US009399728B2  c12)  United States Patent  Sarda et al.  (54)  IN-SITU CROSSLINKING AND CALCIUM  ION COMPLEXATION FOR ACIDIZING A  SUBTERRANEAN FORMATION  (IO)  Patent No.:  US 9,399,728 B2  (45)  Date of Patent:  *Jul. 26, 2016  (71)  Applicant:  HALLIBURTON ENERGY  SERVICES, INC.,  Houston, TX (US)  (72)  Inventors:  Anjali Ramesh Sarda,  Pune (IN);  Shoy  George Chittattukara,  Thissur (IN);  Anupom Sabhapondit,  Pune (IN)  (73)  Assignee:  Halliburton Energy Services, Inc.,  Houston, TX (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 192 days.  This patent is subject to a terminal dis› claimer.  (21)  Appl. No.:  13/661,106  (22)  Filed:  Oct. 26, 2012  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ...  C09K  8174  (2013.01);  C09K  8176  (2013.01);  C09K 2208/32  (2013.01)  ( 58)  Field of Classification Search  CPC ......................................................... C09K 8/74  See application file for complete search history.  (65)  Prior Publication Data  (56)  References Cited  U.S. PATENT DOCUMENTS  (57)  ABSTRACT  23 Claims, No Drawings  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  EP  0278540 Bl  8/1992  PCT/US2013/060035, International Search Report, dated Dec. 9,  2013, 5 pages.  Written Opinion dated Dec. 9, 2013 for Application No. PCT/  US2013/060035.  Jain, R. et al., "Reaction Kinetics of the Uptake of Chromium (III)  Acetate by Polyacrylarnide" SPE Paper 89399, SPE Journal (Sep.  2005), pp. 247-254.  * cited by examiner  Primary Examiner  - Angela M Di Trani  Assistant Examiner  - Andrew H Sue-Ako  (74)  Attorney, Agent, or Firm  - Craig W. Roddy; Baker  Botts L.L.P.  US 2014/0116707 Al  May 1, 2014  A method of treating a zone of a subterranean formation  penetrated by a wellbore, the method including the steps of:  (a) forming a treatment fluid comprising: (i) water; (ii) a  strong acid); (iii) a water-soluble polymer having at least one  functional group that can be crosslinked with aluminum(III);  (iv) a water-soluble aluminum carboxylate; and (v) a com› plexion agent for calcium ions; wherein the pH of the treat› ment fluid is less than the pH required for the aluminum to  crosslink the polymer to form a crosslinked gel; (b) introduc› ing the treatment fluid through the well bore into the zone; and  ( c) allowing time for the strong acid in the treatment fluid to  spend in the formation such that the pH of the fluid increases  sufficiently for the aluminum of the aluminum carboxylate to  crosslink the polymer.  E21B  43122  C09K  8174  C09K  8176  (2006.01)  (2006.01)  (2006.01)  8,720,557 B2 *  2004/0152602 Al  2004/0254079 Al *  2005/0065041 Al  5/2014  8/2004  12/2004  3/2005  Patil et al.  Boles  166/281  Frenier et al. ................. 507 /260  Hill  2005/0197257 Al*  9/2005 Bouwmeester ............... 507 /120  2008/0039347 Al *  2/2008 Welton et al. ................. 507/213  2008/02027 59 Al  8/2008 Welton  2008/0280790 Al  11/2008 Mirakyan et al.  2008/0314594 Al*  12/2008 Still et al.  166/307  2009/00427 50 Al  2/2009 Pauls et al.  2010/0144560 Al*  6/2010 Beall et al. .................... 507/131  2010/0314114 Al  12/2010 Moradi-Araghi et al.  2011/0053807 Al  3/2011 Panga et al. 