( 12 ) United States Patent
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US010208241B2 (12 ) United States Patent ( 10 ) Patent No. : US 10 ,208 ,241 B2 Agrawal et al. ( 45 ) Date of Patent: Feb . 19 , 2019 ( 54 ) RESIN COATED PROPPANTS WITH ( 58 ) Field of Classification Search ANTIMICROBIAL ADDITIVES None See application file for complete search history . (71 ) Applicant : Agienic Inc (72 ) Inventors: Anoop Agrawal, Tucson , AZ ( US ) ; ( 56 ) References Cited Donald R . Uhlmann , Tucson , AZ (US ) ; Nicholas R . Krasnow , Tucson , AZ U . S . PATENT DOCUMENTS ( US ) 4 ,978 , 527 A 12 / 1990 Brink et al. 5 , 180 ,585 A 1/ 1993 Jacobson et al. ( 73 ) Assignee : Agienic , Inc. , Tucson , AZ ( US ) (Continued ) ( * ) Notice : Subject to any disclaimer , the term of this patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS U . S . C . 154 (b ) by 0 days . CA 2735793 AL 3 / 2010 CA 2746980 AL 7 / 2010 (21 ) Appl. No. : 15 / 154 ,458 (Continued ) (22 ) Filed : May 13, 2016 OTHER PUBLICATIONS (65 ) Prior Publication Data US Silica, “ 40 /70 US Silica WhiteTM ” © 2014 U . S . Silica Com US 2016 / 0251571 A1 Sep . 1 , 2016 pany, p . 1 - 2 . * (Continued ) Related U . S . Application Data (63 ) Continuation - in - part of application No . 14 / 866 , 400 , Primary Examiner - Monica A Shin filed on Sep . 25 , 2015 , now abandoned , which is a ( 74 ) Attorney , Agent, or Firm — Rothwell, Figg , Ernst & ( Continued ) Manbeck , P . C . (51 ) Int. Ci. CO9K 8 /80 ( 2006 .01 ) ( 57 ) ABSTRACT CO9K 8 / 60 ( 2006 .01 ) Proppants are used in oil and gas extraction , particularly in (Continued ) fracking operations . The invention relates to resin coated ( 52 ) U . S . CI. proppants . The coatings on proppants have antimicrobial CPC CO9K 8 /805 (2013 . 01 ) ; AOIN 25 / 12 materials incorporated within these coatings. The antimicro ( 2013 .01 ) ; A01N 25 / 26 ( 2013 .01 ) ; A01N bially active agents are incorporated in a concentration less 59 / 20 ( 2013 .01 ) ; A6IK 6 /0017 ( 2013 . 01 ) ; A6IK 8 /0279 ( 2013 .01 ) ; A61K 8 /0283 than 20 % by weight of the coatings or the active agent from (2013 .01 ) ; A61K 8 / 20 (2013 .01 ) ; A61K 8 / 25 these coatings can be released from these coatings in the ( 2013 .01 ); A61K 8 / 736 ( 2013 .01 ) ; A61K environment of the proppants . 8 /8152 ( 2013 .01 ) ; (Continued ) 22 Claims, 4 Drawing Sheets o 43 US 10 ,208 ,241 B2 Page 2 Related U . S . Application Data 2003 /0170314 AI 9 /2003 Burrell et al . 2004 / 0166173 A18 / 2004 Albach et al. continuation - in -part of application No. 14 /089 , 146 , 2005 /0287353 A1 * 12 /2005 Trogolo .. A01N 25 / 34 filed on Nov . 25 , 2013 , now Pat . No. 9 , 155 ,310 , 428 /323 2007 /0081958 AL 4 /2007 Bechert et al . which is a continuation - in - part of application No. 2008 / 0026028 Al 1 / 2008 Schroeder et al. 13 /685 ,379 , filed on Nov . 26 , 2012 , now abandoned , 2008 /0032119 Al 2 / 2008 Feldhan et al. said application No . 14 / 866 , 400 is a continuation - in 2008 / 0102122 A1 5 / 2008 Mahadevan part of application No . 14 /701 ,001 , filed on Apr. 30 , 2008 / 0115936 A1 * 5 /2008 Barmatov . .. .. .. .. .. E21B 43 / 267 2015 , now abandoned . 166 /280 . 1 2008 /0147019 A1* 6 /2008 Song .. .. .. C08B 37 / 003 (60 ) Provisional application No . 61 /800 , 122 , filed on Mar. 604 / 265 15, 2013 , provisional application No . 61 / 820 , 561, 2009 /0010994 Al 1 / 2009 Qvist et al . filed on May 7 , 2013 , provisional application No . 2009 /0035342 A1 2 /2009 Karandikar et al. 2009 /0238988 A1 * 9 /2009 McDaniel CO9K 8 / 805 61/ 881, 318 , filed on Sep . 23 , 2013, provisional 427 / 487 application No . 62 /035 , 388 , filed on Aug . 9 , 2014 , 2010 / 0048573 A1 2 /2010 Sperandio provisional application No. 61/ 987 ,477 , filed on May 2010 /0155310 A1 6 / 2010 Enomura 1 , 2014 . 2010 /0227052 AL 9 /2010 Carter et al. 2010 / 0330146 A112 / 2010 Chauhan et al. (51 ) Int. Ci. 2014 /0110111 AL 5 / 2011 Tanaguay et al . CO9K 8 / 92 2011/ 0159240 A1 * 6 / 2011 Shiao B01J 2 /006 ( 2006 . 