US20210285018A1 - Enhancing product streams from ethanol production - Google Patents
Enhancing product streams from ethanol production Download PDFInfo
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- US20210285018A1 US20210285018A1 US17/200,053 US202117200053A US2021285018A1 US 20210285018 A1 US20210285018 A1 US 20210285018A1 US 202117200053 A US202117200053 A US 202117200053A US 2021285018 A1 US2021285018 A1 US 2021285018A1
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- Prior art keywords
- pretreatment
- acid
- wet cake
- ethanol
- residual material
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
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- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
- A23K10/38—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material from distillers' or brewers' waste
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/02—Pretreatment
- C11B1/025—Pretreatment by enzymes or microorganisms, living or dead
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/14—Multiple stages of fermentation; Multiple types of microorganisms or re-use of microorganisms
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/007—Separation of sugars provided for in subclass C13K
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Definitions
- the present disclosure relates generally to energy production from biomass sources. More specifically, the present disclosure relates to enhancing product and co-product yield from ethanol production processes.
- FIG. 1 illustrates an ethanol production plant 100 representative of current approaches used in the art.
- FIG. 2 illustrates a part of a primary ethanol production plant modified according to an embodiment.
- FIG. 3 illustrates a method for producing a sugar from lignocellulosic material in wet cake, in accordance with an embodiment.
- FIG. 4 illustrates a process for pretreatment of wet cake in accordance with the embodiment of FIG. 3 .
- FIG. 5 illustrates a method for hydrolyzing lignocellulosic material in wet cake, in accordance with one embodiment.
- FIG. 6 illustrates a process for enzymatic hydrolysis in accordance with the embodiment of FIG. 5 .
- FIG. 7 illustrates an exemplary process for recovering cellulosic ethanol in accordance with an embodiment.
- FIG. 8 illustrates an exemplary process for recovering cellulosic ethanol modified in accordance with the embodiment shown in FIG. 2 .
- FIG. 9 illustrates a process for co-product production from fermented wet cake in accordance with an embodiment.
- FIG. 10 illustrates an enhanced ethanol production plant and associated methods in accordance with particular embodiments.
- FIG. 11 illustrates an enhanced ethanol production plant and associated methods in accordance with particular embodiments.
- Reaping the potential benefits of utilizing ethanol production by-products can depend to a significant extent on the ability to recover additional ethanol and co-products from them in a cost- and resource-effective manner. In one aspect, this can involve accomplishing extra treatment steps in a more efficient manner, so that good results are achieved with a judicious use of resources. Another aspect can include increasing the useful qualities of such products and co-products. In another aspect, resource-effectiveness can be enhanced by coupling these additional recovery processes with existing production processes so as to take advantage of reusable inputs and by-products.
- Processes are described herein for realizing an enhanced yield of ethanol and quality of co-products from the by-products (e.g., stillage) of existing ethanol production processes, particularly processes for producing ethanol from starch-based biomass such as corn, or other biomass comprising lignocellulosic material. Also described herein are product outputs of these processes having new and useful properties.
- operably connected to refers to any form of interaction between two or more entities, including mechanical, electrical, magnetic, electromagnetic, fluid, and thermal interaction. Two entities may interact with each other even though they are not in direct contact with each other. For example, two entities may interact with each other through an intermediate entity.
- an ethanol production plant 100 can comprise a plurality of unit operations and processes as follows.
- a corn feedstock is ground by a mill 102 to reduce the corn to particles of a selected size.
- the mill 102 can employ a dry-milling process, i.e., employing mechanical means of breaking or crushing the corn kernels into smaller pieces without the addition of any liquid. Dry-milling techniques include, by way of non-limiting example, hammer milling, roller milling, and ball-milling.
- the fractionated corn undergoes further processes designed to make available fermentable sugars from the carbohydrates (primarily starch) in the corn.
