«2 United States Patent Roddy et al 'US007892352B2 US 7,892,352 B2 Feb. 22, 2011 (10) Patent No. 4s) Date of Patent: (54) WELL TREATMENT COMPOSITIONS AND METHODS UTILIZING NANO-PARTICLES (75) Inventors: Craig W. Roddy, Dunean, OK (US), Siten ChatterJi, Duneso, OK (US); Roger Cromwell, Walters, OK (US) (73) Assignee: Halliburton Energy Services Inc Duncan, OK (US) (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 USC. 1S4(b) by O days. (21) Appl. Nos 121426393 (22) Filed: Apr: 20, 2000 6s) Prior Publication Data US 200910260548.A1 Cet. 22, 2009 Related US. Application Data (62). Division of application No. 11/747,002, filed on May 10, 2007, now Pat. No. 7,559,369. Gb Ince. Coa 1404 (2006.01) (52) US.Cl. 1067737; 106/718; 1060724; 106733; 106/738 (58) Fleld of Clasiication Search 1067737, 1067718, 724, 733, 738 See application ile for complete search history. 66) References Cited U.S. PATENT DOCUMENTS 2805,719 4047 67 911997 Anderson 91977 Childe AQUSSL A 61081 Langton ot a 1982. Comet RESILI90 E1989 Desrit AS88935. A S198 Shela ASS10 A 6184 Chaos M1985 Rao 9/1988, Skok {11990 Dingsoyr 10.1990 Smut 161992 Haris ea. T1992 Fry 5.149.370 A 911902 Claussen Sao7s2 A $1903. afr tal $3390 A 1904 offers 5355981 A 101994 Onan S373901 A 12/1994 Norman ea S308758 A 31905 Onanet al 5518996 A 5/1996 Maroy 570999 A 6.199% Dingsoyr SUSRSA1 A THON Tack S820670 A 101908 Chat ta 6483862 A 112000 Vilar 6227204 BL $2001. Chattess 912002 Reidy ; 122002, Westerman 527.051 BI 32003 Reddy G.SSK07L BI 42003, Reddy al 722438 B2 42004 Brothers ta {6808.S61 12 10.2004 Gonge tal (GS74S78 BL 412008. Gari GO7ESS BL 122008 Chaney {6982000 B2 12006. 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(Continved) FOREIGN PATENT DOCUMENTS DE to2o0vow2078 32009 iP OTR? 121996 FR preT10s 6/2000 Wo WosTadete D7 wo Doosoraiet "32008 wo aoooono7ss 32009 OTHER PUBLICATIONS “Fife of nanoiO2 on heat ofhy dation of poland cement” Xuet al, Nanjing Gngye Drste Nichao, Ziran Kenta (2007), 28), 8546 abstract only “Applicaton of manometer silica in inorganic nonmetallic materials" Deng etal, Taos! ianyang Chips) 2007, (9) 8-12. absuactonly® “Reaction mechanism analyses of cement base composite materials modify nano-iica™ Xu etl, Kuangye Gongcheng (Changsha, (China), 2007, 273), 99-102 abstiactenly* Rescarch on reinfremeeat of cemein composites and relevant mechanism’. Yu et al, Qangdao Koji Daxvo Xuebao, Ziran ‘Kesuean (2006), 270) 148181. abstract ony? Antagonistic fet of superplasiizer ant colloidal aanoriica in ‘he hyation of Ale and Belt pastes, Bjoeenstrom eta, Joural of Materials Science, 2007), 42(11), 3901-3907 abstract oly" (Coutinved) Primary Examiner Paul Maecantoni (94) Atormey, gems or Firm—Craig W. Roddy; Tumey LLP on ABSTRACT Disclosed embodiments relate to well treatment Aids and ‘methods that utilize nano-particles, Exemplary nano-par- ticles are selected from the group consisting of particulate nano-silica, nano-alumina, nano-Zine oxide, nano-boron, ‘nano-ion oxide, and combinations therent. Embodiments also relate to methods of cementing that include the use of fnano-partcls. An exemplary mellod of cementing com- pris introducing a cement composition into a subterranean Tormation, wherein the cement composition comprises ‘cement, Water and a particulate nano-siica. Fmbodiments also relate to use of nano-partcles in drilling Fai, eomple- ‘ion fds, simulation Mids, andl wel elean-up fuids, 27 Claims, No DrawingsUS 7,892,352 B2 Page 2 USS. PATENT DOCUMENTS 7806183 B2 102010 Roddy 2002007384 AL 62002 Genge et doovon20%04 AL 11/2003 Baran ta anoso1e7t0s AL "82005 Roddy 20060075952 AL 42006. Lecoliret a 2oa00e6s03 AL 42006. Rey ta dons0162926 AL 7/3006 Roddy aooso1geKs4 AL 72006 Roddy 2006017766 AL 2006. Sith ta 20060217463 AL 912006 Lecolir aos02s4466 AL 11/2006 Drochon 20060260513 AL 11/2006. Porro Guiverer ea 200602¥9163 AL 122006 Lecolir 20070015668 AL 1/2007 Hamoweret donnions6732 AL 3/2007 Roddy eal, donwonsko29 AL 3/2008 erkland ea. 20080282769 AL 102008. Birgisson et 20080277116 AL 11/2008. Rody e dono0124s22 AL “2009 Roddy d0n90139719 AL 62009 Lupet a. aono02%6007 AL 9/2009 Roddy eal 200910260844 AL 102000 2nrooo16is3 AL 12010 aor00028039 AL 22010 aovoooTssrt AL 32010 2oroo09se71 AL 42010 dowooos6t3s AL 42010 OTHER PUBLICATIONS “Nano-concrte: possible and challenges", Balaguny ct al RILEM Proceedings 2005), PRO 46 Gaal Ia Nanoehnolouyinsomsruton (NICOM2)2005, 233245 abril ly" comparative study onthe polanic activity beeen nano-SiO2 an slca fun. Ye ea, Jounal of Wuhan Univ of Technolog. Marl Siene Eton (2006), 21(3) 158157. abstract ony> “Opaimizatio of silica fume ly ash and amorphous manesilia in supeplasicizedhighh pesformance conette™, Collard eta Anrican Conctte Intute, SP 2004, SP-221 (Eighth CANMET ACTInICont-on Fy asses mess. and natal pola in ‘onerte 2008) 495.505 abst onl “Accelerating eet of colloidal nanoslica for beneficial ealsium silat hydate fomation in cement” Bjomstio et al, Chemial Physics Leers 2008), 302(13), 242-248 absraet oly™ Experimental Sudy on comets based composites with nano-SiO?" Feng eta, Calan Kesue Yu Gongchong Xuebao (2008), 220) 2240277 absract onl" “Sing and bioactive composites contining nansiia fod whis- ers for bone repair, Xue al, Bomatenals (2068), 25(19)4613- 4626 ata aly? “Research on the properics of Portland cement aed with nano SiO", Wang eta, RILEM procodings (2003), PRO 32 (la COnt ‘on Advances in Concrete and Structures, 2008, vo 1) L961 sre only “Comparison of properties of high strength conse with nanSiO2 and sis fume ee” Ye at al, Janes Calo Xuebe0 (2003), (6(4), 381-385 abstract only * “Sinlyon compound efecof sila fume and nno-Si0x orcement- ingeompositemat ls”, ang ota Glsuanyan Xucbao (2003) 318) sms “EMfct of mano-SiOx and silica fume om cement paste water demand” Lic al, Shenyang Tatzhu gongcheag Xueytan Kuch, iran Kesusban 3002), 184}, 278-281. abstract only* “Hyation rection baoween CS and fy ash iin fume, nano= S102, and microstructure of hydrated pasts”, Ba etal. Guisuayan uchao 2002), (6), 780-784, absuakt only? “Nanoilic-an additive fr high strength concrete", Wagner ea Wissnschaliche Zsitchit-Hochachule Fuer Architektur Und Bauwosen Weimar Universitat (1994), 40(8(67), 1837. absact only" ‘RCT International Searching Authority for intermationl Application No. PCT'GB2000 002596 dated Feb 8.2010 CT International Seach Report and Wien Opinion for Interns tional Appliaton No. PCT'G2010 000485 dated May 21,2010 Otfce Acton dated May 5, 2010 from US. App No. 1247255 Oce Acton dated May 82010 fom US. Appl No. 2472.86 Dice Acton dated May 5 2010 GomUS. Appl No. 1226.68, USPTO fie Action from US. App No, 12.85, 189 dated Ost. 2010, USPTOOMice Action arUS, Appl. No, 12183, 189, dated Nov. 10, ovo US. Appl No. 124426648, fled Ape 20,2000, Roy. US. Appl No. 124472,56. ied May 27, 2009. Roy “Konsanin Sabcley and Mil Ferada-Guterez, Nanotechnology of Concrete (printed fom Ineret Feb 20, 2007. ‘Amer. 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No, 11/747,002. filed on May 10, 2007, entitled “Well Treatment Compositions and Methods Utilizing Nano-Particles," the entire disclosure of which is Incomporated herein by reference, BACKGROUND ‘The present invention relates to well trstment composi tions and methoels uilizing nano- particles and, more particu- larly, to well cement compositions and methods utilizing particulate nano-slica ‘In general, well treatments inchudea wide variety of meth- ‘ds that may be performed in oil, gas, geothermal andor > ‘ater wells such as dilling completion and workover meth- ‘ods, The drilling, completion and workover methods may Include but are not limited to, dling, fracturing, acidizing. Jogging. cementing, gravel packing, perforating and con- ommance methods. Many of these ‘well teaiments are ‘designed to enhance andor facilitate the recovery of desirable ‘sid from a subterranean well, lIncementing methods, such as well construction and reme- ial cementing, well cement compositions are commoaly uilzed, For example in subterrncan well constriction, @ pipe string (eg, easingand liners) may berunintoa well bore nd cemented in place using a cement composition. The pro- ‘ess of cementing the pipe string in place is commonly refered to as “primary cementing.” In a typical primary ‘cementing, method, @ cement composition may be pumped into an annulus between the walls of the well bore and the ‘exterior surface of the pipe string disposed therein. The ‘cement composition sets in the annular space, thereby form- Jngan annulae sheath of hardened, substantially impermeable ‘cement that supports snd positions the pipe string i the well, bore and honds the exterior surface ofthe pie sting to the subterranean formation. Among other things, the annular sheath of set cement surrounding the pipe string functions to prevent the migration of Mus in the annulus, as well as protecting the pipe string from corrosion. Cement composi tions also may be used in remedial cementing methods, such 18 squeeze cementing and the placement of eement pligs. Inoperation, the annular sheath of cement formed between the