 100 are exposed to a temperature between about 250°C and about 500°C, such as between about 300°C and about 400°C, or between about 400°C and about 500°C, and may remain stable.
- the amphophilic nanoparticles 100 may remain effective at stabilizing an emulsion at higher salinity concentrations than typical surfactants. Due to the presence of the functional groups on the amphiphilic nanoparticles 100, the amphophilic nanoparticles 100 may be repelled from the salts of a brine solution, whereas non-functionalized particles may tend to agglomerate or gel with a salt.
- the amphiphilic nanoparticles 100 may be stable within a wide pH range.
- the amphiphilic nanoparticles 100 may be formulated to be stable at a pH between about 3.0 and about 12.0.
- the amphiphilic nanoparticles 100 are formulated to be stable at a pH as high as about 12.0 by forming the amphiphilic nanoparticles 100 from anionic functional groups such as hydroxyl groups, carboxylate groups, carboxyl groups, sulfate groups, phosphate groups, or other anionic groups.
- nanoparticles 100 are formulated to be stable at a pH as low as about 3.0 by including terminal ends of cationic groups such as amine groups.
- the amphiphilic nanoparticles 100 may stabilize an emulsion in any application where a stable emulsion is desired.
- the amphiphilic nanoparticles 100 may be used in water flooding applications or floatation cell applications.
- the amphiphilic nanoparticles 100 may stabilize an emulsion by themselves, or the amphiphilic nanoparticles 100 may be used with one or more surfactants.
- the method may include a suspension formation process 200 including forming a flooding suspension including a plurality of amphiphilic nanoparticles; a flooding process 202 including introducing the flooding suspension into a subterranean formation to detach a hydrocarbon material from surfaces of the subterranean formation and form a stabilized emulsion of the hydrocarbon material and an aqueous material; an extraction process 204 including flowing (e.g., driving, sweeping, forcing, etc.) the stabilized emulsion from the subterranean formation; and a emulsion destabilization process 206 including destabilizing (e.g., demulsifying, precipitating, etc.) the emulsion into distinct, immiscible phases.
- a suspension formation process 200 including forming a flooding suspension including a plurality of amphiphilic nanoparticles
- a flooding process 202 including introducing the flooding suspension into a subterranean formation to detach a hydrocarbon material from surfaces of the subterranean formation
- the suspension formation process 200 may include forming a suspension including amphiphilic nanoparticles and at least one carrier fluid.
- the at least one carrier fluid may, for example, comprise water, or a brine solution.
- the term "suspension” means and includes a material including at least one carrier fluid in which amphiphilic nanoparticles are substantially uniformly dispersed.
- the suspension may be a flooding suspension used, such as used in water flooding of a subterranean formation during enhanced oil recovery processes.
- the amphiphilic nanoparticles of the flooding suspension may be compatible with other components (e.g., materials, constituents, etc.) of the flooding suspension.
- the term “compatible” means that a material does not impair the functionality of the amphiphilic nanoparticles or cause the amphiphilic nanoparticles to lose functionality as surfactants and emulsion stabilizers.
- the flooding suspension may be formulated to include a concentration of the amphiphilic nanoparticles ranging from between about 50 ppm to about 50,000 ppm.
- the flooding suspension may have a
- the flooding suspension may have a concentration ranging from between about 50 ppm to about 5,000 ppm.
- the suspension includes a portion of amphiphilic nanoparticles with a carbon-based core and another portion of amphiphilic nanoparticles with another base portion.
- the suspension may include a first portion of amphiphilic nanoparticles including a carbon-containing material, a second portion of amphiphilic nanoparticles including a silica core, and a third portion of amphiphilic nanoparticles including a metal core.
- the emulsion may have the same, a higher, or a lower concentration of amphiphilic nanoparticles than the flooding suspension.
- the flooding process 202 may include introducing the flooding suspension including amphiphilic nanoparticles into a subterranean formation to detach a hydrocarbon material from surfaces of the subterranean formation and form a stabilized emulsion of the hydrocarbon material and an aqueous material.
- the flooding suspension may be provided into the subterranean formation through conventional processes. For example, a pressurized stream of the flooding suspension may be pumped into an injection well extending to a desired depth in the subterranean formation, and may infiltrate (e.g., permeate, diffuse, etc.) into interstitial spaces of the subterranean formation.
- the extent to which the flooding suspension infiltrates the interstitial spaces of the subterranean formation at least partially depends on the properties of the flooding suspension (e.g., density, viscosity, material composition, etc.), and the hydrocarbon materials (e.g., molecular weight, density, viscosity, etc.) contained within interstitial spaces of the subterranean formation.
- properties of the flooding suspension e.g., density, viscosity, material composition, etc.
- hydrocarbon materials e.g., molecular weight, density, viscosity, etc.
- the pH of the flooding suspension may be altered to control the solubility of the amphiphilic nanoparticles within the flooding suspension.
- the amphiphilic nanoparticles include cationic functional groups (e.g., amino groups)
- decreasing the pH of the flooding suspension may increase the solubility of the amphiphilic nanoparticles in the aqueous flooding suspension.
- the amphiphilic nanoparticles include anionic functional groups (e.g., hydroxyl, carboxyl, carbonyl, phosphate, thiol groups, etc.)
- increasing the pH of the flooding suspension may increase the solubility of the amphiphilic nanoparticles in the flooding suspension.
- Altering the pH of the flooding suspension may alter the surface charge of the amphiphilic nanoparticles.
- increasing a pH of a flooding suspension including anionic amphiphilic nanoparticles may increase the net charge of the anionic amphiphilic nanoparticles in the flooding suspension.
- Decreasing a pH of a flooding suspension including cationic amphiphilic nanoparticles may increase the net charge of the cationic amphiphilic nanoparticles.
- the pH of the flooding suspension may be altered to reduce the solubility of the amphiphilic nanoparticles in the aqueous phase of the flooding suspension.
- the pH of the flooding suspension may be reduced to cause the amphiphilic nanoparticles to move to the interface between the aqueous phase and the hydrocarbon phase.
- the pH may be reduced to below about 7.0, such as below 5.0, below 4.0, or below 3.0.
- the pH of the flooding suspension may be increased to cause the amphiphilic nanoparticles to move to the interface between the aqueous phase and the hydrocarbon phase.
- the pH may be increased to above 7.0, such as above 8.0, above 9.0, above 10.0, and up to 12.0.
- the amphiphilic nanoparticles are structured and formulated to facilitate a formation of a stabilized emulsion of a hydrocarbon material and an aqueous material.
- the amphiphilic nanoparticles may be structured and formulated to gather (e.g., agglomerate) at, adhere to, and/or adsorb to interfaces of a hydrocarbon material and an aqueous material to form a Pickering emulsion comprising units (e.g., droplets) of one of the hydrocarbon material and the aqueous material dispersed in the other of the hydrocarbon material and the aqueous material.
- the amphiphilic nanoparticles may prevent the dispersed material (e.g., the hydrocarbon material or the aqueous material) from coalescing, and may thus maintain the dispersed material as units throughout the other material.
- the extraction process 204 may include flowing (e.g., driving, sweeping, forcing, etc.) the stabilized emulsion from the subterranean formation to the surface.
- the amphiphilic nanoparticles prevent the dispersed material from coalescing and enable substantial removal of hydrocarbons from the subterranean formation.
- the emulsion may be destabilized in the emulsion destabilization process 206 to form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase.
- One or more properties (e.g., temperature, pH, material composition, pressure, etc.) of the stabilized emulsion or the aqueous phase may be modified (e.g., altered, changed) to a least partially destabilize the emulsion.
- the pH of the aqueous phase may be modified to increase the solubility of the amphiphilic nanoparticles within the aqueous phase, thereby destabilizing the emulsion and forming distinct, immiscible phases.
- the pH of the emulsion or the aqueous phase may be altered to cause the amphiphilic nanoparticles to move into the aqueous phase and destabilize the emulsion.
- the pH of the aqueous phase may be increased to increase the solubility of the amphiphilic nanoparticles in the aqueous phase.
- the pH of the aqueous phase may be increased by adding a base, such as a hydroxide (e.g., sodium hydroxide) or a bicarbonate (e.g., sodium bicarbonate) to the aqueous phase.
- the pH of the aqueous phase may be reduced to increase the solubility of the amphiphilic nanoparticles in the aqueous phase.
- the pH of the aqueous solution may be decreased by adding hydrochloric acid, phosphoric acid, and acetic acid, or another acid to the aqueous solution.
- a demulsifier may be added to the emulsion to destabilize the emulsion and form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase.
- the emulsion is destabilized by adjusting the pH of at least one of the aqueous phase and the emulsion and by adding a demulsifier to the emulsion.
- the method may include a suspension formation process 300 including forming a suspension including a plurality of amphiphilic nanoparticles; a mixing process 302 including mixing the suspension with a slurry including the bituminous sand and water to form a stabilized emulsion; a transportation process 304 including hydrotransporting the slurry; an extraction process 306 including extracting hydrocarbons from the stabilized emulsion; and a emulsion destabilization process 308 including destabilizing (e.g., demulsifying precipitating, etc.) the emulsion into distinct, immiscible phases.
