Field of the Invention
The present invention generally pertains to an integrated facility for the co-production of ethanol and biodiesel fuel. In particular, corn oil isolated from the whole stillage of a corn ethanol distillation process is utilized as a feedstock for a biodiesel plant, along with alcohol (e.g., methyl alcohol, ethyl alcohol, and mixtures thereof), operating within the same general facility as the corn ethanol plant. By-products of the biodiesel plant, such as liquid crude glycerol and gaseous or liquid alcohols, can be utilized in various parts of the ethanol plant thereby increasing the operating efficiency thereof.
Description of the Prior Art
Corn oil is a by-product of a corn ethanol production. The corn oil is generally carried through the fermentation and distillation portions of a corn ethanol plant into the whole stillage that is removed from the distillation system. The whole stillage is commonly separated into a thin stillage, which includes the corn oil, and a cake that can be dried to produce dried distillers grains with solubles (DDGS), which can be used as an animal feed. The thin stillage can be processed to remove moisture therefrom and form nutritive syrup that can also be used as an animal feed material. Alternatively, the corn oil may be extracted from the thin stillage and be made a saleable product.
The corn oil extracted from the thin stillage has many industrial uses, such as in soaps, paints, rustproofing materials, inks, textiles, and insecticides. Corn oil can also be used as a feedstock in the production of alternative fuels such as biodiesel and renewable diesel. Biodiesel refers to a vegetable oil- or animal fat-based diesel fuel comprising long-chain alkyl (methyl, ethyl, or propyl) esters. Biodiesel is generally not considered to be a full replacement of conventional petrodiesel for use in most diesel engines. Rather, it is generally blended with petrodiesel for use in the retail diesel fuel marketplace. Renewable diesel, on the other hand, is produced by hydrotreatment of corn oil, for example, resulting in a hydrocarbon fuel that is very similar to petroleum diesel in its chemical composition.
A number of reaction schemes exist for conversion of corn oil into renewable diesel. Hydrotreating is one such process in which the corn oil feedstock is reacted with hydrogen under elevated temperature and pressure to change the chemical composition of the feed-stock. In the case of renewable diesel, hydrogen is introduced to the feedstock in the presence of a catalyst convert the triglyceride molecules into paraffinic hydrocarbons. In addition to creating a fuel that is very similar to petrodiesel, this process creates other hydrocarbon by-products including lower hydrocarbon fuel gas compounds (e.g., methane, ethane, propane, and butane) and higher hydrocarbon naphtha.
Production of biodiesel usually involves using corn oil and alcohol as feedstocks to a biodiesel reactor where the corn oil first undergoes an acid esterification reaction whereby the free fatty acids are converted to an alkyl ester through the introduction of a strong acid (e.g., sulfuric acid). The triglycerides are then subjected to a base-catalyzed reaction in the presence of strong base (e.g., KOH) and the alcohol feedstock, in order to form alkyl esters. The ester reaction product is then separated from the glycerol fraction which also contained excess alcohol used in the transesterification reaction.
Generally, the corn oil and/or alcohol feedstocks are produced at a plant location remote from the biodiesel facility, thus requiring transport of these feedstocks via pipeline, railway tankers, or tanker trucks. This added transportation cost increases the overall expense in the manufacture of biodiesel and decreases its competitiveness with petrodiesel as an alternative fuel source.
The following references describe various types of ethanol and biodiesel production methods: U.S. Pat. Nos. 6,927,048, 7,608,729, 7,649,086, 8,152,867, 8,227,015, 8,454,802, US 2008/0176298, US2009/0017164, US2009/0311374, US2010/0021980, US2010/0028484, US2010/0178675, US2010/0260918, US2011/0126448, US2012/0051980, US2012/0064213, US2012/0301598, US2013/0032175, US2013/0102045, US2013/0130343, US2013/0164795,
WO2007/146971, WO2012036857, WO2012/125739, WO2012/145230, and WO2013033369.
The present invention overcomes many of the problems outlined above and provides improved processes and plant systems for the co-production of ethanol and biodiesel fuel in combined facilities having both an ethanol plant and a biodiesel plant, wherein the plants are located in close proximity allowing various products and by-products from each plant to be easily transferred to the other plant as desired to increase the efficiency of the overall, dual-plant facility.
