(12) United States Patent Winsness

US008679353B2

US 8,679,353 B2 *Mar. 25, 2014

(10) Patent N0.: (45) Date of Patent:

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(75) (73)

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METHOD AND SYSTEMS FOR ENHANCING OIL RECOVERY FROM ETHANOL PRODUCTION BYPRODUCTS

Inventor: David J. Winsness, Apharetta, GA (US)

Assignee: GS Cleantech Corporation, New York, NY (US)

Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. This patent is subject to a terminal dis claimer.

Appl. N0.: 13/450,991

Filed: Apr. 19, 2012

Prior Publication Data

US 2012/0199531A1 Aug. 9,2012

Related US. Application Data Continuation of application No. 13/185,841, ?led on Jul. 19, 2011, Which is a continuation of application No. 11/856,150, ?led on Sep. 17, 2007, noW Pat. No. 8,168,037, ?led as application No. PCT/US2006/009238 on Mar. 15, 2006.

Provisional application No. 11/908,891, provisional application No. 60/661,733, ?led on Mar. 16, 2005.

Int. Cl. C02F 1/38 (2006.01) BOID ]/26 (2006.01) US. Cl. USPC ........ .. 210/787; 210/770; 210/790; 159/173;

159/6.1;159/47.3 Field of Classi?cation Search None See application ?le for complete search history.

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(56) References Cited U.S. PATENT DOCUMENTS

313,665 A 11/1884 Greene 365,120 A 6/1887 DeLaval 445,066 A 1/1891 DeLaval

1,200,672 A 10/1916 Waugh 1,310,977 A 7/1919 Barton 1,366,339 A 1/1921 Alexander 2,206,024 A 8/1937 Brown

(Continued) FOREIGN PATENT DOCUMENTS

DD 80874 10/1966 DD 80874 C1 10/1966

(Continued) OTHER PUBLICATIONS

Matthews, H., Harrys old engine, De Laval Separator Company, A bit of history and development of DeLaval milkers, 1995-2008, DeLaval Separator Company, 10 pages.*

(Continued) Primary Examiner * Yate K Cutliff (74) Attorney, Agent, or Firm * Cantor Colburn LLP

(57) ABSTRACT In one aspect of the invention, a method recovers oil from a concentrated byproduct, such as evaporated thin stillage formed during a dry milling process used for producing etha nol. The method includes forming a concentrate from the byproduct and recovering oil from the concentrate. The step of forming the concentrate may comprise evaporating the byproduct. Further, the step of separating the oil from the concentrate may comprise using a centrifuge and, in particu lar, a disk stack centrifuge. Other aspects of the invention include related methods and subsystems for recovering oil from thin stillage.

12 Claims, 11 Drawing Sheets

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US 8,679,353 B2 Page 2

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2003/0093832 A1 5 /2003 szarka et 31 Cattle, Cooperative Extension Services, Extension Extra, ExEx 2003/0180415 A1 9/2003 stiefel et a1 2036, Animal & Range Sciences, College ofAgriculture & Biologi 2004/00g1654 A1 21/2004 schryvers et 31 cal Sciences / South Dakota State University / USDA, Aug. 2002, 5 2004/ 0082044 A1 4/ 2004 Prevost et al. Pg$~ 2004/0087808 A1 * 5/2004 Prevost et a1, ,,,,,,,,,,,,,,,,,, H 554/9 Westfalia Separator AG/ Communication Westfalia Magazine, Edi 2008/0190567 A1 8/2008 Winsness tion No. 3, International, The Latest on Industrial Fish Processing 2010/0028484 A1 2/2010 Kriesler et al. 1979, 103 Pg$~ 201 1/ 0282085 A1 11/ 2011 Cantrell et al. Digital Book provided by GoogleiThesis of WINFIELD, Harriet 2012/0009658 A1 1/2012 Winsness The oil ofmaize (Zea mays); Library ofthe University ofWisconsin, 2012/0205324 A1 8/2012 Cantrell et al. NewYork, 1899; pp. 1-61.

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Dote,Y., et al. Liquefaction of Stillage from Ethanolic Fermentation and Upgrading ofLique?ed Oil Trans. Mat. Res. Soc. Jpn, vol. 18A, 1994, pp. 285-288. GEA Westfalia Separator, Inc. v Greenshift Corporation, Complaint, Case No. 1:09-cv-07686-LMM; ?led Sep. 3, 2009, pp. 1-28, stamped by Judge McKenna. GEA Westfalia Separator", Inc. and Ace Ethanol, LLC v. Greenshift Corporation, Case No. 09 Civ. 7686 (LMM) ECF Case, First Amended Complaint, received in US. District Court S.D.N.Y, Oct. 13, 2009, pp. 1-36. GS Cleantech Corporation v. GEA Westfalia Separator, Inc.; Ace Ethanol, LLC; ICM, Inc.; Lifeline Foods LLC; and Does 1-30, Inclu sive, First Amended Complaint for Patent Infringement; Civil Action No. 09-cv-08642-SAS, ?led Oct. 23, 2009, pp. 1-11. GS Cleantech Corporation, Plaintiff, v. Big River Resources Galva, LLC and Big River Resources West Burlington, LLC, Defendants, Plaintiff s Memorandum of Law in Support of Its Motion for Pre liminary Injunction (with Exhibits 8, 8-1 through 8-8 inclusive), ?led in the United States District Court for the Northern District of Illinois Easter Division, Case No. 10-990, on Feb. 15, 2010, Docu ment 7, Case 1:10-cv-0090, 401 pgs. GS Cleantech Corporation, Plaintiff, v. Cardinal Ethanol, LLC, Defendant, Complaint for Patent Infringement, ?led in United State District Court for the Southern District of Indianapolis Divi sion, Civil Action No. 1:10-cv-0180-LJM-DML; on Feb. 10, 2010; Document 1; Case No. 1:10-cv-00180-LJM-DML, 9 pgs. GS Cleantech Corporation, Plaintiff, v. Cardinal Ethanol, LLC, Defendant, Motion for Preliminary Injunction; ?led in United State District Court for the Southern District of Indiana, Indianapolis Divi sion, Civil Action No. 1:10-cv-0180-LJM-DML, on Feb. 10, 2010, Document 7, Case No. 1:10-cv-00180-LJM-DML, 2 pgs. GS Cleantech Corporation, Plaintiff, v. Cardinal Ethanol, LLC, Defendant; Plaintiff s Reply Brief in Support of its Motion for Preliminary Injunction (with Exhibits 32 and 32-1); ?led in United States District Court for the Southern District of Indiana, Indianapo lis Division, Civil Action No. 1:10-cv-0180-LJM-DML, on Apr. 5, 2010; Document 31, Case 1:10-cv-0180-LJM-DML, 25 pgs. GS Cleantech Corporation, Plaintiff v. Cardinal Ethanol, LLC, Defendant; Plaintiff s Memorandum of Law in Support of its Motion for Preliminary Injunction (with Exhibits 9-1 through 9-15 inclusive), ?led in United States District Court Southern District of Indiana, Indianapolis Division, Civil Action No. 1:10-cv-0180LJM DML, on Feb. 11, 2010, Document 9, Case No. 1:10-cv-00180-LJM DML, 456 pgs. GS Cleantech Corporation, Plaintiff, v. Cardinal Ethanol, LLC, Defendant, Defendants Memorandum of Law in Opposition to Plaintiff s Motion for Preliminary Injunction (with Exhibits 26-1 through 26-24 inclusive), Civil Action No. 1:10-cv-0180 LJM-DML; ?led in United States District Court Southern District of Indiana Indianapolis Division, on Mar. 24, 2010, Document 26, Case 1:10 cv-00180-LJM-DML, 306 pgs. GS Cleantech Corporation, Plaintiff, v. GEA Westfalia Separator, Inc.,' Ace Ethanol, LLC; ICll/I, Inc.,' Lifeline Foods LLC; and Does 1-30, Inclusive, Defendants, Ace Ethanol, LLCs Answer to Plain tiff s First Amended Complaint for Patent Infringement, ?led in United States District Court for the Southern District of New York, Civil Action No. 09-cv-08642-LMM; on Nov. 18, 2009, Document 19, Case 1:09-cv-08642-LMM, 9 pgs. GS Cleantech Corporation, Plaintiff v. GEA Westfalia Separator, Inc. ,' Ace Ethanol, LLC; ICll/I, Inc. ,' Lifeline Foods LLC; and DOES 1-30, Inclusive, Defendant; First Amended Complaint for Patent Infringement; ?led United States District Court for the Southern District of NewYork, Civil Action No. 09 -cv-08642-SAS, on Oct. 15, 2009, Document 3-2; Case 1:09-cv-08642-LMM, 11 pgs. GS Cleantech Corporation, Plaintiff, v. GEA Westfalia Separator, Inc.,' Ace Ethanol, LLC; ICll/I, Inc.,' Lifeline Foods LLC; and Does 1-30, Inclusive, Defendants; GEA Westfalia Separator, Inc.s Answer to Plaintiff s First Amended Complaint for Patent Infringe ment ?led in United States District Court for the Southern District of