- a suspension formation process 300 including forming a suspension including a plurality of amphiphilic nanoparticles
- a mixing process 302 including mixing the suspension with a slurry including the bituminous sand and water to form a stabilized emulsion
- a transportation process 304 including hydrotransporting the slurry
- an extraction process 306 including extracting hydrocarbons from the stabilized e
- the suspension formation process 300 may include forming a suspension including the amphiphilic nanoparticles and at least one carrier fluid.
- the carrier fluid may, for example, comprise water, a brine solution, or a caustic soda (NaOH) solution.
- the suspension may be formulated to include a concentration of amphiphilic nanoparticles similar to the flooding suspension described above with reference to FIG. 2.
- the mixing process 302 may include mixing the suspension with a slurry including a bituminous sand and water to form a stabilized emulsion.
- the slurry may include hot water, caustic soda, and the bituminous sand.
- the transportation process 304 may include hydrotransporting the slurry to a location where the stabilized emulsion may be processed to remove hydrocarbons therefrom (e.g., from the bituminous sand).
- the mixing process 302 may be performed simultaneously with the transportation process 304.
- a pH of the slurry may be adjusted to reduce the solubility of the amphiphilic nanoparticles in a hydrophilic portion of the slurry and increase the solubility of the amphiphilic nanoparticles in the stabilized emulsion during the mixing process and the transportation process 304.
- the amphiphilic nanoparticles are structured and formulated to facilitate a formation of a stabilized emulsion of a hydrocarbon material and an aqueous phase.
- the amphiphilic nanoparticles may be structured and formulated to gather at, adhere to, and/or adsorb to interfaces of the hydrocarbon material and the aqueous material to form a Pickering emulsion comprising units (e.g., droplets) of one of the hydrocarbon material and the aqueous material in the other of the hydrocarbon material and the aqueous material.
- the extraction process 306 may include extracting hydrocarbons from the stabilized emulsion. In some embodiments, the extraction process 306 includes extracting hydrocarbons from the stabilized emulsion of the slurry in a floatation process.
- the stabilized emulsion may be destabilized in the emulsion destabilization process 308 to form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase.
- One or more properties e.g., temperature, pH, material composition, pressure, etc.
- the stabilized emulsion or the aqueous phase may be modified (e.g., altered, changed) to a least partially destabilize the emulsion.
- the pH of the aqueous phase may be modified to increase the solubility of the amphiphilic nanoparticles within the aqueous phase, thereby destabilizing the emulsion and forming distinct, immiscible phases.
- the pH of the stabilized emulsion may be altered to cause the amphiphilic nanoparticles to move into the aqueous phase and destabilize the emulsion, as described above with reference to emulsion destabilization process 206 of FIG. 2.
- a demulsifier may be added to the emulsion to destabilize the emulsion and form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase.
- the hydrocarbon material may be separated from the aqueous material and recovered. Thereafter, the amphiphilic nanoparticles may be recovered from the aqueous phase.
- the pH of the aqueous solution may be adjusted to reduce the solubility of the amphiphilic nanoparticles in the aqueous solution and precipitate the amphiphilic nanoparticles from the aqueous solution.
- the amphiphilic nanoparticles include functional groups such as amine functional groups
- decreasing the pH of the aqueous material may reduce the solubility of the amphiphilic nanoparticles in the aqueous solution, thereby causing them to precipitate out of the aqueous solution.
- the amphiphilic nanoparticles are recovered by filtering the aqueous solution through a filter.
- the filter may have a pore size ranging from between about 10 nm and about 5,000 nm, depending on the size of the amphiphilic nanoparticles.
- more than one filtration step may be performed. For example, a first filtration step may filter out sands and other solid particles having a larger diameter than the amphiphilic nanoparticles. Thereafter, the amphiphilic nanoparticles may be separated from the aqueous solution.
- Embodiment 1 A method of recovering a hydrocarbon material, the method comprising: combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension; contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension to form an emulsion stabilized by the amphiphilic nanoparticles; and removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
- Embodiment 2 The method of Embodiment 1 , wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises combining amphiphilic nanoparticles comprising at least one of carbon nanotubes, carbon nanodiamonds, graphite, graphene, graphene oxide, fullerenes, and bucky onions.
- Embodiment 3 The method of Embodiment 2, wherein wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises combining amphiphilic nanoparticles comprising an amino functional group with the carrier fluid.
- Embodiment 4 The method of any one of Embodiments 1 through 3, further comprising forming the at least one hydrophilic group on a surface of the carbon core opposite the at least one hydrophilic group.
- Embodiment 5 The method of Embodiment 4, wherein forming the at least one hydrophilic group comprises hydrolyzing at least one hydrophilic precursor on the surface of the carbon core.
- Embodiment 6 The method of any one of Embodiments 1 through 5, further comprising forming the at least one hydrophilic group on an outer wall of a carbon nanotube.
- Embodiment 7 The method of any one of Embodiments 1 through 6, further comprising forming the at least one hydrophilic group on one side of graphene platelets.
- Embodiment 8 The method of any one of Embodiments 1 through 7, further comprising increasing a solubility of the amphiphilic nanoparticles in an aqueous phase after removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles
- Embodiment 9 The method of Embodiment 8, wherein increasing a solubility of the amphiphilic nanoparticles in an aqueous phase comprises altering a pH of the aqueous phase.
- Embodiment 10 The method of any one of Embodiments 1 through 9, further comprising mixing amphiphilic nanoparticles comprising a silica base into the carrier fluid.
- Embodiment 1 1 The method of any one of Embodiments 1 through 10, wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises forming the suspension to comprise from about 50 ppm to about 500 ppm of the amphiphilic nanoparticles.
- Embodiment 12 The method of any one of Embodiments 1 through 1 1, further comprising altering a pH of the suspension after contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension.
- Embodiment 13 The method of any one of Embodiments 1 through 12, further comprising decreasing a solubility of the amphiphilic nanoparticles in an aqueous phase and recovering at least a portion of the amphiphilic nanoparticles from the emulsion after removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
- Embodiment 14 The method of any one of Embodiments 1 through 13, further comprising destabilizing the emulsion after removing hydrocarbons stabilized by the amphiphilic nanoparticles.
- Embodiment 15 A method of removing a hydrocarbon from a subterranean formation, the method comprising: fonning at least one hydrophilic group on a surface of a carbon-containing material comprising at least one of a carbon nanotube, a fullerene, a carbon nanodiamond, graphene, and graphene oxide; mixing the carbon-containing material with a carrier fluid to form a suspension; introducing the suspension into a subterranean formation and contacting hydrocarbons within the subterranean formation with the suspension to form an emulsion stabilized by the carbon-containing material; and transporting the emulsion to a surface of the subterranean formation.
- Embodiment 16 The method of Embodiment 15, further comprising forming at least one hydrophobic functional group on another surface of the carbon-containing material.
- Embodiment 17 The method of Embodiment 16, wherein fonning at least one hydrophobic functional group on another surface of the carbon-containing material comprises fonning the at least one hydrophobic functional group on a surface opposite the at least one hydrophilic group.
- Embodiment 18 The method of any one of Embodiments 15 through 17, wherein forming at least one hydrophilic group on a surface of a carbon-containing material comprises forming at least one amine group on the carbon-containing material.
- Embodiment 19 The method of any one of Embodiments 15 through 18, further comprising hydrolyzing at least one hydrophilic group with exposed hydroxyl groups of the at least one hydrophilic group on the carbon-containing material to form hydrophobic groups on the carbon-containing material.
- Embodiment 20 The method of any one of Embodiments 15 through 19, wherein forming at least one hydrophilic group on a surface of a carbon-containing material comprises forming the at least one hydrophilic group on an outer wall of a carbon nanotube.
- Embodiment 21 The method of any one of Embodiments 15 through 19, wherein forming at least one hydrophilic group on a surface of a carbon-containing material comprises forming the at least one hydrophilic group on one side of graphene platelets.
- Embodiment 22 The method of any one of Embodiments 15 through 21, further comprising mixing amphiphilic nanoparticles comprising a silica base into the carrier fluid.
- Embodiment 23 A suspension for removing hydrocarbons from a subterranean formation, comprising: a plurality of carbon-containing amphiphilic nanoparticles, the amphiphilic nanoparticles comprising: hydrophobic functional groups on a surface of the carbon-containing material; and hydrophilic functional groups on another surface of the carbon-containing material; and a carrier fluid.
- Embodiment 24 The suspension of Embodiment 23, wherein the hydrophilic functional groups on another surface of the carbon-containing material are on a surface of the carbon-containing material opposite the hydrophobic functional groups.
