NZ712164B2 - A proppant - Google Patents
A proppant Download PDFInfo
- Publication number
- NZ712164B2 NZ712164B2 NZ712164A NZ71216414A NZ712164B2 NZ 712164 B2 NZ712164 B2 NZ 712164B2 NZ 712164 A NZ712164 A NZ 712164A NZ 71216414 A NZ71216414 A NZ 71216414A NZ 712164 B2 NZ712164 B2 NZ 712164B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- curable composition
- proppant
- acrylate
- particle
- isocyanate
- Prior art date
Links
- 239000000203 mixture Substances 0.000 claims abstract description 212
- 238000000576 coating method Methods 0.000 claims abstract description 196
- 239000011248 coating agent Substances 0.000 claims abstract description 194
- 239000002245 particle Substances 0.000 claims abstract description 188
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 146
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229920005862 polyol Polymers 0.000 claims abstract description 107
- 150000003077 polyols Chemical class 0.000 claims abstract description 107
- 239000003054 catalyst Substances 0.000 claims description 61
- 239000000178 monomer Substances 0.000 claims description 57
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 40
- 239000012530 fluid Substances 0.000 claims description 38
- 230000015572 biosynthetic process Effects 0.000 claims description 31
- 238000005755 formation reaction Methods 0.000 claims description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- 229920000570 polyether Polymers 0.000 claims description 25
- 239000000969 carrier Substances 0.000 claims description 17
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- 150000002978 peroxides Chemical class 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- OKPYIWASQZGASP-UHFFFAOYSA-N N-(2-hydroxypropyl)-2-methylprop-2-enamide Chemical compound CC(O)CNC(=O)C(C)=C OKPYIWASQZGASP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- CZZYITDELCSZES-UHFFFAOYSA-N Diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 4
- RKOOOVKGLHCLTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.OCC(O)CO RKOOOVKGLHCLTP-UHFFFAOYSA-N 0.000 claims description 3
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 150000003819 basic metal compounds Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000010883 coal ash Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 206010017076 Fracture Diseases 0.000 description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 26
- 150000003254 radicals Chemical class 0.000 description 26
- 239000010779 crude oil Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 22
- 239000003208 petroleum Substances 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- 239000004576 sand Substances 0.000 description 22
- 239000000446 fuel Substances 0.000 description 18
- 239000003999 initiator Substances 0.000 description 18
- -1 aromatic isocyanates Chemical class 0.000 description 16
- 239000002318 adhesion promoter Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 244000005700 microbiome Species 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 239000000080 wetting agent Substances 0.000 description 11
- 239000008199 coating composition Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000005528 methosulfate group Chemical group 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZBVOEVQTNYNNMY-UHFFFAOYSA-N O=P1=CCCC1 Chemical compound O=P1=CCCC1 ZBVOEVQTNYNNMY-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- 208000002565 Open Fractures Diseases 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000002708 enhancing Effects 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 102100000368 F8 Human genes 0.000 description 3
- 101700070229 F8 Proteins 0.000 description 3
- 101710029273 HEMA1 Proteins 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- CZMRCDWAGMRECN-GDQSFJPYSA-N Sucrose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)[C@@]1(CO)[C@H](O)[C@@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-GDQSFJPYSA-N 0.000 description 3
- MAJYSQJXMUDACI-UHFFFAOYSA-N [N-]=C=O.[N-]=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 Chemical class [N-]=C=O.[N-]=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 MAJYSQJXMUDACI-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000011068 load Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002365 multiple layer Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 230000002028 premature Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-Aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 2
- YMKWWHFRGALXLE-UHFFFAOYSA-N 4-methyl-1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)C1=CC=CC=C1 YMKWWHFRGALXLE-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 241000723418 Carya Species 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N Dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 241000282346 Meles meles Species 0.000 description 2
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N N-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 2
- 102100010926 PRPF6 Human genes 0.000 description 2
- 101710018068 PRPF6 Proteins 0.000 description 2
- 238000010928 TGA analysis Methods 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229960004418 Trolamine Drugs 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000003111 delayed Effects 0.000 description 2
- 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 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000003301 hydrolyzing Effects 0.000 description 2
- 230000002209 hydrophobic Effects 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- 229940029612 triethanolamine Drugs 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- NTIXPPFPXLYJCT-CFTHBVFTSA-N (3S,5R,7S,8R,9S,10S,12R,13R,14S,17R)-17-[(2R)-6-hydroxy-6-methylheptan-2-yl]-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-3,7,12-triol Chemical compound C([C@@H]1C[C@@H]2O)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCCC(C)(C)O)C)[C@@]2(C)[C@H](O)C1 NTIXPPFPXLYJCT-CFTHBVFTSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-M (Z)-4-butoxy-4-oxobut-2-enoate Chemical compound CCCCOC(=O)\C=C/C([O-])=O UTOVMEACOLCUCK-PLNGDYQASA-M 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- VGYLMOJQAHXYCK-UHFFFAOYSA-N 1-methylimidazolidine Chemical class CN1CCNC1 VGYLMOJQAHXYCK-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 1
- JXGNHEUFHNJWDY-UHFFFAOYSA-N 2,5-dihydro-1H-phosphole Chemical class C1PCC=C1 JXGNHEUFHNJWDY-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N 2-Imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- ZQEKJUQOXJAPRX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C.CCC(CO)(CO)CO ZQEKJUQOXJAPRX-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutyronitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- CKYZEOPDJVLBTQ-UHFFFAOYSA-N 3,4-dihydro-4-methyl-2H-Phosphole 1-oxide Chemical compound CC1CCP(=O)=C1 CKYZEOPDJVLBTQ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-Methylenedianiline Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- LVETZUQNEKLWNP-UHFFFAOYSA-N C(C)O[Si](OCC)(OCC)C(CC[SH-][Si]([S-])([S-])[S-])[Si](OCC)(OCC)OCC Chemical compound C(C)O[Si](OCC)(OCC)C(CC[SH-][Si]([S-])([S-])[S-])[Si](OCC)(OCC)OCC LVETZUQNEKLWNP-UHFFFAOYSA-N 0.000 description 1
- ZRDJCTDPZWCXTP-UHFFFAOYSA-N C(C)O[Si](OCC)(OCC)C(CC[SiH]([S-])[S-])[Si](OCC)(OCC)OCC Chemical compound C(C)O[Si](OCC)(OCC)C(CC[SiH]([S-])[S-])[Si](OCC)(OCC)OCC ZRDJCTDPZWCXTP-UHFFFAOYSA-N 0.000 description 1
- 102100016444 CCDC50 Human genes 0.000 description 1
- 101710023985 CCDC50 Proteins 0.000 description 1
- 240000005497 Cyamopsis tetragonoloba Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M Dimethyldioctadecylammonium chloride Chemical class [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N Diphenylmethane p,p'-diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 241000282619 Hylobates lar Species 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001527806 Iti Species 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N N'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- PHKMWRPYLCNVJC-UHFFFAOYSA-N N'-benzyl-N-[3-[dimethoxy(prop-2-enoxy)silyl]propyl]ethane-1,2-diamine Chemical compound C=CCO[Si](OC)(OC)CCCNCCNCC1=CC=CC=C1 PHKMWRPYLCNVJC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000796522 Olene Species 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- DHHVAGZRUROJKS-UHFFFAOYSA-N Phentermine Chemical compound CC(C)(N)CC1=CC=CC=C1 DHHVAGZRUROJKS-UHFFFAOYSA-N 0.000 description 1
- 229920002176 Pluracol® Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920001228 Polyisocyanate Polymers 0.000 description 1
- 229920000582 Polyisocyanurate Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 229920001021 Polysulfide Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 241001426756 Senna tora Species 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N Silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Toluene diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000111 anti-oxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940027983 antiseptics and disinfectants Quaternary ammonium compounds Drugs 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N furane Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-L maleate(2-) Chemical compound [O-]C(=O)\C=C/C([O-])=O VZCYOOQTPOCHFL-UPHRSURJSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DTBNBXWJWCWCIK-UHFFFAOYSA-M phosphoenolpyruvate Chemical compound OP(O)(=O)OC(=C)C([O-])=O DTBNBXWJWCWCIK-UHFFFAOYSA-M 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical group CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
proppant includes a particle present in an amount of from 90 to 99.5 percent by weight and a polymeric coating disposed about the particle and present in an amount of from 0.5 to 10 percent by weight, based on the total weight of the proppant. The polymeric coating is formed from a curable composition comprising an isocyanate, an acrylate, and a polyol. A method of forming the proppant includes the steps of combining the isocyanate, the acrylate, and the polyol to form the curable composition, coating the particle with the curable composition, and curing the curable composition to form the polymeric coating. tion comprising an isocyanate, an acrylate, and a polyol. A method of forming the proppant includes the steps of combining the isocyanate, the acrylate, and the polyol to form the curable composition, coating the particle with the curable composition, and curing the curable composition to form the polymeric coating.
Description
Docket No. PF75077
A PROPPANT
FIELD OF THE DISCLOSURE
The subject disclosure generally relates to a proppant and a method of forming
the proppant. More cally, the subject disclosure relates to a nt which
includes a particle and a ric coating disposed on the particle, and which is used
during hydraulic ring of a subterranean formation.
DESCRIPTION OF TIIE RELATED ART
Domestic energy needs in the United States tly outpace readily
accessible energy resources, which has forced an sing dependence on foreign
petroleum fuels, such as oil and gas. At the same time, ng United States energy
resources are significantly underutilized, in part due to inefficient oil and gas
ement methods and a deterioration in the quality of raw materials such as
unrefined petroleum fuels.
Petroleum fuels are typically ed from subsurface reservoirs via a
wellbore. Petroleum fuels are currently ed from low-permeability reservoirs
through hydraulic fracturing of subterranean formations, such as bodies of rock
having varying degrees of porosity and permeability Hydraulic fracturing enhances
production by creating fractures that emanate from the subsurface reservoir or
wellbore, and provides increased flow channels for petroleum fuels. During hydraulic
fracturing, specially—engineered carrier fluids are pumped at high pressure and
velocity into the subsurface reservoir to cause res in the subterranean
formations. A propping agent, Le, a proppant, is mixed with the carrier fluids to keep
the fractures open when hydraulic fracturing is complete. The proppant typically
includes a particle and a coating disposed on the particle. The proppant remains in
place in the fractures once the high pressure is removed, and thereby props open the
fractures to enhance eum fuel flow into the wellbore. Consequently, the
proppant increases procurement of petroleum fuel by ng a high-permeability,
ted channel through which the petroleum fuel can flow.
However, many existing nts exhibit inadequate thermal stability for
high temperature and pressure applications, e.g. wellbores and subsurface reservoirs
having temperatures greater than 21.1°C (70°F) and pressures, i.e., closure stresses,
r than 51.7 MPa (7,500 psi). As an example of a high temperature application,
certain wellbores and subsurface reservoirs throughout the world have temperatures of
H&H File No. 065333.00631
PCT/USZOI4/025390
Docket No. PF75077
about 190.6°C ) and 282.2°C (540°F). As an example of a high pressure
application, certain wellbores and subsurface reservoirs throughout the world have
closure stresses that exceed 82.7 MPa (12,000 psi) or even 96.5 MPa 0 psi). As
such, many existing proppants, which include gs, have coatings such as epoxy
or phenolic coatings, which melt, degrade, and/or shear off the particle in an
uncontrolled manner when exposed to such high temperatures and
pressures. Also,
many existing proppants do not include active agents, such as microorganisms and
sts, to improve the y of the petroleum fuel recovered from the subsurface
reservoir.
Further, many existing proppants include coatings having inadequate crush
resistance. That is, many existing proppants include non—uniform coatings that
include defects, such as gaps or indentations, which contribute to premature
breakdown and/or failure of the coating. Since the coating typically provides a
cushioning effect for the proppant and evenly distributes high pressures around the
proppant, premature breakdown and/or failure of the coating undermines the crush
resistance of the proppant. Crushed nts cannot effectively prop open fractures
and often contribute to impurities in unrefined petroleum fuels in the form of dust
particles.
er, many existing proppants also exhibit unpredictable consolidation
patterns and suffer from inadequate permeability in wellbores, i.e., the extent to which
the proppant allows the flow of petroleum fuels. That is, many existing proppants
have a lower permeability and impede petroleum fuel flow. Further, many existing
proppants consolidate into aggregated, near-solid, non-permeable proppant packs and
prevent te flow and procurement of petroleum fuels from subsurface
reservoirs.