New York; Civil Action No. 09-cv-08642-LMM, ?led on Nov. 18, 2009, Document 21; Case 1:09-cv-08642-LMM, 9 pgs. ICll/I, Inc. v. GS Cleantech Corporation Greenshift Corporation, Complaint for Declaratory Judgement, Civil Action No. 09 1315 WEB-KMH, ?led Oct. 13, 2009, pp. 1-6. Jacques et al. The Alcohol Textbook 3rd Edition, published 1999, Part 1 of4 Parts, 53 pgs. Jacques, et al., The Alcohol Textbook, 3rd Edition, published 1999, Part 2 of4 Parts, 50 pgs. Jacques, et al., The Alcohol Textbook, 3rd Edition, published 1999, Part 3 of4 Parts, 50 pgs. Jacques, et al., The Alcohol Textbook, 3rd Edition, published 1999, Part 4 of4 Parts, 42 pgs. Minowa, T., et a1. Oil Production from Buckwheat Stillage by Thermochemical Liquefaction) National Inst. for Resources and Environment Ibaraki (Japan), STN, Abstract, NTIS database, 1999. No Author Available, Thermochemical Liquefaction Wisconsin Biore?ning Development Initiative, www.wisbiore?ne.org. pp. 1-4, dated sometime in 2004 as evidenced by copyright date; Energy Center of Wisconsin. Notice of AllowanceiSupplemental; U.S. Appl. No. 11/688,425, ?led Mar. 20, 2007; First Named Inventor: David J. Winsness; Mail Date: Apr. 21, 2009. Adkins Energy LLC., Third Supplemental Preliminary Invalidity Contentions as to the 858, 516, 517 and 484 Patents, ?led in he United States District Court for the Southern District of Indiana Indianapolis Division, Case Nos. 1:10-ml-02181-LJM-DML, Asso ciated Case No. 1:10-cv-08011-LJM-DML on Feb. 11, 2013; 304 pages with certi?cate of service, appendix and exhibits. Al-Corn Clean Fuels, Amended Invalidity Contentions as to the 858, 516, 517 and 484 Patents, ?led in he United States District Court for the Southern District of Indiana Indianapolis Division, Case No. 1:10-ml-02181-LJM-DML, Associated Case No. 1:10-cv 08004-LJM-DML on Feb. 15, 2013; 114 pages including exhibits. Blue Flint Ethanol LLC., Defendants, Preliminary Invalidity Con tentions for the 858, 516, 517 and 484 Patents , ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case No. 1:10-ml-02181-LJM-DML, on Feb. 11,2013; 10 pages including certi?cate of service. Bushmills Ethanol, Inc., Defendants, Defendants Bushmills Ethanol, Inc., Chippewa Valley Ethanol Company LLLp, Heartland Corn Products and United Wisconsion Grain Products, LLCs Sec ond Amended Preliminary Invalidity Contentions, ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case No. 1:10-ml-02181-LJM-DML,Associ ated Case No. 1:10-cv-08003-LJM-DML, Associate Case No. 1:10 cv-08004-LJM-DML, on Feb. 11, 2013; 253 pages including certi? cate of service and exhibits. GEA Mechanical Equipment US, Inc. and ACE Ethanol LLC., Amended Invalidity Contentions for the 858, 516, 517 and 484 Patents, ?led in he United States District Court for the Southern District ofIndiana Indianapolis Division, Case Nos. 1:10-ml-02181 LJM-DML, on Feb. 11, 2013; 368 pages including certi?cate of service and exhibits. Iroquois Bio -Engergy Company, LLC, Amended Invalidity Conten tions for the 858, 516, 517 and 484 Patents, ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case No. 1:10-ml-02181-LJM-DML, on Feb. 11, 2013; 45 pages including exhibits. Linconlway Engergy-LLC, ., Amended and Supplemental Invalidity Contentions for the 858, 517, 516 and 484 Patents, ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case Nos. 1:10-ml-2181-LJM-DML, related to U.S.DC ND Iowa Civil No. 5:10-cv-4036, on Feb. 11, 2013; 16 pages including certi?cate of service. Linconlway Energys Supplemental Claim Chart re: Claims 8 & 9 Invalidity Contentions, ?led with the Supplemental lnvalidty Con tentions in the United States District Court for the Southern District of Indiana Indianapolis Divsion, Case No. 1:10-ml-2181-LJM DML, related to USDC ND Iowa Civil No. 5:10-cv-4036, on Feb. 11, 2013; 10 pages. Non-Final Of?ce Action issued in United States Patent Application No. 13/450,997, dated Feb. 21, 2013; 27 pages.

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Adkins Energy, LLC, Defendants, Second Supplemental Prelimi nary Invalidity Contentions, ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case Nos. 1:10-ml-0218-LJM-DML and 1:10-Cv-08011-LJM-DML, on Oct. 15, 2012, 17 ppages including certi?cate of service. Defendants, Bushmills Ethanol, Inc., Chippewa Valley Ethanol Company, LLLP, Heartland Corn Products and United Wisconsin Grain Producers LLC, Amended Preliminary Invalidity Contentions; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; In Re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case No. 1:10-ml-02181-LJM-DML; dated Oct. 15,2012; 12 pages. GEA Mechanical Equipment US, Inc. and Ace Ethanol LLC.s Pre liminary Invalidity Contentions, ?led in the United States District Court for the Southern District of Indiana; Indianapolis Division; In Re: Method of Processing Ethanol Byproducts and Related Sub systems (858) Patent Litigation; 1:10-ml-02181-LJM-DML; ?led Oct. 15, 2012; 140 pages. Lincolnway Energy LLC Preliminary Invalidity Contentions; ?led in the United States District Court, Southern District of Indiana, India napolis, Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. 1:10-ml-02 1 8 1 -LJM-DML; Associated Case No. 5: 10-cv-4036; ?led Oct. 15, 2012, 17 pages; Exhibit A, pp. 3 pages and Exhibit B, 4 pages, (pp. 275-278). Preliminary Invalidity Contentions of Defendants ICM, Inc., Cardi nal Ethanol, LLC, Big River Resources Galva, LLC, Big River Resources West Burlington, LLC and Lincolnland Agri-Energy, LLC, for the 516 and 517 Patents; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; In Re: Method for Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; 1: 10-ml-02181-LJM-DML; dated Oct. 15, 2012, 10 pages. Of?ce Action issued in Canadian Patent Application No. 2,576,895, dated Oct. 18, 2012; 3 pages. Hagenmeier et al. Aqueous Processing of Fresh Coconuts for Recovery of Oil and Cocnut Skim Milk Journal of Food Science, vol. 38, 1973, pp. 516-518. PRX the ProEXporter Network PRX Digest Grain Database, dated Jun. 5, 2010; 43 pages (constantly updated). Westfalia Separator Industry Decanters and Separators for Indus trial Fish Processing, 1999, 36 pages. GS Cleantech Corporation v. GEA Westfalia Separator", Inc.; and Does 1-20, Inclusive; Complaint, Case No. 1:09-cv-08642-LMM; ?led Oct. 13, 2009, pp. 1-8. GS Cleantech Corporation, Plainti?v. Big River Resources Galva, LLC and Big River Resources West Burlington, LLC, Defendants; Complaint; ?led in the United States District Court for the North ern District of Illinois, Eastern Division, on Feb. 12, 2010, Document 1; Case 1:10-cv-0090; 9 pgs. GS Cleantech Corporation, Plainti? v. Big River Resources Galva, LLC and Big River Resources West Burlington, LLC, Defendants; Motion for Preliminary Injunction; ?led in the United States Dis trict Court for the Northern District of Illinois, Eastern Division, Case No. 10-990, on Feb. 15, 2010, Document 6; Case 1:10-cv-0090, 2 pgs. Chicago Board of Trade, Chicago Board of Trade (CBOT) SoyBean Oil Prices graph, constantly updated, 1 pg, Data from 2000 to 2009. Notice ofAllowance for US. Appl. No. 12/559,136, ?led Sep. 14, 2009; First Named Inventor: David Fred Cantrell; Mailing Date: Jan. 21, 201 1. Notice of Allowance for US. Appl. No. 11/241,231, ?led Mar. 20, 2007; First Named Inventor: David J. Winsness; Mail Date: Feb. 17, 2010; 4 pgs. Notice of Allowance for US. Appl. No. 11/688,425, ?led Mar. 20, 2007; First Named Inventor: David J. Winsness; Mail Date: Mar. 5, 2009; 7 pgs.

