The present invention relates to the treatment of biomass to be used in the production of ethanol.
Ethanol can be produced from grain-based feedstocks (e.g., corn, sorghum/milo, barley, wheat, soybeans, etc.), from sugar (e.g., from sugar cane, sugar beets, etc.), and from biomass (e.g., from lignocellulosic feedstocks such as switchgrass, corn cobs and stover, wood or other plant material).
Biomass comprises plant matter that can be suitable for direct use as a fuel/energy source or as a feedstock for processing into another bioproduct (e.g., a biofuel such as cellulosic ethanol) produced at a biorefinery such as an ethanol plant. Biomass may comprise, for example, corn cobs and stover (e.g., stalks and leaves) made available during or after harvesting of the corn kernels, fiber from the corn kernel, switchgrass, farm or agricultural residue, wood chips or other wood waste, and other plant matter. In order to be used or processed, biomass will be harvested and collected from the field and transported to the location where it is to be used or processed.
In a conventional ethanol plant producing ethanol from corn, ethanol is produced from starch. Corn kernels are cleaned and milled to prepare starch-containing material for processing. Corn kernels may also be fractionated to separate the starch-containing material (e.g., endosperm) from other matter (e.g., fiber and germ). The starch-containing material is slurried with water and is liquefied to facilitate saccharification where the starch is converted into sugar (e.g., glucose) and fermentation where the sugar is converted by an ethanologen (e.g., yeast) into ethanol. The product of fermentation is beer, which comprises a liquid component containing ethanol, water, and soluble components, and a solids component containing unfermented particulate matter among other things. The fermentation product is sent to a distillation system where it is distilled and dehydrated to yield ethanol. The residual matter (e.g., whole stillage) comprises water, soluble components, oil and unfermented solids (i.e., the solids component of the beer with substantially all ethanol removed that can be dried into dried distillers grains (DDG) and sold as an animal feed product). Other co-products, for example syrup (and oil contained in the syrup), can also be recovered from the stillage. Water removed from the fermentation product in distillation can be treated for re-use at the plant.
In a biorefinery configured to produce ethanol from biomass, ethanol is produced from lignocellulosic material. Lignocellulosic biomass typically comprises cellulose, hemicellulose, and lignin. Cellulose (a type of glucan) is a polysaccharide comprising hexose (C6) sugar monomers such as glucose linked in linear chains. Hemicellulose is a branched chain polysaccharide that may comprise several different pentose (C5) sugar monomers (e.g., xylose and arabinose) and small amounts of hexose (C6) sugar monomers (e.g., mannose, galactose, rhamnose and glucose) in branched chains.
In a typical cellulosic process, the biomass is prepared so that sugars in the lignocellulosic material (e.g., glucose from the cellulose, and xylose from the hemicellulose) can be made accessible and fermented into a fermentation product containing ethanol. After fermentation, the fermentation product is distilled and dehydrated to yield ethanol.
In the preparation of the biomass for fermentation, the biomass is typically pretreated, for example, using an acid such as sulfuric acid. In order to achieve high ethanol concentration from the fermentation of acid-pretreated biomass (e.g., corn cobs), the C6 sugar-containing stream of the pretreated biomass is ideally fed into an enzyme hydrolysis reaction (i.e., a saccharification reaction) at a high solids loading. However, mixtures of acid-pretreated biomass (e.g., corn cobs) above about 10% solids are typically viscous and difficult to process in a traditional stirred tank reactor. As a result, it is typical for the enzymatic hydrolysis reaction to be carried out in either a fed batch mode or at a low solid loading. This lowers the efficiency of the process, however, and results in a lower concentration (i.e., a lower titer) of ethanol in the resulting fermentation product.
In view of the above, it would be advantageous to provide a system that provides one or more features to facilitate improvement in the efficiency and yield of ethanol from biomass.
In one aspect, the invention relates to a biorefinery for producing a fermentation product from biomass comprising: (a) a system for preparing the biomass into prepared biomass; (b) a system for pre-treating the biomass into pre-treated biomass; (c) a separator for separating the pre-treated biomass into a first component comprising glucan and a second component comprising xylose; (d) a first treatment system for liquefying the first component by application of a first enzyme formulation into a liquefied first component; (e) a second treatment system for treating the liquefied first component into a treated first component by application of a second enzyme formulation so that glucose is made available; (f) a fermentation system configured to produce the fermentation product from the treated first component; wherein the fermentation product is produced by fermentation of glucose into ethanol; wherein the biomass comprises lignocellulosic material; wherein the lignocellulosic material comprises at least one of corn cobs, corn plant husks, corn plant leaves and corn plant stalks; and wherein the first enzyme formulation comprises a cellulase enzyme mixture.