Also, many existing proppants are not compatible with low-viscosity carrier
fluids having viscosities of less than about 3,000
cps at 80 °C. Low—viscosity carrier
fluids are typically pumped into wellbores at higher pressures than high-viscosity
r fluids to ensure proper fracturing of the subterranean ion.
Consequently, many existing coatings fail ically, ie, shear off the particle,
when exposed to high pressures or react chemically with scosity carrier fluids
and degrade.
H&H File No. 06533100631
Finally, many existing proppants are coated via noneconomical coating processes and
therefore contribute to increased production costs. That is, many existing proppants e
multiple layers of coatings, which results in time-consuming and expensive coating ses.
Due to the inadequacies of existing proppants, there remains an opportunity to provide
an improved proppant.
SUMMARY OF THE DISCLOSURE AND ADVANTAGES
The subject disclosure provides a proppant for hydraulically fracturing a subterranean
formation. The nt includes a particle present in an amount of from 90 to 99.5 percent
by weight and a polymeric coating disposed about the particle and present in an amount of
from 0.5 to 10 percent by weight, based on the total weight of the proppant. The polymeric
coating is formed from a e composition sing an isocyanate, an acrylate, and a
polyol.
[0010A] In a particular aspect the present invention provides a proppant for hydraulically
fracturing a subterranean formation, said proppant comprising: A. a le present in an
amount of from 90 to 99.5 percent by weight based on the total weight of said proppant; and
B. a polymeric coating disposed about said particle and present in an amount of from 0.5 to 10
percent by weight based on the total weight of said proppant, said polymeric coating formed
from a curable composition comprising: an isocyanate comprising diphenylmethane
diisocyanate and/or polymeric diphenylmethane diisocyanate included in said curable
composition in an amount of from 10 to 70 percent by weight based on the total weight of all
components used to form said curable composition, an acrylate comprising a hydroxyfunctional
acrylate monomer selected from the group of glycerol monomethacrylate, 2-
hydroxyethyl acrylate, yethyl methacrylate, 2- hydroxypropyl methacrylate,
ybutyl methacrylate, N-(2-hydroxypropyl)methacrylamide, poly ethoxy (10) ethyl
methacrylate, rythritol triacrylate, and ations thereof, said te included in
said curable composition in an amount of from 10 to 70 percent by weight based on the total
weight of all components used to form said curable composition, and a polyether polyol
included in said e composition in an amount of from 10 to 70 percent by weight based
on the total weight of all ents used to form said curable composition.
A method of forming the proppant includes the steps of combining the isocyanate, the
acrylate, and the polyol to form the e composition, coating the particle with the curable
composition, and curing the curable composition to form the ric coating.
Advantageously, the proppant of the subject disclosure improves upon the performance
of existing nts.
(followed by page 3a)
[0012A] In a further particular aspect the t invention provides a method of forming a
proppant for hydraulically fracturing a subterranean formation, wherein the proppant comprises a
particle and a ric coating disposed about the particle, the polymeric g formed from a
curable composition comprising an isocyanate comprising diphenylmethane diisocyanate and/or
polymeric diphenylmethane diisocyanate, an acrylate comprising a hydroxy-functional acrylate
monomer selected from the group of glycerol monomethacrylate, 2-hydroxyethyl acrylate,
hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-(2-
hydroxypropyl)methacrylamide, poly ethoxy (10) ethyl methacrylate, pentaerythritol triacrylate,
and combinations thereof, and a polyether polyol, said method comprising the steps of: A.
ing the isocyanate comprising diphenylmethane yanate and/or polymeric
diphenylmethane diisocyanate, the hydroxy-functional acrylate monomer, and the polyether polyol
to form the curable composition; B. coating the particle with the curable composition; and C. curing
the curable composition to form the polymeric coating; wherein said isocyanate is included in said
e composition in an amount of from 10 to 70 percent by weight based on the total weight of
all components used to form said curable composition, said acrylate is included in said curable
ition, in an amount of from 10 to 70 percent by weight based on the total weight of all
components used to form said curable ition, and said polyol is included in said curable
composition, in an amount of from 10 to 70 percent by weight based on the total weight of all
components used to form said curable composition; and wherein the particle is present in an amount
of from 90 to 99.5 percent by weight based on the total weight of the proppant and the polymeric
coating is present in an amount of from 0.5 to 10 percent by weight based on the total weight of the
proppant.
ED DESCRIPTION OF THE SURE
The subject disclosure includes a nt, a method of forming, or preparing, the nt,
a method of hydraulically fracturing a subterranean formation, and a method of filtering a fluid.
The proppant is typically used, in conjunction with a carrier fluid, to hydraulically fracture the
subterranean formation which defines a subsurface reservoir (e.g. a wellbore or reservoir ).
Here, the proppant props open the fractures in the ranean formation after the hydraulic
fracturing. In one embodiment, the proppant may also be used to filter unrefined petroleum fuels,
e.g. crude oil, in fractures to improve feedstock quality for refineries. However, it is to be
appreciated that the proppant of the subject disclosure can also have applications beyond lic
ring and crude oil filtration, ing, but not limited to, water filtration and artificial turf.
The proppant includes a particle and a polymeric coating disposed on the particle. As used
herein, the terminology “disposed on” encompasses the polymeric
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coating being disposed about the particle and also asses both partial and
complete ng of the particle by the polymeric coating. The polymeric coating is
disposed on the particle to an extent ient to change the properties of the particle,
e.g. to form a particle having a polymeric g n which can be effectively
used as a proppant. As such, any given sample of the proppant lly es
particles having the polymeric coating disposed thereon, and the polymeric coating is
typically disposed on a large enough surface area of each individual particle so that
the sample of the proppant can effectively prop open fractures in the subterranean
formation during and after the hydraulic fracturing, filter crude oil, etc. The
polymeric coating is described additionally below.
Although the particle may be of any size, the particle typically has a particle
size distribution of from 10 to 100 mesh, alternatively from 20 to 70 mesh, as
measured in accordance with standard sizing techniques using the United States Sieve
Series. That is, the particle typically has a particle size of from 149 to 2,000,
alternatively from 210 to 841, um. Particles having such particle sizes allow less
polymeric coating to be used, allow the polymeric coating to be applied to the particle
at a lower viscosity, and allow the polymeric g to be disposed on the particle
with increased uniformity and completeness as compared to particles having other
particle sizes.
Although the shape of the particle is not critical, particles having a spherical
shape typically impart a smaller increase in viscosity to a hydraulic fracturing
composition than particles having other shapes, as set forth in more detail below. The
hydraulic fracturing composition is a mixture comprising the carrier fluid and the
proppant. Typically, the particle is either round or roughly spherical.
The particle is present in the proppant in an amount of from 90 to 99.5,
alternatively from 94 to 99.3, alternatively from 94 to 99.0, alternatively from 96 to
99, percent by weight based on the total weight of the proppant. The amount of
particle present in the proppant may vary outside of the ranges above, but is lly
both whole and fractional values within these
ranges.
The particle typically contains less than 1 percent by weight of moisture,
based on the total weight of the particle. Particles containing higher than 1 t by
weight of moisture typically interfere with sizing techniques and prevent uniform
coating of the particle.
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Suitable particles for purposes of the subject disclosure include any known
particle for use during hydraulic fracturing, water filtration, or artificial turf
preparation. Non-limiting es of le particles include minerals, ceramics
such as sintered ceramic particles, sands, nut shells, gravels, mine tailings, coal ashes,
rocks (such as bauxite), smelter slag, diatomaceous earth, crushed charcoals, micas,
sawdust, wood chips, resinous particles, polymeric particles, and combinations
f. It is to be appreciated that other particles not recited herein may also be
suitable for the purposes of the subject disclosure.
Sand is a preferred particle and when applied in this technology is ly
referred to as frac, or fracturing, sand. Examples of suitable sands include, but are not
limited to, Badger sand, Brady sand, rn White sand, 'l'exas Hickory sand, and
Ottawa sand. Based on cost and availability, inorganic materials such as sand and
sintered c particles are typically favored for applications not requiring
filtration.
A specific example of a sand that is suitable as a particle for the purposes of
the subject disclosure is Ottawa sand, commercially available from US. Silica
Company of ey Springs, WV. Yet another specific example of a sand that is
suitable as a particle for the purposes of this disclosure is Wisconsin sand,
cially available from Badger Mining Corporation of Berlin, WI. Particularly
preferred sands for application in this disclosure are Ottawa and Wisconsin sands.
Ottawa and Wisconsin sands of various sizes, such as 30/50, 20/40, 40/70, and 70/140
can be used.
Specific examples of le sintered ceramic particles include, but are not
limited to, aluminum oxide, , bauxite, and combinations thereof. The sintered
ceramic particle may also include ike binders.
An active agent may also be included in the particle. In this t, suitable
active agents include, but are not limited to, organic compounds, microorganisms, and
catalysts. Specific examples of microorganisms include, but are not limited to,
anaerobic microorganisms, aerobic microorganisms, and ations thereof. A
suitable microorganism for the purposes of the subject disclosure is commercially
available from LUCA Technologies of Golden, Colorado. Specific examples of
suitable catalysts include fluid tic cracking catalysts, hydroprocessing catalysts,
and combinations thereof. Fluid catalytic ng catalysts are typically ed for
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applications requiring petroleum gas and/or gasoline production from crude oil.
Hydroprocessing catalysts are lly selected for applications requiring gasoline
andior kerosene production from crude oil. It is also to be appreciated that other
catalysts, organic or inorganic, not d herein may also be suitable for the
purposes of the subject disclosure.
Such additional active agents are typically favored for applications requiring
filtration. As one e, sands and sintered ceramic particles are typically useful as
a particle for support and propping open fractures in the subterranean formation which
defines the subsurface reservoir, and, as an active agent, microorganisms and catalysts
are typically useful for removing impurities from crude oil or water. Therefore, a
ation of sands/sintered ceramic particles and microorganisms/catalysts as
active agents are particularly preferred for crude oil or water filtration.
Suitable particles for purposes of the present disclosure may even be formed
from resins and rs. Specific examples of resins and polymers for the particle
include, but are not limited to, ethanes, polycarbodiimides, polyureas, acrylates,
polyvinylpyirolidones, acrrylonitrile-butadiene styrenes, yrenes, polyvinyl
chlorides, fluoroplastics, polysulfides, nylon, ide imides, and combinations
thereof.
As indicated above, the proppant includes the polymeric coating ed on
the particle. The ric coating is selected based on the desired properties and
expected operating conditions of the proppant. The polymeric coating may provide
the particle with protection from operating temperatures and pressures in the
subterranean formation and/or subsurface reservoir. Further, the polymeric g
may protect the particle against closure stresses exerted by the subterranean
formation. The ric coating may also t the particle from ambient
conditions and minimizes disintegration and/or dusting of the particle. In some
embodiments, the polymeric coating may also provide the proppant with desired
al reactivity and/or filtration capability.
The polymeric coating is formed from a curable composition comprising an
isocyanate and an acrylate and optionally a polyol. In a typical ment, the
polymeric coating is formed from a curable composition comprising an isocyanate, an
acrylate, and a polyol. The curable composition is formulated and formed such that
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the physical properties of the polymeric coating, such as ss, strength,
toughness, creep, and brittleness are optimized.
The curable composition includes the isocyanate. The isocyanate may be a
polyisocyanate having two or more functional groups, e.g. two or more NCO
onal groups. Suitable isocyanates for purposes of the t disclosure include,
but are not d to, aliphatic and aromatic isocyanates. In various embodiments,
the isocyanate is selected from the group of diphenylmethane diisocyanates (MDIs),
polymen'c diphenylmethane diisocyanates (pMDIs), toluene diisocyanates (TDIs),
hexamethylene diisocyanates (HDIs), rone diisocyanates (IPDIs), and
combinations thereof.
The isocyanate may be an isocyanate pre-polymer. 'l‘he isocyanate pre-
polymer is typically a reaction t of an isocyanate and a polyol and/or a
polyamine. The isocyanate used in the pre-polymer can be any isocyanate as
described above. The polyol used to form the pre-polymer is typically selected from
the group of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
butane diol, glycerol, trimethylolpropane, anolamine, pentaerythritol, sorbitol,
biopolyols, and ations thereof. The polyamine used to form the pre-polymer is
typically selected from the group of ne diamine, toluene e,
diaminodiphenylmethane and polymethylene polyphenylene polyamines,
aminoalcohols, and combinations thereof. Examples of le lcohols
include ethanolainine, diethanolamine, triethanolamine, and combinations thereof.