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Alfa Laval, NS 934 DD Decanter, PFT00017EN 0207, PFT00018EN 0207, PFT0007EN 0207, dated prior to Sep. 17,2007; 6 pgs. Singh, et al., Extraction of Oil from Corn Distillers Dried Grains with Soluables Transactions of the ASAE, 1998, vol. 41(6), pp. 1775-1777. Yokoyama et al., Liquid Fuel Production from Ethanol Fermenta tion Stillage, The Chemical Society of Japan, 1986, pp. 649-652. Blue Flint Ethanol, LLCs Preliminary Invalidity Contentions; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; In Re: Method or Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Case No. 1:10-ml-02181-LJM-DML; Exhibits A-F included, dated Jan. 24, 2011; 77 pages. Blue Flint Ethanol LLC regarding US Patent No. 8,168,037; ?led in the United States District Court for the Southern District of Indiana; Indianapolis Division; Preliminary Invalidity Contentions; In Re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. 1:10-ml-02181-LJM DML; Associated Case No. 1:10-Cv-08001-LJM-DML: dated Dec. 24, 2012; 39 pages. Bushmills Ethanol, Inc., Chippewa Valley Ethanol Company, LLLP, Heartland Corn Products and United Wisconsin Grain Producers LLC, Preliminary Invalidity Contentions; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; In Re: Method of Processing Ethanol Byproducts and Related Sub systems (858) Patent Litigation; Master Case No. 1:10-mL-02181 LJM-DMl; dated Jan. 24,2011; 23 pages. Bushmills Ethanol, Inc., Defendants, Defendants Bushmills Ethanol, Inc., Chippewa Valley Ethanol Company LLLp, Heartland Corn Products and United Wisconsin Grain Products, LLC s Second Amended Preliminary Invalidity Contentions, ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case No. 1: 10-ml-02181-LJM-DML, Associated Case No. 1:10-cv-08003-LJM-DML, Associate Case No. 1:10-cv-08004 LJM-DML, on Feb. 11, 2013; 253 pages including certi?cate of service and exhibits. Declaration ofDavid Fred Cantrell et al.; U.S. Appl. No. 13/107, 197; Filing Date: May 13, 201 1; GroupArtUnit: 1622; dated Jul. 10,2012; PP~ 6 Declaration of David Fred Cantrell dated Nov. 5, 2010 with Exhibits A and B; 9 pgs. Flottweg Separation Technology, Inc.s Preliminary Invalidity Con tentions; In Re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case No. 1: 10 MLO-02181-LJM-DML; Associated Case No. 1:10-cv-8010-LJM DML; dated Jan. 24, 2011; 12 pages. GEA Westfalia Separator, Inc. and Ace Ethanol LLC.s Preliminary Invalidity Contentions, ?led in the United States District Court for the Southern District of Indiana; Indianapolis Division; In Re: Method of

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Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; l:l0-ml-02l8l-LJM-DML; ?led Jan. 24, 201 l: 28 pages. GS Cleantech Corporation; Plaintiff v. Adkins Energy, LLC, Defen dant; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l: l0-ml-2l8 l -LJM-DML, on Feb. 27, 2012, Docu ment 242; Case l:l0-ml-02l8l-LJM-DML l0 pgs. GS Cleantech Corporation; Plaintiff vs. Amaizing Energy, LLC, Defendant; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 233; Case l:l0-ml-02l8l-LJM-DML l2 pgs. GS Clean Tech Corporation; Plaintiff vs. Big River Resources Galva, LLC and Big River Resources West Burlington, LLC Defendants; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l: l0-ml-2l8 l -LJM-DML, on Feb. 27, 2012, Docu ment 235; Case l:l0-ml-02l8l-LJM-DML ll pgs. GS CleanTech Corporation; Plaintiff v. Big River Resources Galva, LLC and Big River Resources West Burlington, LLC, Defendants; Answer of Big River Resources Galva, LLC and Big River Resources West Burlington, LLC to Plaintiff GS CleanTech Corpo rationss First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l: l0-ml-2l8 l -LJM-DML, on Mar. 15, 2012, Docu ment 260; Case l:l0-ml-02l8l-LJM-DML ll pgs. GS CleanTech Corporation; Plaintiff vs. Blue Flint Ethanol, LLC, Defendant; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 238; Case l:l0-ml-02l8l-LJM-DML l0 pgs. GS CleanTech Corporation; Plaintiff v. Bushmills Ethanol, Inc., Defendant; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 243; Case l:l0-ml-02l8l-LJM-DML l4 pgs. GS Clean Tech Corporation; Plaintiff v. Cardinal Ethanol, LLC, Defendant; Answer of Cardinal Ethanol, LLC to Plaintiff GS CleanTech Corporations First Amended Complaint for Patent Infringement; ?led in the United States District Court for the South ern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Mar. 15, 2012, Document 261; Case I: l0-ml-02l8l-LJM-DML ll pgs. GS Clean Tech Corporation; Plaintiff vs. Flotwegg Separation Tech nology, Inc., Defendant; Second Amended Complaint for Patent Infringement; ?led in the United States District Court for the South ern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 237; Case l:l0-ml-02l8l-LJM-DML l2 pgs. GS CleanTech Corporation; Plaintiff v. Iroquois Bio-Energy Com pany, LLC, Defendant; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the South ern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 240; Case l:l0-ml-02l8l-LJM-DML l0 pgs. GS CleanTech Corporation; Plaintiff vs. Iroquois Bio-Enery Com pany, LLC, Defendant; Iroquois Bio-Energy Company, LLCs Answer and Af?rmative Defenses to GS CleanTech Corporations First Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0- ml-2l8l-LJM-DML, on Mar. 15, 2012, Document 259; Case l:l0-ml-02l8 l -LJM-DML ll pgs. GS CleanTech Corporation; Plaintiff v. Lincolnland Agri-Energy, LLC, Defendant; Second Amended Complaint for Patent Infringe ment; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 241; Case l:l0-ml-02l8l-LJM-DML l0 pgs.

GS CleanTech Corporation; Plaintiff v. Lincolnland Agri-Energy, LLC, Defendant; Answer of Lincolnland Agri-Energy, LLC to Plaintiff GS CleanTech Corporations Second Amended Complaint for Patent Infringement; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0-ml-2l8l LJM-DML, on Mar. 15, 2012, Document 262; Case l:l0-ml-02l8l LJM-DML l0 pgs. GS Clean Tech Corporation; Plaintiff v. United Wisconsin Grain Pro ducers, LL C, Defendant; First Amended Complaint for Patent Infringement; ?led in the United States District Court for the South ern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Feb. 27, 2012, Document 239; Case l:l0-ml-02l8l-LJM-DML l0 pgs. ICM, Inc., David Vander Griend, Cardinal Ethanol, LLC, Big River Resources Galva, LLC, Big River Resources WEst Burlington, LLC and Lincolnland Agri-Energy, LLC., Defendants, Amended Inval idity Contentions for the 85 8, 516, 5 l 7 and 4 84 Patents, ?led in the United States District Court for the Southern District of Indiana Indianapolis Division, Case No. l:l0-ml-02l8l-LJM-DML, on Feb. 11, 2013; 10 pages including certi?cate of service. ICM Inc, and ICM-related Ethanol Plant Defendants Memorandum in Support of Their Motion for Summary Judgment of Non-Infringe ment; ?led in the United States District Court, Southern District of Indiana, Indianapolis, Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. l:l0-ml-02l8 l -LJM-DML; dated May 23, 2012, 25 pages; Certi?cate of Service, 1 page (p. 26). ICM, Inc., Cardinal Ethanol, LLC, Big River Resoruces Galva, LLC, Big River Resources West Burlington, LLC and Lincolnland Agri Energy, LLC; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; Preliminary Invalidity Contentions; In Re: Method for Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; l:l0-ml-02l8l-LJM DML; dated Jan. 24, 201 l, 9 pages. I Cll/I, Inc., KMH, Plaintiff v. GS Cleantech CorporationiGreenshift Corporation, Defendant; First Amended Complaint for Declaratory Judgment; ?led in United States District Court, District of Kansas, Civil Action No. 09-l3l5-WEB-, on Oct. 14, 2009, Document 4; Case 6:09-cv-0l3l5-WEB-KMH; 6 pgs. ICM; Plaintiff vs. GS CleanTech Corporation, Defendant; Fourth Amended Complaint for Declaratory Judgement Jury Trial Requested; ?led in the United States District Court for the Southern District of Indiana, Master Case No. l:l0-ml-2l8l-LJM-DML, on Mar. 15, 2012, Document 255; Case l:l0-ml-02l8l-LJM-DML l0 PgS~ Iroquois Bio -Energy Company LLC., Memorandum in Support of its Motion for Summary Judgment of Non-Infringement; ?led in the United States District Court, Southern District of Indiana, Indianapo lis, Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. l: 10 ml-02l8l-LJM-DML; Document No. 362; dated May 23, 2012, 27 pages; Certi?cate of Service, 1 page (pp. 28). Iroquois Bio-Energy Company, LLCs Preliminary Invalidity Con tentions; ?led in the United States District Court for the Southern District of Indiana; Indianapolis Division; In Re: Method for Pro cessing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; MDL Master Case No. l:l0-ml-02l8 l -LJM-DML; dated Jan. 24, 201 l; 25 pages. Lincolnway Energy, LLC; Preliminary Invalidity Contentions ?led in the United States District Court, Southern District of Indiana; India napolis Division; In re: Method for Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Docket: l:l0-ml-02l8l-LJM-DML; dated Jan. 24, 201 l; 18 pages. Lincolnway Energy LLC Preliminary Invalidity Contentions; ?led in the United States District Court, Southern District of Indiana, India napolis, Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. l:l0-ml-02 l 8 l -LJM-DML; Associated Case No. 5 : l0-cv-4036; ?led Oct. 15, 2012, 17 pages; Exhibit A, pp. 3 pages and Exhibit B, 4 pages, (pp. 275-278). Lincolnway Energy LLC Preliminary Invalidity Contentions regard ing US Patent No. 8,168,037; ?led in the United States District Court for the Southern District of Indiana; Indianapolis Division; In Re:

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Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. 1: 10-ml-02181-LJM DML; Associated Case No. 1: 10-Cv-08001-LJM-DML: dated Dec. 24, 2012; 46 pages. International Preliminary Report on Patentability for Search Report for PCT/US2005/028937 dated Feb. 20, 2007. Adkins Energy LLC, Fourth Supplemental Invalidity Contentions; ?led in the United States District Court for the Southern District of Indiana , Indianapolis Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems ( 858) Patent Litigation; Master Case. No. 1:10-ml-02181-LJM-DML: Associated Case No. 1:10 CV-08011-LJM-DML; ?led Jul. 16, 2013, 3 pages and Certi?cate of Service 2 pages. Al-Corn Clean Fuels, Supplemental Invalidity Contentions as to the 858, 516, 5 17, and 484 Patents; ?led in the United States District Court for the Southern District of Indiana, Indianapolis Division, in re: Method of Processing Ethanol Byproducts and Related Sub systems (858) Patent Litigation; Master Case. No. 1:10-ml-02181 LJM-DML; Associated Case No. 1:10-cv-08004-LJM-DML; ?led Jul. 16,2013, 2 pages. Alfa Laval, Dep. Ex. 329; Instruction Book: Separator, BRPX 413XGD-14C-74C, 2003; 146 pgs. Alfa Laval, Dep. Ex. 518; Operators Manual: Separator, MiS 600 PX TGD-14CGRX, 1997; 115 pgs. Alther, George, Put the Breaks on Wastewater Emulsions, Chemical Engineering, Mar. 1998; pp. 82-88. National Research Council/National Academy Press, Catalog Card No. 1-4396, Feeding Value of Ethanol Production By-Products 1981, 80 pgs. Tj ardes et a1., Feedin Corn Distillers Co-Products to Beef Cattle, Extension Extra. Aninal and Range Science. College of Agriculture and Biological Sciences/ South Dakota State University, Aug. 2002; 5 pages. Monceaux, et al., The Alcohol Textbook, 5th Edition, published 2009, pp. 303-322. Blue Flint Ethanol LLC, Supplemental Invalidity Contentions Regarding US. Patent Nos. 7,601,858; 8,008,516; 8,008,517; and 8,283,484 ?led in the United States District Court for the Southern District of Indiana, Indianapolis Division, in re: Method of Process ing Ethanol Byproducts and Related Subsystems (858) Patent Liti gation; Master Case. No. 1:10-ml-02181-LJM-DML; Associated Case No. 1:10-cv-8002-JLM-DML; ?led Jul. 16, 2013, 5 pages and Certi?cate of Service 1 page. Defendants Bushmills Ethanol, Inc., Chippewa Valley Ethanol Com pany LLLP, Heartland Corn Products and United Wisconsion Grain Producers, LLC, Supplemental Invalidity Contentions; ?led in the United States District Court for the Southern District of Indiana, Indianapolis Division, in re: Method of Processing Ethanol

Byproducts and Related Subsystems ( 85 8) Patent Litigation; Master Case. No. 1: 10-ml-02181-LJM-DML; Associated Case No. 1:10-cv 08003-LJM-DML; 1:10-cv-08004-LJM-DML, ?led Jul. 16, 2013, 17 pages and Certi?cate of Service 1 page. GEA Mechanical Equipment US, Inc. and Ace Ethanol LLC, Supple mental Amended Invalidity Contentions; ?led in the United States District Court for the Southern District of Indiana, Indianapolis Divi sion, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. 1: 10-ml 02181-LJM-DML; Associated Case Nos. 1: 10-CV-8006-LJM-DML and 1: 10-CV-8007-LJM-DML; ?led Jul. 16, 2013, 6 pages and Cer ti?cate of Service 1 page. Notice of Adoption of Amended Invalidity Contentions of Defen dants ICM, Cardinal Ethanol, LLC, Big River Resources Galva, LLC, Big River Resources West Burlington, LLC and Lincolnland Agri-Energy, LLC for the 858, 516, 517, and 484 Patents; ?led in the United States District Court Southern District of Indiana, India napolis Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Master Case. No. 1:10-ml-02181-LJM-DML; ?led Jul. 16, 2013, 2 pages and Certi? cate of Service 1 page. Iroquois Bio-Energy Company LLC, Preliminary Invalidity Conten tions; ?led in the United States District Court for the Southern Dis trict of Indiana, Indianapolis Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems (858) Patent Litiga tion; Master Case. No. 1:10-ml-02181-LJM-DML; Associated Case No. 1: 10-cv-8005-LJM-DML; ?led Jul. 16, 2013, 3 pages and Cer ti?cate of Service 1 page. Linconlnway Energy LLC, Supplemental Invalidity Contentions; ?led in the United States District Court for the Southern District of Indiana, Indianapolis Division, in re: Method of Processing Ethanol Byproducts and Related Subsystems ( 85 8) Patent Litigation; Master Case. No. 1:10-ml-02181-LJM-DML; USDC ND Iowa Civil No. 5:10-cv-4036; ?led Jul. 16, 2013, 9 pages and Certi?cate of Service 1 page. Notice ofAllowance; U.S. Appl. No. 11/122,859, ?led May 5,2005; Mail Date: Apr. 8, 2009. Blue Flint Ethanol, LLCs Amended Preliminary Invalidity Conten tions; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; In Re: Method or Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Case No. 1: 10-ml-02181-LJM-DML, Associated Case No. 1: 10-cv-8002 LJM-DML; dated Sep. 17, 2013; 2 pages. Peliminary Invalidity Contentions by Lincolnway Energy LLC; ?led in the United States District Court; Southern District of Indiana; Indianapolis Division; in Re: Method or Processing Ethanol Byproducts and Related Subsystems (858) Patent Litigation; Case No. 1: 10-ml-2181-LJM-DML, USDC ND Iowa Civil No. 5:10-cv 4036; dated Sep. 17, 2013; 31 total pages (037 Patent Further Amended & Supplemented Invalidity Claim Chart) included.