In another aspect, the invention relates to a method for producing a fermentation product from biomass comprising: (a) preparing the biomass into prepared biomass; (b) pre-treating the biomass into pre-treated biomass; (c) separating the pre-treated biomass into a first component comprising glucan and a second component; (d) treating the first component by application of a first enzyme formulation into a liquefied first component; (e) treating the liquefied first component by application of a second enzyme formulation so that glucose is made available; (f) supplying an ethanologen to the treated first component so that the glucose can be converted to ethanol; wherein the first enzyme formulation comprises a cellulase enzyme mixture; wherein the biomass comprises lignocellulosic material; and wherein the lignocellulosic material comprises at least one of corn cobs, corn plant husks, corn plant leaves and corn plant stalks.
In an exemplary embodiment, the process features the use of a continuous stirred tank reactor (CSTR) to continuously liquefy the first component (i.e., the C6 stream comprising glucan) by enzymatic action. The liquefaction results in a reduction in viscosity of the C6 slurry thereby allowing it to be readily handled (e.g., pumped) at a higher solids loading in the downstream processes (e.g., enzyme hydrolysis and fermentation). The use of a higher solids loading enables the production of ethanol at a higher concentration from the process.
In a further aspect, the invention relates to a continuous process for making ethanol from biomass, the process comprising the steps of: (a) providing a continuous stirred tank reactor (CSTR) with an outlet stream that is in fluid communication with two or more batch reactors; (b) pre-treating the biomass into pre-treated biomass; (c) separating the pre-treated biomass into a C6 solid comprising glucan and a second component; (d) continuously feeding the C6 solid into the CSTR and treating the C6 solid with a first enzyme formulation in order to liquefy the C6 solid into a C6 slurry; (e) continuously feeding the C6 slurry from the CSTR into one or more of the batch reactors; wherein the C6 slurry is treated in the one or more batch reactors with a second enzyme formulation so that glucose is made available; and (f) fermenting the glucose to form a fermentation product comprising ethanol; wherein the biomass comprises lignocellulosic material selected from corn cobs, corn plant husks, corn plant leaves, corn plant stalks, and mixtures thereof; and wherein the first enzyme formulation comprises a cellulase enzyme mixture.
The embodiments as disclosed and described in the application (including the FIGURES and Examples) are intended to be illustrative and explanatory of the present inventions. Modifications and variations of the disclosed embodiments, for example, of the apparatus and processes employed (or to be employed) as well as of the compositions and treatments used (or to be used), are possible; all such modifications and variations are intended to be within the scope of the present inventions.
The word “exemplary” is used to mean serving as an example, instance, or illustration. Any embodiment or design described as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments or designs, nor is it meant to preclude equivalent exemplary structures and techniques known to those of ordinary skill in the art. Rather, use of the word exemplary is intended to present concepts in a concrete fashion, and the disclosed subject matter is not limited by such examples.
The term “or” is intended to mean an inclusive “or” rather than an exclusive “or.” To the extent that the terms “comprises,” “has,” “contains,” and other similar words are used in either the detailed description or the claims, for the avoidance of doubt, such terms are intended to be inclusive in a manner similar to the term “comprising” as an open transition word without precluding any additional or other elements.
Referring to
As shown in
As shown in
A biomass preparation system may comprise apparatus for receipt/unloading of the biomass, cleaning (i.e. removal of foreign matter), grinding (i.e. milling, reduction or densification), and transport and conveyance for processing at the plant. According to an exemplary embodiment, biomass in the form of corn cobs and stover may be delivered to the biorefinery and stored (e.g., in bales, piles or bins, etc.) and managed for use at the facility. According to an embodiment, the biomass may comprise at least about 20% to about 30% corn cobs (by weight) with corn stover and other matter. According to other exemplary embodiments, the preparation system of the biorefinery may be configured to prepare any of a wide variety of types of biomass (i.e. plant material) for treatment and processing into ethanol and other bioproducts at the plant.
In some embodiments, the biomass comprises plant material from the corn plant, such as corn cobs, husks and leaves and stalks (e.g., at least upper half or three-quarters portion of the stalk). In some embodiments, the composition of the plant material (i.e., cellulose, hemicellulose, and lignin) will be approximately as shown in TABLES 1A and 1B (i.e., after at least initial preparation of the biomass, including removal of any foreign matter). According to some embodiments, the plant material comprises corn cobs, husks/leaves and stalks; for example, the plant material may comprise up to 100% by weight cobs, up to 100% by weight husks/leaves, about 50% cobs and about 50% husks/leaves, about 30% cobs and about 50% husks/leaves and about 20% stalks. Any of a wide variety of other combinations of cobs, husks/leaves and stalks from the corn plant may also be useful. According to other embodiments, the lignocellulosic plant material may comprise fiber from the corn kernel (e.g., in some combination with other plant material). TABLE 1B provides ranges believed to be representative of the composition of biomass comprising lignocellulosic material from the corn plant. According to some embodiments, the lignocellulosic plant material of the biomass (from the corn plant) will comprise cellulose at about 30% to about 55% by weight, hemicellulose at about 20% to about 50% by weight, and lignin at about 10% to about 25% by weight. According to an exemplary embodiment, the lignocellulosic plant material of the biomass (i.e., cobs, husks/leaves and stalk portions from the corn plant) will comprise cellulose at about 35% to about 45% by weight, hemicellulose at about 24% to about 42% by weight, and lignin at about 12% to about 20% by weight.