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Abstract
Suspensions comprising amphiphilic nanoparticles and at least one carrier fluid. The amphiphilic nanoparticles may be formed from a carbon-containing material and include at least a hydrophilic portion and a hydrophobic portion. The hydrophilic portion comprises at least one hydrophilic functional group and the hydrophobic portion includes at least one hydrophobic functional group. Methods of forming the flooding suspension and methods of removing a hydrocarbon material using the flooding suspensions are disclosed.
Description
SUSPENSIONS FOR ENHANCED HYDROCARBON RECOVERY, AND METHODS OF RECOVERING HYDROCARBONS USING THE SUSPENSIONS PRIORITY CLAIM
This application claims the benefit of the filing date of United States Patent Application Serial No. 14/519,728, filed October 21, 2014, for "SUSPENSIONS FOR ENHANCED OIL RECOVERY, AND METHODS OF RECOVERING HYDROCARBONS USING THE SUSPENSIONS," which is a continuation-in-part of U.S. Patent Application Serial No. 14/169,432, filed January 31, 2014, for
"NANO-SURFACTANTS FOR ENHANCED HYDROCARBON RECOVERY, AND METHODS OF FORMING AND USING SUCH NANO-SURFACTANTS," the disclosure of each of which is hereby incorporated herein in its entirety by this reference.
TECHNICAL FIELD
Embodiments of the disclosure relate generally to methods and systems of forming a stabilized emulsion and extracting a hydrocarbon material from a subterranean formation.
BACKGROUND
Water flooding is a conventional process of enhancing the extraction of hydrocarbon materials (e.g., crude oil, natural gas, etc.) from subterranean formations. In this process, an aqueous fluid (e.g., water, brine, etc.) is injected into the subterranean formation through injection wells to sweep a hydrocarbon material contained within interstitial spaces (e.g., pores, cracks, fractures, channels, etc.) of the subterranean formation toward production wells offset from the injection wells. One or more additives may be added to the aqueous fluid to assist in the extraction and subsequent processing of the hydrocarbon material.
For example, in some approaches, a surfactant, solid particles (e.g., colloids), or both are added to the aqueous fluid. The surfactant and/or the solid particles can adhere to or gather at interfaces between a hydrocarbon material and an aqueous material to form a stabilized emulsion of one of the hydrocarbon material and the aqueous material dispersed in the other of the hydrocarbon material and the aqueous
material. Surfactants may decrease the surface tension between the hydrocarbon phase and the water phase, such as, for example, in an emulsion of a hydrocarbon phase dispersed within an aqueous phase. Stabilization by the surfactant, the solid particles, or both, lowers the interfacial tension between the hydrocarbon and water and reduces the energy of the system, preventing the dispersed material (e.g., the hydrocarbon material, or the aqueous material) from coalescing, and maintaining the one material dispersed as units (e.g., droplets) throughout the other material. Reducing the surface tension increases the permeability and the flowability of the hydrocarbon material. As a consequence, the hydrocarbon material may be more easily transported through and extracted from the subterranean formation as compared to water flooding processes that do not employ the addition of a surfactant and/or solid particles. The effectiveness of the emulsion is determined in large part by the ability of the emulsion to remain stable and ensure mixing of the two phases.
However, application of surfactants is usually limited by the cost of the chemicals and their adsorption and loss onto the rock of the hydrocarbon-containing formation. Disadvantageously, the affectivity of various surfactants can be detrimentally reduced in the presence of dissolved salts (e.g., such as various salts typically present within a subterranean formation). In addition, surfactants can have a tendency to adhere to surfaces of the subterranean formation, requiring the economically undesirable addition of more surfactant to the injected aqueous fluid to account for such losses. Solid particles can be difficult to remove from the stabilized emulsion during subsequent processing, preventing the hydrocarbon material and the aqueous material thereof from coalescing into distinct, immiscible components, and greatly inhibiting the separate collection of the hydrocarbon material. Furthermore, the surfactants are often functional or stable only within particular temperature ranges and may lose functionality at elevated temperatures or various conditions encountered within a subterranean formation.
DISCLOSURE
Embodiments disclosed herein include methods of recovering hydrocarbon material from a subterranean formation or from a bituminous sand, as well as related stabilized emulsions. For example, in accordance with one embodiment, a method of recovering a hydrocarbon material comprises combining amphophilic nanoparticles
comprising a carbon core, at least one hydrophilic group, and at least one hydrophobic group with a carrier fluid to form a suspension, contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension to form an emulsion stabilized by the amphiphilic nanoparticles, and removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
In additional embodiments, a method of removing a hydrocarbon from a subterranean formation comprises forming at least one hydrophilic group on a surface of a carbon-containing material comprising at least one of a carbon nanotube, a fullerene, a carbon nanodiamond, graphene, and graphene oxide, mixing the carbon- containing material with a carrier fluid to form a suspension, introducing the suspension into a subterranean formation and contacting hydrocarbons within the subterranean formation with the carrier fluid suspension to form an emulsion stabilized by the carbon-containing material, and transporting the emulsion to a surface of the subterranean formation.
In further embodiments, a suspension for removing hydrocarbons from a subterranean formation comprises a plurality of carbon-containing amphiphilic nanoparticles, the amphiphilic nanoparticles comprising hydrophobic functional groups on a surface of the carbon-containing material, and hydrophilic functional groups on another surface of the carbon-containing material. The suspension further comprises a carrier fluid carrier fluid.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the invention, the advantages of embodiments of the disclosure may be more readily ascertained from the following description of certain embodiments of the disclosure when read in conjunction with the accompanying drawings, in which:
FIG. 1 A through FIG. 1C are simplified schematics of an amphiphilic nanoparticle in accordance with embodiments of the disclosure;
FIG. 2 is a simplified flow diagram depicting a method of extracting hydrocarbons from a subterranean formation, in accordance with embodiments of the disclosure; and
FIG. 3 is a simplified flow diagram depicting a method of recovering hydrocarbons from bituminous sand, in accordance with embodiments of the disclosure. MODE(S) FOR CARRYING OUT THE INVENTION
Illustrations presented herein are not meant to be actual views of any particular material, component, or system, but are merely idealized representations that are employed to describe embodiments of the disclosure.
The following description provides specific details, such as material types, compositions, and processing conditions in order to provide a thorough description of embodiments of the disclosure. However, a person of ordinary skill in the art will understand that the embodiments of the disclosure may be practiced without employing these specific details. Indeed, the embodiments of the disclosure may be practiced in conjunction with conventional techniques employed in the industry. Only those process acts and structures necessary to understand the embodiments of the disclosure are described in detail below. Additional acts or materials to extract a hydrocarbon material from a subterranean formation or from bituminous sands (e.g., oil sands, tar sands, etc.) may be performed by conventional techniques.
Methods of forming amphiphilic nanoparticles with dual functionality are described. As used herein, the term "nanoparticle" means and includes a particle having an average particle width or diameter of less than about 1 ,000 nm. As used herein, "amphiphilic nanoparticle" means and includes a nanoparticle exhibiting both hydrophilic and hydrophobic properties (e.g., similar to a Janus nanoparticle). The amphiphilic nanoparticle may include a two-dimensional structure with one side of the structure exhibiting hydrophobic characteristics and another, opposite side of the structure exhibiting hydrophilic characteristics. For example, an amphiphilic nanoparticle may include both hydrophilic and hydrophobic functional groups. In other embodiments, the amphiphilic nanoparticle may be formed of a hydrophobic core material and at least one side or portion of the hydrophobic core material may be functionalized with hydrophilic functional groups. Surfactants including such amphiphilic nanoparticles may have a higher surface area and may be stable at higher temperatures and salt concentrations than conventional particle surfactants used to stabilize emulsions. In addition, functional groups on the amphiphilic nanoparticles
may be formulated to interact with various media of different subterranean environments.
The amphiphilic nanoparticles may gather at, adhere to, and/or adsorb onto minerals within a subterranean formation, may adsorb to interfaces of a hydrocarbon material and an aqueous material, or both. The amphiphilic nanoparticles may form a stabilized emulsion (e.g., a Pickering emulsion) comprising units of one of the hydrocarbon material and the aqueous material. As used herein, the term "emulsion" refers to suspensions of droplets of one immiscible fluid dispersed in another fluid. The emulsion may reduce the interfacial tension between a continuous phase and a dispersed phase. Decreasing interfacial tension between, for example, a dispersed hydrocarbon phase and a continuous aqueous phase may increase the hydrocarbon (e.g., oil) mobility and recovery from a subterranean formation or from a slurry of a bituminous sand including the hydrocarbon.
The amphiphilic nanoparticles may be formulated to remain at an interface between a polar phase and a nonpolar phase, between a hydrophilic phase and a hydrophobic phase, and/or between a hydrocarbon phase and an aqueous phase, such as at an interface between a gas phase and an aqueous phase, an interface between a liquid hydrocarbon phase and an aqueous phase, or an interface between a solid phase and at least one of an aqueous phase and a hydrocarbon phase. The amphiphilic nanoparticles may stabilize an emulsion of the hydrocarbon phase within the aqueous phase or an emulsion of the aqueous phase within the hydrocarbon phase. Stabilizing the emulsion may prevent the emulsion from coalescing once the emulsion interface is formed. One side (e.g., the hydrophilic side) of the amphiphilic nanoparticles may be formulated to be attracted to the aqueous phase while the other side (e.g., the hydrophobic side) of the amphiphilic nanoparticles may be formulated to be attracted to the hydrocarbon phase.