* cited by examiner

US. Patent Mar. 25, 2014 Sheet 1 0f 11 US 8,679,353 B2

WHOLE STILLAOE CASE 1 "MEOMAMIOAL SEPARATION" "BEFORE"

MOISTURE OOMTEMT OT OISTILLERS MET GRAINS: 55.0Z SOLIOS CONCENTRATION IN THIN STILLAEE: 5.70Z MOISTURE OOMOEMTRATIOM IN SYRUP: 00.02

5P_M LBS/HR TOTAL cAPAcITY 145 72,210

-TOTAL MOISTURE 110 50,702 -TOTAL SOLIOS 27 13,500

OISTILLERSMET [[EEEAIINSLBS/HR 7 THIN STILLAGE GP_M LBS/HR l TOTAL v0LUME 07.5 43,575

TOTAL v0LUME 57.5 20,534 MOISTURE: 00.5 40,090 92.02 MOISTURE: 37.4 10,512 55.02 TOTAL SOLIOS 20 1 10022 35 DZ OIL CONTENT 1" 566 "m

' 7 ' SOLIDS: 5.9 2,920 5.707,

FMS-El EVAPORATOR REMOVES _ ?_> 25,145 LBS/HR OF WATER, 0R

' 53 5PM 0T wATER DJ J, 350.90 OPERATING OOST (S/HR)

SYRUP _M LBS/HR A TOTAL VOLUME 35 0 17,430 MOISTURE: 20.0 13,944 50.0% 0IL CONTENT: 1 1 555 3.22 SOLIOS 59 2,920 17.02

0RIE0 PRODUCT-HAVING lOZ MOISTURE cOMTEMT [LBS/HR): 15,009 MOISTURE T0 EVAPORATE (LBS/HR): 31,055 OR, IN EPM: 52.4

TUEL REOUIREO IN DRYER (IN DEEATHERMS]: 52.4 DRYER OPERATING EOST 005.00 DEEATHERM (E/HR): 3252.22 PRODUCT vALUE (IT/HR): 3500.35

Fig.1

US. Patent Mar. 25, 2014 Sheet 2 0f 11 US 8,679,353 B2

N 1111012 511111102 H "2152 1" 11221111111241 522411111011 411211

1101510112 1201112111 0F 111511112115 1121 011111151 65.02 501105 20002111211100 111 111111 5111111121 6.101 1101510112 00112201041100 111 SYRUP: 00.01

_0r_11 105/111 101111 2112112111 145 12,210

-TOTAL 1101510112 110 50,102 -TOTAL 5011115 21 13,500

10111 v01u112 01.5 43,510 10112 VOLUME 51.5 20,034 1101510122. 00.5 40,090 92.02 11015101121 21.4 10,012 65.02 _ 10141 501105 201 10022 35 oz 0- EONTENT' 1" 5 "3oz

' 1 ' s0110s= 5.9 2,920 6.102

1 ,1 EVAPORATUR REHOVES

_ ' , 26,146 LBS/HR 01 W211, 011 ' 53 GPM 01 101211

Fig 2 W l $50.98 012211111115 2051 (11/111) qua

SYRUP 511 105/1111 A 10111 v010112 35.0 11,430

10 1101510112: 20.0 13,944 00.02 01L 2011121111 1.1 566 2.21 5021115 5.9 2,920 11.01!

SYRUP (LBS/HR): 16,092 i 1, 11013101121 02.52

1101510112 (LBS/HR): 12,044 14 OIL 201112111 110/1111): 20 5011115 001112111 (105/1120 2,920 1

1r LBS/HR 6PM 01L 112201121120 (LB/HR}: 530 1.1 011 v11102 111/1111) 11102

20

1111120 PRODUCI-HAVINE 1011 1101510112 201112111 (1115/1111: 14,411 1101510112 10 EVAPDRATE 1205/1100 31,115 OR, 111 02111 62.5

FUEL 1120011220 111 0111211 1111 112011112111151= 52.5 11111211 02211111111; 2051 0115.00 020111121111 10/1111)= 11262.13 PRODUCI VALUE (11/111111 11516.46

US. Patent Mar. 25, 2014 Sheet 3 0f 11 US 8,679,353 B2

WHOLE sTILLA8E cAsE 2 "MECHANIEAL SEPARATION" "BEFORE"

MOISTURE CONTENT OF DISTILLERS wET BRAINS: 80.02 sOL1Os OOMOEMTRATIOM IN THIN STILLABE: 3.877. MOISTURE cOMcEMTRATIOM IN SYRUP: 80.02

8P;M LBS/HR TOTAL cAPAEITY 145 72,210

-TOTAL M0IsTuRE 118 58,702 -TOTAL SOLIDS 27 13,508

DISTILLERS MET 8RA1Ms THIN STILLAGE ? LBS/HR l w M A

TOTAL vOLuME 88.1 43885 TOTAL VOLUME 55'9 281325 MOISTURE: 83.7 41,707 95.02 MOISTURE: 34.1 18,995 60.0Z OIL CONTENT: 1.1 566 1.3OZ TOTAL SOLIDS 22.8 11330 40.0Z

SOLIDS: 3.2 1,612 3.671

l, EvAP0RATOR REMOVES _ ' , 8 38440 LBS/HR OF WATER OR

a 77 8PM 0F wATER OJ 1 874.98 OPERATIMO cOsT (MIR)

SYRUP _M LBS/HR A TOTAL vOLuME 10.9 5,445 MOISTURE: 8.8 3,287 80.02 OIL CONTENT: 1.1 588 10.42 SOLIDS 32 1,812 30.07:

ORIEO PRODUCT-HAVING IOZ MOISTURE CONTENT [LBS/HR): 15,009 MOISTURE TO EvAPORATE (LBS/HR): 18,781 OR, IN GPM: 37.7

FUEL REOuIREO IN ORYER (IN DEEATHERMS): 31.7 ORYER OPERAT1M8 [:OST 035.00 DECATHERM (?/MR): 8158.41 PRODUCT vALuE (IT/HR): 3800.38

Fig. 3

US. Patent Mar. 25, 2014 Sheet 4 0f 11 US 8,679,353 B2

wHOLE STILLAOE H "BASE 2| "MEIIMANIOAL SEPARATION AETER

MOISTURE cONTENT OE OISTILLERS wET BRAINS: 50.02 SOLTOS CONCENTRATION IN THIN STILLAGE: 3.572 MOISTURE cONcENTRATION IN SYRUP: 5002

w LBS/HR TOTAL CAPACITY 145 72,210

-TOTAL MOISTURE 110 50,702 -TOTAL SOLIOS 27 13,505

0ISTTLLERSwET glgcllNSLBs/HR Z THIN STILLABE w M l TOTAL vOLUME 00.1 43,555

TOTAL v0LUME 55.9 20,325 MOISTURE: 53.7 41,707 95.02 MOISTURE: 34.1 15,995 50.02 , TOTAL SOLIOS 22 5 11330 40 07 ML CONTENT 1'1 556 "302

' ' SOLIDS: 3.2 1,512 3.572

r- i EvAPORATOR REMOvES _ ' , 5 30440 LBS/HR OEwATER OR

' a 7'7 EPM OE wATER

Fig 4 11 O, l 374.95 OPERATTNO OOST (O/HR)

SYRUP 5P_M LBS/HR 2 TOTAL mm 10.9 5,445 MOISTURE: 5.5 3,257 50.02 OIL CONTENT: 1.1 555 10.42 SOLIOS 3.2 1,512 30.02

" SYRUP (LBS/HR]: 4,907

MOISTURE: 55.52 MOISTURE (LBS/HR): 3,257 14 OIL cONTENT (LB/HR): 2a SOLIOS 0ONTENT (LBS/HR): 1,512 1

| LBS/HR 5PM OIL REOOVEREO (LB/HR): 535 1.1 OIL vALUE (E/HR) S102

0RIEO PRO0UcT-HAvIN5 102 MOISTURE OONTENT (LBS/HR): 14,411 MOISTURE TO EvAPORATE (LBS/HR): 10,521 OR, IN 5PM: 37.0

FUEL REOUIREO IN DRYER (IN UECATHERMS): 31.0 ORYER OPERATING COST 055.00 DECATHERM (ii/MR): $155.92 PRODUCT vALUE [S/HR): $575.45

US. Patent Mar. 25, 2014 Sheet 5 0111 US 8,679,353 B2

OIL 2.42 4,000 LBS/HR 30515513 16-3; 33,620 OIL/EMULSION 5,818 M E 01.3 152,500 05L 25X 5,454 ;

3 PHASE 0EEANTER wATER 752 4,353

LBS/HR 15 0EEANTER I LIQUID 132,541

LBS/HR TR B/R B/R " [IISTILLERS wET GRAINS 51,541 WASH w Y H L 5 H L S H M 5.42 3,346 50w OIL CONTENT 73,970| IDEEANTER LIQUID 50,571 | SOLIDS 37.52 23,150 : WATER 57,511 35,135 Y 5->| WASH WATER RETURN 77,471 I

3 ................ 5 3 LBS/HR 5

wET 5RA1Ns+wAsH wATER 135,511 5 LBS/HR OIL 2.52 3,345 5 THIN STILLAEE 141,050 souns 17.12 23,150 5 015 2.12 2,959.9 wATER 50.52 109,105 5 SOLIDS 5.7 2 9,450