Specific isocyanates that may be used to prepare the polymen'c coating
e, but are not limited to, toluene diisocyanate; 4,4'-diphenylmethane
diisocyanate; m—phenylene diisocyanate; 1,5—naphthalene diisocyanate; 4-chloro—l; 3—
phenylene diisocyanate; tetramethylene diisocyanate; hexamethylene yanate;
1,4-dicyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate, 2,4,6-toluylene
triisocyanate, 1,3-diisopropylphenylene—2,4—dissocyanate; l-methyl—3,5-
diethylphenylene-2,4—diisocyanate; l,3,5—triethylphenylene-2,4-diisocyanate; 1,3,5—
triisoproply—phenylene-Z,4-diisocyanate; 3,3‘-diethyl-bisphenyl-4,4'—diisocyanate;
3,5 tetraethyl-diphenylmethane-4,4'—diisocyanate; 3,5 ,3',5’-
tetraisopropyldiphenylniethane-4,4'-diisocyanate; 1-ethylethoxy-phenyl-2,5~
diisocyanate; 1,3,5-triethyl benzene-2,4,6-triisocyanate; l-ethyl-3,5-diisopropyl
benzene-2,4,6-t1iisocyanatc and 1,3,5-triisopropyl benzene—2,4,6—triisocyanatc. Other
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suitable polymeric coatings can also be prepared from aromatic diisocyanates or
isocyanates having one or two aryl, alkyl, arakyl or alkoxy substituents wherein at
least one of these tuents has at least two carbon atoms. Specific examples of
suitable isocyanates include LUPRANATE® L5120, LUPRANATE M,
ATE® ME, LUPRANA’I'E® Ml, A'I‘E® M20, and LUPRANATE®
M70, all commercially available from BASF Corporation of Florham Park, NJ.
In a preferred embodiment, the isocyanate has an NCO content of from 20 to
45, alternatively from 25 to 35, weight percent. In a specific embodiment, the
isocyanate is a polymeric isocyanate, such as LUPRANATE® M20. LUPRANATE
M20 es polymeric diphenylmethane diisocyanate and has an NCO t of
31.5 weight percent. In another specific embodiment, the isocyanate is a
diphenylmethane diisoeyanate, such as LUPRANATE® MI. LUPRANATE® MI
es diphenylmethane diisocyanate and has an NCO content of about 33.5 weight
percent.
The isocyanate is typically included in the curable composition in an amount
of from 10 to 90, alternatively from 20 to 70, percent by weight based on the total
weight of all components used to form the curable composition. The amount of
isocyanate used may vary outside of the ranges above, but. is typically both whole and
fractional values within these ranges. Further, it is to be appreciated that more than
one isocyanate may be included in the curable composition, in which case the total
amount of all isocyanates included is within the above ranges.
The curable ition also includes the acrylate. Of course, the curable
composition can include one or more acrylates. As used , acrylate refers to both
acrylates and methacrylates (the salts and esters of methacrylic acid) and also refers to
both monomers and oligomers, polymers, and copolymers which include acrylate
units. The use of the acrylate in the curable composition allows for the curing of the
composition because acrylates typically e double bonds which are chemically
reactive.
The curable composition can e any acrylate known in the art. The
curable composition typically includes one or more acrylate monomers. The te
monomer may include isocyanate-reactive functional groups, e.g. hydroxy-functional
groups, amine-functional , and combinations thereof. For purposes of the
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subject disclosure, an isocyanate-reactive functional group is any functional group
that is reactive with at least one of the isocyanate groups of the nate. In one
embodiment, the e composition includes an acrylate monomer which includes
isocyanate-reactive functional groups and also an acrylate r that does not
include isocyanate-reactive functional groups.
The curable composition can include a C1 to C20 alkyl (meth)acrylate. The i)
C] to C20 alkyl (meth)acrylate can be selected from the group of methyl
(meth)acry1ate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate,
isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acry1ate, hexyl
acrylate, cyclohexyl (meth)acrylate, benzyl acrylate, Z—ethylhexyl
(meth)acrylate, heptyl (meth)acrylate, n-oetyl acrylate, nonyl (meth)acrylate,
decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl
(meth)acrylate, lauryl (meth)acrylate, l (meth)aerylate, isobornyl (meth)acrylate,
nyl (meth)acrylate, 4—tertbuty1cyclohexy1 (meth)acrylate, 3,3,5-
tn'methylcyclohexyl (Ineth)acrylate, yl maleate, n-butyl maleate, propylene
glycol (meth)acrylate, carbodiimide (meth)acry1ate, t-butylaminoethyl (meth)acrylate,
tylarninoethyl (meth)acry1ate, N,N-dimethylaminoethyl (meth)acry1ate, l, 4
butanediol dimethyacrylate, and combinations thereof.
In a preferred embodiment, the curable composition includes an acrylate
which includes hydroxy— and/or an amine-functionality. Suitable, non-limiting
examples of hydroxy—functional acrylate monomers include, glycerol
monomethaerylate, 2-hydroxyethy1 acrylate (HEA), hydroxyethyl methacrylate
, 2—hydroxypropyl methacrylate (HPMA), hydroxybutyl methacrylate
(HEMA), N—(2-hydroxypropyl)methacrylamide, hydroxypolyethoxy (10) ally] ether,
(HEMA 10) poly ethoxy (10) ethyl methacrylate, pentaerythritol ylate,
poly(propylene glycol), trimethylolpropane diallyl ether (mono/di/tiiallyl
mixture), trimethylolpropane mono-ally] ether, and combinations thereof.
In a preferred embodiment the curable composition comprises a hydroxyalkyl
methacrylate. Specific non—limiting es of hydroxyalkyl methacrylates include
HEA, HEMA, HPMA, and HBMA.
The curable composition can also include an acrylate copolymer. The
copolymer can include hydroxy- and/or an amine-functionality. As is known in the
art, a polymer is formed from many “mers” or units. The term unit is used herein to
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describe a unit formed from a ular monomer. For example, a 2-ethylhexyl
acrylate unit Within a polymer chain which is formed from 2-ethylhexyl acrylate.
Further, the copolymer is described as including various t by weight units, as
used throughout this disclosure, percent by weight units refers to percent by weight
units, based on the total weight of the copolymer.
In one embodiment, the curable composition includes an acrylate copolymer
which es both styrene and acrylate units. In this embodiment, the styrene units
of the mer are typically selected from the group of styrene units, 0t-
methylstyrene units, and combinations thereof. The acrylate units are typically
ed from the group of methacrylate units, methyl methacrylate units, ethyl
methacrylate units, butyl methacrylate units, propyl methacrylate units, methacrylic
acid units, acrylic acid units, hydroxyethyl methacrylate units, glycidyl methacrylate
units, 2-ethylhexyl acrylate units, and combinations thereof.
The acrylate is typically included in the curable composition in an amount of
from 10 to 70, alternatively from 15 to 50, percent by weight based on the total weight
of all components used to form the curable composition. The amount of acrylate
vary outside of the ranges above, but is typically both whole and fractional values
within these ranges. Further, it is to be appreciated that more than one acrylate may
be included in the curable composition, in which case the total amount of all acrylate
included is within the above ranges.
The curable composition optionally includes a polyol. The curable
ition can include any polyol known in the art. Of course, the curable
compostion may include one or more polyols. The polyol es one or more OH
functional groups, typically at least two OH functional
. Typically, the polyol
is selected from the group of polyether s, polyester polyols, polyether/ester
polyols, and combinations thereof; however, other polyols may also be employed.
The polyol typically has a nominal functionality of greater than 1.5,
alternatively from 1.5 to 6, alternatively from 2 to 5, alternatively from 2 to 4.5,
alternatively from 2 to 4; a number average lar weight of from 200 to 15,000,
alternatively from 200 to 8,000, alternatively from 300 to 5,000, g/mol; a hydroxyl
number of from 30 to 500, alternatively from 200 to 500, alternatively from 350
450, mg KOH/g; and a viscosity at 25°C of from 300 to 2,000, alternatively from 5 to
100, alternatively from 300 to 700, cps at 25°C when tested in accordance with DIN
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EN ISO 3219. It should be appreciated that more than one polyol may be included in
the curable composition, in which case the average values of all polyols ed is
within the above ranges.
In one embodiment, the polyol comprises a polyether . The polyether
polyol typically has a weight average molecular weight of from 200 to 5,000,
alternatively from 300 to 4,000, alternatively from 300 to 1,000, alternatively from
300 to 500, g/mol. In certain embodiments, the polyether polyol is a polyether triol.
As known in the art, polyether s are generally produced by reacting an alkylene
oxide with an initiator in the ce of a catalyst, such as a basic st or a
double metal cyanide (DMC) catalyst. In certain embodiments the polyether polyol
of the curable composition comprises a polyether triol or a polyether tetraol. In these
embodiments, the chains of the polyether polyol comprise random and/or ing
units formed from 130, PO, and/or B0, and the terminal
caps of the polyether polyol
typically comprise PO groups, but may also comprise E0 or B0 groups, or any
ation of E0, PO, and B0 groups. In this embodiment, the polyether polyol
typically has a hydroxyl number of from 35 to 750, alternatively from 60 to 650,
alternatively from 200 to 600, mg KOH/g. Suitable polyether polyols are
commercially available from BASF of Florham Park, NJ under the trade name
PLURACOL®.
In one specific embodiment, the e composition includes a tri-functional
polyether polyol formed via the reaction of hylol propane and propylene oxide,
having a molecular weigh of about 400, a hydroxyl number of from 383 to 413 mg
KOH/g, and a viscosity at 25°C of 600 cps.
In another specific embodiment, the curable composition includes a tetra-
functional polyether polyol formed via the reaction of tetrol glycol and propylene
oxide, having a molecular weigh of about 400, a hydroxyl number of from 500 to 600
mg KOH/g, and a viscosity at 25°C of 2000 cps.
In another ic embodiment, the curable composition includes a bi—
functional polyol formed via the reaction of propylene oxide and propylene glycol,
having hydroxyl number of from 102 to 112 mg KOH/g and a viscosity at 25°C of
150 cps.
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In yet another specific ment, the curable composition includes a tri-
functional polyol having a hydroxyl number of from 920 mg KOH/g and a Viscosity at
°C of 3400 cps.
It is believed that polyols having a higher functionality may help improve the
hydrolytic resistance of the polymeric coating. Accordingly, in a one embodiment,
the curable ition includes a sucrose initiated polyether polyol having number
average molecular weight of from 460 to 1200, atively from 530 to 930 g/mol;
having a hydroxyl number of from 280 to 570, alternatively from 310 to 500 mg
KOH/g; and having a functionality of from 4 to 6.5, alternatively from 3.7 to 5.7. In a
preferred embodiment, the curable composition includes a sucrose glycerin initiated
polyether polyol having hydroxyl number of about 470 mg KOH/g.
The polyol is lly included in the curable composition in an amount of
from 10 to 70, alternatively from 15 to 50, t by weight based on the total weight
of all components used to form the curable composition. The amount of polyol may
vary outside of the ranges above, but is typically both whole and fractional values
within these ranges. r, it is to be appreciated that more than one polyol may be
included in the curable composition, in which case the total amount of all polyol
included is within the above ranges.
The curable composition can also include a free radical generator (also
referred to as an initiator) such as peroxide and/or an azo initiator. The free radical
initiator, if used, initiated the curing of the curable composition. Suitable es of
initiators can be found in “The Handbook of Free Radical Initiators” by E. T.
Denisov, T. G. Denisova, and T. S. va which is incorporated in its entirety
herein by reference. Suitable non-limiting examples of azo tors include 22’-
Azobis(2-methylbutyronitrile), 2,2‘—Azobis[2-methyl—N-(2-
hydroxyethyl)propionamide], and sodium persulfate.
If a peroxide initiator is included in the curable composition, a dialkyl— and/or
a monoperoxy carbonate-type peroxide can be used. Suitable non-limiting examples
of peroxide initiators include c peroxides such as dialkyl peroxides, diphenyl
des, benzoyl peroxide, 1,4—dichlorobenzoyl de, chlorobenzoyl
peroxide, di-t~butyl peroxide, dicumyl peroxide, ry butyl-perbenzoate,
monochlorobenzoy] peroxide, ditertiary-butyl peroxide, 2,5-bis—(tertiarybutyl-
pcroxy)—2,5—dimcthylhcxanc, tcrtiary-butyl-tn'mcthyl pcroxidc, tcrtiary~butyl-tcrtiary—
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butyl-tertiary-triphenyl de, 1 ,1—bis(t—butylperoxy)-3,3 ,5-trinietl1ylcyclohexane,
t-butyl perbenzoate, utylperoxy Z-ethylhexyl carbonate. In one embodiment,
tert-butylperoxy Z-ethylhexyl carbonate is included in the composition
Of course, the initiator does not have to be included in the composition The
curable composition can be cured by heat, ed radiation, ultraviolet radiation,
aging/time, al inclusion in or al re to a chemical free l
generator, or any combination thereof to form the polymeric coating.