The amphiphilic nanoparticles formed by the methods described herein may have a higher surface area than conventional surfactants. The functionalized surfaces of the amphiphilic nanoparticles may be formulated to interact with the interface between the hydrocarbon phase and the aqueous phase or with solid surfaces (e.g., minerals) within the subterranean formation, thereby forming a stable emulsion of a continuous aqueous or hydrocarbon phase and a dispersed phase of the other of the hydrocarbon and aqueous phase. The stability of the emulsion may be controlled by
one or more of controlling the solubility of the amphiphilic nanoparticles within the aqueous phase, controlling the pH of the emulsion and/or the aqueous phase, and controlling the surface charge of the amphiphilic nanoparticles.
Referring to FIG. 1A, an amphiphilic nanoparticle 100 is shown. The amphiphilic nanoparticle 100 may include a base portion. The amphiphilic nanoparticle 100 may include a hydrophilic portion 102 and a hydrophobic portion 104. Surfaces of the base portion may be modified with functional groups to impart desired physical and chemical properties to the surface of the amphiphilic nanoparticle 100. For example, the hydrophilic portion 102 may include at least one hydrophilic functional group on a surface of the base portion and the hydrophobic portion 104 may include at least one hydrophobic group on a surface of the base portion. In other embodiments, the hydrophobic portion 104 may be formed of the base portion and the hydrophilic portion 102 may include at least one hydrophilic functional group on a surface of the hydrophobic base portion.
The base portion may include any material that may be chemically modified with functional groups to form the hydrophilic portion 102 and the hydrophobic portion 104. In some embodiments, the base portion includes a silica base. In other embodiments, the base portion includes a metal or a metal oxide. For example, the base portion may include a metal such as iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, cobalt, oxides thereof, and combinations thereof. In yet other embodiments, the base portion may include a carbon-based material, such as at least one of carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNTs), multi- walled carbon nanotubes (MWCNTs), and combinations thereof), carbon
nanodiamonds, graphite, graphene, graphene oxide, fullerenes, onion-like structures (e.g., a "bucky onion"). Thus, the base portion may include silica, a metal such as one of iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, cobalt, carbon nanotubes, carbon nanodiamonds, graphene, graphene oxide, fullerenes, bucky onions, and combinations thereof.
The amphiphilic nanoparticle 100 may be formed from a plurality of hydrophilic precursors and a plurality of hydrophobic precursors. As used herein, the term "hydrophilic precursor" includes materials having at least one atom of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt, and at least one hydrophilic functional group. As used herein, the term "hydrophobic
precursor" includes materials having at least one atom of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt, and at least one hydrophobic functional group. In some embodiments, a plurality of hydrophilic precursors may react to form a nanoparticle including a base of at least one of carbon, silica, a metal, and a metal oxide with one or more hydrophilic functional groups attached to the surface thereof. The hydrophilic functional groups of the hydrophilic portion 102 may be formed from the hydrophilic functional group of the hydrophilic precursor.
The surface of the base portion may be chemically modified to form amphophilic nanoparticles 100 including a hydrophobic portion 104 in addition to the hydrophilic portion 102. The hydrophobic portion 104 may be formed from hydrophobic groups attached to the surface of the base portion. The hydrophobic groups may include nonpolar groups, such as, for example, alkyl chains. Where the base portion is formed of carbon (e.g., carbon nanotubes, carbon nanodiamonds, graphite, graphene, graphene oxide, fullerenes, bucky onions, etc.) the hydrophobic portion 104 may be comprised of the base portion and the hydrophilic portion 102 may be formed on at least some surfaces of the hydrophobic base portion. The hydrophilic portion 102 may be soluble in an aqueous phase, whereas the hydrophobic portion 104 may be soluble in an organic phase.
The amphophilic nanoparticle 100 may be formed of various shapes. The shape of the amphiphilic nanoparticle 100 may be controlled by growing the amphiphilic nanoparticles 100 in the presence of a structure-directing agent. Non-limiting examples of structure-directing agents include polymers such as a polypyrrole (e.g., polyvinylpyrrolidone (PVP)), an oxidized polypyrrole, a diphenyl ester, and cetyltrimethylammonium bromide (CTAB). With continued reference to FIG. 1 A, the amphiphilic nanoparticle 100 may include a tubular-shaped base with a solid hydrophilic portion 102 and a hollow-tubular shaped hydrophobic portion 104.
Amphiphilic nanoparticles 100 formed from SWCNTs and MWCNTs may be tubular- shaped as shown in FIG. 1A. Referring to FIG. I B, the amphiphilic nanoparticle 100 may be generally spherical in shape with a hydrophilic portion 102 on one side and a hydrophobic portion 104 on an opposite side. Amphiphilic nanoparticles 100 formed from carbon nanodiamonds, fullerenes, and bucky onions may exhibit the spherical shape shown in FIG. I B. Referring to FIG. 1 C, the amphiphilic nanoparticle 100 may
have a platelet shape. One side of the platelet may be a hydrophilic portion 102 and the other side of the platelet may be a hydrophilic portion 104. Where the amphiphilic nanoparticles 100 are formed from a base including graphene or graphene oxide, the amphiphilic nanoparticles 100 may have the platelet shape as shown in FIG. 1 C.
In some embodiments, the hydrophilic portion 102 of the amphiphilic nanoparticles 100 is formed before forming the hydrophobic portion 104. In some embodiments, the hydrophilic portion 102 is formed by hydrolyzing the hydrophilic precursor. The hydrophilic precursor may include an organosilane having the general formula, R„SiX(4-n), where X is a hydrolyzable group, such as an alkoxy, acyloxy, amine, or halide group, and Rn includes a hydrophilic functional group. As used herein, the term "hydrolyzable group" means and includes a group that can be at least partially depolymerized to lower molecular weight units by hydrolysis (i.e., the cleavage of a chemical bond by the reaction with water). The hydrolyzable group may be reactive with an aqueous material, such as water.
The hydrophilic precursor may include one or more hydrophilic functional groups such as a hydroxyl group (-OFT), a carboxyl group (-COOH"), a carbonyl group (-C=0), an amino group (-NH3 +, -NH2, -NHR,-NRR', where R and R' include a hydrocarbon group, such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, each of which may include one or more hydrogen atoms substituted with one or more halides, hydroxyl groups, amine groups, or sulfur-containing groups), a thiol group (-SH), a phosphate group (-PO4 "), or other hydrophilic or polar functional groups in addition to the hydrolyzable group.
In some embodiments, a carbon-containing material that forms the base portion may include one or more exposed functional groups such as a hydroxyl group, a carboxyl group, a carbonyl group, an amino group, a thiol group, a phosphate group, an azo group, or another hydrophilic or polar functional group. By way of example, carbon nanotubes may include one or more hydrophilic functional groups on at least one of the outside or the inside (e.g., an inner wall or an outer wall) of the carbon nanotube. In other embodiments, at least one side of graphite platelets, graphene platelets or graphene oxide platelets may be functionalized with at least one type of hydrophilic functional group.
By way of non-limiting example, a carbon-containing material may be functionalized by oxidation with concentrated nitric acid, sulfuric acid, and
combinations thereof. The oxidation may form carboxyl groups on exposed surfaces of the carbon-containing material, such as on sidewalls of carbon nanotubes or on exposed surfaces of a graphene plate. The exposed carboxyl groups may form reaction sites for further functionalizing the carbon-containing material. In some embodiments, the exposed carboxyl groups may be exposed to an amine (primary amine (RNH2), a secondary amine (RR'NH), or a tertiary amine (RR'R"N), where R, R', and R" include a hydrocarbon group, such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, each of which may include one or more hydrogen atoms substituted with one or more halides, hydroxyl groups, amine groups, or
sulfur-containing groups), an alkanolamine (a compound including a hydroxyl group and at least one of NH2, NHR, and NRR' where R and R' include the same groups described above with respect to amines) to form amine functionalized nanotubes. The amine groups attached to the carbon-containing base may form hydrophilic groups attached to the hydrophobic carbon-containing base.
In other embodiments, exposed hydroxyl groups of a carbon-containing core may react with other hydrophilic precursors including terminal hydroxyl groups in a condensation reaction to attach the hydrophilic portion 102 to the carbon-containing material. By way of example only, the terminal hydroxyl groups of a carbon- containing material may react with materials such as a hydroxylamine (e.g., HO- NRR', where R and R' include a hydrocarbon group as described above and include at least one hydrogen substituted with at least one of a halide, a hydroxyl group, an amine group, and a sulfur-containing compound) in a condensation reaction.