01 ) 428 / 144 ADIN 59 / 20 ( 2006 .01 ) 2011/ 0195108 A1* 8 / 2011 Fujimori .. .. A61K 9 / 10 AOIN 59 / 16 ( 2006 .01 ) 424 / 443 A01N 25 / 26 ( 2006 .01 ) 2011 /0262513 Al 10 / 2011 Fujimori et al. 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A61K 8 /81 ( 2006 . 01 ) A61K 8 / 73 ( 2006 . 01 ) FOREIGN PATENT DOCUMENTS A61K 8 /85 ( 2006 . 01 ) A61K 8 / 87 ( 2006 .01 ) CA 2776363 4 / 2011 WO WO9107697 5 / 1991 A610 19 / 10 (2006 . 01) wo WO99 /56542 11/ 1999 C09D 5 / 16 ( 2006 .01 ) WO WO2010 / 125323 A111 / 2010 ( 52 ) U . S . CI. WO WO 2011009083 A1 * 1 / 2011 . AOIN 25 / 08 CPC .. .. A61K 8 /8176 (2013 .01 ) ; A61K 8 /85 WO WO2011 / 035988 3 / 2011 (2013 . 01 ) ; A61K 8 /87 (2013 . 01 ) ; A61K 33 / 18 WO WO2011075855 6 /2011 (2013 .01 ) ; A61K 33 /34 (2013 .01 ) ; A61Q 3 /02 WO WO 2012151109 A1 * 11 /2012 . .. .. CO2F 1 / 001 (2013 .01 ) ; A61Q 5 /02 ( 2013. 01 ) ; A61Q 17/ 005 (2013 .01 ) ; A61Q 19 / 10 ( 2013 .01 ) ; OTHER PUBLICATIONS C09D 5 / 14 ( 2013 .01 ) ; CO9D 5 / 1618 “ Antimicrobial, ” Merriam -Webster , < https: / / www .merriam -webster . ( 2013 .01 ) ; CO9K 87605 ( 2013 .01 ) ; AIK com / dictionary antimicrobial > , updated on Jan . 12 , 2018 , p . 3 . * 2800 /412 ( 2013 .01 ) Ren et al 2007 , International Journal of Antimicrobial Agents 33 ( 2009 ) p . 587 -590 . ( 56 ) References Cited Pramanik et al 2012 , Colloids and Surfaces B : Biointerfaces, ( 2012 ) vol. 96 ( 1 ) p . 50 -55 . U . S . PATENT DOCUMENTS Cooper , 2007 , International wound Journal, ( 2007 ) vol. 4 ( 2 ), p . 124 . 5 , 597 , 784 A * 1 / 1997 Sinclair .. .. CO9K 8 /62 Kumar et al , 2008 , Mar . 2 , 2008 , Salt Selection in Drug Develop 166 /280 . 2 ment , Pharmaceutical Technology, vol. 3 , Issue 32 URL : http : / / 5 , 700 ,615 A 12 / 1997 Silence et al. www .pharmtech .com / salt - selection - drug - development. 6 , 365 , 130 B1 4 / 2002 Barry et al . Kauffmann , 1983 , Inorganic Synthesis , vol. 22 , ( 2007 ) , Chapter 20 . 6 ,752 , 867 B1 6 / 2004 Kurihara et al. 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Patent Feb . 19 , 2019 Sheet 1 of 4 US 10 ,208 ,241 B2 P . aureginosa Under Defined Growth Conditions of 3hrs at 25C 0 . 05 7 0 .045 0 . 04 0 . 035 0. 03 30. 025 0. 02 0. 015 0 .01 0 . 005 0 + Ag0.5Cu051, 10ppmAg Ag0.5Cu051, Cul,59ppmCu 59ppmCu Ag0.25Cu0751,10ppmAg Ag0.25Cu0751, 59ppmCu Ag0.75Cu0251, 10ppmAg Ag0.75Cu0251, 59ppmCu Control FIGURE 1 U . S . Patent Feb . 19 , 2019 Sheet 2 of 4 US 10 ,208 ,241 B2 S . Aureus Under Defined Growth Conditions of 3hrs at 25C 0 .05 7 0 .045 0 .04 0 .035 0 .03 = 0. 025 0 .02 0 . 015 0 .01 0 . 005 Ag0.5Cu051, 10ppmAg Ag0.5Cu051, Cul,59ppmCu 59ppmCu Ag0.25Cu0751, 10ppmAg Ag0.25Cu0751, 59ppmCu Ag0.75Cu0251, 10ppmAg Ag0.75Cu0251, 59ppmCu Control FIGURE 2 U . S . Patent Feb . 19 , 2019 Sheet 3 of 4 US 10 ,208 ,241 B2 Germination of Bacillus cereus spores under defined growth conditions 124 Hour Incubation at 25°C OD600 024 Hour Incubation at 37°C 44444444444444444444444444444444444444444444444444 ????? Intial Control Cul- PVP FIGURE 3 atent Feb . 19 , 2019 Sheet 4 of 4 US 10 ,208 ,241 B2 43 Figure 4 US 10 , 208 , 241 B2 RESIN COATED PROPPANTS WITH crobial effect , including increased production of reactive ANTIMICROBIAL ADDITIVES oxidation species such as singlet oxygen and hydroxide radicals, covalent binding of copper metal to reactive sites in CROSS REFERENCE TO RELATED enzymes and co - factors , interference with lipid bilayer APPLICATIONS 5 transport proteins , and interaction of copper ions with moi eties of microorganisms analogous to what have been pro This application is continuation in part of U . S . application posed for silver ions . Ser. No. 14 / 866 , 400 filed on Sep . 25 , 2015 , which applica tion claims priority to two applications ( i ) a continuation in SUMMARY OF THE INVENTION part of U . S . application Ser .