Referring to
As shown in
Referring now to
According to an embodiment, in the pre-treatment system 404 an acid will be applied to the prepared biomass to facilitate the breakdown of the biomass for separation into the liquid component (i.e., the C5 stream from which fermentable C5 sugars can be recovered) and the solids component (i.e., the C6 stream from which fermentable C6 sugars can be accessed). According to an embodiment, the acid can be applied to the biomass in a reaction vessel under determined operating conditions (e.g., acid concentration, pH, temperature, time, pressure, solids loading, flow rate, supply of process water or steam, etc.), and the biomass can be agitated/mixed in the reaction vessel to facilitate the breakdown of the biomass. Useful acids include, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, and the like, or mixtures thereof. According to an exemplary embodiment, sulfuric acid is applied to the biomass in the pre-treatment system.
During pre-treatment, the severity of operating conditions (e.g., pH, temperature, and time) may cause formation of components that may be inhibitory to fermentation. For example, under some conditions, the dehydration of C5 sugars (e.g., xylose or arabinose) may cause the formation of furfural. Acetic acid may also be formed, for example, when acetate is released during the break down of hemicellulose in pre-treatment. Sulfuric acid, which may be added to prepared biomass to facilitate pre-treatment, may also be inhibitory to fermentation if not removed or neutralized. According to an exemplary embodiment, by adjusting pre-treatment conditions (e.g., pH, temperature, and time), the formation of inhibitors can be reduced or managed. According to some embodiments, components of the pre-treated biomass may be given further treatment to remove or reduce the level of inhibitors or other undesirable matter.
After pretreatment, the pre-treated biomass can then be separated into a liquid component (i.e., a C5 stream) and a solids component (i.e., a C6 stream) using a separation device such as a centrifuge (e.g., a decanter centrifuge, or basket centrifuge), screw press, or other type of solid-liquid separator.
After separation, the liquid component (i.e., the C5 stream) typically comprises water, dissolved sugars (e.g., xylose, arabinose, and glucose) for fermentation into ethanol, acids, and other soluble components recovered from the hemicellulose. TABLE 2B provides ranges believed to be representative of the composition of biomass comprising lignocellulosic material from the corn plant. According to some embodiments of the invention, the liquid component may comprise about 5% to about 7% solids by weight (i.e., suspended/residual solids such as partially-hydrolyzed hemicellulose, cellulose and lignin). According to other embodiments, the liquid component may comprise about 2% to about 4% xylose by weight. According to yet other embodiments, the liquid component may comprise no less than about 1% to about 2% xylose by weight. TABLES 2A and 2B list the composition of the liquid component of pre-treated biomass (prepared from the biomass as indicated in TABLES 1A and 1B). According to an exemplary embodiment, pre-treatment of the biomass will yield a liquid component that comprises xylose at no less than about 1.0% by weight and a solids component that comprises cellulose (from which glucose can be made available) at no less than about 45% by weight.
After separation, the solids component (i.e., the C6 stream) typically comprises water, acids, and solids (e.g., cellulose which is a source of glucose), and lignin. TABLE 3B provides ranges believed to be representative of the composition of biomass comprising lignocellulosic material from the corn plant. According to some embodiments of the invention, the solids component may comprise about 10% to about 40% solids by weight after separation. According to other embodiments of the invention, the solids component will comprise about 20% to about 30% solids by weight. According to yet other embodiments, the solids in the solids component comprise no less than about 30% by weight cellulose, and the solids component may further comprise other dissolved sugars such as glucose and xylose. TABLES 3A and 3B list the composition of the solids component of pre-treated biomass prepared from the biomass as indicated in TABLES 1A and 1B.
Referring now to
Referring now to
According to an embodiment as shown in
In some embodiments, the C5 stream (liquid component) is treated to remove components that are inhibitory to efficient fermentation (e.g., furfural, HMF, sulfuric acid and acetic acid) and to remove residual lignin or other matter that may not be fermentable. The C5 sugars in the C5 stream may also be concentrated to improve the efficiency of fermentation (e.g., to improve the titer of ethanol for distillation).
Treatment of the C6 stream (solids component) of the biomass may be performed to make the C6 sugars available for fermentation. As discussed further herein, the C6 stream may also be treated in order to liquefy (i.e., reduce the viscosity) of the C6 stream so that it can be more readily handled (e.g., pumped) in the downstream process. The C6 stream may also be treated by enzyme hydrolysis to access the C6 sugars in the cellulose. Treatment may also be performed in an effort to remove lignin and other non-fermentable components in the C6 stream or to remove components such as residual acid or acids that may be inhibitory to efficient fermentation.
In the fermentation system, a suitable fermenting organism (i.e., an ethanologen) is typically used. The selection of an ethanologen may be based on various considerations including, for example, the predominant types of sugars present in the slurry. Dehydration and/or denaturing of the ethanol produced from the C5 stream and the C6 stream may be performed either separately or in combination.