The hydrophilic precursor may include oxysilanes, orthosilicates, aminosilanes, silanols, epoxy silanes, metal oxides, hydroxides, metal hydroxides, or combinations thereof. As used herein, the term "oxysilane" means and includes materials including a silicon atom bonded to at least one oxygen atom (e.g., -Si~OR, where R is a hydrocarbon material or hydrogen). As used herein, the term "orthosilicate" means and includes materials including a silicon atom bonded to four oxygen atoms (e.g., Si(OR)4, where R is a hydrocarbon material or hydrogen).
The hydrophilic precursor may include orthosilicates, such as, for example, tetramethyl orthosilicate, tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate, trimethylmethoxysilane, triethylethoxysilane, or tripropylpropoxysilane. The hydrolysis of trimethylmethoxysilane, triethylethoxysilane, or tripropylpropoxysilane
may form a silanol such as trimethylsilanol, triethylsilanol, or tripropyl silanol, respectively. In other embodiments, the hydrophilic precursor includes ethyoxysilanes such as trimethoxysilane, triethoxysilane, or tributyl(ethoxy)silane.
In other embodiments, the hydrophilic precursor includes metal hydroxides and metal salts. For example, the hydrophilic precursor may include metal hydroxides such as an iron hydroxide, titanium hydroxide (e.g., TiO(OH)2, Ti(OH)4), germanium hydroxide, tin hydroxide, lead hydroxide, zirconium hydroxide, ruthenium hydroxide, nickel hydroxide, and cobalt hydroxide. In some embodiments, the hydrophilic precursor includes a metal salt such as salts of at least one of iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt. In some embodiments, a hydrophilic precursor including a metal hydroxide may react with an exposed hydroxyl group on a surface of the base of the nanoparticle.
In other embodiments, the hydrophilic precursor includes a metal oxide. For example, the hydrophilic precursor may include iron oxide (Fe203, Fe3C>4), titanium dioxide, germanium oxide (GeO, Ge02), tin oxide (SnO, Sn02), lead oxide (PbO, Pb02, Pb3C>4), zirconium oxide, ruthenium oxide (Ru02, R.UO4), nickel oxide (NiO, Ni203), and cobalt oxide (CoO, ί¾03, C03O4). In other embodiments, the hydrophilic precursor may include a metal alkoxide. For example, the hydrophilic precursor may include iron ethoxide, titanium isopropoxide, titanium ethoxide, germanium ethoxide, tin ethoxide, lead ethoxide, zirconium ethoxide, and nickel(II) methoxide.
In other embodiments, the hydrophilic precursor may include an aminosilane including at least one amino group. The at least one amino group may be in addition to at least two oxysilane groups. Non-limiting examples of suitable aminosilanes include (3-aminopropyl)-diethoxy-methylsilane (APDEMS), (3-aminopropyl)- trimethoxysilane (APTMS), (3-aminopropyl)-methyldiethoxysilane, (3-aminopropyl)- triethoxysilane (APTES), 3-aminopropyltriethoxysilane, bis(3-triethoxysilylpropyl) amine, and bis(3-trimethoxysilylproply) amine. Hydrolysis of the aminooxysilanes may form a hydroxyl terminated hydrophilic portion 102 including amino groups. In some embodiments, the aminosilanes may be reacted with, for example, an ethylene carbonate to form a hydrophilic portion 102 including exposed hydroxyl groups.
In other embodiments, the hydrophilic precursor may include an epoxy silane. Non-limiting examples of epoxy silanes include 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane, and 3-glycidyloxypropyltriethoxysilane. The epoxy silane may be hydrolyzed to form exposed hydroxyl groups on the hydrophilic portion 102.
The synthesis of the hydrophilic portion 102 of the amphophilic nanoparticles 100 may be carried out in a polar solvent. The hydrophilic portion 102 may be soluble in the solvent. The solvent may include an alcohol such as methanol, ethanol, propanol, butanol, pentanol, other alcohol, acetone, or combinations thereof. The hydrophilic precursor may be soluble in the solvent.
Additional agents may be added to the reaction solution. For example, structure-directing agents, such as polyvinylpyrrolidone (PVP), may be mixed into the reaction solution. The pH of the reaction solution may be varied by adding various acids or bases. For example, the pH of the solution may be increased by adding sodium bicarbonate, sodium hydroxide, or other base to the solution. The pH of the solution may be decreased by adding an acid such as hydrochloric acid, acetic acid, or other acid to the solution.
The synthesis of the hydrophilic portion 102 may be carried out at room temperature. In some embodiments, the reaction solution may be heated to increase a reaction rate of formation of the hydrophilic portion 102 of the amphiphilic nanoparticles 100. In other embodiments, the reaction rate may be increased by microwave irradiation. The reaction may proceed for between about one minute and several hours. In some embodiments, the size of the hydrophilic portion 102 may be increased by increasing the synthesis time of forming the hydrophilic portion 102. In embodiments where the hydrophilic portion 102 is formed by hydrolysis, the reaction may leave one or more exposed hydroxyl groups on the hydrophilic portion 102. The hydrophilic portion 102 may include one or more additional functional groups, such as additional hydroxyl groups, a carboxyl group, a carbonyl group, an amino group, a thiol group, and a phosphate group.
The hydrophilic precursor may be hydrolyzed to form a plurality of hydrophilic precursors with exposed hydroxyl groups. The exposed hydroxyl groups of the hydrophilic precursors may react with each other in a condensation reaction, forming the hydrophilic portion 102 including a base material and hydrophilic functional groups on a surface of the base material. The exposed functional groups may be the same functional groups as the functional groups of the hydrophilic precursor. A
surface of the hydrophilic portion 102 may have the general structure as shown below, where Rn includes a hydrophilic group, and M is at least one of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt. In embodiments where M is carbon or a metal (e.g., iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt), adjacent metal atoms may be directly bonded to each other without intervening oxygen atoms and the carbon based materials may include hydrophilic substitution (e.g., adjacent carbon atoms may be directly bonded to each other or may be connected via a hydrophilic functional group).
A hydrophobic precursor may be added to the reaction solution including the hydrophilic portion 102. An organic solvent in which the hydrophobic precursor is soluble may be added to the reaction mixture. In some embodiments, the organic solvent is a nonpolar solvent. The hydrophobic functional group of the hydrophobic precursor may be soluble in an organic phase whereas the hydrophilic functional group on the surface of the base material may be soluble in an aqueous phase.
The amphiphilic nanoparticles 100 may be formed by reacting at least some of the exposed hydroxyl groups of the hydrophilic portion 102 with one or more of the hydrophobic precursors. The hydrophobic precursor may include one or more exposed hydroxyl groups. In some embodiments, the hydrophobic precursor is hydrolyzed to create exposed hydroxyl groups on the hydrophobic precursor.
In some embodiments, the hydrophobic portion 104 grows from one end of the hydrophilic portion 102. Without being bound by any theory, it is believed that only a portion of the hydrophilic portion 102 contacts the nonpolar solvent in which the hydrophobic precursors are dissolved because of the insolubility of the hydrophilic portion 102 in the nonpolar solvent. The hydroxyl groups of a portion of the hydrophilic portion 102 that contacts the hydrophobic precursor (e.g., at an interface between the nonpolar solvent and the polar solvent of the hydrophilic portion 102) may react with the hydrophobic precursors to form the hydrophobic portion 104 of the amphiphilic nanoparticle 100. An exposed surface of the hydrophobic portion 104
may have a general structure as shown below, where Rm includes a hydrophobic functional group, and M is at least one of carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt. In embodiments where M is a metal (e.g., iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt), adjacent metal atoms may be directly bonded to each other without intervening oxygen atom.
The amphiphilic nanoparticle 100 may include one or more exposed hydrophobic, nonpolar organic groups from the hydrophobic precursor, and one or more functional groups (e.g., hydroxyl, carboxyl, carbonyl, amino, thiol, phosphate, a metal, a metal oxide) from the hydrophilic precursor.
The hydrophobic precursor may include an oxysilane including a nonpolar, organic component. The hydrophobic precursor may include at least one central atom such as carbon, silicon, iron, titanium, germanium, tin, lead, zirconium, ruthenium, nickel, and cobalt, one or more hydrocarbon groups bonded to the central atom, and one or more alkoxy groups bonded to the central atom. In other embodiments, the hydrophobic precursor includes a hydrocarbon bonded to an isocyanate functional group (-N=C=0), such as octadecyl isocyanate. In some embodiments, the hydrocarbon group is an alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, and/or octadecyl groups, an alkaryl group such as benzyl groups attached via the aryl portion (e.g., 4-methylphenyl, 4 hydroxymethylphenyl, or
4-(2-hydroxyethyl)phenyl, and/or aralkyl groups attached at the benzylic (alkyl) position, such as in a phenylmethyl and 4-hydroxyphenylmethyl groups, and/or attached at the 2-position, such as in a phenethyl and 4-hydroxyphenethyl groups); lactone groups, imidazole, and pyridine groups. In some embodiments, the alkoxy group is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. The hydrophobic precursors may include alkyloxysilanes, such as trialkoxysilanes including trimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane. hexadecyltrimethoxysilane (HDTMOS),
methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane,
octyltriethoxysilane, or other oxysilanes.