wellbore andthe pipe string often suffers structural il ‘ure due o pipe movements Which cause shear stesses to be ‘exerted on the set cement, Suc stress conditions are com= monly the result of relatively high fuid pressures andor temperatures inside the cemented pipe sii during testing perforating, Fluid injection or fluid production. For example, such stress may oocur in wells subjected to steam recovery oF production of hot formation fuids from high-temperature Tormations. The highsintemal pipe pressure and/or tempera- turecan resultinthe expansion ofthe pipe string, both radially ‘and longitudinally, which places stresses on the cement sheath causing the ementbond between the exterior surfaces ‘of the pipe or the well bore walls, or both, to fail and thus allow leakage formation fds and so forth. Accordingly, it ‘may’ be desirable for the cement composition utilized for ‘cementing pipe strings in the well bores to develop high strength afer setting and to have sufficient resiliency (eg clasticity and ductility) to resist loss of the cement bond between the exterior surfaces of the pipe or the well bore 0 o 2 alls, or both. Also, itmay be desirable forthe cement com- position to be able to resist cracking and/or shattering that ‘may result from other oroes on the cement sheath, For ‘example, t may be desirable forthe cement sheath to include structural characterises that protect is structural integrity from forces associated with formation shifting, overburden pressure, subsidence, tectonic creep, pipe movements, Impacts and shocks subsequently generated by drilling and other well operations. Tn addition to including components that improve ‘mecuanieal properties of the cement, in a number of eement- ing methods, it may also be desirable include one or more setaceelerorsin thewell coment compositions to counteract ‘certain constituents andor enviromental charaeteristis that excessively slow set times. For example, among other things, low temperatures andcement additives (eg, uid loss contol additives and dispersans) can eavse or contibutetoan exces- five set time for a cement ton. Accordingly in cer- ‘ain situations, itmay be desirable to reduce the set time by includinga se accelerator in the cement composition, Thais the set accelerator may be inchided in # cement composition {o counteract components of the cement composition or eon- sions surounding the cement composition that are casing fan excessive set time. SUMMARY, The present invention relates to well treatment compos tions and methods wilizing nano-paticles and, more paricu- Jarly to well cement compositions snd methods utilizing particulate nano-silic, ‘An exemplary embodiment of the present invention pro- vides a method of cementing. The method compris itro- ducing cement composition into subterranean formation, ‘wherein the cement composition comprises cement, water and at least one nano-particle selected from the group con- sisting of particulate nanoilica, nano-alumina, vano-zine ‘oxide, ano-boron, naneiron oxide and combinations thereat ‘Another exemplary embodiment ofthe presen invention provides a method of cementing in a subterranean formation ‘Themethod comprises inclading encapsulated nano-particles in a cement composition. The method further comprises introducing the cement composition into the subtersnean Tormation, ‘Another exemplary embodiment ofthe present invention provides a method of accelerating set ime of a cement com- Position. The method comprises including particulate nano- ica ina cement composition. The method futher comprises ‘nrocising the cement composition into a subterranean for ‘mation, The method further comprises allowing the cement ‘composition to set in the subterranean formation. Another exemplary embodiment of the present invention ravi a well cement composition. The well eement com- position comprises cement Water and atleast one nano-par- fice selected from the group consisting of particulate nano- ica, nano-alumina, nano-zine oxide, nano-boron, nano fon oxide und combinations thereo. ‘Another exemplary embodiment ofthe present invention provides a method of treating subterranean formation. The ‘cthod includes introducing a retment uid into a subter ranean formation, wherein the teatment Tid comprises at Teast one nano-particle selected from the group omssting of particulate nanosilca, nano-alumina, nan0-rine oxide, ‘hano-horon,nano-ion oxide, and combinations thereo. "Another exemplary embodiment ofthe present invention provides a method of sing nano-parteles ina well reatment