2 PHASE DEEANTER 5 WATER JI-EZ 139,440

10 ------------ FIJUIQQ H " LBS/HR 52 U EvAP0RAT0R LBS/HR

wAsHEn wET GRAINS 50,140 E? wATER EVAPORATED 100,451

21115103 335% 23,1353 1' LBS/HR ' 1

WATER 55oz 33,540 1:0NT:ENTRATET1 STILLAEE 41,399 F5 6 01L 7.12 2,959.9 LBS/HR SOLIDS 22.92 9,450

wET GRAINS+SYRUP 99,539 WATER 70-0Z 38,979 OIL 2.12 2,135 SOLIDS 32-87; 32,520 M EENTRIFUGE wATER 55.12 52,119

====== _ [lRYER l4

" wATEREvAP0RATE0 59,097

' LBS/HR 0005 37,770 LBS/HR souns 55.32 32,520 EUR" OIL 21554 wATER 5.02 3,022

OPERATING 1:0sTs ii/HR PRODUCT VALUE LBS/HR E/HR FUEL REOu1REO BY DRYER (DEEATHERMS) 99.9 0055 (CAPACITY) 37770.3

UPERATING [:UST PER HOUR AT E5/UECATHERM $499.27 VALUED AT 370/5055 35 322_24 1

US. Patent Mar. 25, 2014 Sheet 7 0111 US 8,679,353 B2

LBS/HR RAw MATERIAL 200,000 OIL 3-4Z 4,800 50 MMGY ETHANOL PLANT 501105 16.31 32,620 mm 01 .32 162,500

2 PHASE 0EcA11TER

LBS/HR 160 IJEEANTER 1 110010 130 359| [IISTILLERS wET GRAINS 61,641 1' LBS/HR LBS/HR 01L 5 42 3346 |wAsH wATER 73,970| IUEEANTER LIQUID 64,309I

. , I

SOLIDS 37.61 23,160 + WATER 57-01 35,136 1 ,.-->| WASH wATER RETURN 77,471 |

< --------------- :

" LBS/HR i wET GRAINS+WASH wATER 135,611 5 1, LBS/HR OIL 2.57., 3,346 i THIN STILLAGE 141,060 SOLIDS 17.17. 23,160 5 OIL 2.1Z 2,959.9 wATER 00.51 109,105 1 SOLIDS 6.7 2 9,460

2 PHASE DECANTER 5 WATER 91.2Z 129,440

10 -------------- i F. 5,]! H H LBS/HR 12 U EvAP0RAT0R LBS/HR

WASHED wET GRAINS 50,140 E? |wATER EvAP0RATE0 100,461 | 01L 3.22; 1,840 1 LBS/HR

CONCENTRATED sT1LLA6E 41,399 " OIL 7.1Z 2,959.9

1, LBS/HR SOLIDS 22.9Z 9,460 wET GRAINS+SYRUP 99,539 WATER 70-0Z 35,979 01L 2.11 2,136 1 . 501105 32.02 32,620 7 wATER 65.12 62,119

l4 ====== _ DRYER

" wATER EvAPORATEO 59,097

' LBS/HR

3?? 5 .7 33332 301103 06.32 32,620 CORN 0 24664 wATER 0.01 3,022

0PERAT1116 cosTs ?/HR PRODUCT VALUE LBS/HR 3/HR FUEL RET1u1REE| BY 0RYER IUEEATHERMS) 99.9 T1063 (CAPACITY) 37770.3

OPERATING COST PER HOUR AT ASIUEEATHERM $499.27 VALUED AT gm/ToN 31 32234 K119 RE0u1REE| BY 0EcANTER 1011 A110 EONFIBURE 523.0

OPERATING COST PER HOUR AT 305/1019 1126.15 EUR" 0 (CAPACITY) 3553-9 FUEL REOu1RET1 BY EVAPORATOR (T1EcAT1lER11s1 56.5 VALUEI] AT 3300/1011 0399.59

0PERAT1116 COST PER HOUR AT 1T5/T1EEATHER14 3202.63 TOTAL OPERATING COST (3/HR) 3006.05 TOTAL VALUE (IT/HR) 31,721.03

US. Patent Mar. 25, 2014 Sheet 0 0111 US 8,679,353 B2

LBS/HR RAW MATERIAL 200,000 01L NZ 4,800 50 MMGY ETHANOL PLANT SOLIDS 10.32 32,020 WATER 01.32 102,500

2 PHASE [IEEANTER LBS/HR

I60 ANT R LBS/HR 0E:c EBS/I RE10u10 130 55/ R

DISTILLERS NET GRAINS 01,041 I V L H I I L H I OIL Hz 3345 N450 WATER 73,970 nEcANTER LIQUID 04,309 SOLIDS 37.02 23,100 I WATER 57-01 35,135 1 Ir ------------- WASH WATER RETURN 07,999|

< ----------------------- --9 :

LBS/HR 5 NET 0RA1Ns+wAsH WATER 135,011 5 LBS/HR OIL 2.52 3,340 i THIN STILLAGE 132,300 SOLIDS 17.12 23,100 A 01L 0,41 593 WATER 00.52 109,105 i SOLIDS 7.12 9,400

3 PHASE DEEANTER i WATER 92.42 [22,336 i F 12

100 ----------------- --J "- IJHIQE/ LBS/HR LBS/HR EVAPORATOR LBS/HR

WASHEU "NET GRAINS" 59,140 OIL/EMULSION 9 m u WATER EVAPURATED 100,401

OIL 35271 1,640 01L 252 2,300 l LBS/HR SOLIDS 39.82 23,160 WATER 751 7 104 WATER 57% 33,140 EONEENTRATED STILLAEE 41,399

01L 7.12 2,900 LBS/HR SOLIDS 22.92 9,400

NET GRAINS+SYRUP 99,539 WATER 70.02 20,979 OIL 2.12 2,130 SOLIDS 32.02 32,020 CENTRIFUGE WATER 05.12 02,119

14 ====== DRYER _

WATER EVAPORATED 59,097 F lg. 8 ' LBS/HR

01105 37,770 01E 5.72 2,130 3011115 00.32 32,020 WATER 0.02 3,022

OPERATING COSTS ii/HR PR0T1ucT VALUE LBS/HR 3/HR FUEL REOuTREO BY DRYER (IJEEATHERMS) 99.9 0005 (CAPACITY) 37770.3

UPERATINE COST PER HOUR AT ?5/UEEATHERH 3499.27 VALUED AT gm/ToN $1 322.24 KWH REOu1REO BY DEEANTER 181] AND E0NE100RE 024.7

0PER4T1N0 COST PER HOUR AT 0.05/10111 031.24 EUR" 01L (CAPACITY) 3503-9 FUEL REOuTREO BY EVAPORATOR (DECATHERMS) 50.5 VALUEIJ AT 3300/TON 3399.59

0PER4T1N0 COST PER HOUR AT $5/0E04THERN $202.03 TOTAL 0PERATINO [303T (it/HR) 3013.14 TOTAL VALUE (B/HR) $1,721.03

US. Patent Mar. 25, 2014 Sheet 9 0111 US 8,679,353 B2

1115/1111 00010000 00,000

011 2.4; 4,800 105/1111 SOLIDS 16.3 00 32,620 OIL/RECOVERY L498 WATER 81.32 162,580 0IL 1372 B454 INPIJUERPIEFNIQIEANTTIOOJL _

3 PHASE 0111111111 011111 3 Z 44

1115/1111 1 5 0111111111 1 110010 136,861

1115/1111 , 01511111115 1111 01111115 61,641 ,fMSH WATER 1" H LBS/HR LBS/HR OIL 5'4 Z 3,346 | 10w 011 001111111 13,910 | | 0101111111 110010 62,891 | SOLIDS 37.6Z E3,|60 WATER 57,02 35|36 Y r-->| WASH WATER RETURN 77,47] I

< --------------- i LBS/HR 1

011 ERAINS+WASH 011111 135,61 1 i 0 1115/1111 011 2.571 3,346 1 111111 51111101 140,362 501105 11. 1 71 23,160 1 011 1 . 1 1 1,501.10 011111 80.52 109,105 5 501105 0 1 Z 9,460

2 PHASE 0111111111 5 WATER 93-31 1390385 "

10 _____________ F1115} H H LBS/HR U EVAPURATOR 105/111

01511111 011 GRAINS 58,140 91 011111 1v1P0R1110 103,81 1 OIL 3.22 1,840 l LBS/HR 501105 39.01 23 160 WATER 57.02 33:14,] 10111111111110 51111101 36,551

_ 011 4. 1 z 1,605.5 105/111 501105 25.9% 9,460

011 ERAINS+ SYRUP 94,691 WATER 70-07 350585 011 2. 1 1 1,941 SOLIDS 34.41 32,620 M [IENTRIFUEE .0 1111111 63.5Z 58,126 Fl 9. 9