The hydrophobic precursor may include a compound configured to form hydrophobic functional groups on a surface of the amphiphilic nanoparticle 100. In some embodiments, a hydroxyl group of the alcohol or the hydrophobic precursor may react with an exposed hydroxyl group on the base of the amphiphilic nanoparticle in a condensation reaction to form the hydrophobic portion 104. By way of non-limiting example, a hydrophobic precursor may react with an exposed hydroxyl group on a carbon-containing material to form the hydrophobic portion 104. In other embodiments, a hydroxyl group of the hydrophobic precursor may react with exposed hydroxyl groups of the hydrophilic portion 102 in a condensation reaction to form the hydrophobic portion 104. By way of example only, the hydrophobic precursor may include an alcohol having the general formula RR'R"- OH, where R, R', and R" may include hydrogen, or an organic group, such as an alkyl group, alkenyl group, alkynyl group, aryl group, etc. The alcohol may include one or more hydroxyl groups (e.g., a diol, a triol, etc.). The hydrophobic portion 104 may be formed on only one side of the amphiphilic nanoparticle 100 (e.g., an opposite side as the hydrophilic portion 102).
The hydrophobicity of the hydrophobic portion 104 may be controlled by altering the number of functional groups and the size of the functional groups of the hydrophobic precursor. In some embodiments, the hydrophobicity of the hydrophobic portion 104 is increased by increasing the carbon content of the functional group of the hydrophobic precursor. For example, ethyltrimethoxysilane may be more hydrophobic than methyltrimethoxysilane. Similarly, hexadecyltrimethoxysilane may be more hydrophobic than ethyltrimethoxysilane. The hydrophobicity of the amphiphilic nanoparticles 100 may also be increased by increasing a concentration of the hydrophobic functional group relative to a concentration of the hydrophilic functional group in the reaction mixture or by decreasing a reaction time of forming the hydrophilic portion 102 relative to a reaction time of forming the hydrophobic portion 104. In yet other embodiments, where the base includes a carbon-containing material, the hydrophobic portion 104 of the amphiphilic nanoparticle 100 may be the core and the hydrophilic portions 1 02 may be any hydrophilic functional groups attached to the carbon-containing material.
The amphiphilic nanoparticles 100 may be removed from the reaction solution by centrifugation, ultrafiltration, or combinations thereof. In some embodiments, the amphiphilic nanoparticles 100 are recovered by flowing the solution through a membrane filter. The filter may have a pore size ranging from between about 10 nm and about 1 ,000 nm, such as between about 10 nm and about 100 nm, between about 100 nm and about 200 nm, between about 200 nm and about 400 nm, or between about 400 nm and about 1 ,000 nm. In some embodiments, the solution is flowed through a filter having a pore size of between about 200 nm and about 400 nm. The resulting solid residue may be dried and collected. The solid residue may include amphiphilic nanoparticles 100 with a hydrophilic portion 102 and a hydrophobic portion 104. The hydrophobic portion 104 may be opposite the hydrophilic portion 102 such that one portion of the amphiphilic nanoparticle 100 is attracted to and soluble in a hydrocarbon phase and another portion of the amphiphilic nanoparticle 100 is attracted to and soluble in an aqueous phase.
The amphiphilic nanoparticles 100 may have a size distribution ranging from between about 10 nm and about 1,000 nm. In some embodiments, the size distribution may correspond to the size of the filter through which the solution was passed to separate the nanoparticles from the reaction solution. The amphiphilic nanoparticles 100 may be monodisperse wherein each of the amphiphilic nanoparticles 100 has substantially the same size, shape, and material composition, or may be polydisperse, wherein the amphiphilic nanoparticles 100 include a range of sizes, shapes, and/or material composition. In some embodiments, each of the amphiphilic nanoparticles 100 has substantially the same size and the same shape as each of the other amphiphilic nanoparticles 100.
The amphiphilic nanoparticles 100 may stabilize an emulsion at higher temperatures than a typical surfactant. For example, typical surfactants may degrade or otherwise lose functionality at temperatures in excess of about 250°C. However, the amphiphilic nanoparticles 100 described herein may be stable at high temperatures that may be encountered within a subterranean formation. For example, the amphiphilic nanoparticles 100 may be stable at temperatures up to about 500°C. In some embodiments, the amphiphilic nanoparticles 100 are exposed to a temperature between about 250°C and about 500°C, such as between about
300°C and about 400°C, or between about 400°C and about 500°C, and may remain stable.
The amphophilic nanoparticles 100 may remain effective at stabilizing an emulsion at higher salinity concentrations than typical surfactants. Due to the presence of the functional groups on the amphiphilic nanoparticles 100, the amphophilic nanoparticles 100 may be repelled from the salts of a brine solution, whereas non-functionalized particles may tend to agglomerate or gel with a salt.
The amphiphilic nanoparticles 100 may be stable within a wide pH range. For example, the amphiphilic nanoparticles 100 may be formulated to be stable at a pH between about 3.0 and about 12.0. In some embodiments, the amphiphilic nanoparticles 100 are formulated to be stable at a pH as high as about 12.0 by forming the amphiphilic nanoparticles 100 from anionic functional groups such as hydroxyl groups, carboxylate groups, carboxyl groups, sulfate groups, phosphate groups, or other anionic groups. In other embodiments, the amphiphilic
nanoparticles 100 are formulated to be stable at a pH as low as about 3.0 by including terminal ends of cationic groups such as amine groups.
The amphiphilic nanoparticles 100 may stabilize an emulsion in any application where a stable emulsion is desired. For example, the amphiphilic nanoparticles 100 may be used in water flooding applications or floatation cell applications. The amphiphilic nanoparticles 100 may stabilize an emulsion by themselves, or the amphiphilic nanoparticles 100 may be used with one or more surfactants.
Referring to FIG. 2, a simplified flow diagram illustrating a method of recovering a hydrocarbon material contained within a subterranean formation, in accordance with embodiments of the disclosure is shown. The method may include a suspension formation process 200 including forming a flooding suspension including a plurality of amphiphilic nanoparticles; a flooding process 202 including introducing the flooding suspension into a subterranean formation to detach a hydrocarbon material from surfaces of the subterranean formation and form a stabilized emulsion of the hydrocarbon material and an aqueous material; an extraction process 204 including flowing (e.g., driving, sweeping, forcing, etc.) the stabilized emulsion from the subterranean formation; and a emulsion destabilization process 206 including
destabilizing (e.g., demulsifying, precipitating, etc.) the emulsion into distinct, immiscible phases.
The suspension formation process 200 may include forming a suspension including amphiphilic nanoparticles and at least one carrier fluid. The at least one carrier fluid may, for example, comprise water, or a brine solution. As used herein, the term "suspension" means and includes a material including at least one carrier fluid in which amphiphilic nanoparticles are substantially uniformly dispersed. The suspension may be a flooding suspension used, such as used in water flooding of a subterranean formation during enhanced oil recovery processes. The amphiphilic nanoparticles of the flooding suspension may be compatible with other components (e.g., materials, constituents, etc.) of the flooding suspension. As used herein, the term "compatible" means that a material does not impair the functionality of the amphiphilic nanoparticles or cause the amphiphilic nanoparticles to lose functionality as surfactants and emulsion stabilizers.
The flooding suspension may be formulated to include a concentration of the amphiphilic nanoparticles ranging from between about 50 ppm to about 50,000 ppm. For example, in some embodiments, the flooding suspension may have a
concentration of amphiphilic nanoparticles ranging from between about 50 ppm and about 500 ppm, between about 500 ppm and about 1 ,000 ppm, between about 1 ,000 ppm and about 5,000 ppm, or above 5,000 ppm. In some embodiments, the flooding suspension may have a concentration ranging from between about 50 ppm to about 5,000 ppm. In some embodiments, the suspension includes a portion of amphiphilic nanoparticles with a carbon-based core and another portion of amphiphilic nanoparticles with another base portion. By way of example, the suspension may include a first portion of amphiphilic nanoparticles including a carbon-containing material, a second portion of amphiphilic nanoparticles including a silica core, and a third portion of amphiphilic nanoparticles including a metal core. The emulsion may have the same, a higher, or a lower concentration of amphiphilic nanoparticles than the flooding suspension.
With continued reference to FIG. 2, the flooding process 202 may include introducing the flooding suspension including amphiphilic nanoparticles into a subterranean formation to detach a hydrocarbon material from surfaces of the subterranean formation and form a stabilized emulsion of the hydrocarbon material and
an aqueous material. The flooding suspension may be provided into the subterranean formation through conventional processes. For example, a pressurized stream of the flooding suspension may be pumped into an injection well extending to a desired depth in the subterranean formation, and may infiltrate (e.g., permeate, diffuse, etc.) into interstitial spaces of the subterranean formation. The extent to which the flooding suspension infiltrates the interstitial spaces of the subterranean formation at least partially depends on the properties of the flooding suspension (e.g., density, viscosity, material composition, etc.), and the hydrocarbon materials (e.g., molecular weight, density, viscosity, etc.) contained within interstitial spaces of the subterranean formation.