The curable ition can include a catalyst The curable composition can
include one or more catalysts. That is, the curable composition can include any
suitable catalyst or mixtures of sts known in the art which catalyze the reaction
between the components therein. Generally, the catalyst is selected from the group of
amine catalysts, orous compounds, basic metal compounds, carboxylic acid
metal salts, non-basic organo-metallic compounds, and combinations f. The
catalyst can be included in the curable composition in any amount sufficient to
catalyze the reaction of the components within the curable composition.
The curable composition can include a “polyurethane catalyst”, Le, a catalyst
which catalyzes the reaction between an isocyanate and a hydroxy functional
group.
For example, the curable composition can include a tertiary amine st, a tin
catalyst, etc.
In one embodiment, the curable composition includes 1,8—
Diazabicyelo[5.4.0]undec-7~ene, CAS No. 6674-22—2 (DBU).
The curable composition can also include a “polycarbodiimide catalyst”, i.e., a
catalyst which catalyzes the reaction between two isocyanate functional groups. For
example, the curable composition can include phospholene oxide catalyst. Suitable,
non limiting examples of phospholene oxides include phospholene oxides such
as 3-
methyl-1—phenyl—2—phospholene oxide (MPPO), y1-r~2—phospholen-l—oxide, 3—
methyl—1phospholen-l-oxide, l—ethyl—Z—phospholen-l-oxide, 3-methyl-l-phenyl
phospholen-l—oxide, 3-phospholene isomers thereof, and 3—methy1—l-ethyl
phospholene oxide . Two particularly suitable olene oxides are
MPPO and MEPO.
'lhe curable composition can also include an antistatic component. The
antistatic component includes one or more antistatic compounds or antistats. The
antistat reduces, removes, and prevents the buildup of static electricity on the
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proppant. The antistat can be a non-ionic antistat or an ionic or amphoteric antistat
(which can be further classified as anionic or cationic). Ionic ats are compounds
that include at least one ion, i.e., an atom or molecule in which the total number of
electrons is not equal to the total number of protons, giving it a net positive or
negative electrical charge. Non-ionic antistats are organic compounds composed of
both a hilic and a hydrophobic portion. Of , the antistatic component
can include a combination of ionic and non~ionic antistats.
One suitable antistatic component is a quaternary um compound. The
quaternary ammonium compound includes a quaternary ammonium cation, often
ed to as a quat. Quats are positively charged polyatomic ions of the structure
NR4+, R being an alkyl group or an aryl group. Unlike the ammonium ion (NH,4+)
and the y, secondary, or tertiary ammonium cations, quats are permanently
d, independent of the pH of their on.
One such quaternary ammonium compound is dicocoyl ethyl
hydroxyethylmonium methosulfate. Dicocoyl ethyl hydroxyethylmonium
methosulfate is the reaction product of triethanol amine, fatty acids, and methosulfate.
Notably, dicocoyl ethyl hydroxyethylmonium methosulfate is a cationic
antistat having a ic-active matter content of 74 to 79 percent when tested in
accordance with International Organization for Standardization (“ISO”) 2871-122010.
ISO 2871 specifies a method for the determination of the ic-active matter
content of high—molecular-mass cationic-active materials such as quaternary
ammonium compounds in which two of the alkyl groups each contain 10 or more
carbon atoms, e. g. distearyl-dimethyl—ammonium chlorides, or salts of imidazoline or
3-methylimidazoline in which long—chain acylaminoethyl and alkyl groups are
substituted in the 1- and 2—positions, respectively.
Dicocoyl ethyl hydroxyethylmonium methosulfate has an acid value of not
greater than 12 when tested in accordance with ISO 4314—1977 (Surface active agents
—- Determination of free nity or free acidity
-— Titrimetric method) and a pH of
from 2.5 to 3 when tested in accordance with ISO 4316:1977 (Determination of pH of
aqueous solutions -- Potentiometric method).
In addition to the quaternary ammonium compound, eg. dicocoy] ethyl
hydroxyethylmonium methosulfate, the antistatic component may further include a
t, such as ene glycol. In one such ment, the antistatic component
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includes mixture of dicocoyl ethyl yethylmonium methosulfate and propylene
The quaternary ammonium nd can be included in the e
composition or applied to the proppant in an amount of from 50 to 1000, alternatively
from 100 to 500, PPM (PPM by weight particle, i.e., 100 grams of particle x 200 PPM
surface treatment equals 002 grams of surface treatment per 100
grams of particle.
The amount of the quaternary ammonium compound present in the surface treatment
may vary outside of the ranges above, but is typically both whole and fractional
values within these ranges.
The curable composition can also include a silicon~containing adhesion
promoter. ’l‘his silicon-containing adhesion promoter is also commonly referred to in
the art as a coupling agent or as a binder agent. The silicon—containing adhesion
er binds the polymeric coating to the particle. More specifically, the silicon—
containing adhesion promoter lly has organofunctional silane groups to improve
adhesion of the polymeric coating to the particle. t being bound by theory, it
is t that the silicon-containing adhesion promoter allows for covalent bonding
between the le and the polymeric coating. In one embodiment, the surface of
the particle is activated with the silicon-containing adhesion promoter by applying the
silicon—containing adhesion promoter to the particle prior to coating the particle with
the curable ition/polymeric coating. In this embodiment, the silicon-
containing adhesion promoter can be applied to the particle by a wide y of
application techniques including, but not limited to, spraying, dipping the particles in
the polymeric coating, etc. In r embodiment, the silicon-containing adhesion
promoter may be added to the e composition. As such, the particle is then
simply exposed to the silicon-containing adhesion promoter when the polymeric
coating is applied to the particle. The silicon—containing adhesion promoter is useful
for applications requiring excellent adhesion of the polymeric g to the particle,
for example, in applications where the proppant is subjected to shear forces in an
aqueous environment. Use of the silicon-containing adhesion promoter provides
adhesion of the ric coating to the particle such that the polymeric coating will
remain adhered to the surface of the particle even if the proppant, including the
polymeric coating, the particle, or both, res due to closure stress.
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Examples of suitable adhesion promoters, which are silicon-containing,
include, but are not limited to, glycidoxypropyltrimethoxysilane,
aminoethylaminopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane,
gamma-aminopropyltriethoxysilane,
vinylbenzylaminoethylaminopropyltrimethoxysilane,
oxypropylmethyldiethoxysilane, chloropropyltrimethoxysilane,
phenylh‘imethoxysilane, vinyltriethoxysilane, tetraethoxysilane,
methyldimethoxysilane, bis-triethoxysilylpropyldisulfidosilane, bis-
triethoxysilylpropyltetrasulfidosilane, phenyltriethoxysilane, aminosilanes, and
combinations thereof.
Specific examples of suitable silicon-containing on promoters e,
but are not limited to, STm A1100, SILQUEST‘“ A1110, SILQUESTW
A1120, SILQUESTW 1130, SILQUEST” A1170, SILQUESTTM A-189, and
SILQUESTm Y9669, all commercially available from Momentive Performance
Materials of Albany, NY. A particularly suitable n-containing adhesion
promoter is SILQUESTTH A1100, i.e., gamma-aminopropyltriethoxysilane. The
silicon-containing adhesion er may be present in the proppant in an amount of
from 0.001 to 5, alternatively from 0.01 to 2, atively from 0.02 to 1.25, percent
by weight based on the total weight of the proppant. The amount silicon—containing
adhesion promoter present in the proppant may
vary outside of the ranges above, but
is typically both whole and fractional values within these
ranges.
The curable composition can also include a wetting agent. The wetting agent
is also commonly referred to in the art as a surfactant. The proppant may include
more than one wetting agent. The g agent may e any suitable wetting
agent or mixtures of wetting agents known in the art. The wetting agent is employed
to increase a surface area contact n the polymeric coating and the particle. In a
typical embodiment, the wetting agent is included in the curable composition. In
another embodiment, the surface of the particle is activated with the g
agent by
applying the wetting agent to the particle prior to coating the particle with the
polymeric coating.
A suitable wetting agent is BYK® 310, a polyester modified poly-dimethyl-
siloxane, commercially ble from BYK Additives and Instruments of
Wallingford, CT. The wetting agent may be t in the proppant in an amount of
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from 0.01 to 10, alternatively from 0.02 to 5, alternatively from 0.02 to 0.04, percent
by weight based on the total weight of the proppant. The amount of wetting agent
present in the proppant may vary outside of the ranges above, but is typically both
whole and onal values within these ranges.
The polymeric coating of this sure may also include the active agent
already described above in the context of the le. In other words, the active agent
may be included in the polymeric coating independent of the particle. Once again,
suitable active agents include, but are not limited to organic nds,
microorganisms, catalysts, and salts. Suitable non—limiting examples of salts include
sodium perboate and sodium persulfate.
'lhe e ition may also include various additives. le
additives include, but are not limited to, blowing agents, blocking agents, dyes,
pigments, diluents, sts, solvents, specialized functional additives such as
antioxidants, ultraviolet stabilizers, es, fire retardants, fragrances, and
combinations of the group. For example, a pigment allows the polymeric coating to
be visually evaluated for thickness and integrity and can provide various marketing
advantages. Also, physical blowing agents and chemical blowing agents are typically
selected for polymeric coatings requiring foaming. That is, in one embodiment, the
coating may include a foam coating ed on the particle. Again, it is to be
understood that the ology “disposed on” encompasses both partial and complete
covering of the particle by the polymeric coating, a foam coating in this instance. The
foam coating is typically useful for applications requiring enhanced contact n
the proppant and crude oil. That is, the foam coating typically defines microchannels
and increases a surface area for contact between crude oil and the catalyst and/or
microorganism.
As set forth above, the polymeric coating is formed from the curable
composition. Once formed, the polymeric coating is chemically and physically stable
over a range of temperatures and does not typically melt, degrade, and/or shear off the
particle in an uncontrolled manner when exposed to higher pressures and
temperatures, e.g. pressures and temperatures greater than res and temperatures
typically found on the earth’s surface. As one example, the polymeric g is
particularly applicable when the proppant is exposed to significant re,
compression and/or shear forces, and temperatures exceeding 200°C (392°F) in the
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subterranean formation and/or subsurface oir d by the formation. The
polymeric g is lly viscous to solid nature, and depending on molecular
weight.
The polymeric coating is present in the proppant in an amount of from 0.5 to
, alternatively from 0.7 to 6, alternatively from 1 to 6, alternatively from 1 to 4,
percent by weight based on the total weight of the proppant. The amount of
polymeric coating present in the proppant may vary outside of the ranges above, but is
typically both whole and fractional values within these ranges.
The ric coating may be formed in-situ where the ric coating is
disposed on the le during formation of the polymeric coating. Typically the
ents of the polymeric coating are combined with the particle and the
polymeric coating is disposed on the particle.
However, in one embodiment a polymeric coating is formed and some time
later applied to, e.g. mixed with, the particle and d to temperatures exceeding
100°C (212013) to coat the particle and form the nt. Advantageously, this
embodiment allows the polymeric coating to be formed at a location designed to
handle chemicals, under the control of personnel enced in handling chemicals.
Once formed, the ric coating can be transported to another location, applied to
the particle, and heated. There are numerous logistical and practical advantages
associated with this embodiment. For example, if the polymeric coating is being
applied to the particle, e.g. frac sand, the polymeric coating may be applied
immediately following the manufacturing of the frac sand, when the frac sand is
already at elevated temperature, eliminating the need to reheat the polymeric coating
and the frac sand, thereby reducing the amount of energy required to form the
proppant.
In another embodiment, the curable composition can be formed in solution.
The solution includes a solvent such as acetone or tetrahydrofuran (THF). The
solution viscosity is controlled by stoichiometry, monofunctional reagents, and a
polymer solids level. After the curable composition is formed in the solution, the
solution is applied to the particle. The solvent evaporates g the curable
composition/polymeric coating disposed on the particle. Once the polymeric coating
is disposed on the particle to form the proppant, the proppant can be heated to r
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cure the polymeric coating. Generally, the curing, which occurs as a result of the
heating, optimizes physical properties of the polymeric coating.