In one aspect of the invention, an integrated process for the co-production of ethanol and biodiesel fuel comprises the steps of fermenting a corn feedstock to produce an ethanol-containing beer and distilling the ethanol-containing beer within distillation apparatus of an ethanol plant, thereby producing ethanol and a corn oil product. Thereafter, the corn oil product is directed from the ethanol plant to a proximal biodiesel fuel plant; the corn oil product and an alcohol are used as joint feedstocks in the diesel plant, where the corn oil product and alcohol are reacted to produce a biodiesel fuel and by-products comprising an alcohol, e.g., ethanol and/or methanol, and glycerol. These by-products, which generally is low in ester compound concentration, are then transferred back to the ethanol plant for use therein.
In one embodiment, the transferring step comprises the steps of initially condensing the gaseous alcohol by-product to generate a condensed liquid by-product. This liquid by-product is directed back to the ethanol plant for mixing with the ethanol-containing beer. Alternately, the gaseous alcohol by-product may be combined with the CO2-containing overhead from the beer prior to stripping of the CO2. Still further, this gaseous by-product may 92 be combined with a process steam overhead generated by an evaporation system used to recover the corn oil by-product.
In another aspect of the invention, the liquid crude glycerol generated as a by-product in the diesel fuel plant is directed back to the ethanol plant for post-fermentation mixing with the beer, and/or may be added to a concentrated thin stillage product, which is further processed to generate a syrup.
A still further aspect of the invention involves use of the bottoms of the biodiesel distillation apparatus of the diesel fuel plant. These bottoms, principally comprising high boiling components and unreacted mono-, di-, and triglycerides, can be added to the solids output from the ethanol plant (e.g., a cake), which are normally used to produce animal feeds.
The invention also provides integrated plants for the co-production of ethanol and biodiesel fuel corresponding to the foregoing method aspects of the invention. Thus, such a facility may include an ethanol plant comprising fermentation apparatus operable to produce an ethanol-containing beer from a corn feedstock and distillation apparatus operable to produce ethanol and a corn oil product from the ethanol-containing beer; and a biodiesel plant comprising a reactor assembly operably coupled with the ethanol plant apparatus to receive at least some of the corn oil product from the ethanol plant, and to react the corn oil product with alcohol to produce biodiesel fuel and outputs such as the gaseous and/or liquid by-product containing alcohol; the liquid crude glycerol; and/or the bottoms from a biodiesel distillation device. Transfer structure(s), typically standard interconnecting transfer pipes or lines, are provided to direct one or more of the biodiesel outputs from the biodiesel plant as desired to the ethanol plant for use therein, in some or all of the ethanol plant locations described previously.
It will be appreciated that the present invention maximizes the efficiencies of both the ethanol and diesel fuel plants forming a part of the overall production facilities contemplated by the invention. Thus, the principal products of the ethanol plant, namely ethanol and corn oil, need not be transported great distances thereby giving significant savings. Nor is there a need for commercial sourcing of the alcohol or corn oil needed for the biodiesel fuel plant.
Turning now to
Ethanol plant 12 may be configured in a conventional manner, with the starting bio-mass material undergoing initial processing and fermentation to produce an ethanol-containing “beer.” In the particular embodiment illustrated, the ethanol plant 12 utilizes a biomass material as the source of carbohydrates and sugars for the fermentation process. A plant or vegetable oil is an important by-product of the ethanol plant 12, inasmuch as this by-product forms the feedstock to the biodiesel plant 14, so that the biomass material should contain suitable amounts of plant oils. Exemplary biomass feed materials include corn, sorghum, and pearl millet. In the U.S., corn is the predominant feedstock for fuel ethanol production. Accordingly, the description set forth below is made with respect to corn and corn by-products. However, it should be understood that this description is exemplary only, and should not be taken as a limitation on the scope of the present invention.
The preparation and fermentation of corn feedstock within ethanol plant 12 may be carried out in any number of apparatus and according to any number of methods known to those skilled in the art, and thus need not be fully described herein. In any case, following fermentation, the resultant ethanol-containing beer may be stored within a beer well 16 while it awaits further processing. Typically, the beer comprises from about 10-20% by volume ethanol, more preferably about 15% by volume ethanol. The beer also contains from about 5-20% by weight solids, more preferably about 10% by weight solids.