The pH of the flooding suspension may be altered to control the solubility of the amphiphilic nanoparticles within the flooding suspension. For example, where the amphiphilic nanoparticles include cationic functional groups (e.g., amino groups), decreasing the pH of the flooding suspension may increase the solubility of the amphiphilic nanoparticles in the aqueous flooding suspension. Where the amphiphilic nanoparticles include anionic functional groups (e.g., hydroxyl, carboxyl, carbonyl, phosphate, thiol groups, etc.), increasing the pH of the flooding suspension may increase the solubility of the amphiphilic nanoparticles in the flooding suspension. Altering the pH of the flooding suspension may alter the surface charge of the amphiphilic nanoparticles. For example, increasing a pH of a flooding suspension including anionic amphiphilic nanoparticles may increase the net charge of the anionic amphiphilic nanoparticles in the flooding suspension. Decreasing a pH of a flooding suspension including cationic amphiphilic nanoparticles may increase the net charge of the cationic amphiphilic nanoparticles.
After the flooding suspension is introduced into the subterranean formation, the pH of the flooding suspension may be altered to reduce the solubility of the amphiphilic nanoparticles in the aqueous phase of the flooding suspension. For example, where the amphiphilic nanoparticles include cationic functional groups, the pH of the flooding suspension may be reduced to cause the amphiphilic nanoparticles to move to the interface between the aqueous phase and the hydrocarbon phase. In some embodiments, the pH may be reduced to below about 7.0, such as below 5.0, below 4.0, or below 3.0. Where the amphiphilic nanoparticles comprise anionic functional groups, the pH of the flooding suspension
may be increased to cause the amphiphilic nanoparticles to move to the interface between the aqueous phase and the hydrocarbon phase. In some embodiments, the pH may be increased to above 7.0, such as above 8.0, above 9.0, above 10.0, and up to 12.0.
The amphiphilic nanoparticles are structured and formulated to facilitate a formation of a stabilized emulsion of a hydrocarbon material and an aqueous material. For example, the amphiphilic nanoparticles may be structured and formulated to gather (e.g., agglomerate) at, adhere to, and/or adsorb to interfaces of a hydrocarbon material and an aqueous material to form a Pickering emulsion comprising units (e.g., droplets) of one of the hydrocarbon material and the aqueous material dispersed in the other of the hydrocarbon material and the aqueous material. The amphiphilic nanoparticles may prevent the dispersed material (e.g., the hydrocarbon material or the aqueous material) from coalescing, and may thus maintain the dispersed material as units throughout the other material.
The extraction process 204 may include flowing (e.g., driving, sweeping, forcing, etc.) the stabilized emulsion from the subterranean formation to the surface. The amphiphilic nanoparticles prevent the dispersed material from coalescing and enable substantial removal of hydrocarbons from the subterranean formation.
Once the hydrocarbons are removed from the subterranean formation, at least a portion of the emulsion may be destabilized in the emulsion destabilization process 206 to form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase. One or more properties (e.g., temperature, pH, material composition, pressure, etc.) of the stabilized emulsion or the aqueous phase may be modified (e.g., altered, changed) to a least partially destabilize the emulsion. For example, the pH of the aqueous phase may be modified to increase the solubility of the amphiphilic nanoparticles within the aqueous phase, thereby destabilizing the emulsion and forming distinct, immiscible phases.
In some embodiments, the pH of the emulsion or the aqueous phase may be altered to cause the amphiphilic nanoparticles to move into the aqueous phase and destabilize the emulsion. Where the amphiphilic nanoparticles comprise anionic functional groups, the pH of the aqueous phase may be increased to increase the solubility of the amphiphilic nanoparticles in the aqueous phase. The pH of the aqueous phase may be increased by adding a base, such as a hydroxide (e.g., sodium
hydroxide) or a bicarbonate (e.g., sodium bicarbonate) to the aqueous phase. Where the amphiphilic nanoparticles comprise cationic functional groups, the pH of the aqueous phase may be reduced to increase the solubility of the amphiphilic nanoparticles in the aqueous phase. The pH of the aqueous solution may be decreased by adding hydrochloric acid, phosphoric acid, and acetic acid, or another acid to the aqueous solution.
A demulsifier may be added to the emulsion to destabilize the emulsion and form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase. In some embodiments, the emulsion is destabilized by adjusting the pH of at least one of the aqueous phase and the emulsion and by adding a demulsifier to the emulsion.
Referring to FIG. 3, a simplified flow diagram illustrating a method of recovering a hydrocarbon material from bituminous sand in accordance with other embodiments of the disclosure is shown. The method may include a suspension formation process 300 including forming a suspension including a plurality of amphiphilic nanoparticles; a mixing process 302 including mixing the suspension with a slurry including the bituminous sand and water to form a stabilized emulsion; a transportation process 304 including hydrotransporting the slurry; an extraction process 306 including extracting hydrocarbons from the stabilized emulsion; and a emulsion destabilization process 308 including destabilizing (e.g., demulsifying precipitating, etc.) the emulsion into distinct, immiscible phases.
The suspension formation process 300 may include forming a suspension including the amphiphilic nanoparticles and at least one carrier fluid. The carrier fluid may, for example, comprise water, a brine solution, or a caustic soda (NaOH) solution. The suspension may be formulated to include a concentration of amphiphilic nanoparticles similar to the flooding suspension described above with reference to FIG. 2.
The mixing process 302 may include mixing the suspension with a slurry including a bituminous sand and water to form a stabilized emulsion. The slurry may include hot water, caustic soda, and the bituminous sand. The transportation process 304 may include hydrotransporting the slurry to a location where the stabilized emulsion may be processed to remove hydrocarbons therefrom (e.g., from the bituminous sand). In some embodiments, the mixing process 302 may be performed simultaneously with the transportation process 304. In some
embodiments, a pH of the slurry may be adjusted to reduce the solubility of the amphiphilic nanoparticles in a hydrophilic portion of the slurry and increase the solubility of the amphiphilic nanoparticles in the stabilized emulsion during the mixing process and the transportation process 304.
The amphiphilic nanoparticles are structured and formulated to facilitate a formation of a stabilized emulsion of a hydrocarbon material and an aqueous phase. For example, the amphiphilic nanoparticles may be structured and formulated to gather at, adhere to, and/or adsorb to interfaces of the hydrocarbon material and the aqueous material to form a Pickering emulsion comprising units (e.g., droplets) of one of the hydrocarbon material and the aqueous material in the other of the hydrocarbon material and the aqueous material.
The extraction process 306 may include extracting hydrocarbons from the stabilized emulsion. In some embodiments, the extraction process 306 includes extracting hydrocarbons from the stabilized emulsion of the slurry in a floatation process.
After the hydrocarbons are removed from the aqueous phase in the floatation process, at least a portion of the stabilized emulsion may be destabilized in the emulsion destabilization process 308 to form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase. One or more properties (e.g., temperature, pH, material composition, pressure, etc.) of the stabilized emulsion or the aqueous phase may be modified (e.g., altered, changed) to a least partially destabilize the emulsion. For example, the pH of the aqueous phase may be modified to increase the solubility of the amphiphilic nanoparticles within the aqueous phase, thereby destabilizing the emulsion and forming distinct, immiscible phases. The pH of the stabilized emulsion may be altered to cause the amphiphilic nanoparticles to move into the aqueous phase and destabilize the emulsion, as described above with reference to emulsion destabilization process 206 of FIG. 2. In other embodiments, a demulsifier may be added to the emulsion to destabilize the emulsion and form distinct, immiscible phases including an aqueous phase and a hydrocarbon phase.
After the emulsion is destabilized, the hydrocarbon material may be separated from the aqueous material and recovered. Thereafter, the amphiphilic nanoparticles may be recovered from the aqueous phase. In some embodiments, the
pH of the aqueous solution may be adjusted to reduce the solubility of the amphiphilic nanoparticles in the aqueous solution and precipitate the amphiphilic nanoparticles from the aqueous solution. For example, where the amphiphilic nanoparticles include functional groups such as amine functional groups, decreasing the pH of the aqueous material may reduce the solubility of the amphiphilic nanoparticles in the aqueous solution, thereby causing them to precipitate out of the aqueous solution. In embodiments where the functional group of the amphiphilic nanoparticles are hydroxyl, carboxyl, carbonyl, thiol, phosphate, or other anionic groups, increasing the pH of the aqueous solution may cause the amphiphilic nanoparticles to precipitate out of the aqueous solution. In other embodiments, the amphiphilic nanoparticles are recovered by filtering the aqueous solution through a filter. The filter may have a pore size ranging from between about 10 nm and about 5,000 nm, depending on the size of the amphiphilic nanoparticles. In some embodiments, more than one filtration step may be performed. For example, a first filtration step may filter out sands and other solid particles having a larger diameter than the amphiphilic nanoparticles. Thereafter, the amphiphilic nanoparticles may be separated from the aqueous solution.