In yet another embodiment, the polymeric coating may also be further defined
as lled—release. That is, the polymeric coating may systematically dissolve,
hydrolyze in a controlled , or physically expose the particle to the petroleum
fuels in the subsurface reservoir. In one such embodiment, the polymeric coating
typically lly dissolves in a consistent manner over a pre-determined time period
to decrease the thickness of the polymeric coating. This embodiment is especially
useful for ations utilizing the active agent such as the microorganism and/or the
catalyst. That is, the polymeric coating is typically controlled—release for applications
requiring filtration of petroleum fuels or water.
The polymeric coating may exhibit excellent non-wettability in the presence of
water, as measured in accordance with standard t angle measurement methods
known in the art. The ric coating may have a contact angle of greater than 90°
and may be categorized as hydrophobic. Consequently, the proppant of such an
embodiment can lly float in the subsurface reservoir and is typically useful for
applications requiring foam coatings. Alternatively, the polymeric coating may be
categorized as hyllic.
Further, the polymeric g typically ts excellent hydrolytic
resistance and will not lose th and durability when exposed to water.
Consequently, the proppant can be submerged in the face reservoir and exposed
to water and will maintain its strength and durability.
The polymeric coating can be cured/cross-linked prior to pumping of the
proppant into the subsurface reservoir, or the polymeric coating can be curable/cross-
linkable whereby the polymeric coating cures in the subsurface oir due to the
conditions inherent therein. These concepts are described further below.
The proppant of the subject disclosure may include the particle encapsulated
with a cured polymeric coating. The cured polymeric coating typically provides crush
strength, or resistance, for the proppant and prevents agglomeration of the nt.
Since the cured polymeric coating is cured before the proppant is pumped into
subsurface reservoir, the proppant typically does not crush or agglomerate
even under
high pressure and ature conditions.
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Alternatively, the proppant of the subject disclosure may include the particle
encapsulated With a curable polymeric g. The e polymeric coating
typically consolidates and cures subsurface. The curable polymeric g is
typically not cross—linked, i.e., cured, or is partially linked before the proppant is
pumped into the subsurface reservoir. Instead, the e polymeric coating
typically cures under the high pressure and temperature conditions in the subsurface
reservoir. Proppants comprising the particle ulated with the curable polymeric
coating are often used for high pressure and temperature conditions.
Additionally, proppants comprising the particle encapsulated with the curable
polymeric coating may be classified as curable proppants, subsurface-curable
proppants and partially-curable nts. face-curable proppants typically
cure entirely in the subsurface reservoir, while partially-curable proppants are
typically partially cured before being pumped into the face reservoir. The
partially-curable proppants then typically fully cure in the subsurface oir. The
proppant of the t disclosure can be either subsurface-curable or partially-
curable.
Multiple layers of the polymeric coating can be applied to the particle to form
the proppant. As such, the proppant of the subject disclosure can include a particle
having a cross—linked polymeric coating disposed on the particle and a curable
polymeric coating disposed on the cross—linked coating, and Vice versa. Likewise,
multiple layers of the polymeric coating, each individual layer having the same or
different physical properties can be applied to the particle to form the nt. In
addition, the polymeric coating can be applied to the particle in combination with
coatings of different materials such as polyurethane coatings, polycarbodiimide
coatings, polyamide imide coatings, polyisocyanurate gs, polyoxizolidone
coatings, polyacrylate coatings, epoxy coatings, furan coatings, sodium silicate
coatings, hybrid coatings, and other material coatings.
The polymeric coating typically exhibits excellent adhesion to inorganic
ates. That is, the polymer wets out and bonds with inorganic surfaces, such as
the surface of a sand particle, which consists primarily of silicon dioxide. As such,
when the particle of the proppant is a sand particle, the ric coating bonds well
with the particle to form a proppant which is especially strong and durable.
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The proppant of the subject disclosure exhibits excellent thermal stability for
high temperature and pressure applications. The polymeric coating is typically stable
at temperatures greater than 200 (392), alternatively greater than 250 (572), °C (°F).
The thermal stability of the polymeric coating is typically determined by thermal
gravimetric analysis (TGA).
Further, the polymeric coating does not degrade or delaminate from the
particle at pressures (even at the temperatures described in the preceding paragraph)
of r than 51.7 MPa (7,500 psi), alternatively greater than 68.9 MPa (10,000 psi),
alternatively r than 86.2 MPa (12,500 psi), alternatively greater than 103.4 MPa
(15,000 psi). Said differently, the proppant of this disclosure does not typically suffer
from failure of the polymeric g due to shear or degradation when exposed to the
atures and pressures set forth in the ing two paragraphs.
Further, with the polymeric coating of this disclosure, the proppant typically
exhibits excellent crush strength, also commonly referred to as crush resistance. With
this crush strength, the polymeric coating of the proppant is uniform and is
substantially free from defects, such as gaps or indentations, which often bute to
premature breakdown and/or e of the polymeric coating. In particular, the
proppant typically exhibits a crush strength of 15 percent or less maximum fines as
measured in accordance with American Petroleum Institute (API) RP60 or DIN EN
ISO 13503-2 at res ranging from 51.7 MPa (7,500 psi) to 103.4 MPa (15,000
psi), including at specific stress pressures of 51.7 MPa (7,500 psi), 68.9 MPa 0
psi), 862 MPa (12,500 psi), and 103.4 MPa (15,000 psi).
When 40/70 Ottawa sand is utilized as the particle, a typical crush th
associated with the proppant of this disclosure is 15 percent or less, alternatively 10
percent or less, alternatively 5 percent or less maximum fines as measured in
accordance with DIN EN ISO 13503—2 by compressing a proppant sample, which
weighs 23.78 grams, 2 lb/It2 loading density, in a test cylinder (having a diameter of
1.5 inches as specified in DIN EN ISO 13503-2) for 2 minutes at 68.9 MPa (10,000
psi) and 23°C (73°F). After compression, t fines and agglomeration are
determined. As a ison, uncoated sand typically has a crush strength of 21.7%
fines under the same ions.
In one ment, the proppant has an unconfined compressive strength of at
least 0.69 MPa (150 psi), alternatively 1.37 MPa (200 psi). Compressive strength is
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tested by forming a porous plug after exposure to a standardized set of conditions
(typical 250°F, 1000 psi, and DI water with 2% KC] for 24 . After g a
porous plug, it is removed from the test cell, cut into 3 inch pieces, and tested by
tensile load until failure to determine unconfined compressive strength.
The polymeric coating of this disclosure typically es a cushioning effect
for the proppant and evenly distributes high pressures,
e.g. closure stresses, around the
proppant. Therefore, the proppant of the subject disclosure effectively props open
fractures and minimizes unwanted impurities in unrefined petroleum fuels in the form
of dust particles.
Although customizable according to carrier fluid selection, the proppant
typically has a bulk density of from 0.1 to 3.0, alternatively from 1.0 to 2.5,
alternatively from 1.0 to 2.0, alternatively from 1.1 to 1.9. One skilled in the art
typically selects the specific gravity of the proppant according to the specific gravity
of the carrier fluid and whether it is desired that the proppant be lightweight or
substantially neutrally buoyant in the selected carrier fluid. Further, depending on the
non-wettability of the polymeric coating, the proppant of such an embodiment
typically has an apparent density of from 2.0 to 3.0, atively from 2.3 to 2.7,
g/cm3 according to API Recommended Practices RP60 (or DIN EN ISO 13503-2)
for testing nts. It is believed that the non-wettability of the polymeric coating
may contribute to flotation of the proppant depending on the selection of the carrier
fluid in the wellbore.
Further, the proppant typically zes unpredictable consolidation. That
is, the nt only consolidates, if at all, in a predictable, desired manner according
to r fluid selection and operating atures and
pressures. Also, the proppant
is typically compatible with low-viscosity carrier fluids having viscosities of less than
3,000 cps at 80°C (176°F) and is typically substantially free from mechanical failure
and/or al degradation when exposed to the carrier fluids and high pressures.
Finally, the nt is typically coated via ical coating processes and
typically does not require multiple coating layers, and therefore minimizes tion
costs.
As set forth above, the subject disclosure also provides the method of forming,
or preparing, the proppant. The method of forming the proppant includes the steps of
combining the isocyanate, the acrylatc, and optionally the polyol to form the e
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composition, coating the particle with the curable composition and curing the curable
composition to form the polymeric coating.
The method of forming the proppant typically includes the steps of combining
the nate, the acrylate, and the polyol to form the curable composition, coating
the particle with the curable composition and curing the curable composition to form
the polymeric coating. It is to be appreciated that when the language “optionally the
polyol” is used to describe the steps of the method that both embodiments with and
Without polyol are being bed. Said ently, at least two distinct steps are
being described.
For this method, the isocyanate, the acrylate, and ally the polyol are
typically provided. As with all other components which may be used in the method of
the subject disclosure (e.g. the particle), the isocyanate and the te are just as
described above with respect to the curable composition and the polymeric coating
formed therefrom.
The isocyanate, the acrylate, and optionally the polyol are combined to form
the curable composition. The curable composition is not required to be formed prior
to exposure of the particle to the individual components.
That is, the isocyanate, the acrylate, and optionally the polyol and other
components may be combined to form the curable composition simultaneous with the
coating of the particle with curable composition. atively, as is indicated in
certain embodiments below, the isocyanate, the acrylate, and optionally the polyol and
other ents may be combined to form the curable composition prior to the
coating of the particle. The steps of combining and coating are conducted, either
sequentially or simultaneously at a temperature of from ~10 to 120, atively from
-lO to 80, °C.
Prior to the step of coating, the particle may ally be heated to a
temperature greater than 50°C (122°F) prior to or simultaneous with the step of
coating the particle. If heated, a preferred ature
range for heating the particle is
typically from 50 (122°F) to 220°C (428°F). The particle may also optionally be pre-
treated with a silicon-containing adhesion promoter prior to the
step of g the
particle.
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In this method, the steps of combining and coating the le are typically
collectively ted in 60 minutes or less, alternatively in 30 minutes or less,
alternatively in 1 to 20 minutes.
Various techniques can be used to coat the particle. These ques
e, but are not limited to, mixing, pan coating, fluidized-bed coating, co—
extrusion, spraying, u formation of the polymeric coating, and spinning disk
encapsulation. The technique for applying the polymeric coating to the particle is
selected ing to cost, production efficiencies, and batch size.
In one ment, the curable composition is disposed on the particle
via mixing in a vessel, e.g. a reactor. In particular, the individual components of the
proppant, are added to the vessel to form a reaction mixture. 'lhe components may be
added in equal or unequal weight ratios. The reaction e is typically agitated at
an agitator speed surate with the ities of the components. Further, the
reaction e is typically heated at a temperature commensurate with the
polymeric coating technology and batch size. It is to be appreciated that the technique
of mixing may include adding components to the vessel sequentially or concurrently.
Also, the components may be added to the vessel at various time intervals and/or
temperatures.
In another ment, the polymeric coating is disposed on the
particle via spraying. In particular, individual components of the polymeric coating
are contacted in a spray device to form a coating mixture. The coating mixture is then
d onto the particle to form the nt. Spraying the polymeric coating onto
the particle typically results in a uniform, complete, and defect-free polymeric coating
disposed on the particle. For example, the polymeric coating is typically even and
unbroken. The polymeric coating also typically has adequate thickness and
acceptable integrity, which allows for ations requiring controlled—release of the
proppant in the fracture. Spraying also typically results in a thinner and more
consistent ric coating disposed on the particle as compared to other techniques,
and thus the proppant is coated economically. Spraying the particle even permits a
continuous manufacturing process. Spray temperature is typically selected by one
known in the art according to polymeric coating technology and ambient humidity
conditions. Further, one skilled in the art typically sprays the components of the
polymeric g at a viscosity commensurate with the viscosity of the components.
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In another embodiment, the polymeric g is disposed on the
particle in—situ, i.e., in a reaction mixture comprising the components of the ric
coating and the particle. In this embodiment, the polymeric coating is formed or
partially formed as the polymeric coating is disposed on the particle. In-situ
polymeric coating formation steps typically include providing each component of the
ric coating, providing the particle, combining the components of the polymeric
coating and the le, and disposing the polymeric coating on the particle. In-situ
formation of the polymeric coating typically allows for reduced production costs by
way of fewer processing steps as ed to existing methods for forming a
proppant.
'lhe formed proppant is typically prepared according to the method as
set forth above and stored in an offsite location before being pumped into the
subterranean formation and the subsurface reservoir. As such, g typically
occurs offsite from the subterranean formation and subsurface reservoir. However, it
is to be appreciated that the proppant may also be prepared just prior to being pumped
into the ranean ion and the subsurface reservoir. In this scenario, the
proppant may be prepared with a portable coating apparatus at an onsite location of
the subterranean formation and subsurface reservoir.