Referring now to
As shown in
In some embodiments, as shown in
Referring now to
Typically, the continuous enzyme liquefaction process is conducted at a solids loading ranging from about 10% to about 30% solids dry weight; more typically ranging from about 10% to about 25% solids dry weight; and most typically about 13% to about 17% solids dry weight.
With respect to enzyme loading (e.g., using Cellic CTEC2 enzyme), a typical range is about 2 to about 20 mg of enzyme protein per gram of glucan, more typically ranging from about 3 to about 9 mg of enzyme protein per gram of glucan, and most typically ranging from about 4 to about 6 mg of enzyme protein per gram of glucan.
With respect to pH, continuous enzymatic liquefaction is typically conducted at an acidic pH. A typical pH range is from about 4.0 to about 6.0, more typically from about 4.5 to about 6.0, and most typically about 5.0 to about 6.0.
Continuous enzymatic liquefaction is typically conducted at a temperature ranging from about 30° C. to about 60° C., more typically ranging from about 45° C. to about 55° C., and most typically ranging from about 49° C. to about 51° C.
The residence time for continuous enzyme liquefaction in the CSTR typically ranges from about 1 hour to about 30 hours, more typically ranging from about 4 hours to about 16 hours, and most typically ranging from about 8 to about 12 hours.
The invention will now be further described with reference to the following non-limiting examples.
A sample of solids component (C6 stream) was prepared as a slurry comprising a solids loading of about 15% with about 57% glucan (by dry weight of the solids). The sample was treated in a continuously stirred tank reactor (CSTR) under operating conditions as indicated in TABLE 4. The pH of the sample was adjusted to about pH 5.7. An enzyme formulation was added to the sample at a concentration of about 6 mg of enzyme protein per gram of glucan. (The enzyme formulation comprised a cellulase enzyme available under the trade name Celtic CTEC2 from Novozymes North America.) Treatment of the sample by liquefaction through the application of the enzyme formulation was performed at a temperature of about 50° C. with a retention time of about 10 hours. The sample/slurry after liquefaction (i.e. liquefied solids component) was supplied to the fermentation system for combined enzyme hydrolysis/fermentation into ethanol. It was observed that the viscosity of the sample (slurry) could be reduced by treatment (liquefaction) as to facilitate effective operation at a solids loading of about 15%. It was also observed that treatment and fermentation of samples could be performed continuously for a period of about 35 days at a solids loading of about 15%. It was further observed that liquefaction increased the glucose concentration into the solids component from about 1% to about 2%.
This application is a U.S. national stage filing of Patent Cooperation Treaty (PCT) application serial number PCT/US11/29047 entitled “SYSTEM FOR TREATMENT OF BIOMASS” filed on Mar. 18, 2011, which claims the benefit of U.S. Provisional Application Ser. No. 61/315,830, entitled “SYSTEM FOR TREATMENT OF BIOMASS”, filed on Mar. 19, 2010. The entireties of the aforementioned applications are herein incorporated by reference.
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/US2011/029047 | 3/18/2011 | WO | 00 | 9/28/2012 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2011/116317 | 9/22/2011 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
3212932 | Hess et al. | Oct 1965 | A |
4014743 | Black | Mar 1977 | A |
4029515 | Kiminki et al. | Jun 1977 | A |
4152197 | Lindahl et al. | May 1979 | A |
4168988 | Riehm et al. | Sep 1979 | A |
4342831 | Faber et al. | Aug 1982 | A |
4425433 | Neves | Jan 1984 | A |
4427453 | Reitter | Jan 1984 | A |
4432805 | Nuuttila et al. | Feb 1984 | A |
4461648 | Foody | Jul 1984 | A |
4529699 | Gerez et al. | Jul 1985 | A |
4552616 | Kauppi | Nov 1985 | A |
4612286 | Sherman et al. | Sep 1986 | A |
