Proppant with enhanced interparticle bonding
Polymer-coated proppants for hydraulic fracturing of oil and gas wells have an outer layer portion that comprises an organofunctional coupling agent, preferably an organofunctional silane coupling agent. The use of an organofunctional silane coupling agent in the outer layer portion of the proppant coating is preferably chosen to expose functionalities that will be reactive towards similar functionalities of adjacent and similarly coated proppants so that, when introduced downhole, these proppants form interparticle bonds at the temperatures and crack closure pressures found downhole in fractured strata. Such enhanced interparticle bonding helps keep the proppant in the fracture and maintains conductivity with reduced flowback. The invention also helps proppants designed for low temperature well to bond more firmly and allows proppants designed for high temperature wells to bond well even at lower downhole temperatures, thereby extending their useful range.
1. A coated proppant comprising: a core and a coating, wherein the coating comprises:
a first layer comprising a first organofunctional silane coupling agent adhered to the core;
a second layer comprising a polymer coupled to the core through the first layer; and
a third layer comprising a second organofunctional silane coupling agent admixed with the second layer, wherein the second organofunctional silane coupling agent is exposed on the outer surface of the coated proppant and can form bonds with other organofunctional silane coupling agents exposed on proppants adjacent to the coated proppant,
wherein the first and second organofunctional silane coupling agents can be the same or different.
2. A coated proppant according to claim 1 wherein said first and second organofunctional silane coupling agent, independently, have, the general structure: Si(R 1 )(R 2 )(R 3 )(R 4 ), in which R 1 , R 2 , R 3 , and R 4 may the same or different and are independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkylene, alkynyl, alkoxy, alkynoxy, aryl, aryloxy, substituted aromatic, heteroaromatic, amino, aminoalkyl, arylamino, epoxide, thiol, and haloalkyl, ether, ester, urethane, amide, provided that at least one of R 1 , R 2 , R 3 , and R 4 comprises an organic moiety.
3. A coated proppant according to claim 1 wherein said first and second organofunctional silane comprise an organic functionality independently selected from the group consisting of methyl, amino, mercapto, chloropropyl, methacryl, methacryloxy, vinyl, benzylamino, ureido, tetrasulfido, and C 1 -C 4 alkoxy groups.
4. A coated proppant according to claim 1 wherein said first and second organofunctional silane are an aminofunctional silane.
5. A coated prop pant according to claim 4 wherein said first and second organofunctional silane are independently selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane.
6. A coated proppant according to claim 1 wherein said first and second organofunctional silanes are, independently, selected from the group consisting of 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (CAS No. 35141-30-1); 3-mercaptopropyl-trimethoxysilane (CAS No. 4420-74-0); n-propyltrimethoxysilane (CAS No. 1067-25-0); [3-(2-aminoethyl)aminopropyl] trimethoxysilane (CAS No. 1760-24-3); silane n-dodecyltrimethoxysilane (CAS No. 3069-21-4); bis (trimethoxysilylpropyl) amine (CAS No. 82985-35-1); 1,2-bis(trimethoxysilyl)ethane (CAS No. 18406-41-2); vinyltri(2-methoxyethoxy) silane (CAS No. 1067-53-4); n-octyltriethoxysilane (CAS No. 2943-75-1); bis[3-(triethoxysilyl) propyl] tetrasulfide (CAS No. 40372-72-3); vinyltriethoxysilane (CAS No. 78-08-0); 3-glycidoxypropyl-trimethoxysilane (CAS No. 2530-83-8); and 3-mercaptopropyl-triethoxysilane (CAS No. 14814-09-6);
3-glycidoxypropyltriethoxysilane (CAS No. 2602-34-8); 2-(3, 4-epoxycyclohexyl)ethyl] trimethoxysilane (CAS No. 3388-04-3); 3-aminopropyltrimethoxysilane (CAS No. 13822-56-5);
2-(3, 4- epoxycyclohexyl)ethyl ]triethoxysilane (CAS No. 10217-34-2);
3-aminopropyltriethoxysilane (CAS No. 919-30-2); 3-glycidoxypropyl-methyldimethoxysilane (CAS No. 65799-47-5); bis(triethoxysilylpropyl)amine (CAS No. 13497-18-2);
3-(2-aminoethylamino) propyldimethoxymethylsilane (CAS No. 3069-29-2); N-(n-Butyl)-3-aminopropyltrimethoxysilane (CAS No. 31024-56-3); n-propyltriethoxysilane (CAS No. 2550-02-9); vinyltrimethoxysilane (CAS No. 2768-02-7); 3-ureidopropyltriethoxy-silane (CAS No. 23779 32-0); and 3-methacryloxypropyl-trimethoxysilane (CAS No. 2530-85-0).