- These processes can include slurrying performed in a slurrying tank 104 , cooking in a cook tank 106 , and liquefaction in a liquefaction tank 108 .
- the resulting mash is transferred to a fermentation tank 110 , where simple sugars produced by these processes undergo fermentation to produce ethanol.
- the resulting mixture of corn solids, water and ethanol, termed beer is then sent to a distillation system 112 , which strips the ethanol from the beer, yielding an ethanol solution product stream and whole stillage—mostly non-fermentable solids and water—as a by-product. Residual water is removed from the ethanol solution in one or more steps in a dehydration system 114 .
- the whole stillage can be further treated to recover co-products.
- separation equipment such as a centrifuge 116 to separate the whole stillage into its solid and liquid fractions, respectively termed hereinafter as “wet cake” and “first thin stillage” or “centrate.”
- the wet cake can be combined with syrup produced by evaporating the thin stillage, and then dried to produce dried distillers grains with solubles (DDGS), commonly utilized in animal feed.
- Distillers corn oil can be extracted from the syrup produced by evaporating water from the first thin stillage, for example by using evaporator 118 .
- first whole stillage can contain significant amounts of polysaccharides that exited those processes in a still unfermented or unfermentable state.
- First whole stillage, or more particularly the solid fraction thereof, can therefore be used as a feedstock for processes designed to convert these materials into sugars that can be fermented to produce an additional ethanol stream, i.e., cellulosic ethanol.
- fermentation residual material any such material, which can be generally termed “fermentation residual material”, can be used as a feedstock for processes described herein. Therefore while the term “wet cake” is used herein by way of non-limiting example to refer to such feedstock, the discussion is intended to apply generally to fermentation residual materials.
- a method comprising a two-stage acid pretreatment process can operate on a feedstock of wet cake from primary ethanol production to effectively break up a fraction of the lignocellulosic material contained therein and convert the starch, cellulose and hemicellulose in that fraction into oligomeric and monomeric sugars.
- the composition of wet cake entering the process is modified by treating the first whole stillage stream. More specifically, protein contained in the first whole stillage is removed therefrom so as to lower the protein content of the wet cake before further processing.
- the first whole stillage is directed to equipment configured to remove a portion of the protein contained in the first whole stillage.
- FIG. 2 shows part of the primary ethanol production plant illustrated in FIG.
- the first whole stillage from the distillation system 112 is passed—optionally with wash water—through a screener 202 configured to filter the first whole stillage so that a filtrate stream containing a portion of the protein is separated from the first whole stillage before the filtered first whole stillage enters the centrifuge 116 .
- Equipment suitable for this purpose are known to those of skill in the art with the aid of the present disclosure. These include pressure screen devices, paddle screen devices and centrifuges with screens to allow protein to be separated which employ pressure, paddles or centrifugal force, respectively to bring a material to be filtered into contact with one or more screens by which liquid and constituents dissolved or suspended therein are separated from solids.
- the screener 202 includes one or more screens each having a mesh size selected so as to separate liquid from the first whole stillage and thereby separate some of the protein from the solids.
- the screener includes a screen having a mesh size of from 100 openings/in 2 to 500 openings/in 2 , or more specifically any one of 100, 150, 200, 250, 300, 350, 400, 450, or 500 openings/in 2 .
- the screener includes a plurality of stages through which the first whole stillage passes sequentially, where the plurality of stages may comprise screens of different mesh sizes.
- the filtered first whole stillage is then separated by the centrifuge 116 into first thin stillage and wet cake, and the wet cake is subjected to processes such as the two-stage acid pretreatment process described below.
- the protein in the filtrate bypasses the two-stage acid pretreatment process and can be recovered in a downstream stage.
- a method for producing sugar from lignocellulosic material in wet cake 300 can comprise a step of washing 302 the wet cake to remove a liquid fraction from the wet cake.
- the washing step can be accomplished in the screening step described above or employed in addition to or in alternative to the screening described above.