4668340 | Sherman | May 1987 | A |
4752579 | Arena et al. | Jun 1988 | A |
4908098 | DeLong et al. | Mar 1990 | A |
4941944 | Chang | Jul 1990 | A |
4997488 | Gould et al. | Mar 1991 | A |
5125977 | Grohmann et al. | Jun 1992 | A |
5171592 | Holtzapple et al. | Dec 1992 | A |
5221357 | Brink | Jun 1993 | A |
5328562 | Rafferty et al. | Jul 1994 | A |
5338366 | Grace et al. | Aug 1994 | A |
5366558 | Brink | Nov 1994 | A |
5370999 | Stuart | Dec 1994 | A |
5411594 | Brelsford | May 1995 | A |
5424417 | Torget et al. | Jun 1995 | A |
5498766 | Stuart et al. | Mar 1996 | A |
5536325 | Brink | Jul 1996 | A |
5562777 | Farone et al. | Oct 1996 | A |
5580389 | Farone et al. | Dec 1996 | A |
5597714 | Farone et al. | Jan 1997 | A |
5628830 | Brink | May 1997 | A |
5693296 | Holtzapple et al. | Dec 1997 | A |
5705369 | Torget et al. | Jan 1998 | A |
5711817 | Titmas | Jan 1998 | A |
5726046 | Farone et al. | Mar 1998 | A |
5733758 | Nguyen | Mar 1998 | A |
5769934 | Ha et al. | Jun 1998 | A |
5782982 | Farone et al. | Jul 1998 | A |
5820687 | Farone et al. | Oct 1998 | A |
5865898 | Holtzapple et al. | Feb 1999 | A |
5879463 | Proenca | Mar 1999 | A |
5916780 | Foody et al. | Jun 1999 | A |
5932452 | Mustranta et al. | Aug 1999 | A |
5932456 | Van Draanen et al. | Aug 1999 | A |
5972118 | Hester et al. | Oct 1999 | A |
5975439 | Chieffalo et al. | Nov 1999 | A |
6022419 | Torget et al. | Feb 2000 | A |
6090595 | Foody et al. | Jul 2000 | A |
6228177 | Torget | May 2001 | B1 |
6379504 | Miele et al. | Apr 2002 | B1 |
6419788 | Wingerson | Jul 2002 | B1 |
6423145 | Nguyen et al. | Jul 2002 | B1 |
6555350 | Ahring et al. | Apr 2003 | B2 |
6620292 | Wingerson | Sep 2003 | B2 |
6660506 | Nguyen et al. | Dec 2003 | B2 |
6692578 | Schmidt et al. | Feb 2004 | B2 |
6770168 | Stigsson | Aug 2004 | B1 |
7198925 | Foody | Apr 2007 | B2 |
7238242 | Pinatti et al. | Jul 2007 | B2 |
7354743 | Vlasenko et al. | Apr 2008 | B2 |
7455997 | Hughes | Nov 2008 | B2 |
7501025 | Bakker et al. | Mar 2009 | B2 |
7503981 | Wyman et al. | Mar 2009 | B2 |
7585652 | Foody et al. | Sep 2009 | B2 |
7604967 | Yang et al. | Oct 2009 | B2 |
7649086 | Belanger et al. | Jan 2010 | B2 |
7666637 | Nguyen | Feb 2010 | B2 |
7670813 | Foody et al. | Mar 2010 | B2 |
7709042 | Foody et al. | May 2010 | B2 |
7754456 | Penttila et al. | Jul 2010 | B2 |
7754457 | Foody et al. | Jul 2010 | B2 |
7807419 | Hennessey et al. | Oct 2010 | B2 |
7815741 | Olson | Oct 2010 | B2 |
7815876 | Olson | Oct 2010 | B2 |
7819976 | Friend et al. | Oct 2010 | B2 |
7875444 | Yang et al. | Jan 2011 | B2 |
7901511 | Griffin et al. | Mar 2011 | B2 |
8057639 | Pschorn et al. | Nov 2011 | B2 |
8057641 | Bartek et al. | Nov 2011 | B2 |
8110383 | Jönsson et al. | Feb 2012 | B2 |
8123864 | Christensen et al. | Feb 2012 | B2 |
8288600 | Bartek et al. | Oct 2012 | B2 |
8449728 | Redford | May 2013 | B2 |
8597431 | McDonald et al. | Dec 2013 | B2 |
8815552 | Narendranath et al. | Aug 2014 | B2 |
9139857 | Retsina et al. | Sep 2015 | B2 |
10174351 | Smits et al. | Jan 2019 | B2 |
20020192774 | Ahring et al. | Dec 2002 | A1 |
20040060673 | Phillips et al. | Apr 2004 | A1 |
20040252580 | Nagy et al. | Dec 2004 | A1 |
20050069998 | Ballesteros Perdices et al. | Mar 2005 | A1 |
20060188965 | Wyman et al. | Aug 2006 | A1 |
20060281157 | Chotani et al. | Dec 2006 | A1 |
20080026431 | Saito et al. | Jan 2008 | A1 |
20080057555 | Nguyen | Mar 2008 | A1 |
20080277082 | Pschorn et al. | Nov 2008 | A1 |
20080295981 | Shin et al. | Dec 2008 | A1 |
20090035826 | Tolan et al. | Feb 2009 | A1 |
20090042259 | Dale et al. | Feb 2009 | A1 |
20090098616 | Burke et al. | Apr 2009 | A1 |
20090308383 | Shin et al. | Dec 2009 | A1 |
20100003733 | Foody et al. | Jan 2010 | A1 |
20100144001 | Horton | Jun 2010 | A1 |
20100233771 | McDonald et al. | Sep 2010 | A1 |
20100285553 | Delmas et al. | Nov 2010 | A1 |
20110011391 | Burke | Jan 2011 | A1 |
20110079219 | McDonald et al. | Apr 2011 | A1 |
20110094505 | Bulla et al. | Apr 2011 | A1 |