The beer is fed to distillation apparatus 18 via stream 20 for separation and recovery of the ethanol contained therein. Distillation apparatus 18, which may comprise one or more distillation columns, produces an overhead stream 22 primarily comprising ethanol and some water (e.g., from about 80-99% by volume ethanol, preferably from about 90-98% by volume ethanol, and most preferably about 95% by volume ethanol), with the balance of the stream primarily including water. In order to be suitable for use as fuel-grade ethanol, the remaining water needs to be removed from overhead stream 22. This water separation may be accomplished by means of a dehydration unit 24, which can be equipped with molecular sieve technology to achieve this separation. In certain embodiments, the molecular sieve comprises an alumino silicate material. In certain embodiments, stream 22 is condensed so that a portion can be refluxed back to apparatus 18, however, this need not always be the case. In those embodiments in which stream 22 was previously condensed, the stream should be vaporized before it is passed to dehydration unit 24. This vaporization can be accomplished by one or more heat exchangers 26 feed with steam supplied via a plant distribution header. A substantially pure ethanol stream 28 (i.e., greater than 99% by volume ethanol, or approximately 200 proof) exits dehydration unit 24 and is stored in a storage vessel 30 to await further processing.
As illustrated in
The bottoms from distillation apparatus 18 comprise a whole stillage stream 36. Several products can be produced from whole stillage stream 36 including corn oil, a nutritive corn syrup, and dried distillers grains with solubles (DDGS). The whole stillage stream 36 may be separated by a centrifuge 38 into a thin stillage stream 40 and a cake stream 42. The thin stillage stream 40 generally comprises between about 5% to about 10% by weight solids, and more preferably about 7% by weight solids. The balance of the thin stillage comprises mainly water and corn oil. The thin stillage is concentrated within a multiple-effect evaporator 44. Steam from the steam distribution header is introduced into a first effect 46 in indirect heat exchange relationship with the thin stillage stream 40. Moisture is evaporated from the thin stillage and removed from first effect 46 as process steam stream 48. The concentrated stillage product is removed from first effect 46 via line 50 and a portion of the corn oil contained therein is separated as stream 52. The separation of the corn oil may be achieved through the use of a mechanical separation device (not shown), such as a decanter system (e.g., the TRICANTER from Flottweg Separation Technology, Germany), or a disc stack unit. The concentrated stillage product (minus the corn oil that was removed) is passed through a second effect 54 wherein steam from stream 48, through indirect heat exchange, causes a portion of the moisture contained within the concentrated stillage product to evaporate. This vapor is returned to distillation apparatus 18 via stream 56.
The stillage product now comprises a viscous syrup and is withdrawn from the second effect 54 via stream 58. Additional corn oil is removed from the viscous syrup in stream 58 by means of a secondary separation device (not shown), and this additional corn oil is directed via line 60 to stream 52. This forms a combined stream 62 which is directed to biodiesel plant 14 as a feedstock input thereto. The syrup having the oil removed therefrom is recovered as a product stream 64.
In an alternate embodiment of the present invention, the corn oil may be extracted prior to fermentation. For example, the corn oil may be extracted via pressing or solvent extraction prior to fermentation. In such case, the processing of the thin stillage occurs as mentioned above, with the exception of corn oil recovery.
The cake stream 42 from centrifuge 38 is conveyed toward drying apparatus 66 in which moisture is removed and DDGS produced. Drying apparatus 66 comprises one or more dryer drums 68 that are supplied by a hot air stream from a conventional fuel-fired heater (not shown).
The gaseous overhead from beer well 16 comprises carbon dioxide. This overhead is directed via line 70 to a CO2 scrubber 72 having a water inlet line 74. In scrubber 72, the CO2 is stripped and vented through vent line 76, and an underflow line 78 principally containing water, along with some alcohol (in certain embodiments, approximately 3% ethanol), is generated.
