(12) United States Patent (10) Patent No.: US 9.284,203 B2 Josse Et Al
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USOO92842O3B2 (12) United States Patent (10) Patent No.: US 9.284,203 B2 Josse et al. (45) Date of Patent: Mar. 15, 2016 (54) SYNGAS BIOMETHANATION PROCESS AND (56) References Cited ANAEROBC DIGESTION SYSTEM U.S. PATENT DOCUMENTS (71) Applicant: ANAERGIA INC., Burlington (CA) 4,289,625 A 9, 1981 Tarman et al. 4,880,473 A 11/1989 Scott et al. (72) Inventors: Juan Carlos Josse, Mission Viejo, CA 5,017,196 A 5, 1991 Dewitz (US); Andrew Benedek, Rancho Santa 5,395.455 A 3, 1995 Scott et al. 5,417,492 A 5/1995 Christian et al. Fe, CA (US) 5,424,417 A 6/1995 Torget et al. 5,605,551 A 2f1997 Scott et al. (73) Assignee: ANAERGIA INC., Burlington (CA) 5,865,898 A 2/1999 Holtzapple et al. 5,959,167 A 9, 1999 Shabtai et al. (*) Notice: Subject to any disclaimer, the term of this 6,022,419 A 2/2000 Torget et al. 6,048,374. A 4/2000 Green patent is extended or adjusted under 35 6,228, 177 B1 5/2001 Torget U.S.C. 154(b) by 0 days. 7,229,483 B2 6/2007 Lewis 7,494.637 B2 2/2009 Peters et al. (21) Appl. No.: 14/373,714 7,578,927 B2 8, 2009 Marker et al. 7,608.439 B2 10/2009 McTavish et al. 7.972,824 B2 7/2011 Simpson et al. (22) PCT Filed: Jan. 21, 2013 8,383,871 B1 2/2013 Sellars et al. 2006, O112639 A1 6/2006 Nicket al. (86). PCT No.: PCT/CA2013/050037 2007/0117195 A1 5/2007 Warner et al. 2007/0217995 A1 9/2007 Matsumura et al. S371 (c)(1), 2008, 0236042 A1 10/2008 Summerlin (2) Date: Jul. 22, 2014 2008/0280338 A1 11/2008 Hall et al. 2009. O151253 A1 6/2009 Manzer et al. 2009/0229595 A1 9/2009 Schwartz, Jr. (87) PCT Pub. No.: WO2013/110186 2009/02392.79 A1 9, 2009 Hall et al. PCT Pub. Date: Aug. 1, 2013 2010, 0021979 A1 1/2010 Facey et al. 2010, 0133085 A1 6/2010 Huctchins et al. (65) Prior Publication Data (Continued) US 2015/00271 79 A1 Jan. 29, 2015 FOREIGN PATENT DOCUMENTS BR OO940 1102 A 11, 1994 CA 2628323 * 6, 2007 ................ CO2F 2/12 Related U.S. Application Data (Continued) (60) Provisional application No. 61/589,663, filed on Jan. OTHER PUBLICATIONS 23, 2012, provisional application No. 61/652,260, Guiot et al. Env, Sci. Tech, vol. 45, Issue 5, pp. 2006-2012.* filed on May 28, 2012. Guiot, S.R. et al. (Mar. 2011), Potential of wastewater-treating anaerobic granules for biomethanation of synthesis gas, Environ (51) Int. Cl. mental Science and Technology, vol. 45, Issue 5, pp. 2006-2012. CO2F 3/28 (2006.01) Bredwell, M.D., et al., (1999), Reactor Design Issues for Synthesis CI2P 5/02 (2006.01) Gas Fermentations, Biotechnology Process, vol. 15, Issue 5, pp. CO2F 3/12 (2006.01) 834-844. Cozzani et al. A fundamental study on conventional pyrolysis of a CO2F II/04 (2006.01) refuse-derived fuel, Ind. Eng. Chem. Res. 1995, 34, 2006-2020. CO2F II/O (2006.01) International Search Report of PCT/CA2013/050037 dated Apr. 4, CIOK L/04 (2006.01) 2013. CIOB 53/00 (2006.01) Lewis, F.M. et al.; A Powerful byproduct, WEFTEC, Jan. 2008, pp. CIOB 53/02 (2006.01) 64-69. C05E II/00 (2006.01) Yang, Bin et al.; Pretreatment: the key to unlocking low-cost cellu CO2F ( 1/12 (2006.01) losic ethanol, Biofuels, Bioprod. Bioref 2:26-40 (2008). (52) U.S. Cl. (Continued) CPC ................. C02F 3/2893 (2013.01); C02F 3/12 Primary Examiner – Paul V Ward (2013.01); C02F II/04 (2013.01); C02F 1 1/10 (74) Attorney, Agent, or Firm — Borden Ladner Gervais (2013.01); C05F II/00 (2013.01); CIOB 53/00 LLP (2013.01); CIOB 53/02 (2013.01); CIOK I/04 (2013.01); C12P5/023 (2013.01); C02F 3/28 (57) ABSTRACT (2013.01); C02F 1 1/12 (2013.01); C02F 1 1/121 An anaerobic digester is fed a feedstock, for example sludge (2013.01); C02F 2203/00 (2013.01); Y02E from a municipal wastewater treatment plant, and produces a 50/14 (2013.01); Y02E 50/343 (2013.01); Y02W digestate. The digestate is dewatered into a cake. The cake 10/40 (2015.05): Y02W 30/47 (2015.05); Y10T may be dried further, for example in a thermal drier. The cake 137/85978 (2015.04) is treated in a pyrolysis system to produce a synthesis gas and (58) Field of Classification Search biochar. The gas is sent to the same or another digester to CPC ............... C02F 3/28: C12P3/28: C05F 11/00 increase its methane production. The char may be used as a USPC .......................................................... 