20110171708 | Larsen | Jul 2011 | A1 |
20120027027 | Yamaura et al. | Feb 2012 | A1 |
20120129234 | McDonald et al. | May 2012 | A1 |
20120138246 | Christensen et al. | Jun 2012 | A1 |
20120201947 | Stuart | Aug 2012 | A1 |
20130143290 | Narendranath | Jun 2013 | A1 |
20130164804 | Walther et al. | Jun 2013 | A1 |
20130337521 | Carlson et al. | Dec 2013 | A1 |
20140024826 | Narendranath et al. | Jan 2014 | A1 |
20140209092 | McDonald et al. | Jul 2014 | A1 |
20140234911 | Narendranath et al. | Aug 2014 | A1 |
20150128932 | Kwiatkowski et al. | May 2015 | A1 |
Number | Date | Country |
---|---|---|
0 044 658 | Jan 1982 | EP |
0 098 490 | Jan 1984 | EP |
0 159 795 | Oct 1985 | EP |
0 884 391 | Dec 1998 | EP |
1 259 466 | Nov 2002 | EP |
1 130 085 | Oct 2005 | EP |
2 397 486 | Feb 1979 | FR |
2 609 046 | Jul 1988 | FR |
WO 9408027 | Apr 1994 | WO |
WO 9429475 | Dec 1994 | WO |
WO 9508648 | Mar 1995 | WO |
WO 9814270 | Apr 1998 | WO |
WO 9856958 | Dec 1998 | WO |
WO 9906133 | Feb 1999 | WO |
WO 0014120 | Mar 2000 | WO |
WO 0061858 | Oct 2000 | WO |
WO 00073221 | Dec 2000 | WO |
WO 0132715 | May 2001 | WO |
WO 0160752 | Aug 2001 | WO |
WO 0214598 | Feb 2002 | WO |
WO 0224882 | Mar 2002 | WO |
WO 0238786 | May 2002 | WO |
WO 02051561 | Jul 2002 | WO |
WO 02067691 | Sep 2002 | WO |
WO 02070753 | Sep 2002 | WO |
WO 03013714 | Feb 2003 | WO |
WO 03071025 | Aug 2003 | WO |
WO 03078644 | Sep 2003 | WO |
WO 2004081193 | Sep 2004 | WO |
WO 2005099854 | Oct 2005 | WO |
2005118828 | Dec 2005 | WO |
WO2005118828 | Dec 2005 | WO |
WO 2006032282 | Mar 2006 | WO |
WO 2006034590 | Apr 2006 | WO |
WO 2006056838 | Jun 2006 | WO |
WO2006101832 | Sep 2006 | WO |
WO 2007009463 | Jan 2007 | WO |
WO 2008095098 | Aug 2008 | WO |
WO 2008131229 | Oct 2008 | WO |
WO 2009003167 | Dec 2008 | WO |
WO 2009045651 | Apr 2009 | WO |
2009090480 | Jul 2009 | WO |
2009095781 | Aug 2009 | WO |
WO 2009108773 | Sep 2009 | WO |
WO 2010071805 | Jun 2010 | WO |
WO 2010113129 | Oct 2010 | WO |
WO 2010113130 | Oct 2010 | WO |
WO 2011061400 | May 2011 | WO |
WO 2011116317 | Sep 2011 | WO |
WO 2011159915 | Dec 2011 | WO |
2012027843 | Mar 2012 | WO |
WO 2012042497 | Apr 2012 | WO |
WO 2012042498 | Apr 2012 | WO |
WO 2012103281 | Aug 2012 | WO |
WO 2012131665 | Oct 2012 | WO |
Entry |
---|
Marchal et al. Large-scale enzymatic hydrolysis of agricultural lignocellulosic biomass. Part 2: conversion into acetone-butanol. Bioresource Technology. 1992;42:205-217. |
Larsen et al. The IBUS process—lignocellulosic bioethanol close to a commercial reality. Chem. Eng. Technol. 2008;31(5):765-772. |
Sun et al. Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresource Technology. 2002;83:1-11. |
Haagensen et al. Enzymatic hydrolysis and glucose fermentation of wet oxidized sugarcane bagasse and rice straw for bioethanol production. Riso-R-1517 (EN). 2002;1:184-195. |
Blunk et al. Combustion properties of lignin residue from lignocellulose fermentation. National Renewable Energy Laboratory. 2000;1-15. |
Aden et al. Lignocellulosic Biomass to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and . NREL. 2002;1-154. |
Enzyme. Enzyme: 3.2.1.91. KEGG. 2005;1-6. |
International Search Report and Written Opinion for International Application No. PCT/US2011/029047 dated Jul. 18, 2011, 12 pages. |
Marchal, et al., “Large-scale enzymatic hydrolysis of agricultural lignocellulosic biomass: Part 2. Conversion into acetone-butanol”. Bioresource Technology, Elsevier BV, GB, vol. 42, No. 3, Jan. 1, 1992, pp. 205-217, XP002596773, ISSN: 0960-8524, p. 206, col. 1, figure 1, 14 pages. |
Larsen, et al., “The IBUS Process—Lignocellulosic Bioethanol Close to a Commercial Reality”. Chemical Engineering and Technology, Weinheim, DE, vol. 21, No. 5, Apr. 22, 2008, pp. 765-772, XP002517673, ISSN: 0930-7516, DOI:10.1002/CEAT.200800048, 8 pages. |
Sun, et al., “Hydrolysis of lingnocellulosic materials for ethanol production: a review”, Bioresource Technology, Elsevier BV, GB, vol. 83, Jan. 1, 2002, pp. 1-11, XP002988039, ISSN: 0960-8524, DOI: DOI10.1016/S0960-8524(01)00212-7, 11 pages. |