As previously described, there are two feedstock inputs to plant 14, namely alcohol feedstock 35 and corn oil stream 62. These feedstocks are directed to biodiesel reactor system 80 where the corn oil first undergoes an acid esterification reaction whereby the free fatty acids are converted to alkyl esters through the introduction of a strong acid (e.g., sulfuric acid) via line 82. The triglycerides are then subjected to base-catalyzed reaction in the presence of a strong base (e.g., KOH) and the alcohol feedstock 35, in order to form alkyl (methyl, ethyl and/or propyl) esters and glycerol. The ester reaction product is then directed to a wash/dry tank (not shown) forming a part of system 80, in which the esters are separated from the glycerol. In alternate embodiments, the washing and drying of the ester reaction product may be conducted within the same vessel where the transesterification reaction is conducted thereby reducing the capital costs associated with a separate wash/dry tank. The latter fraction, also containing excess alcohol used in the transesterification reactions, is directed via line 84 to a storage tank 86. In certain embodiments, the composition of the stream in line 84 comprises less than 10% esters by weight, preferably less than 7.5% esters by weight, more preferably less than 5% esters by weight, even more preferably less than 1% esters by weight, and most preferably the composition is substantially free of esters. The ester fraction is sent via line 88 to a biodiesel distillation column where the biodiesel final product is separated for use, and the distillation bottoms (principally comprising high boiling components and unreacted mono- and polyglycerides, e.g., di- and triglycerides) are sent via line 90 and are combined with the cake stream 42 prior to drying thereof In certain embodiments, the composition of the distillation bottoms in line 90 comprises less than 10% biodiesel product by weight, preferably less than 7.5% biodiesel product by weight, more preferably less than 5% biodiesel product by weight, even more preferably less than 1% biodiesel product by weight, and most preferably is substantially free of biodiesel product. In certain preferred embodiments, the biodiesel final product is a fuel comprised of mono-alkyl esters of long chain fatty acids, commonly designated B100, and meeting the requirements of ASTM D 6751, incorporated by reference herein.
A liquid fraction of the alcohol/glycerol mixture within storage tank 86 is directed via line 92 to beer well 16, as shown, where it is mixed, post-fermentation, with the ethanol-containing beer. The ethanol-containing beer within beer well 16 is sent subsequently to distillation apparatus 18. In certain embodiments, the composition of the stream in line 92 comprises less than 10% esters by weight, preferably less than 7.5% esters by weight, more preferably less than 5% esters by weight, even more preferably less than 1% esters by weight, and most preferably is substantially free of esters. In certain embodiments, the composition of the stream in line 92 is comprises glycerol as the predominant component. In other embodiments, the stream in line 92 comprises greater than 50% glycerol by weight, greater than 75% glycerol by weight, greater than 90% glycerol by weight, or greater than 95% glycerol by weight. In alternate embodiments, some or all of the contents of line 92 may be directed through line 94 to the concentrated stillage line 50 for mixing therein, prior to entering the second effect 54. In the effect 54, the alcohol is vaporized along with water, and this water/alcohol mixture is returned via stream 56 to distillation apparatus 18. The gaseous alcohol-containing overheads from reactor system 80 and tank 86 are directed through lines 96 and 97 to vent condenser 98. These alcohol-containing overheads may also comprise water vapor that is carried along with the alcohol. The resultant condensed alcohol liquid fraction from condenser 98 is then sent through line 100, and ultimately to beer well 16 for further processing in plant 12. In an alternative embodiment, some or all of the gaseous overheads in lines 96 and 97 are directed through a line 102 equipped with a blower 104 for mixing with the beer well overhead 70 prior to entrance into scrubber 72. In a still further alternate embodiment, some of all of the contents of line 102 may be directed via line 106 for mixture with the contents of stream 56 directed from evaporator 54 to distillation apparatus 18. In certain embodiments, the composition of the condensed liquid fraction in line 100 or the vapor stream carried in line 102 comprises less than 10% esters by weight, preferably less than 8% esters by weight, more preferably less than 5% esters by weight, even more preferably less than 1% esters by weight, and most preferably is substantially free of esters. In certain embodiments, the composition of the condensed liquid fraction in line 100 or the vapor stream carried in line 102 comprises one or more alcohol compounds (e.g., ethanol, methanol, or a combination thereof) as the predominant component(s). In other embodiments, the stream in line 100 or the vapor stream carried in line 102 comprises greater than 50% alcohol compounds by weight, greater than 75% alcohol compounds by weight, or greater than 90% alcohol compounds by weight.
In conventional biodiesel plants, the crude glycerol directed to tank 86 contains methanol produced in the biodiesel reaction, and this methanol must be separated before the glycerol is disposed of or used as a commercial product. This requires additional separation equipment, which represents a significant capital expense, and moreover the glycerol/methanol separation requires an energy input. In the present invention, however, use is made of the existing separation equipment present in the ethanol plant to further process the glycerol/methanol mixture, namely distillation apparatus 18, second effect 54, associated recovery lines 58, 60, and 62, overhead vent line 96, condenser 98, and recovery line 100. As such, capital equipment costs are reduced and very little additional energy is required.