11111111 011111 1v1P0R1110 55,120

' 105/1112

35? 0 000 31313 LBS/HR 501105 86.02 32,620 CORN 0 21853 1111111 0.02 3,006

OPERATING c0515 1/1111 PRODUCT 0101 1115/1111 0/111 1011 1110011110 111 0111111 (0111111111115) 94. 1 111105 (CAPACITY) 31612.8

OPERATING COST PER HUUR AT ES/UECATHERM 3470-74 VALUED AT Em/TON 3] 3]5_05 1011 1110011110 01 0111111111 l8l 1 1110 [IONFIGURE 680.8

0P111111110 1:051 PER 110011 11 11 05/001 133.04 50R" W (CAPACITY) 3853-9 1011 1110011110 111 EVAPORATDR (0101111111115) 50.4 01010 11 1300/1011 1421.96

0P111111116 1:051 PER 110011 11 15/011111111111 $292.05 10111 OPERATING 1051 (S/HR) $195.84 10111 v1101 (B/HR] 31,143.00

US. Patent Mar. 25, 2014 Sheet 10 0111 US 8,679,353 B2

LBS/HR RAW MATERIAL 200,000 50 MMGY ETHANOL PLANT OIL 2.42 4,500 LBS/HR SOLIDS [6.32; 32,520 GIL/RECOVERY 1,527 wATER 51.32 152,550 mL 951 1,454 ;

3 PHASE 0EEATTTER mm 5 2 73

LBS/HR 15 DECANTER 1 LIQUID 135,551 |

LBS/HR WASH wATER BS/HR J, BS/HR DISTILLERSWET GRAINS 51,541 H ' H L L OIL HZ 3,346 Low 01L EUNTENT 73,970| IDEEANTER LIQUID 52,552| SOLIDS 37.52 23,150 : wATER 57.02 35,135 Y |r-->|WASH wATER RETURN 77,255|

--------------- i LBS/HR 5 01L DISCHARGE [W/POSSIBLE OIL

wET GRAINS+WASHWATER 135,511 5 \ IMPURIHES' I'E' WATER) PURIFICATION OIL 2.52 3,345 5 I; LBS/HR (AS RE001RE0) SOLIDS 17.12 23,150 5 THIN STILLAGE 140,147 wATER 50.52 109,105 5 01L 1.42 1,920.0

: SOLIDS 5.7 7 9450 PHA ANT R . ~ 4 3 SE DEE E 5 wATER 91.92 125,757 I

'80 : + :- r-EI U 14 EvAP0RAT0R LBS/HR

.. .. |wATER EVAPORATED 102,214| WASHEI] wET GRAINS 55,325 9 OIL 3.32 1,920 LBS/HR SOLIDS 39.72 23,160 EONEENTRATED STILLAEE 37,933 wATER 57.02 33,245 01L 4.12 1,920.0

|'

US. Patent Mar. 25, 2014 Sheet 11 0111 US 8,679,353 B2

LBS/HR RAw MATERIAL 200,000 01L HZ 4,800 50 141401 ETHANOL PLANT 5011115 10.32 32,020 wATER 31.32 102,500

5, 2 PHASE 0EEA11TER LBS/HR =511E0A11TER 1 110010 130 359|

160 5, LBS/HR LBS/HR LBS/HR |wAsH wATER 13,910| IDECANTER 110010 04,309I

DISTILLERS wET GRAINS 01,041 5 OIL 5.42 3,340 i 5 ------------------ -->|wAs11 wATER RETURN 10,131| 3011115 31.02 23,100 i 5 wATER 51.02 35,130 Y 5

( ______________________ -E 5 LBS/HR 5 LBS/HR 5 THIN STILLAGE 140,520

wET 0RA1Ns+wAs1-1 wATER 135,011 5 01L 1 02 1,454 OIL 2.52 3,340 5 $011115 0 12 9,400 5011115 11.12 23,100 4 WATER 92-271 129,812 wATER 00.52 109,105 5 L 055

3 PHASE UEEANTER i PURIFICATION 5 I (AS RE11u1RE11) 100 ------------- --4' F511; \_

A H H V LBS/HR a EvAP0RAT0R LBS/HR

WASHEU wET GRAINS 51,151 RECOVERED U55 U23 wATER EVAPORATED 104,195 OIL 2.92 1,673 055 972 5,573 LBS/HR SOLIDS 40.12 23,160 WATER 3 Z 55] WATER 57.02 32,958 EUNEENTRATED STILLAGE 36,381 "

01L 4.02 1,454 1 LBS/HR 501105 20.02 0,400

wET GRAINS+SYRUP 94,132 \ wATER 10.02 25,400 OIL 2.12 1,954 3011113 34.12 32,020 wATER 03.32 53,305

IJRYER

' LBS/HR 01105 31,591 OIL 5.22 1,904 5011115 39.02 32,020 mm 5.02 3,001

w E/HR PRonucT VALUE LBS/HR B/HR FUEL RE0u1RET1 BY DRYER (IJECATHERMS) 93.0 111105 (CAPACITY) 31091.0

OPERATING COST PER HOUR AT RS/UEEATHERM 3457.35 VALUED AT 370/50" 35,355.50 KWH REQUIRED BY 11E1:A11TER 11111 AND 1:011E10uRE 012.2

0PERAT1N0 1:051 PER HOUR AT 11.05/10111 330.81 50R" W (CAPACITY) 383M FUEL REOu1REO BY EvAP0RAT0R IDEEATHERMS) 50.0 VALUED AT 3300/1011 11420.45

0PERAT1110 cosT PER HOUR AT 35/0E0AT11ER11 3203.13 T0TAL 0PERAT1110 COST (S/HR) 3191.59 TOTAL VALUE (B/HR) 31,141.13

US 8,679,353 B2 1

METHOD AND SYSTEMS FOR ENHANCING OIL RECOVERY FROM ETHANOL PRODUCTION BYPRODUCTS

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of US. patent applica tion Ser. No. 13/185,841, ?led Jul. 19, 2011, Which is a continuation ofU.S. application Ser. No. 11/856,150 ?led on Sep. 17, 2007 and Ser. No. 11/908,891 ?led on Sep. 17,2007, Which claim the bene?t of PCT Application PCT/US2006/ 009238 ?led on Mar. 5, 2006, Which claims the bene?t of US. Provisional Application No. 60/661,733, ?led on Mar. 16, 2005, the disclosures of Which are incorporated herein by reference.

COPYRIGHT STATEMENT

A portion of the disclosure of this document contains mate rial subject to copyright protection. No objection is made to the facsimile reproduction of the patent document or this disclosure as it appears in the Patent and Trademark O?ice ?les or records, but any and all rights in the copyright(s) are otherWise reserved.

TECHNICAL FIELD

The present invention relates generally to producing oil from corn and, more particularly, to recovering oil from a byproduct of the dry milling process used to obtain ethanol from corn.

BACKGROUND OF THE INVENTION

Over the past thirty years, signi?cant attention has been given to the production of ethyl alcohol, or ethanol, for use as an alternative fuel. Ethanol not only burns cleaner than fossil fuels, but also can be produced using com, a reneWable resource. At present, an estimated sixty-nine dry milling plants in the United States produce over three billion gallons of ethanol per year. Additional plants presently under con struction are expected to add billions of gallons to this total in an effort to meet the current high demand As noted in the foregoing discussion, a popular method of

producing ethanol from corn is knoWn as dry milling.As is Well knoWn in the industry, the dry milling process utiliZes the starch in the corn to produce the ethanol through fermenta tion, and creates a Waste stream or byproduct termed Whole stillage (Which may be further separated into byproducts commonly referred to as distillers Wet grains and thin stillage). Despite containing valuable oil, these byproducts have for the most part been treated as Waste and used prima rily to supplement animal feed. This feed is mostly distributed in the form of distillers dried grains With solubles, Which is created by evaporating the thin stillage, recombining the resulting concentrate or syrup With the distillers Wet grains, and drying the product to a moisture content of less than about 10% by Weight.

Signi?cant attention has recently been given to the use of oil, including corn oil, as an alternative fuel. This fuel oil, frequently termed biodiesel, is a cleaner fuel than petro leum-based diesel (less emissions), environmentally safe (spills biodegrade quickly), and can be mixed at: any concen tration to diesel Without engine modi?cation. The current value of corn oil as biodiesel is approximately $2.40 per gallon, or $648/ton, Which is essentially double the value of

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2 the commercial feed that Would normally include this oil. Although the market for the biodiesel is groWing rapidly and the potential pro?t is signi?cant, key limiting factors are the cost of obtaining the oil using current techniques and the resulting quality.