Reith, J.H. et al. “Co-Production of Bio-Ethanol, Electricity and Heat From Biomass Residues”, Contribution to the 12th European Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection, Jun. 17-21, 2002, Amsterdam, the Netherlands, pp. 1-22. |
Taherzadeh, M.J. et al. “Enzyme-Based Hydrolysis Processes for Ethanol From Lignocellulosic Materials: A Review”, BioResources 2(4), 2007, pp. 707-738. |
Thomsen, M.H. et al., “Preliminary Results on Optimization of Pilot Scale Pretreatment of Wheat Straw Used on Coproduction of Bioethanol and Electricity”, Applied Biochemistry and Biotechnology, vol. 129-132, 2006, p. 448. |
Varga, E., et al., “High Solid Simultaneous Saccharification and Fermentation of Wet Oxidized Corn Stover to Ethanol”, Biotechnol. Bioeng. 88(5), 2004, Abstract. |
Adney, B. et al., “Measurement of Cellulase Activities”, Technical Report NREL/TP-510-42628 (2008) Cover; p. 1-8. |
Caparros, S. et al., “Xylooligosaccharides Production from Arundo donax”, J. Agric. Food Chem. 55 (2007): p. 5536-5543. |
Cort, J. et al., “Minimize Scale-Up Risk”, www.aiche.org/cep, (2010): p. 39-49. |
Demain, A.L. et al., “Cellulase, Clostridia, and Ethanol”, Microbiology and Molecular Biology Reviews 69(1) (2005): p. 124-154. |
Dien, B.S. et al., “Enzyme characterization for hydrolysis of AFEX and liquid hot-water pretreated distillers' grains and their conversion to ethanol”, Bioresource Technology 99 (2008): p. 5216-5225. |
Gibbons, W.R. et al., “Fuel Ethanol and High Protein Feed from Corn and Corn-Whey Mixtures in a Farm-Scale Plant”, Biotechnology and Bioengineering XXV (1983): p. 2127-2148. |
Goodman, B. J., “FY 1988 Ethanol from Biomass Annual Report” (1989): p. 1-458. |
Grohmann, K. et al., “Optimization of Dilute Acid Pretreatment of Biomass”, Biotechnology and Bioengineering Symp. 15 (1985): p. 59-80. |
Grohmann, K. et al., “Dilute Acid Pretreatment of Biomass at High Solids Concentrations”, Biotechnology and Bioengineering Symp. 17 (1986): p. 135-151. |
Humbird, D. et al., “Process Design and Economics for Biochemical Conversion of Lignocellulosic Biomass to Ethanol: Dilute-Acid Pretreatment and Enzymatic Hydrolysis of Corn Stover”, National Renewable Energy Laboratory (2011): Covers with Introduction; p. 1-114. |
Jeoh, T. “Steam Explosion Pretreatment of Cotton Gin Waste for Fuel Ethanol Production”, Thesis submitted to Virginia Polytechnic Institute and State University (1998): Cover with Introduction; p. 1-138. |
Jorgensen, H. et al., “Enzymatic conversion of lignocellulose into fermentable sugars: challenges and opportunities”, Biofuels, Bioprod. Bioref. 1 (2001): p. 119-134. |
Kumar, R. et al., “Effect of Enzyme Supplementation at Moderate Cellulase Loadings on Initial Glucose and Xylose Release from Corn Stover Solids Pretreated by Leading Technologies”, Biotechnology and Bioengineering 102(2) (2009): p. 457-467. |
Lynd, L.R. et al. “Consolidated bioprocessing of cellulosic biomass: an update”, Current Opinion in Biotechnology 16 (2005): p. 577-583. |
Mosier, N. et al., “Features of promising technologies for pretreatment of lignocellulosic biomass”, Bioresource Technology 96 (2005): p. 673-686. |
McMillan, J.D. “Processes for Pretreating Lignocellulosic Biomass: A Review”, National Renewable Energy Laboratory (1992): Covers with Introduction; p. 1-44. |
Nandini, C. et al. “Carbohydrate composition of wheat, wheat bran, sorghum and bajra with good chapatti/roti (Indian flat bread) making quality”, Food Chemistry 73 (2001): p. 197-203. |
Sanchez, O.J. et al., “Trends in biotechnological production of fuel ethanol from different feedstocks”, Bioresource Technology 99 (2008): p. 5270-5295. |
Saska, M. et al., “Aqueous Extraction of Sugarcane Bagasse Hemicellulose and Production of Xylose Syrup”, Biotechnology and Bioengineering 45 (1995): p. 517-523. |
Sepulveda-Huerta, E. et al. “Production of detoxified sorghum straw hydrolysates for fermentative purposes”, Journal of the Science of Food and Agriculture 86 (2006): p. 2579-2586. |