In the
It is understood that the various integrations between biodiesel plant 14 and ethanol plant 12 described above may be carried out jointly, individually, or in any combination thereof, as the requirements of any given facility 10 dictate. However, use of the alcohol and corn oil outputs from the ethanol plant 12, coupled with the use of the biodiesel fuel plant by-products, is preferred and is believed to the give maximum efficiency advantages.
This application is a continuation in part of application Ser. No. 14/243,352, filed Apr. 2, 2014, which is a division of application Ser. No. 14/168,174, filed Jan. 30, 2014, now U.S. Pat. No. 8,722,924, and claims the benefit of provisional application Ser. No. 61/898,828, filed Nov. 1, 2013, and all of these applications are incorporated by reference herein in their entirety.
Number | Name | Date | Kind |
---|---|---|---|
5710030 | Anderson | Jan 1998 | A |
6355456 | Hallberg et al. | Mar 2002 | B1 |
6927048 | Verser et al. | Aug 2005 | B2 |
7263934 | Copeland et al. | Sep 2007 | B2 |
7297236 | Vander Griend | Nov 2007 | B1 |
7321052 | Miller et al. | Jan 2008 | B2 |
7524418 | Hirl | Apr 2009 | B2 |
7544495 | Wilkening et al. | Jun 2009 | B2 |
7572353 | Vander Griend | Aug 2009 | B1 |
7604743 | Hirl | Oct 2009 | B2 |
7608729 | Winsness et al. | Oct 2009 | B2 |
7649086 | Belanger et al. | Jan 2010 | B2 |
7857872 | Krasutsky et al. | Dec 2010 | B2 |
7867365 | Brown | Jan 2011 | B2 |
7927491 | Kotelko et al. | Apr 2011 | B2 |
7943791 | McNeff | May 2011 | B2 |
7989646 | Bakshi | Aug 2011 | B2 |
8123822 | Morgan | Feb 2012 | B2 |
8152867 | Dumenil | Apr 2012 | B2 |
8153850 | Hall et al. | Apr 2012 | B2 |
8168037 | Winsness | May 2012 | B2 |
8207362 | Morris | Jun 2012 | B2 |
8227015 | Bruinsma et al. | Jul 2012 | B2 |
8288138 | Birkmire et al. | Oct 2012 | B2 |
8354564 | Brown et al. | Jan 2013 | B2 |
8454802 | Redford | Jun 2013 | B2 |
8540880 | Shah et al. | Sep 2013 | B1 |
8540881 | Shah et al. | Sep 2013 | B1 |
8546627 | Gruber et al. | Oct 2013 | B2 |
8722924 | Overheul | May 2014 | B1 |
8840853 | Overheul | Sep 2014 | B1 |
20030019736 | Garman | Jan 2003 | A1 |
20070099278 | Aare | May 2007 | A1 |
20070117195 | Warner et al. | May 2007 | A1 |
20070260078 | Bhat et al. | Nov 2007 | A1 |
20080176298 | Randhava et al. | Jul 2008 | A1 |
20080229653 | Iversen et al. | Sep 2008 | A1 |
20080282606 | Plaza et al. | Nov 2008 | A1 |
20090017164 | Shisler et al. | Jan 2009 | A1 |
20090031615 | Joshi et al. | Feb 2009 | A1 |
20090126262 | Asthana et al. | May 2009 | A1 |
20090148920 | Schreck | Jun 2009 | A1 |
20090239185 | Deline et al. | Sep 2009 | A1 |
20090288988 | Mayeur et al. | Nov 2009 | A1 |
20090311374 | Beaver et al. | Dec 2009 | A1 |
20100021980 | McDonald et al. | Jan 2010 | A1 |
20100028484 | Kriesler et al. | Feb 2010 | A1 |
20100155296 | Aves et al. | Jun 2010 | A1 |
20100178675 | Lawton, Jr. et al. | Jul 2010 | A1 |
20100187818 | Bivins | Jul 2010 | A1 |
20100221804 | Veit et al. | Sep 2010 | A1 |
20100252346 | Khouw et al. | Oct 2010 | A1 |
20100260918 | Wang et al. | Oct 2010 | A1 |
20100317091 | Veit et al. | Dec 2010 | A1 |
20110035393 | Loescher | Feb 2011 | A1 |
20110062054 | Gao et al. | Mar 2011 | A1 |
20110126448 | Dumenil | Jun 2011 | A1 |
20110315541 | Xu | Dec 2011 | A1 |
20120048716 | Sonnek et al. | Mar 2012 | A1 |