The method also includes the step of curing the curable ition to
form the polymeric coating. The curable composition can be cured by heat, infrared
radiation, iolet ion, aging/time, internal inclusion chemical free radical
tor, external exposure to a chemical free radical tor, or any combination
thereof to form the polymeric coating. The curable composition/polymeric coating
may include an initiator. In one embodiment, the particle with the curable
composition thereon is exposed to a chemical a free l initiator, e.g. submerged
in a water solution including a free radical initiator.
Once coated, the proppant can be heated to cure the e
composition or to further cure the polymeric coating. The curing optimizes physical
properties of the polymeric g as well as the performance of the proppant. In one
embodiment, the proppant is heated to a temperature of greater than 150 (302),
alternatively r than 180 (356), °C (°F). In one specific embodiment, the
proppant is heated to the second temperature of 190 °C (374°F) for 60 minutes. In
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another embodiment, the proppant is further heated by exposure to higher
temperatures in the well.
The steps of combining the components to form the curable
composition and the polymeric coating can be conducted sequentially. In one
embodiment, the step of combining the nate, the acrylate, and optionally the
polyol to form the curable ition is further defined as first ing the
isocyanate and the polyol and then combining the acrylate with the isocyanate and the
polyol (or reaction product thereof). In this embodiment, a polyurethane pre—polymer
is . The polyurethane pre-polymer can have isocyanate functionality which
can further reacted with an acrylate having isocyanate functional groups (hydroxyl or
amine) to form another isocyanate pre-polymer which has acrylate functionality and
can be cured with a free radical initiator. Of course, the isocyanate and the polyol can
react to form a polyurethane pre-polymer that is not isocyanate functional but can be
mixed with another acrylate to form a curable ition which can be cured with a
free radical initiator.
In another embodiment, the step of combining the isocyanate, the
acrylate, and optionally the polyol to form the e composition is further defined
as first combining the isocyanate and the acrylate having isocyanate functional groups
(hydroxyl or amine) and then combining the polyol with the isocyanate and the
acrylate (or reaction product thereof). In this embodiment, a polyurethane pre—
r having acrylate onality is formed and optionally isocyanate
functionality. When the polyurethane pre~polymer of this embodiment has isocyanate
functionality, the polyurethane pre-polymer can r react with a polyol to form
another isocyanate pre—polymer which has te functionality and can be cured
with a free radical initiator. Of course, the isocyanate and the polyol can react to form
a polyurethane pre-polymer that is not isocyanate functional but can be mixed with
another acrylate to form a curable composition which can be cured with a free l
initiator.
In yet another embodiment, the step of combining the nate, the
acrylate, and optionally the polyol to form the curable composition is further defined
as first combining the isocyanate and a polycarbodiimide catalyst, eg.
a phospholene
oxide, to form a polyearbodiimide ymer which may have isocyanate
functionality. When the polycarbodiimide pre-polymer of this embodiment has
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isocyanate functionality, the rbodiimide lymer can further react with a
polyol and/or a isocyanate reactive acrylate to form another polycarbodiimide pre-
polymer which has acrylate functionality and can be cured with a free radical initiator.
Of course, the isocyanate can react to form a polycarbodiimide pre-polymer that is not
isocyanate functional but can be mixed with another acrylate to form a curable
composition which can be cured with a free radical initiator.
Depending on the sequence of the addition of components during the
step of combining, various pre-polymers can be formed which can then be used to
form and or react to form the polymeric g. For example, the polymeric g
can be formed from a polyurethane pre-polymer optionally having acrylate
functionality, rbodiimide functionality, and/or isocyanate functionality. As
another example, the polymeric coating can be formed from a polycarbodiimide
pre-
polymer optionally having isocyanate onality and/or acrylate functionality
In one embodiment, a rbodiimide pre—polymer is formed and
functionalized with methacrylic/acrylic acid acrylate functionality or other reactive
functional groups (e.g. amine, acrylate, vinyl) which is then used to form the
polymeric coating. This pre-polymer is discussed at length in US. Patent No.
,115,072, which is incorporated in its entirety .
Of course the step of combining the isocyanate, the te, and
optionally the polyol to form the curable composition can be further defined as first
combining the polyol and the acrylate and then combining the isocyanate with the
polyol and the acrylate. In such an embodiment, a pre-polymer is not typically
formed.
The proppant is useful for hydraulic fracturing of the ranean
formation to enhance recovery of petroleum and the like. In a typical hydraulic
fracturing operation, a hydraulic fracturing composition, Le, a mixture, sing
the carrier fluid, the proppant, and optionally various other
components, is prepared.
The carrier fluid is selected according to wellbore conditions and is mixed with the
proppant to form the e which is the hydraulic fracturing composition. The
carrier fluid can be a wide variety of fluids including, but not limited to, kerosene and
water. Typically, the r fluid is water. Various other components which can be
added to the mixture include, but are not limited to,
guar, polysaccharides, and other
components know to those skilled in the art.
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The mixture is pumped into the face reservoir, which may be the
wellbore, to cause the subterranean formation to fracture. More specifically,
hydraulic pressure is applied to introduce the hydraulic fracturing composition under
re into the subsurface reservoir to create or enlarge res in the subterranean
formation. When the hydraulic re is released, the proppant holds the fractures
open, thereby enhancing the ability of the fractures to extract petroleum fuels or other
subsurface fluids from the subsurface reservoir to the wellbore.
For the method of filtering a fluid, the proppant of the subject
sure is provided according to the method of forming the proppant as set forth
above. In one embodiment, the subsurface fluid can he ned petroleum or the
like. However, it is to be appreciated that the method of the subject disclosure may
include the filtering of other subsurface fluids not specifically recited herein, for
example, air, water, or natural gas.
To filter the subsurface fluid, the fracture in the subsurface reservoir
that contains the unrefined petroleum, e.g. unfiltered crude oil, is fied by
methods known in the art of oil extraction. Unrefined petroleum is typically procured
via a subsurface reservoir, such as a wellbore, and provided as feedstock to ries
for production of refined products such as petroleum gas, naphtha, gasoline, kerosene,
gas oil, lubricating oil, heavy gas, and coke. However, crude oil that resides in
subsurface reservoirs includes impurities such as sulfur, undesirable metal ions, tar,
and high molecular weight hydrocarbons. Such impurities foul refinery equipment
and lengthen ry production cycles, and it is desirable to minimize such
impurities to prevent breakdown of refinery equipment, minimize me of
refinery equipment for maintenance and cleaning, and maximize efficiency of refinery
processes. Therefore, filtering is desirable.
For the method of filtering, the hydraulic fracturing composition is
pumped into the subsurface reservoir so that the hydraulic fracturing composition
contacts the unfiltered crude oil. The hydraulic fracturing composition is typically
pumped into the subsurface oir at a rate and pressure such that one or more
fractures are formed in the subterranean ion. The
pressure inside the fracture in
the subterranean ion may be greater than 5,000, r than 7,000,
or even
greater than 68.9 MPa (10,000 psi), and the temperature inside the fracture is typically
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greater than 21°C (70°F) and can be as high 191°C (375°F) depending on the
ular subterranean formation and/or subsurface reservoir.
Although not required for filtering, the proppant can be a controlled-
release proppant. With a controlled—release proppant, while the lic fracturing
composition is inside the fracture, the polymeric coating of the nt typically
dissolves in a controlled manner due to pressure, temperature, pH change, and/0r
dissolution in the r fluid in a controlled manner or the polymeric coating is
disposed about the particle such that the particle is partially exposed to achieve a
controlled-release. Complete ution of the polymeric coating depends on the
thickness of the polymeric coating and the temperature and pressure inside the
fracture, but typically occurs within 1 to 4 hours. It is to be understood that the
terminology “complete dissolution” generally means that less than 1 percent of the
coating remains disposed on or about the particle. The controlled—release allows a
delayed exposure of the particle to crude oil in the fracture. In the embodiment where
the particle includes the active agent, such as the microorganism or catalyst, the
particle typically has reactive sites that must contact the fluid, 6. g. the crude oil, in a
controlled manner to filter or ise clean the fluid. If implemented, the
controlled—release provides a l exposure of the reactive sites to the crude oil to
protect the active sites from saturation. rly, the active agent is typically
sensitive to immediate contact with free oxygen. The controlled—release es the
gradual exposure of the active agent to the crude oil to protect the active agent from
saturation by free oxygen, especially when the active agent is a microorganism or
catalyst.
To filter the fluid, the particle, which is substantially free of the
polymeric coating after the controlled—release, contacts the face fluid, e.g. the
crude oil. It is to be understood that the terminology “substantially free” means that
complete dissolution of the polymeric coating has occurred and, as d above, less
than 1 percent of the polymeric coating remains disposed on or about the particle.
This terminology is commonly used interchangeably with the terminology “complete
dissolution” as described above. In an embodiment where an active agent is utilized,
upon contact with the fluid, the particle typically filters ties such as sulfur,
unwanted metal ions, tar, and high molecular weight hydrocarbons from the crude oil
through biological digestion. As noted above, a combination of sands/sintered
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ceramic particles and rganisms/catalysts are particularly useful for filtering
crude oil to provide adequate support/propping and also to , i.e., to remove
impurities. The proppant therefore typically filters crude oil by allowing the delayed
exposure of the particle to the crude oil in the fracture.
The filtered crude oil is typically extracted from the subsurface
reservoir via the fracture, or fractures, in the subterranean formation through methods
known in the art of oil extraction. The filtered crude oil is typically provided to oil
refineries as feedstock, and the particle lly remains in the fracture.
Alternatively, in a fracture that is nearing its end-of-life, cg. a fracture
that contains crude oil that cannot be ically ted by current oil extraction
methods, the particle may also be used to extract natural gas as the fluid from the
fracture. The particle, particularly where an active agent is utilized, digests
hydrocarbons by contacting the ve sites of the particle and/or of the active agent
with the fluid to convert the arbons in the fluid into propane or methane. The
propane or methane is then typically harvested from the fracture in the subsurface
reservoir through s known in the art of natural gas extraction.
The following examples are meant to illustrate the disclosure and are
not to be viewed in any way as limiting to the scope of the disclosure.
EXAMPLES
Polymeric Coatings 1-4
Polymeric Coatings 1—4 are formed from curable compositions
according to the subject disclosure. Polymeric Coatings 1-4 are formed with the
components listed in Table 1 below. The amounts in Table 1 are in grams, unless
otherwise specified.
Polymeric Coatings 1—4 are formed with a curable composition that
comprises Isocyanate A, Polyol A or B, Acrylate Monomer A, and Catalyst A. To
form Polymeric gs 1-4, a pre—polymer is made by adding nate A along
with a single drop of Catalyst A (~0.02g) to a reaction vessel. Polyol A or B is then
added slowly to the reaction vessel over 30 minutes. The e of the lsocyanate
A, the Catalyst A, and the Polyol A or B is mixed for 1.5 hours at 70-80°C to form a
polyurethane pro—polymer (in Examples 1 and 2 having isocyanatc functionality and
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in Examples 3 and 4 having isocyanate and acrylate functionality). Acrylate
Monomer A (which has hydroxyl functionality) is added, all at once, to the reaction
vessel.
The mixture of the polyurethane pre-polymer (which has isocyanate
functionality) and the Acrylate Monomer A is ed to form the curable
composition.
Activator A is added to the curable composition. Film plaques of the
e composition are then formed with a draw~down bar on a number 10 setting.
The curable composition is heated to a temperature of 123°C for greater than 5
minutes to cure the e composition and form Polymeric gs 1—4. Examples
1 and 3 hardened in 5 s, Example 2 hardened in 8 minutes, and Example 4 took
longer than 8 minutes to harden.
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Table 1
Isocyanate A
Polyol A
Polyol B
Acrylate
Monomer A
ethane
.0
Pie-polymer
Free Radical
Physical Properties
Melting
Endotherm (°C)
Shore D
TGA 10% Wt.
Loss (°C)
Isocyanate A is diphenylmethane diisocyanate having an NCO content
of 33.5 weight percent, a nominal functionality of 2.0, and a viscosity at 25°C of 15
cps.
Polyol A is a tri—functional polyol formed via the reaction of propylene
oxide and trimethylo] propane, having hydroxyl number of from 383 to 413 mg
KOH/g and a viscosity at 25°C of 600 cps.
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Polyol B is a tri—functional polyol having a hydroxyl number of 920
mg KOH/g and a viscosity at 25°C of 3400 cps.
Acrylate Monomer A is hydroxyethyl methacrylate.