Spindler, D. et al., “Evaluation of Pretreated Woody Crops for the Simultaneous Saccharification and Fermentation Process”, Ethanol from Biomass. FY 1988, Annual Report (1989): p. B33-B43. |
Taherzadeh, M.J. et al., “Acid-based Hydrolysis Processes for Ethanol from Lignocellulosic Materials: A Review”, BioResources 2(3) (2007): p. 472-499. |
Taherzadeh, M.J. et al., “Enzyme-based Hydrolysis Processes for Ethanol from Lignocellulosic Materials: A Review”, BioResources 2(4) (2007): p. 707-738. |
Texeira, R.H. et al., “Ethanol Annual Report FY 1990”, (1991): p. 1-346. |
Torget, R. et al., “Dilute Acid Pretreatment of Short Rotation Woody and Herbaceous Crops”, Applied Biochemistry and Biotechnology 24/25 (1990): p. 115-126. |
Torget, R. et al., “Initial Design of a Dilute Sulfuric Acid Pretreatment Process for Aspen Wood Chips”, Solar Energy Research Institute (1988): p. 89-104. |
Torget, R. et al., “Dilute Acid Pretreatment of Corn Cobs, Corn Stover, and Short-Rotation Crops”, FY 1990 Ethanol Annual Report (1991): p. 71-82. |
Weil, J. et al., “Pretreatment of Corn Fiber by Pressure Cooking in Water”, Applied Biochemistry and Biotechnology 73 (1998): p. 1-17. |
Wyman, Charles E., “What is (and is not) vital to advancing cellulosic ethanol”, Trends in Biotechnology 25(4) (2007): p. 153-157. |
Wyman, C.E. et al., “Coordinated development of leading biomass pretreatment technologies”, Bioresource Technology 96 (2005): p. 1959-1966. |
Yang, B. et al., “Pretreatment: the key to unlocking low-cost cellulosic ethanol”, Biofuels, Bioprod. Bioref. 2 (2008): p. 26-40. |
Zhang, Y-H.P. et al., “Outlook for cellulose improvement: Screening and selection strategies”, Biotechnology Advances 24 (2006): p. 452-481. |
Zhang, Y.P. et al., “Toward an Aggregated Understanding of Enzymatic Hydrolysis of Cellulose: Noncomplexed Cellulase Systems”, Biotechnology and Bioengineering 88(7) (2004): p. 797-824. |
U.S. Appl. No. 12/716,989, filed Mar. 2010, Kwiatkowski. |
U.S. Appl. No. 12/827,948, filed Jun. 2010, Bootsma et al. |
U.S. Appl. No. 13/209,170, filed Aug. 2011, Bly et al. |
U.S. Appl. No. 14/459,977, filed Aug. 2014, Bootsma. |
U.S. Appl. No. 14/465,177, filed Aug. 2014, Narendranath et al. |
Bura, R. et al., “Influence of Xylan on the Enzymatic Hydrolysis of Steam-Pretreated Corn Stover and Hybrid Poplar”, Biotechnol. Prog. 25(2) (2009): p. 315-322. |
Cara, C. et al., “Influence of solid loading on enzymatic hydrolysis of steam exploded or liquid hot water pretreated olive tree biomass”, Process Biochemistry 42 (2007): p. 1003-1009. |
Gao, D. et al., “Strategy for Identification of Novel Fungal and Bacterial Glycosyl Hydrolase Hybrid Mixtures that can Efficiently Saccharify Pretreated Lignocellulosic Biomass”, Bioenerg. Res. 3 (2010): p. 67-81. |
Guo, G.L. et al., “Characterization of enzymatic saccharification for acid-pretreated lignocellulosic materials with different lignin composition”, Enzyme and Microbial Technology 45 (2009): p. 80-87. |
Kumar, S. et al., “Recent Advances in Production of Bioethanol from Lignocellulosic Biomass”, Chem. Eng. Technol. 32(4) (2009): p. 517-526. |
Li, X.L. et al., “Two cellulases, CelA and Ce1C, from the polycentric anaerobic fungus Orpinomyces strain PC-2 contain N-terminal docking domains for a cellulose-hemicellulase complex”, Applied and Environmental Microbiology 63(12) (1997): p. 4721-4728. |
Olsson, L. et al., “Fermentation of lignocellulosic hydrolysates or ethanol production”, Enzyme Microb. Technol., 18 (1996): p. 312-331. |
Xiao, Z. et al., “Effects of Sugar Inhibition on Cellulases and β-Glucosidase During Enzymatic Hydrolysis of Softwood Substrates”, Applied Biochemistry and Biotechnology 113-116 (2004): p. 1115-1126. |
Communication pursuant to Article 94(3) EPC for European Application No. 11710394.5, dated Mar. 8, 2017 (5 pages). |
Number | Date | Country | |
---|---|---|---|
20130065289 A1 | Mar 2013 | US |
Number | Date | Country | |
---|---|---|---|
61315830 | Mar 2010 | US |