20120051980 | Gallop et al. | Mar 2012 | A1 |
20120064213 | Lee | Mar 2012 | A1 |
20120142983 | Vermeiren et al. | Jun 2012 | A1 |
20120181161 | Mahler | Jul 2012 | A1 |
20120205324 | Cantrell et al. | Aug 2012 | A1 |
20120240452 | Erdoes, Jr. et al. | Sep 2012 | A1 |
20120279118 | Blasco Garcia | Nov 2012 | A1 |
20120294977 | Bruinsma et al. | Nov 2012 | A1 |
20120301598 | Karges et al. | Nov 2012 | A1 |
20130010987 | Abolfathi et al. | Jan 2013 | A1 |
20130032175 | Redford | Feb 2013 | A1 |
20130131343 | Purtle et al. | May 2013 | A1 |
20130164795 | Lowe et al. | Jun 2013 | A1 |
20130216688 | Bruinsma et al. | Aug 2013 | A1 |
20130309738 | Barr et al. | Nov 2013 | A1 |
Number | Date | Country |
---|---|---|
2007146971 | Dec 2007 | WO |
2010088748 | Aug 2010 | WO |
2011075671 | Jun 2011 | WO |
2012036857 | Mar 2012 | WO |
2012125739 | Sep 2012 | WO |
2012145230 | Oct 2012 | WO |
2013033369 | Mar 2013 | WO |
Entry |
---|
https://www.citylab.com/life/2015/07/power-your-car-with-a-biofuel-made-from-beer/397946/ John Metcalfe Jul. 8, 2015 Power your Car with a biofuel made from Beer. |
http://www.triplepundit.com/2009/02/make-biofuel-from-your-home-using-leftover-beer/ Ashwin Seshagiri Feb. 6, 2009 Make Biofuel from your home using leftover Beer. |
http://news.cornell.edu/print/734 Anne Ju Jun. 20, 2012 Researchers convert beer into a better-than-ethanol biofuel. |
Alles, et al. “Integrated Corn-Based Biorefinery: A Study in Sustainable Process Development” Sustainable Development in the Process Industries: Cases and Impact, Edited by Jan Harmsen and Joseph B. Powell; John Wiley & Sons, Inc.; 2010. |
Cardona et al. “Fuel ethanol production: Process design trends and integration opportunities” Bioresource Technology 98 (2007) 2415-2457. |
Dien et al. “Fermentation of ‘Quick Fiber’ Produced from a Modified Corn-Milling Process into Ethanol and Recovery of Corn Fiber Oil” Applied Biochemistry and Biotechnology (2004) vol. 113-116. |
Leoneta, et al. “Glycerol as a by-product of biodiesel production in Brazil: Alternatives for the use of unrefined glycerol” Renewable Energy 45 (2012) 138-145. |
Moser et al. “Biodiesel from Corn Distillers Dried Grains with Solubles: Preparation, Evaluation, and Properties” Bioenergy Research (Jun. 2012), vol. 5, No. 2, pp. 439-449. |
Nigam et al. “Production of liquid biofuels from renewable resources” Progress in Energy and Combustion Science 37 (2011) 52-68. |
Shi et al. “Bioresource Technology” Bioresource Technology 128 (2013) 100-106. |
Biomass Program: Integrated Corn-Based Bio-Refinery; U.S. Dept of Energy Brochure 2006. |
Wang et al. “Effect of the Corn Breaking Method on Oil Distribution between Stillage Phases of Dry-Grind Corn Ethanol Production” J. Agric. Food Chem. 2008, 56, 9975-9980. |
Wukovits et al. “Energy self supply of a bio-ethanol production plant by utilisation of renewable energy from residues from feedstock and ethanol production” CHISA 2006—17th International Congress of Chemical and Process Engineering (2006). (Abstract only). |
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20150125913 A1 | May 2015 | US |
Number | Date | Country | |
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61898828 | Nov 2013 | US |
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Parent | 14168174 | Jan 2014 | US |
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