Catalyst A is 33 wt. % solution of ylenediamine in dipropylene
glycol.
Free Radical Generator A is 2,2'—Azobis(2-methylbutyronitrile).
Polymeric Coatings 5-10
Polymeric Coatings 5-10 are also from e compositions according
to the t disclosure. ric Coatings 5—10 are formed with the components
listed in Table 2 below. The amounts in Table 2 are in grams, unless otherwise
specified.
To form ric Coatings 5-9, a pre-polymer is formed by adding
Isocyanate A along with a drop of Catalyst A and/or B, and Acrylate Monomer B to a
reaction vessel. The mixture of the Isocyanate A, the Catalyst A and/or B, and the
te Monomer B (which is hydroxyl functional) is mixed for 1.5 hours at 70-
80°C to form curable compositions 5-9 comprising the polyurethane pre-polymer
which has acrylic functionality.
Activator A is added to the curable composition. Film plaques of the
curable composition are then formed with a draw-down bar on a number 10 setting.
The curable composition is heated to a temperature of 120 °C for 30 minutes to
cure
the curable composition and form Polymeric Coatings 5—9.
Polymeric Coating 10 is formed with a curable composition that
comprises Isocyanate A, Polyol C, te Monomer B, and Catalyst A. To form
ric gs 14, a polyurethane pre—polymer having acrylic and isocyanate
functionality is made by adding nate A, Acrylate Monomer B, and a drop of
st A to a reaction vessel. Polyol C is then added slowly to the reaction vessel
over 30 minutes. The mixture of the polyurethane pre—polymer having acrylic and
isocyanate functionality and the Polyol C having hydroxyl functionality is mixed for
1.5 hours at 70—80°C.
Activator A is added to the curable composition. Film plaques of the
curable ition are then formed with a draw-down bar on a number 10 setting.
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The curable composition is heated to a temperature of 120 °C for 30 minutes to cure
the curable composition and form Polymeric Coating 10.
Table 2
PC 5 PC 6 PC 7 PC 8 PC 9 PC 10
Step1
IsocyanateA 52.44 5.11 2.46 0.63 13.48 27.25
MonomerB
Catalyst A 0.05 -—— -_- ___ .002
Catalyst B
Solvent A 29.29
Step 2
Step 3
Pre-polymer 7 1
Free Radical—[—
GeneratorA L '02
Physical Properties (DSC; Heat-Cool—Heat, Second Numbers)
'1‘g(°C)
Polyol C is a bi~functional polyol formed Via the reaction of ene
oxide and propylene glycol, having hydroxyl number of from 102 to 112
mg KOH/g
and a viscosity at 25°C of 150 cps.
Acrylate Monomer B is oxypropyl methacrylate (CAS No 6674-
22—1).
Catalyst B is 3-methylpheny1—2-phospholene oxide.
t A is Tetrahydrofuran.
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Polymeric gs 11-15
Polymeric Coatings 11-15 are also formed from polyurethane pre-
polymers according to the subject disclosure. Polymeric Coatings 11-15 are formed
with the components listed in Table 3 below. The s in Table 3 are in grams,
unless otherwise specified.
] To form Polymeric Coatings 11-15, a pre—polymer is formed by adding
Isocyanate B, Polyol, Acrylate Monomer B, and optionally Activator A are added to
the reaction vessel. The polyurethane pre—polymer and the Acrylate Monomer B are
mixed for 4 minutes at 170°C to form the Polymeric Coatings 11-15.
Table 3
J PC. 11 ‘PC. 12 l‘PC.131PC. 14 ' PC. 15
Polyurethane Pre—polynier
Step 1
Isocyanate B
Polyol A
'14
Monomer B
Polymeric Coating
Pie—polymer
Free Radical
torA
Physical Properties
Tg i>120°C >120°C >120°EJ >120°C >120°C
Isocyanate B is polymeric diphenylmethane diisocyanate having an
NCO content of 31.4 weight percent, a l functionality of 2.7, and
a viscosity at
°C of 200 cps.
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Examples 1-4
Examples 1-4 are proppants formed according to the subject
disclosure. The polymeric coatings of Examples 1-4 are formed with the components
listed in Table 4 below. The amounts in Table 4 are in grams, unless otherwise
specified.
A e composition comprising Isocyanate B, Catalyst A, Polyol A,
and Acrylate Monomer B is used to form the polymeric coatings of Examples 1—4. To
form the polymeric coatings, Isocyanate B, a drop of Catalyst C, Polyol A, and
Acrylate Monomer A are added all at once to a Hobart mixer heated to a temperature
of 170 °C and having Particle A therein. The ents are mixed for 4 minutes to
form Examples 1-4.
Examples 1- 4 are tested for crush ance. The appropriate formula
for ining percent fines is set forth in DIN EN ISO 13503—2. The crush strength
of Examples 1-4 are tested by compressing a proppant sample, which weighs 40
grams, in a test er (having a diameter of 5 cm (2 in) as specified in DIN EN ISO
2) with a 2 minute ramp rate and for 2 minutes at 55.2 MPa (8000 psi) and
23°C. (73°F) The crush strength values for Examples 1-4 are also set forth in Table 4
below.
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Table 4
Isocyanate B
Acrylate r B
Acrylate Monomer B 20.61
Proppant
Particle A 100 100 100 100
Polymeric Coating 3.00 3.00 3.00 3.00
Crush Strength
Crush Strength
8
(% Fines <40 sieve) ‘
Crush Strength
(% Fines <40 sieve) 10.9
3 hours in H20
Crush Strength
(% Fines <40 sieve)
3 hours 7.04
in H20, Sodium
Persulfate (1% by weight coating)
Catalyst C is a tin catalyst.
Particle A is Hickory sand having a sieve size of 20/40 (US Sieve No.)
or 0841/0420 (mm).
Examples 5-10
es 5—10 are proppants formed according to the subject
disclosure. The polymeric gs of Examples 5-10 are formed with the
components listed in Table 5 below. The amounts in Table 5 are in grams, unless
otherwise specified.
To form Examples 5-10, Particle A is added to a Hobart mixer and
heated to a temperature of 170 0C. nate B and Acrylate Monomer B are then
added to the Hobart mixer and mixed for 4 minutes to form Examples 5-10. This is
referred to herein as u formation of a pre—polymer.
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Examples 5-10 are tested for crush strength ing to the
parameters set forth above (for Examples 1-4). The crush strength values for
Examples 5—10 are also set forth in Table 5 below.
Table 5
Ex. 5 EX. 6 Ex. 7 Ex. 8 Ex. 8 Ex. 8
(110-1) (110—2) (110—3) (110-4) (110—5) (110'6)__|
Step 1
Isocyanate B
Acrylate Monomer B
Catalyst B
Free l
Generator A
Proppants
Particle A
Polymeric Coating
Crush Strength
Crush Strength
(% Fines <40 sieve)
Crush Strength
(% Fines <40 sieve)
16 hours in DI H20 16.9
@ 120°C
Examples 11 and 12
Examples 11 and 12 are proppants formed according to the subject
sure. The polymeric coatings of Examples 11 and 12 are formed with the
components listed in Table 6 below. The amounts in Table 6 are in grams, unless
otherwise specified.
To form Examples 11 and 12, Particle A is added to a Hobart mixer
and heated to a temperature of 170 °C. Isocyanate B, Acrylate Monomer B, Catalyst
B, Free Radical Generator B, and other additives are added to the Hobart mixer.
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These ents are mixed are mixed for 4 minutes at 170°C to form each
respective e.
Examples 11 and 12 are tested for crush strength according to the
parameters set forth above (for Examples 1-4). The crush strength values for
Examples 11 and 12 are also set forth in Table 6 below.
Table 6
Ex. 5 Ex. 6
1_(l 13-3) (113-4)
Isocyanate B 10.5 10.5
Acrylate Monomer B 4.5 4.5
. —1
st B 0.18 0.36
Colorant
Free Radical
Generator B
Proppants
Particle A
Polymeric Coating
Surface Treatment
Physical Properties
Crush Strength
13'4 14'4
(% Fines <40 sieve)
Crush th
(% Fines <40 sieve) 12.1 7.6
24 hours in H20
Crush Strength
(% Fines <40 sieve) 13.4 7.9
24 hours in H20
Free Radical Generator B is 2,2'-Azobis[2-methyl-N—(2-
hydroxyethyl)propionamide].
Colorant is CHROMATINT YELLOW® X-2742.
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Surface Treatment is yl ethyl hydroxyethylmonium
methosulfate.
Example 13
Example 13 is a proppant formed according to the subject sure.
The polymeric coating of Example 13 is formed with the components listed in Table 7
below. The amounts in Table 7 below are in grams, unless otherwise specified.
To form Example 13, a pre-polymer is formed by adding Isocyanate B,
Polyol D, and Catalyst B, to a reaction vessel. These components are mixed for 4
minutes at 48°C to form the ethane pre-polymer having isocyanate onality
of Example 13. The pre-polymer is mixed with Acrylate Monomer B and added a
Hobart mixer and mixed for 2 s to form Example 13.
Table 7
Step 1
Isocyanate B
Polyol D
Catalyst A
Step 2
Acrylate Monomer B
Free Radical
Generator A
Proppant
Particle A
Polymeric Coating
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Polyol D is a sucrose glycerin initiated polyether polyol having
hydroxyl number of from 470 mg KOI-I/g and a Viscosity at 25°C of 3500 cps.
Polymeric Coatings 16-21
Polymeric Coatings 16-21 are also formed ing to the subject
sure. Polymeric Coatings 16—21 are formed with the components listed in Table
8 below. The amounts in Table 8 are in grams, unless otherwise specified.
Polymeric Coatings 16—21 are formed with a coating composition that
comprises Isocyanate B, Polyol A, Acrylate Monomer B (which is hydroxyl
functional), Catalyst C, and Acrylate r C (which is not hydroxyl functional).
Said differently, this embodiment is formed with a mixture of a polyurethane pre-
polymer having acrylate functionality (the on product of Isocyanate B, Polyol A,
and Acrylate Monomer B, in the presence of st C) and Acrylate Monomer C,
which is not hydroxy functional, and thus does not react to with the polyurethane
pre-
polymer having acrylate functionality until the coating composition is exposed to Free
Radical Generator B, i.e., cured.
To form Polymeric gs 22-27, Isocyanate B, Polyol A, Acrylate
Monomer B, Catalyst C, and Acrylate r C are added to a reaction vessel and
mixed for 4 minutes at 170°C. Sample s are then formed from the coating
composition. The plaques are submerged in an aqueous solution of Free Radical
Generator B at 120°C for 3 hours to cure the coating composition and form the
ric coatings.
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Isocyanate B
Acrylate
3.58
Monomer B
Polyol A 32.32
iAcrylate
.01
Monomer C
yst C
Physical Properties
Durometer
Shore D
Duroeter
Shore D
(3 hours in an
H20/Free 78
Generator B
on, 120°C)
Acrylate Monomer C is 2—ethylhexyl acrylate.
Polymeric gs 22-27
Polymeric Coatings 22-27 are also formed according to the subject
disclosure. ric Coatings 22—27 are formed with the components listed in Table
9 below. The amounts in Table 9 are in grams, unless otherwise specified.
Polymeric Coatings 22-27 are formed with a coating composition that
comprises lsocyanate B, Polyol A, Acrylate Monomer B (which is hydroxyl
functional), Catalyst C, and Acrylate Monomer D (which is not hydroxyl functional).
Said differently, this embodiment is formed with a mixture of a polyurethane
pre—
r having acrylate onality (the reaction product of Isocyanate B, Polyol A,
and Acrylate Monomer B, in the presence of Catalyst C) and Acrylate Monomer D,
which is not hydroxy functional, and thus does not react to with the polyurethane
pre-
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polymer having acrylate functionality until the g composition is exposed to Free
Radical Generator B, i.e., cured.
To form Polymeric Coatings 22-27, nate B, Polyol A, Acrylate
Monomer B, Catalyst C, and Acrylate Monomer D are added to a reaction vessel and
mixed for 4 minutes at 170°C. The ing composition, i.e., the curable
composition, is added to a weigh pan and analyzed.
Table 9
PC 23 PC 24 PC 25
IsocyanateB 48.59 46.29 43.86 41.40 34.08
Acrylate
.28 4.86 4.61 4.35 4.09 3.58
MonomerB
43.90 41 60- 39.26
Acrylate
4.95
Monomer D
Catalyst C .05
Physical Properties
Durometer
79 80 68 71
Shore D 80
Durometer
Shore D
(3 hours in an
H20/Free 84 78 84 78
Radical
Generator B
solution, 120°C)
[001 69] Acrylate Monomer D is hexanediol diacrylate.