7. A coated proppant according to claim 1 wherein said first and second organofunctional silanes are, independently, selected from the group consisting of mercaptosilanes possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group, blocked mercaptosilane possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group; mercaptosilanes in which the silicon atoms of the mercaptosilane units are bonded to each other through a bridging dialkoxy group, each silane unit optionally possessing at least one hydroxyalkoxysilyl group or a cyclic dialkoxysilyl group; blocked mercaptosilane dimers in which the silicon atoms of the blocked mercaptosilane units are bonded to each other through a bridging dialkoxy group, each silane unit optionally possessing at least one hydroxyalkoxysilyl group or a cyclic dialkoxysilyl group; silane dimers possessing a mercaptosilane unit the silicon atom of which is bonded to the silicon atom of a blocked mercaptosilane unit through a bridging dialkoxy group, each silane unit optionally possessing at least one hydroxyalkoxysilyl group or a cyclic dialkoxysilyl group; mercaptosilane oligomers in which the silicon atoms of adjacent mercaptosilane units are bonded to each other through a bridging dialkoxy group, the terminal mercaptosilane units possessing at least one hydroxyalkoxysilyl group or a cyclic dialkoxysilyl group; blocked mercaptosilane oligomers in which the silicon atoms of adjacent blocked mercaptosilane units are bonded to each other through a bridging dialkoxy group, the terminal mercaptosilane units possessing at least one hydroxyalkoxysilyl group or a cyclic dialkoxysilyl group; and silane oligomers possessing at least one mercaptosilane unit and at least one blocked mercaptosilane unit, the silicon atoms of adjacent silane units being bonded to each other through a bridging dialkoxy group, the terminal silane units possessing at least one hydroxyalkoxysilyl group or a cyclic dialkoxysilyl group.
8. A coated proppant according to claim 1 wherein said first and second organofunctional silanes comprise a mixture of silanes.
9. A coated proppant according to claim 1 wherein the polymer is a polyurethane based polymer.
10. A coated proppant according to claim 1 wherein the polymer is a polyurea based polymer.
11. A coated proppant according to claim 1 wherein said second organofunctional silane comprises a silane-terminated polymer.
12. A coated prop pant according to claim 11 wherein said second organofunctional silane comprises a silane-terminated polyether or silane-terminated polyurethane.
13. A coated proppant according to claim 11 wherein said second organofunctional silane is a silane-terminated polyether.
14. A coated prop pant according to claim 11 wherein said second organofunctional silane is a silane-terminated polyurethane.
15. A composition comprising a plurality of coated proppants according to claim 1 , wherein the coated proppant comprising the second organofunctional silane coupling agent exposed on the outer surface of the coated proppant binds to another organofunctional silane coupling agent exposed on an adjacent proppant comprising the second organofunctional silane coupling agent exposed on the outer surface.
16. A method for propping open a fractured strata by a process that comprises introducing into said fractured strata a coated proppant according to claim 1 .
17. A method according to claim 16 wherein downhole conditions of said fractured strata include a temperature within the range from about 75° F. to about 125° F.
18. A method according to claim 16 wherein downhole conditions of said fractured strata include a temperature within the range from about 150° F. to about 350° F.