USOO9388345B2 (12) United States Patent (10) Patent No.: US 9,388,345 B2 McNeff et al. (45) Date of Patent: *Jul. 12, 2016 (54) HYDROCARBON SYNTHESIS METHODS, (58) Field of Classification Search APPARATUS, AND SYSTEMS USPC ............. 585/240; 44/306, 307, 308,385,605 See application file for complete search history. (71) Applicant: SarTec Corporation, Anoka, MN (US) (56) References Cited (72) Inventors: Clayton V. McNeff, Andover, MN (US); U.S. PATENT DOCUMENTS Larry C. McNeff. Anoka, MN (US); Daniel Thomas Nowlan, Hugo, MN 2,154,835 A 4, 1939 Eisenlohr (US); Bingwen Yan, Shoreview, MN 4,138,336 A 2f1979 Mendel et al. (US); Peter G. Greuel, Anoka, MN (US) (Continued) (73) Assignee: SarTec Corporation, Anoka, MN (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this AU 2011 200090 2, 2011 patent is extended or adjusted under 35 BR 060016O2 10/2007 U.S.C. 154(b) by 0 days. (Continued) OTHER PUBLICATIONS This patent is Subject to a terminal dis claimer. Adebanjo, Adenike O. et al., “Production of Diesel-Like Fuel and Other Value-Added Chemicals from Pyrolysis of Animal Fat'. (21) Appl. No.: 13/934,713 Energy & Fuels, vol. 19, 2005, pp. 1735-1741. (Continued) (22) Filed: Jul. 3, 2013 Primary Examiner — In Suk Bullock (65) Prior Publication Data Assistant Examiner — YoungSul Jeong (74) Attorney, Agent, or Firm — Pauly, DeVries Smith & US 2014/0046104A1 Feb. 13, 2014 Deffner, L.L.C. Related U.S. Application Data (57) ABSTRACT Embodiments of the invention include apparatus and systems (60) Provisional application No. 61/667,813, filed on Jul. 3, for hydrocarbon synthesis and methods regarding the same. 2012, provisional application No. 61/680,360, filed on In an embodiment, the invention includes a process for cre Aug. 7, 2012, provisional application No. 61/702,582, ating a hydrocarbon product stream comprising reacting a reaction mixture in the presence of a catalyst inside of a filed on Sep. 18, 2012. reaction vessel to form a product mixture, the reaction mix ture comprising a carbon Source and water. The temperature (51) Int. C. inside the reaction vessel can be between 450 degrees Celsius CIOG 3/00 (2006.01) and 600 degrees Celsius and the pressure inside the reaction CIOL L/04 (2006.01) vessel can be above Supercritical pressure for water. In an (Continued) embodiment, the invention includes an extrusion reactor sys tem for creating a hydrocarbon product stream. The tempera (52) U.S. C. ture inside the extrusion reactor housing between 450 degrees CPC ................. CI0G 3/44 (2013.01); B01J 21/063 Celsius and 600 degrees Celsius. Pressure inside the reaction (2013.01); B01J 21/066 (2013.01); B01J 23/30 vessel can be above supercritical pressure for water. Other (2013.01); embodiments are also included herein. (Continued) 23 Claims, 63 Drawing Sheets 2 Biomass Feedstock High Pressure Pumps w S! 8 Backpressure Regulator