Additional non-limiting example embodiments of the disclosure are set forth below.
Embodiment 1 : A method of recovering a hydrocarbon material, the method comprising: combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension; contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension to form an emulsion stabilized by the amphiphilic nanoparticles; and removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
Embodiment 2: The method of Embodiment 1 , wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises combining amphiphilic nanoparticles comprising at least one of carbon nanotubes, carbon nanodiamonds, graphite, graphene, graphene oxide, fullerenes, and bucky onions.
Embodiment 3: The method of Embodiment 2, wherein wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises combining amphiphilic nanoparticles comprising an amino functional group with the carrier fluid.
Embodiment 4: The method of any one of Embodiments 1 through 3, further comprising forming the at least one hydrophilic group on a surface of the carbon core opposite the at least one hydrophilic group.
Embodiment 5: The method of Embodiment 4, wherein forming the at least one hydrophilic group comprises hydrolyzing at least one hydrophilic precursor on the surface of the carbon core.
Embodiment 6: The method of any one of Embodiments 1 through 5, further comprising forming the at least one hydrophilic group on an outer wall of a carbon nanotube.
Embodiment 7: The method of any one of Embodiments 1 through 6, further comprising forming the at least one hydrophilic group on one side of graphene platelets.
Embodiment 8: The method of any one of Embodiments 1 through 7, further comprising increasing a solubility of the amphiphilic nanoparticles in an aqueous phase after removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles
Embodiment 9: The method of Embodiment 8, wherein increasing a solubility of the amphiphilic nanoparticles in an aqueous phase comprises altering a pH of the aqueous phase.
Embodiment 10: The method of any one of Embodiments 1 through 9, further comprising mixing amphiphilic nanoparticles comprising a silica base into the carrier fluid.
Embodiment 1 1 : The method of any one of Embodiments 1 through 10, wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a
suspension comprises forming the suspension to comprise from about 50 ppm to about 500 ppm of the amphiphilic nanoparticles.
Embodiment 12: The method of any one of Embodiments 1 through 1 1, further comprising altering a pH of the suspension after contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension.
Embodiment 13: The method of any one of Embodiments 1 through 12, further comprising decreasing a solubility of the amphiphilic nanoparticles in an aqueous phase and recovering at least a portion of the amphiphilic nanoparticles from the emulsion after removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
Embodiment 14: The method of any one of Embodiments 1 through 13, further comprising destabilizing the emulsion after removing hydrocarbons stabilized by the amphiphilic nanoparticles.
Embodiment 15: A method of removing a hydrocarbon from a subterranean formation, the method comprising: fonning at least one hydrophilic group on a surface of a carbon-containing material comprising at least one of a carbon nanotube, a fullerene, a carbon nanodiamond, graphene, and graphene oxide; mixing the carbon-containing material with a carrier fluid to form a suspension; introducing the suspension into a subterranean formation and contacting hydrocarbons within the subterranean formation with the suspension to form an emulsion stabilized by the carbon-containing material; and transporting the emulsion to a surface of the subterranean formation.
Embodiment 16: The method of Embodiment 15, further comprising forming at least one hydrophobic functional group on another surface of the carbon-containing material.
Embodiment 17: The method of Embodiment 16, wherein fonning at least one hydrophobic functional group on another surface of the carbon-containing material comprises fonning the at least one hydrophobic functional group on a surface opposite the at least one hydrophilic group.
Embodiment 18: The method of any one of Embodiments 15 through 17, wherein forming at least one hydrophilic group on a surface of a carbon-containing
material comprises forming at least one amine group on the carbon-containing material.
Embodiment 19: The method of any one of Embodiments 15 through 18, further comprising hydrolyzing at least one hydrophilic group with exposed hydroxyl groups of the at least one hydrophilic group on the carbon-containing material to form hydrophobic groups on the carbon-containing material.
Embodiment 20: The method of any one of Embodiments 15 through 19, wherein forming at least one hydrophilic group on a surface of a carbon-containing material comprises forming the at least one hydrophilic group on an outer wall of a carbon nanotube.
Embodiment 21 : The method of any one of Embodiments 15 through 19, wherein forming at least one hydrophilic group on a surface of a carbon-containing material comprises forming the at least one hydrophilic group on one side of graphene platelets.
Embodiment 22: The method of any one of Embodiments 15 through 21, further comprising mixing amphiphilic nanoparticles comprising a silica base into the carrier fluid.
Embodiment 23: A suspension for removing hydrocarbons from a subterranean formation, comprising: a plurality of carbon-containing amphiphilic nanoparticles, the amphiphilic nanoparticles comprising: hydrophobic functional groups on a surface of the carbon-containing material; and hydrophilic functional groups on another surface of the carbon-containing material; and a carrier fluid.
Embodiment 24: The suspension of Embodiment 23, wherein the hydrophilic functional groups on another surface of the carbon-containing material are on a surface of the carbon-containing material opposite the hydrophobic functional groups.
While the disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, the disclosure is not intended to be limited to the particular forms disclosed. Rather, the disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure as defined by the following appended claims and their legal equivalents.
Claims
What is claimed is: 1. A method of recovering a hydrocarbon material, the method comprising:
combining a plurality of amphiphilic nanoparticles comprising a carbon core,
hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension;
contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension to form an emulsion stabilized by the amphiphilic nanoparticles; and
removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
2. The method of claim 1, wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises combining amphiphilic nanoparticles comprising at least one of carbon nanotubes, carbon nanodiamonds, graphite, graphene, graphene oxide, fullerenes, and bucky onions.
3. The method of claim 2, wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises combining amphiphilic nanoparticles comprising an amino functional group with the carrier fluid.
4. The method of claim 1 , further comprising forming the at least one hydrophilic group on a surface of the carbon core opposite the at least one hydrophilic group.
5. The method of claim 4, wherein forming the at least one hydrophilic group comprises hydrolyzing at least one hydrophilic precursor on the surface of the carbon core.
6. The method of claim 1 , further comprising forming the at least one hydrophilic group on an outer wall of a carbon nanotube.
7. The method of claim 1, further comprising forming the at least one hydrophilic group on one side of graphene platelets.
8. The method of claim 1, further comprising increasing a solubility of the amphiphilic nanoparticles in an aqueous phase after removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
9. The method of claim 8, wherein increasing a solubility of the amphiphilic nanoparticles in an aqueous phase comprises altering a pH of the aqueous phase.
10. The method of any one of claims 1 through 9, further comprising mixing amphiphilic nanoparticles comprising a silica base into the carrier fluid.
1 1. The method of any one of claims 1 through 9, wherein combining a plurality of amphiphilic nanoparticles comprising a carbon core, hydrophilic functional groups on a surface of the carbon core, and hydrophobic functional groups on another surface of the carbon core with a carrier fluid to form a suspension comprises forming the suspension to comprise from about 50 ppm to about 500 ppm of the amphiphilic nanoparticles.
12. The method of any one of claims 1 through 9, further comprising altering a pH of the suspension after contacting at least one of a subterranean formation and a slurry comprising bituminous sand and water with the suspension.
13. The method of any one of claims 1 through 9, further comprising decreasing a solubility of the amphiphilic nanoparticles in an aqueous phase and recovering at least a portion of the amphiphilic nanoparticles from the emulsion after removing hydrocarbons from the emulsion stabilized by the amphiphilic nanoparticles.
14. A suspension for removing hydrocarbons from a subterranean formation, comprising:
a plurality of amphiphilic nanoparticles comprising:
a carbon core;
hydrophobic functional groups on a surface of the carbon core; and hydrophilic functional groups on another surface of the carbon core; and a carrier fluid.
15. The suspension of claim 14, wherein the hydrophilic functional on another surface of the carbon core are on a surface of the core opposite the hydrophobic functional groups.
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RU2017116553A RU2672116C1 (en) | 2014-10-21 | 2015-10-19 | Slurry for improved hydrocarbon recovery and methods of hydrocarbon recovery with use of specified slurry |
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US14/519,728 US9708896B2 (en) | 2014-01-31 | 2014-10-21 | Methods of recovering hydrocarbons using a suspension |
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WO2022245388A1 (en) * | 2020-05-20 | 2022-11-24 | University Of Wyoming | Quantum dot nanofluids |
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US11167993B2 (en) * | 2017-06-19 | 2021-11-09 | Daicel Corporation | Surface-modified nanodiamond, liquid dispersion including surface-modified nanodiamond, and resin dispersion |
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CN113698921A (en) * | 2020-05-22 | 2021-11-26 | 中石化石油工程技术服务有限公司 | Controllable preparation method of novel amphiphilic particle material |
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