Example 14
Example 14 is a proppant formed according to the subject sure.
The ric coating of Example 14 is formed with the
ents listed in Table
below. The amounts in Table 10 below are in
grams, unless otherwise specified.
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Example 14 is a proppant that is formed with a coating composition
that comprises Isocyanate B, Polyol A, Acrylate Monomer B (which is hydroxyl
functional) and Acrylate Monomer D (which is not hydroxyl functional). Said
differently, this embodiment is formed with a mixture of a ethane pre—polymer
having acrylate functionality and (the reaction product of Isocyanate B, Polyol A,
Acrylate Monomer B), Catalyst C, and Acrylate Monomer D, which is not hydroxy
functional, and thus does not react to with the polyurethane pre—polymer until it is
exposed to Free l Generator B and cured.
To form e 14, Isocyanate B, Polyol A, Acrylate Monomer B,
Catalyst C, and Acrylate Monomer D are added to a Hobart Mixer having Particle A
heated to a temperature of 100°C n. The ents are then mixed for 2
minutes at IOU—103°C to form Particle A having the coating composition thereon.
Particle A having the coating composition thereon is then submerged in an aqueous
solution of Free Radical Generator B at 120°C for 3 hours to cure the coating
composition and form the polymeric coating.
Table 10
Isocyanate B
Polyol A
Acrylate Monomer B
Acrylate Monomer D
Catalyst C
te r B
Free Radical
Generator A
Particle A
LPolymeric g
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Examples 15 and 16
Examples 15 and 16 are proppants formed according to the subject
disclosure. The polymeric coatings of Examples 15 and 16 are formed with the
ents listed in Table 11 below. The amounts in Table 11 below are in grams,
unless otherwise specified.
Examples 15 and 16 are formed with a coating composition that
comprises the reaction t of Polyol A, Acrylate Monomers B and E, and
Isocyanate B.
To form Examples 15 and 16, Polyol A, Acrylate Monomers B and E,
Catalyst D, Isocyanate B, nt, and Peroxide are added to a Hobart Mixer having
Particle A heated to a temperature of 80°C therein. The components are then mixed
for 2 minutes at temperature setting of 80°C to form a nt comprising Particle B
having a polymeric coating thereon.
Acrylate Monomer B
Acrylate Monomer E —-- 1.31
Catalyst D
Isocyanate B
Free Radical
tor C
Colorant
Total Coating Amount
le B 500 500
4_ [—
Polymeric Coating
(% by wt. proppant)
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Particle B is Northern White Sand having a sieve size of 20/40 (US
Sieve No.) or 0841/0420 (mm).
] Acrylate Monomer E is 1, 4 butanediol dimethyacrylate (BDODM).
Catalyst D is azabicyclo[5.4.0]undecene, CAS No. 66742
(DBU).
Free Radical Generator C is tert-Butylperoxy 2-ethylhexyl carbonate,
CAS No. 12~4 (TBEC).
Examples 15 and 16 are tested for unconfined compressive strength
and crush resistance. The testing results and testing ters are set forth in Table
12 below.
Compressive strength is tested by forming a porous plug after exposure
to a standardized set of conditions (typical 250°F, 1000 psi, and DI water with 2%
KC] for 24 hours). After forming a porous plug, it is removed from the test cell, cut
into 3 inch pieces, and tested by e load until failure to determine unconfined
compressive strength.
Crush resistance is determined with the formula for determining
percent fines set forth in DIN EN ISO 13503-2. The crush resistance is tested by
compressing a proppant sample, which weighs 40 grams, in a test cylinder (having a
diameter of 5 cm (2 in) as specified in DIN EN ISO 13503—2) with a 2 minute
ramp
rate and for 2 s at 68.95 MPa 0 psi) and 23°C (73°F).
Table 12
Ex. 15 Ex. 16 I
Unconflnéd 3.34 2.39
ssrve Strength
(484) (346)
MPa (PSI)
Crush Resistance 7.3 l 4.2
Refering now to Table 12, the Examples 15 and 16 have excellent
unconfined compressive strength and crush resistance. Further, the s is
conducted quickly and at relatively low temperatures (80°C).
It is to be understood that the appended claims are not limited to
express and particular compounds, compositions, or methods described in the detailed
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description, which may vary between particular embodiments which fall within the
scope of the appended claims. With respect to any Markush groups relied upon
herein for describing particular features or aspects of s embodiments, it is to be
appreciated that different, special, and/or unexpected results may be obtained from
each member of the tive Markush group independent from all other Markush
members. Each member of a Markush group may be relied upon individually and or
in combination and provides adequate support for specific embodiments within the
scope of the ed .
It is also to be understood that any ranges and subranges relied upon in
describing various embodiments of the present disclosure independently and
collectively fall within the scope of the appended claims, and are understood to
describe and contemplate all ranges including whole and/or fractional values n,
even if such values are not expressly written . One of skill in the art readily
recognizes that the enumerated ranges and subranges sufficiently describe and enable
various embodiments of the present disclosure, and such ranges and subranges
may be
further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one
example, a range “of from 0.1 to 0.9” may be further delineated into a lower third,
i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from
0.7 to 0.9, which individually and collectively are within the
scope of the appended
claims, and may be relied upon individually and/or collectively and provide adequate
t for specific embodiments within the scope of the appended claims. In
addition, With respect to the language which defines or es a range, such as “at
least,9.‘ er than,” “less than,” “no more than,” and the like, it is to be tood
that such language includes subranges and/or an upper or lower limit. As another
example, a range of “at least 10” inherently includes a subrange of from at least 10 to
, a subrange of from at least 10 to 25, a ge of from 25 to 35, and so on, and
each subrange may be relied upon individually and/or collectively and provides
adequate support for specific ments within the scope of the appended claims.
Finally, an individual number within a disclosed range may be relied upon and
provides adequate support for specific embodiments within the scope of the appended
claims. For example, a range “of from 1 to 9” includes various individual integers,
such as 3, as well as individual numbers including a decimal point (or on), such
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as 4.1, which may be relied upon and e adequate support for specific
embodiments within the scope of the ed claims.
The present disclosure has been described in an illustrative manner,
and it is to be understood that the terminology which has been used is ed to be
in the nature of words of description rather than of limitation, Obviously, many
modifications and variations of the present disclosure are possible in light of the
above teachings. It is, therefore, to be understood that within the scope of the
appended claims, the present disclosure may be practiced otherwise than as
specifically described.
H&H File No. 06533100631
Claims (20)
1. A proppant for hydraulically fracturing a subterranean formation, said proppant comprising: A. a le present in an amount of from 90 to 99.5 percent by weight based on the total weight of said nt; and B. a polymeric coating disposed about said particle and present in an amount of from 0.5 to 10 percent by weight based on the total weight of said proppant, said ric g formed from a curable composition sing: an isocyanate comprising diphenylmethane diisocyanate and/or polymeric diphenylmethane yanate included in said curable composition in an amount of from 10 to 70 percent by weight based on the total weight of all components used to form said curable composition, an acrylate comprising a hydroxy-functional acrylate monomer selected from the group of glycerol thacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate, ybutyl methacrylate, N-(2- hydroxypropyl)methacrylamide, poly ethoxy (10) ethyl methacrylate, pentaerythritol triacrylate, and combinations thereof, said acrylate included in said curable composition in an amount of from 10 to 70 percent by weight based on the total weight of all components used to form said curable composition, and a polyether polyol included in said curable composition in an amount of from 10 to 70 percent by weight based on the total weight of all ents used to form said curable composition.
2. A proppant as set forth in claim 1 wherein said curable composition r comprises a catalyst selected from the group of phosphorous compounds, tertiary amines, basic metal compounds, carboxylic acid metal salts, non-basic organo-metallic compounds, and combinations thereof.
3. A proppant as set forth in claim 1 or 2 wherein said curable composition comprises a chemical free radical generator selected from peroxides, azo compounds, and combinations thereof.
4. A proppant as set forth in any one of the ing claims wherein said curable composition further comprises an amine-functional acrylate monomer.
5. A proppant as set forth in any one of the preceding claims wherein said curable composition comprises a yalkyl methacrylate.
6. A nt as set forth in any one of the preceding claims wherein said isocyanate comprises a polymeric isocyanate having an NCO content of about 31.5 weight
7. A proppant as set forth in any one of the preceding claims wherein said isocyanate is included in said curable composition, in an amount of from 20 to 70 percent by weight based on the total weight of all components used to form said curable composition, said acrylate is included in said curable composition, in an amount of from 10 to 70 t by weight based on the total weight of all components used to form said curable composition, and said polyol is included in said curable composition, in an amount of from 10 to 70 percent by weight based on the total weight of all components used to form said curable ition.
8. A nt as set forth in any one of the preceding claims wherein said le is selected from the group of minerals, ceramics, sands, nut shells, gravels, mine tailings, coal ashes, rocks, smelter slag, diatomaceous earth, crushed charcoals, micas, sawdust, wood chips, resinous particles, polymeric particles, and combinations thereof.
9. A proppant as set forth in any one of the ing claims that is lly stable at temperatures greater than 200°C.
10. A proppant as set forth in any one of the preceding claims that has an unconfined compressive strength of at least 0.69 MPa (150 psi).
11. A method of hydraulically fracturing a subterranean formation which defines a subsurface reservoir with a mixture comprising a carrier fluid and a proppant as set forth in any one of the preceding claims, said method comprising the step of pumping the mixture into the subsurface reservoir to re the subterranean formation.
12. A method of forming a proppant for hydraulically fracturing a subterranean formation, wherein the proppant comprises a particle and a polymeric coating disposed about the particle, the polymeric coating formed from a curable composition comprising an isocyanate comprising diphenylmethane diisocyanate and/or polymeric diphenylmethane yanate, an acrylate comprising a y-functional acrylate r selected from the group of glycerol monomethacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-(2- hydroxypropyl)methacrylamide, poly ethoxy (10) ethyl methacrylate, pentaerythritol triacrylate, and combinations thereof, and a polyether polyol, said method comprising the steps A. ing the isocyanate comprising diphenylmethane diisocyanate and/or polymeric diphenylmethane diisocyanate, the hydroxy-functional acrylate monomer, and the polyether polyol to form the curable composition; B. coating the particle with the curable composition; and C. curing the curable ition to form the polymeric coating; wherein said isocyanate is included in said curable composition in an amount of from 10 to 70 percent by weight based on the total weight of all components used to form said curable composition, said acrylate is included in said e ition, in an amount of from 10 to 70 percent by weight based on the total weight of all components used to form said curable composition, and said polyol is ed in said e composition, in an amount of from 10 to 70 percent by weight based on the total weight of all components used to form said curable composition; and wherein the particle is t in an amount of from 90 to 99.5 percent by weight based on the total weight of the proppant and the ric coating is present in an amount of from 0.5 to 10 percent by weight based on the total weight of the nt.
13. A method as set forth in claim 12 wherein the step of combining is conducted simultaneous with the step of coating.
14. A method as set forth in claim 13 wherein the steps of combining and coating are conducted at a temperature of from -10 to 80 °C and/or are collectively conducted in 10 minutes or less.
15. A method as set forth in any one of claims 12 through 14 wherein the step of curing the curable composition to form the polymeric coating is further defined as heating the particle with the curable composition thereon.
16. A method as set forth in any one of claims 12 through 15 wherein the step of curing the curable composition to form the polymeric coating is further defined as exposing the particle with the curable composition thereon to a free radical tor.
17. A method as set forth in any one of claims 12 through 16 wherein the step of combining the isocyanate, the acrylate, and the polyol to form the curable composition is further defined as first combining the polyol and the acrylate and then combining the isocyanate with the polyol and the acrylate.
18. A method as set forth in any one of claims 12 through 17 wherein the polymeric coating is formed from a polyurethane pre-polymer having acrylate onality, rbodiimide functionality, and/or isocyanate functionality.
19. The proppant as set forth in claim 1, substantially as herein described with nce to any one of the Examples thereof.
20. The method as set forth in claim 12, substantially as herein described with reference to any one of the Examples thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361790489P | 2013-03-15 | 2013-03-15 | |
US61/790,489 | 2013-03-15 | ||
PCT/US2014/025390 WO2014151294A1 (en) | 2013-03-15 | 2014-03-13 | A proppant |
Publications (2)
Publication Number | Publication Date |
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NZ712164A NZ712164A (en) | 2020-11-27 |
NZ712164B2 true NZ712164B2 (en) | 2021-03-02 |
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