US 9,388,345 B2 Page 2 (51) Int. Cl. 2010/0324310 A1 12/2010 Dumesic et al. 2011 OOO95O1 A1 1/2011 Ernst CIOL 9/08 (2006.01) 2011/0035993 A1 2/2011 Loescher BOI 2/06 (2006.01) 2011/0105814 A1 5/2011 Koivusalmi et al. BOI. 23/30 (2006.01) 2011/0213040 Al 9, 2011 Hassan et al. BOI. 23/34 (2006.01) 2011/0287991 A1 11, 2011 Dubois BOII 2.3/755 (2006.01) 3: E. A 3: OlliaSFE et al. BOI 35/02 (2006.01) 2012/0055077 A1 3/2012 Savage et al. BOI 35/10 (2006.01) 2014/O115955 A1 5, 2014 McNeff et al. (52) U.S. Cl. CPC ................ B01J 23/34 (2013.01); B01J 23/755 FOREIGN PATENT DOCUMENTS (2013.01); B01J 35/023 (2013.01); B01.J 35/1014 (2013.01); B01J 35/1038 (2013.01); A : !: 38. B01J 35/1061 (2013.01); CIOL I/04 (2013.01); CN 10187O989 10, 2010 CI0L 9/086 (2013.01); Y02P 30/20 (2015.11) DE 1962O378 2, 1999 EP 1642560 4/2006 (56) References Cited EP 1869.173 12/2007 EP 2290035 3, 2011 U.S. PATENT DOCUMENTS EP 2290045 3, 2011 FR 293.8536 5, 2010 4,911,941 A 3, 1990 Katz et al. FR 294,7564 1, 2011 5,108,597 A 4, 1992 Funkenbusch et al. JP O2289692 11, 1990 5, 182,016 A 1/1993 Funkenbusch et al. WO 9108677 6, 1991 5,254,262 A 10/1993 Funkenbusch et al. WO 9627632 9, 1996 5,271,833. A 12/1993 Funkenbusch et al. WO 97O7187 2, 1997 5,346,619 A 9, 1994 Funkenbusch et al. WO 02102337 12/2002 5,540,834 A 7, 1996 Carr et al. WO 2004 108873 12, 2004 6,153,773 A 1 1/2000 Kolstad et al. WO 2006096834 9, 2006 6,713,051 B2 3/2004 Mayes et al. WO 2006121584 11, 2006 7,179,379 B2 2/2007 Appel et al. WO 2007068097 6, 2007 7,288,685 B2 10/2007 Marker WO 2008152199 12/2008 7.301,060 B2 11/2007 Appel et al. WO 2009003039 12/2008 7,452,841 B2 11/2008 Ignatchenko et al. WO 2009115322 9, 2009 7,476.296 B2 1/2009 Appel et al. WO 20091431.59 11, 2009 7,501,379 B2 3/2009 Ignatchenko et al. WO 2010005391 1/2010 7,659,432 B2 2/2010 Ignatchenko et al. WO 2010036333 4/2010 7,683.232 B2 3/2010 Schmidt et al. WO 2010 132628 11, 2010 7.691,159 B2 * 4/2010 Li ................................... 44f605 WO 2010.141794 12/2010 7,771,699 B2 8/2010 Adams et al. WO 2010147955 12/2010 7,772,414 B1 8/2010 Hybertson et al. WO 2010148057 12/2010 7,777,085 B2 8/2010 Berry et al. WO 2011004111 1, 2011 7,780.946 B2 8/2010 Wormsbecher WO 2011012438 2, 2011 7,850,841 B2 12/2010 Koivusalmi et al. WO 2011012439 2, 2011 7,883,882 B2 2/2011 Franklin et al. WO 201101.2440 2, 2011 7,925.273 B2 4/2011 Fomukong et al. WO 2011 130573 10, 2011 7,928,273 B2 4/2011 Bradin WO 2011 150410 12/2011 7,935,515 B2 5/2011 Franklin et al. WO 2011 150411 12/2011 7,967,973 B2 6/2011 Myllyoja et al. WO 20140O8355 1, 2014 7.998.339 B2 8/2011 Myllyoja et al. 8,003,833 B2 8/2011 Appel et al. OTHER PUBLICATIONS 2008. R R388 Risa. Albrecht, Ko et al., “A Brief Literature Overview of Various Routes to 2003.0143156 A1 7/2003 Wormsbecher Biorenewable Fuels from Lipids for the National Alliance for 2004/O18834.0 A1 9/2004 Appel et al. Advanced Biofuels and Bio-products (NAABB) Consortium', U.S. 2004/O192980 A1 9/2004 Appel et al. Department of Energy, PNNL-20279, 2011, pp. 1-16. 