435/167 soil enhancer. See application file for complete search history. 14 Claims, 1 Drawing Sheet US 9,284.203 B2 Page 2 (56) References Cited and Soil Quality Enhancement, Proceedings of the Sustainable Feed stocks for Advance Biofuels Workshop, Atlanta, GA, Sep. 28-30, U.S. PATENT DOCUMENTS 2010 pp. 257-281. Garcia-Perez, Manuel; Challenges and Opportunities of Biomass 2010, 0162627 A1 7/2010 Clomburg et al. Pyrolysis to Produce Second Generation Bio-fuels and Chemicals, 2010/0223839 A1 9, 2010 Garcia-Perez et al. Auburn University, Jun. 13, 2012. 2010/0317070 A1 12/2010 Agaskar Parry, Dave; Biosolids Technology Advances, Jan. 2012. 2011/0033908 A1 2/2011 Cheong et al. Melin, K. et al. Evaluation of lignocellulosic biomass upgrading 2011/01797OO A1 7, 2011 Monroe et al. routes to fuels and chemicals, Cellulose Chemistry and Technology 2011/0248218 A1* 10, 2011 Sutradhar et al. ............. 252/373 44 (4-6), 117-137 (2010). 2012fOO73199 A1 3/2012 Lewis Gullu, Dogan et al. Biomass to methanol via pyrolysis process, 2012/0322130 A1 12/2012 Garcia-Perez et al. Energy Conversion and Management, vol. 42, Issue 11, Jul. 2001, pp. 1349-1356. FOREIGN PATENT DOCUMENTS Demirbas, Ayhan, Biomass resource facilities and biomass conver sion processing for fuels and chemicals, Energy Conversion and CA 2641270 12/2009 Management, vol. 42, Issue 11, Jul. 2001, pp. 1357-1378. DE 101.07712 A1 9, 2002 Excerpts from Traite De Polarimetrie, Georges Bruhat, Paris, France, JP 2003-089793. A 3, 2003 1930. WO O1791.23 A1 10, 2001 Demirbas, Ayhan, The influence of temperature on the yields of WO 2004060587 A1 T 2004 compounds existing in bio-oils obtained from biomass samples via WO 2010001137 A2 1, 2010 pyrolysis, Fuel Processing Technology 88 (2007) 591-597. WO 2012166771 A2 12/2012 Lehmann et al. "Bio-Char Sequestration in Terrestrial Ecosys WO 2012166771 A3 12/2012 tems—A Review” Mitigation and Adaptation Strategies for Global WO 2013110186 A1 8, 2013 Change (2006) 11:403-427. OTHER PUBLICATIONS Linden et al. "Gaseous Product Distribution in Hydrocarbon Liaw, Shi-Shen et al.; Effect of pyrolysis temperature on the yield and Pyrolysis” Industrial and Engineering Chemistry vol. 47, No. 12, pp. properties of bio-oils obtained from the augerpyrolysis of douglas fir 2470-2774. Sustarsic “Wastewater Treatment: Understanding the Activated wood, Journal of Analytical and Applied Pyrolysis, vol. 93, Jan. Sludge Process' CEP Nov. 2009, pp. 26-29. 2012, pp. 52-62. 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No. 13/826,507 dated Jul. 7, 2014. Laemsak, Nikhom, Wood Vinegar presentation, Undated. Office Action for U.S. Appl. No. 13/826,507 dated Mar 18, 2015. Jones, S. B. et al.: Production of Gasoline and Diesel from biomass Advisory Action for U.S. Appl. No. 13/826,507 dated May 22, 2015. via Fast Pyrolysis Hydrotreating and Hydrocracking: A Design Zhang, Shou-Yu et al., “Influence of manure types and pyrolysis Case, U.S. Department of Energy, PNNL-18284 Feb. 28, 2009. conditions on the Oxidation behavior manure char”. Bioresource Laird, David A. et al., Sustainable Alternative Fuel Feedstock Oppor Technology 100 (2009) 4278-4283. tunities, Challenges and Roadmaps for Six U.S. Regions; Chapter 16: Pyrolysis and Biochar—Opportunities for Distributed Production * cited by examiner U.S. Patent Mar. 15, 2016 US 9.284,203 B2 US 9,284,203 B2 1. 2 SYNGAS BOMETHANATION PROCESS AND Synthesis gas, also called syngas or producer gas, is a ANAEROBC DIGESTION SYSTEM combination of CO, H, and CO, that results from the thermal degradation of biomass without combustion, through pyroly CROSS-REFERENCES TO RELATED sis orgasification. This process occurs typically attempera APPLICATIONS tures between 500 and 700 deg C with minimal introduction of oxygen, if any. Other components of syngas are water This application is a National Stage Entry of International vapor, methane, light hydrocarbons, particulates and volatile Application No. PCT/CA2013/050037, filed Jan. 21, 2013, impurities. Syngas has a low heat value, for example 120 to which is a non-provisional application of U.S.