(45)  Date of Patent:  Apr. 29, 2014  (10)  Patent No.:  US 8,709,376 B2  c12)  United States Patent  Barnicki et al.  (54)  PROCESS FOR RECOVERING AND  RECYCLING AN ACID CATALYST  (75)  Inventors:  Scott Donald Barnicki,  Kingsport, TN  (US);  Stephen Neal Falling,  Kingsport,  TN (US);  Jeffrey Scott Kanel,  Kingsport, TN (US);  Robert Sterling  Kline,  Kingsport, TN (US);  Peter  Borden Mackenzie,  Kingsport, TN (US)  (73)  Assignee:  Eastman Chemical Company,  Kingsport, TN (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 522 days.  (21)  Appl. No.:  12/889,045  (22)  Filed:  Sep.23,2010  (51)  Int. Cl.  (52)  U.S. Cl.  USPC ..............  423/531;  562/45; 562/579; 562/580  ( 58)  Field of Classification Search  CPC ................................ CO1B17/9O; CO7C51/48  See application file for complete search history.  FOREIGN PATENT DOCUMENTS  OTHER PUBLICATIONS  (57)  ABSTRACT  18 Claims, No Drawings  (56)  References Cited  (65)  Prior Publication Data  C0JB 17190  C07C 309/30  C07C 59/06  C07C 51142  (2006.01)  (2006.01)  (2006.01)  (2006.01)  2,152,852  A  2,153,064  A  *  2,211,624  A  2,211,625  A  2,298,138  A  2,436,209  A  2,443,482  A  3,333,924  A  3,751,453 A  3,754,028  A  3,801,627  A  3,859,349  A  3,911,003  A  3,927,078  A  3,948,977  A  3,948,986  A  4,016,208 A  4,052,452  A  4,087,470 A  4,112,245 A  4,128,575  A  4,136,112 A  4,140,866 A  4,153,809 A  4,228,305  A  4,275,234  A  4,291,007 A  4,308,397  A  4,366,333  A  4/ 1939 Loder  4/1939 Larson .......................... 562/518  8/ 1940 Loder et al.  8/ 1940 Loder  10/1942 Loder  2/ 1948 Elgin  6/ 1948 Shattuck  8/1967 Hazen et al.  4/ 1973 Kurkov et al.  8/ 1973 Lapporte et al.  8/1974 Kurkov et al.  1/1975 Cody  10/1975 Suzuki  12/1975 Lapporte et al.  4/1976 Suzuki  4/1976 Suzuki  4/ 1977 Suzuki  10/1977 Scardigno et al.  5/ 1978 Suzuki  9/ 1978 Zehner et al.  12/1978 Leupold et al.  l/ 1979 Bakshi  2/ 1979 Nielsen  5/ 1979 Suzuki  10/ 1980 Suzuki  6/1981 Baniel et al.  9/ 1981 Baniel  12/1981 Suzuki  12/1982 Wilkes  4,409,395  A  10/1983  4,431,486 A  2/1984  4,440,734 A  4/1984  4,501,917 A  2/1985  4,691,048 A  9/1987  4,824,997  A  4/1989  4,935,102  A  6/1990  4,966,658  A  10/1990  4,990,629  A  2/1991  5,026,927  A  6/1991  5,210,335  A  5/1993  5,214,219 A  5/1993  5,276,181 A  1/1994  5,423,955  A  6/1995  5,455,372  A  10/1995  5,723,662  A  3/1998  5,932,772  A  8/1999  5,952,530  A  9/1999  6,252,121 Bl  6/2001  6,291,725 Bl  9/2001  6,294,700 Bl  9/2001  6,303,829 Bl  10/2001  6,307,108 Bl  10/2001  6,307,109 Bl  10/2001  6,307,110 Bl  10/2001  6,310,260 Bl  10/2001  Miyazaki et al.  Balmat  Kougioumoutzakis  Schmidt et al.  Hugues et al.  Macfarlane et al.  Berg  Berg  Souma  Andrews et al.  Schuster et al.  Casale et al.  Casale et al.  Berg  Hirai et al.  Ebmeyer et al.  Argyropoulos et al.  Argyropoulos et al.  Argyropoulos et al.  Chopade et al.  Kane! et al.  Kane! et al.  Argyropoulos et al.  Kane! et al.  Argyropoulos et al.  Argyropoulos et al.  DE  EP  3133353 C2  3/1983  0 114 657 Bl  3/1987  (Continued)  (Continued)  US0087093 76B2  Notification of Transmittal of the International Search Report and the  Written Opinion of the International Search Authority with Mail Date  of Mar. 15, 2012 for International Application No. PCT/US2011/  051490.  Notification of Transmittal of the International Search Report and the  Written Opinion of the International Search Authority with Mail Date  of Nov. 28, 2011 for International Application No. PCT/US2011/  047842.  Celik et al., "Synthesis of precursors to ethylene glycol from form› aldehyde and methyl formate catalyzed by heteropoly acids", Journal  of Molecular Catalysis A: Chemical 288, (2008), pp. 87-96.  Celik et al., "Vapor-phase carbonylation of dimethoxymethane of  H-Faujasite",Angewandte. Chemie Int. Ed. 2009, 48, pp. 4813-4815.  Hou-Yong, Sun, et al. "Reactive extraction of glycolic acid in high  content solution with tri-n-octylamine" Journal of Chemical Engi› neering of Chinese Universities vol. 21 pp. 26-30.  (Continued)  Primary Examiner  - Paul A Zucker  (74)  Attorney, Agent, or Firm  - Jennifer Knight; Eric  Middlemas  Disclosed is a process for the extractive recovery of an acid  catalyst from an aqueous mixture of glycolic acid with an  extraction solvent comprising a tertiary amine or an onium  carboxylate compound, a modifier, and a diluent. The acid  catalyst, which can comprise strong acids such as sulfuric  acid, alkyl sulfonic acids, and fluoroalkyl sulfonic acids, can  be recovered by back extraction with aqueous formaldehyde  and recycled to a process for the preparation of glycolic acid  by the acid-catalyzed carbonylation of formaldehyde.  U.S. PATENT DOCUMENTS  US 2012/OO78O1OAl  Mar. 29, 2012 