2004/O192981 A1 9/2004 Appel et al. Alonso, David M. et al., “Catalytic Conversion of Biomass to 2006/0004237 A1 1/2006 Appel et al. Biofuels', Green Chem., vol. 12, 2010, pp. 1493-1513. 2006/0246141 A1 1 1/2006 Liversidge et al. Alonso, David M. et al., “Production of Liquid Hydrocarbon Trans 2007/0098625 A1 5, 2007 Adams et al. portation Fuels by Oligomerization of Biomass-Derived C9 2007, 0137097 A1 6, 2007 Ikura Alkenes”. Green Chem., vol. 12, 2010, pp. 992-999. 2008. O194811 A1 8, 2008 McNeff An, Luet al., “The Influence of NiLoading Coke Formation in Steam 2008/0275144 A1 11, 2008 Van Hardeveld et al. Reforming of Acetic Acid', Renewable Energy, vol. 36, 2011, pp. 2009/00 14354 A1 1/2009 Knuuttila et al. 930-935. 2009 OO69586 A1 3/2009 Oku et al. Barteau, Mark A., “Organic Reactions at Well-Defined Oxide Sur 2009,0255.171 A1 10/2009 Dumesic et al. faces', Chem. Rev., vol. 96, 1996, pp. 1413-1430. 2009,0297495 A1 12, 2009 Kerovo et al. Billaud, F. et al., “Catalytic Cracking of Octanoic Acid'. Journal of 2010/0010246 A1 1/2010 Yan et al. Analytical and Applied Pyrolysis, vol. 58-59, 2001, pp. 605-616. 39882, A. 53.8 Estel Busca, Guido, “Bases and Basic Materials in Industrial and Environ 2010.0081181 A1 4/2010 Ber etal mental Chemistry: A Review of Commerical Processes'. Ind. Eng. 2010.0081835 A1 4, 2010 WE al Chem. Res., vol. 48, 2009, pp. 6486-6511, 2010.0113849 A1 5/2010 Bartek et al. .................. 585,240 Catallo, W. J. et al., “Transformation of Glucose to Volatile and 2010. O151535 A1 6, 2010 Franklin et al. Semi-Volatile Products in Hydrothermal (HT) Systems”. Biomass 2010, 0151539 A1 6, 2010 Franklin et al. and Bioenergy, vol. 34, 2010, pp. 1-13. 2010/0170147 A1 7, 2010 McNeffet al. .................. 44f605 Danuthai, Tanate et al., “Conversion of Methylesters to Hydrocar 2010/0287823 A1 11/2010 Misra et al. bons over an H-ZSM5 Zeolite Catalyst”. Applied Catalyst A: Gen 2010/0305346 A1 12/2010 Hara et al. eral. vol. 361, 2009, pp. 99-105. US 9,388,345 B2 Page 3 (56) References Cited Priecel, Peter et al., “The Role of Ni Species in the Deoxygenation of Rapeseed Oil Over NiMo-Alumina Catalysts'. Applied Catalysis A: OTHER PUBLICATIONS General, vol. 397, 2011, 127-137. Quirino, Rafael L. et al., “Studying the Influence of Alumina Cata Deng, Li et al., “Upgraded Acidic Components of Bio-Oil through lysts Doped with Tin and Zinc Oxides in the Soybean Oil Pyrolysis Catalytic Ketonic Condensation”. Energy & Fuels, vol. 23, 2009, pp. Reaction”, JAm Oil Chem Soc, vol. 86, 2009, pp. 167-172. 564-568. Renz, Michael, “Ketonization of Carboxylic Acids by Decarboxyla Fu, Jie et al., “Catalytic Hydrothermal Deoxygenation of Palmitic tion: Mechanism and Scope'.