In this regard, efforts to recoverusable oil from the byprod ucts of the dry milling process used to create ethanol have not been terribly successful in terms of e?iciency. One proposed approach involves attempting to separate the oil from the thin stillage before the evaporation stage, such as using a centri fuge. HoWever, spinning the thin still age at this stage using a centrifuge creates an emulsion phase that typically requires further processing before useable oil can be recovered. More over, the volume of thin stillage is generally 2 to 10 times greater than the syrup, Which is a considerable capital require ment to purchase the number of centrifuges required. Known techniques also lack the capability to maximiZe the oil recov ery, Which leads to decreased ef?ciency and concomitant loWer pro?ts. Together, these obstacles make past and current attempts to recover oil from ethanol production byproducts, such as corn thin stillage, someWhat inef?cient and uneco nomical. US. Pat. No. 5,250,182 (the disclosure of Which is incor

porated herein by reference) describes the use of ?lters for removing substantially all solids and recovering lactic acid and glycerol from the thin stillage Without the need for evapo ration. Despite eliminating a step in the conventional process, the proposal results in a more complicated arrangement requiring multiple ?ltration steps. Wholesale elimination of the evaporator in the vast majority of existing plants is also unlikely and otherWise uneconomical. Filters, and especially the micro?ltration and ultra?ltration types proposed for use in this patent, are also susceptible to frequent plugging and thus deleteriously increase the operating cost. For these reasons, the ?ltration process proposed in this patent has not gained Widespread commercial acceptance.

Accordingly, a need exists for more e?icient and economi cal manners of recovering oil from byproducts created during the dry milling of corn to produce ethanol.

SUMMARY OF THE INVENTION

In accordance With one aspect of the invention, a method of processing concentrated thin stillage created during a dry milling process used for producing ethanol from corn is dis closed. The method comprises recovering oil from the concen

trated thin stillage and further evaporating the concentrated thin stillage. The recovered oil may be used, for example, as biodiesel, and the leftover concentrated thin stillage dried and used as feed.

In one embodiment, the recovering step comprises sepa rating the oil from the concentrate using a disk stack centri fuge. The disk stack centrifuge produces suspended solids, Which may be mixed With distillers Wet grains. The disk stack centrifuge also produces a syrup, and the method may further comprise mixing the syrup, the suspended solids and distillers Wet grains to form a mixture. The method may further include the step of drying the mixture.

In accordance With another aspect of the invention, a method of processing thin stillage created by a dry milling process used for producing ethanol from corn to recover oil is disclosed. The method comprises evaporating the thin stillage to form a concentrate. At some point in time during the evaporating step, but before it is completed, the method also

US 8,679,353 B2 3

includes the step of introducing the concentrate to a disk stack centrifuge. The disk stage centrifuge then recovers oil from the concentrate.

The method may further include the step of evaporating the concentrate after the step of using the disk stage centrifuge to recover oil. Preferably, the evaporating step comprises using a multi-stage evaporator to form the concentrate from the thin stillage and the step of introducing the concentrate to a disk stack centrifuge is completed before the last stage of the evaporator. The evaporator most preferably includes at least one scraped surface heat exchanger.

In accordance With still another aspect of the invention, a method of recovering oil from thin stillage created by a dry milling process used for producing ethanol from corn is dis closed. The method comprises using a multi-stage evaporator to form a concentrate from the thin stillage. Before the last stage of the evaporator, the method includes recovering oil from the concentrate. In one embodiment, the method of this aspect of the invention further includes the step of further evaporating the concentrate remaining after the recovering step.

In accordance With a further aspect of the invention, a method of processing Whole stillage resulting from the dry milling of corn to form ethanol is disclosed. The method comprises recovering thin stillage including solids from the Whole stillage; concentrating the thin stillage including the solids; and recovering oil from the thin stillage before the concentrating step is complete.

In accordance With yet another aspect of the invention, a subsystem for intended use in a system for producing ethanol by dry milling corn and creating thin stillage as a byproduct is disclosed. The system comprises a multi-stage evaporator for evaporating the thin stillage, as Well as means for receiving thin stillage before the last stage of the evaporator and recov ering oil therefrom.

In one embodiment, the multi-stage evaporator includes tWo distinct evaporators. These evaporators are separated by a disk stack centrifuge serving as the receiving and recovering means. Most preferably, the evaporator includes at least one scraped surface heat exchanger.

In accordance With another aspect of the invention, a method of processing a byproduct of a dry milling process used for producing ethanol from corn is disclosed. The method comprises Washing the byproduct to create Wash Water including oil, concentrating the Wash Water; and recov ering oil from the concentrated Wash Water.

In one embodiment, the byproduct is Whole stillage and the Washing step comprises delivering the Whole stillage to a ?rst decanter for producing thin stillage and distillers Wet grains. In such case, the method may further include the step of Washing the distillers Wet grains. In particular, the step of Washing the distillers Wet grains may comprise delivering the distillers Wet grains to a second decanter for producing Washed Wet grains and the Wash Water used in the concentrat ing step. The thin stillage may be combined With the Wash Water before the concentrating step.

In accordance With still a further aspect of the invention, a system for processing Whole stillage produced from dry mill ing corn is disclosed. The system comprises a ?rst separator for receiving the Whole stillage and creating at least thin stillage and distillers Wet grains. A second separator receives the distillers Wet grains and Wash Water for creating Washed Wet grains and an oil-bearing discharge (e.g., Wash Water or an oil phase). Means for recovering oil from the oil-bearing discharge is also provided.

In one embodiment, the ?rst separator is a tWo phase decanter for producing Wash Water delivered to the second

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4 separator. Preferably, the second separator is a tWo phase decanter, but may instead be a three phase decanter. An evapo rator may be provided for receiving the thin stillage and Wash Water to form a concentrate, along With a third separator for recovering oil from the concentrate. The system may further include a dryer for drying a combination of the Washed Wet grains and any concentrate remaining after recovering oil using the third separator. The evaporator may be a multi-stage evaporator and the third separator comprises a disk-stack centrifuge that receives the concentrate before the last stage of the evaporator.

In accordance With still another aspect of the invention, a system for processing thin stillage and distillers Wet grains produced from dry milling corn is disclosed. The system comprises a ?rst separator for receiving the distillers Wet grains and creating at least Washed Wet grains and Wash Water. An evaporator evaporates the thin stillage and Wash Water to form a concentrate. A second separator recovers oil from the concentrate.

Preferably, the ?rst separator is a second decanter doWn stream of a ?rst decanter for forming the distillers Wet grains and thin stillage. Either the ?rst or second decanter may be a tWo phase decanter, or a three phase decanter. The second separator preferably comprises a disk-stack centrifuge.

In accordance With yet a further aspect of the invention, a system for processing Whole stillage produced from dry mill ing corn is disclosed. The system comprises means for receiv ing the Whole stillage and creating at least thin stillage, means for concentrating the thin stillage, and means for recovering oil from the concentrated thin stillage.

In one embodiment, the means for receiving the Whole stillage is a tWo phase decanter. In another, the means for receiving the Whole stillage is a three phase decanter. In still another, the means for receiving the Whole stillage includes a tWo phase decanter folloWed by a three phase decanter, or vice versa. Yet another option is for the means for receiving the Whole stillage to include a three phase decanter folloWed by a three phase decanter. Preferably, the means for concentrating is a multi-stage evaporator, and the recovering means is a disk-stack centrifuge. HoWever, the means or device for recovering may comprise any suitable device for separating oil from a mixture, such as a gravity separator, a centrifuge, a centrifugal decanter, or an evaporator. Means for recovering oil using knoWn techniques of chemical addition (pH adjust ment, enzymatic action, etc.) may also be effective.

In accordance With one more aspect of the invention, a method for processing Whole stillage including oil produced from dry milling corn includes the steps of: (I) Washing the Whole stillage to create oil-laden Wash Water; and (2) recov ering oil from the Wash Water. The Washing step may further include separating the Whole stillage into at least thin stillage and distillers Wet grains, as Well as possibly oil. The method may further include the step of concentrating the thin stillage and recovering oil from the concentrated thin stillage. Still further, the method may include the step of combining the Wash Water With the thin stillage before the concentrating step.

In one embodiment, the recovering step comprises sepa rating the oil from the concentrate using a disk stack centri fuge. The method may further include the step of drying the concentrate after the removing step.

In accordance With still another aspect of the invention, a method of recovering oil from thin stillage is disclosed. The method comprises evaporating the thin stillage to create a concentrate having a moisture content of greater than 15% by