- an acidification 304 step an amount of an acid is mixed into the wet cake.
- Two stages of pretreatment are included in the embodiment, where a first pretreatment stage 306 , comprises agitating the wet cake and the acid for a first pretreatment time at a first pretreatment temperature.
- a second pretreatment stage 308 comprises pretreating the wet cake with the acid in a pretreatment reactor for a second pretreatment time at a second pretreatment temperature.
- the method can comprise mixing an amount of an acid into the wet cake.
- the acid is added in an amount so that the concentration of the acid in the wet cake is from about 0.5 wt % to about 7 wt %.
- the acid may be added in an amount so as to achieve a pH of the wet cake of from about 1.5 to about 2.5.
- the acid can be added to the wet cake and mixed therewith using mechanical systems to achieve thorough mixing.
- a mixer 402 designed for mixing high viscosity fluids also known as a pug mill mixer or mingler, can be used for this purpose.
- the acid used can be a mineral acid such as sulfuric, phosphoric, hydrochloric, hydrofluoric, formic, or nitric acid, or a mixture thereof, or an organic acid such as maleic, oxalic, acetic, or fumaric acid, or a mixture thereof.
- a mineral acid such as sulfuric, phosphoric, hydrochloric, hydrofluoric, formic, or nitric acid, or a mixture thereof
- an organic acid such as maleic, oxalic, acetic, or fumaric acid, or a mixture thereof.
- other acids may be used to decrease the pH of the wet cake in accordance with present embodiment.
- the first pretreatment stage can comprise heating and agitating the acidified wet cake to begin hydrolysis of the lignocellulosic material in the wet cake. Heating may not be necessary if the wet cake is already at a sufficiently high temperature.
- the acidified wet cake can be transferred to a pretreatment vessel 304 for this purpose.
- this vessel is a cone-bottomed tank equipped with an agitator, where agitation of the material is performed for a first pretreatment time.
- a horizontal or vertical pipe could be used for this step.
- the acidified wet cake is heated before it is transferred to the pretreatment vessel 404 , for example while it is in the mixer 402 . In another embodiment, the acidified wet cake is heated in the pretreatment vessel 404 .
- this first pretreatment stage is accomplished without employing high pressures.
- the first stage is conducted with the acidified wet cake at a first pretreatment pressure that is from slightly negative (about ⁇ 1 psig) to about 10 psig.
- the first pretreatment pressure can be from about ⁇ 1 psig to about 5 psig, or from 0 psig to about 6 psig, or from 0 psig to about 10 psig.
- the wet cake is heated to a first pretreatment temperature for the first stage of pretreatment. This can be done during acidification in the mixer 402 or during agitation in the pretreatment vessel 404 . Alternatively, the wet cake may be hot (e.g., 170° F. or above) as it exits from the first whole stillage decanter and therefore may not need to be heated further.
- the first pretreatment temperature is from about 170° F. to about 225° F.
- the first pretreatment temperature is from about 180° F. to about 215° F., or from about 190° F. to about 200° F., or from about 170° F. to about 200° F., or from about 180° F. to about 225° F.
- the first pretreatment pressure is at atmospheric pressure and the boiling temperature of pure water at the elevation at which this step is conducted is the upper limit for the first pretreatment temperature.
- the first pretreatment time can be selected so as to achieve thorough mixing of the acid and wet cake based on the mass of wet cake resident in this step.
- the first pretreatment time can be from about 10 minutes to about 300 minutes.
- the first pretreatment time can be from about 30 minutes to about 180 minutes, or about 20 minutes to about 120 minutes, or from about 5 minutes to about 90 minutes, or from about 15 minutes to about 60 minutes.
- the first pretreatment stage achieves effective hydrolysis of cellulose and hemicellulose to a desired yield of soluble sugars (e.g., glucose, xylose, galactose, arabinose, and mannose).
- soluble sugars e.g., glucose, xylose, galactose, arabinose, and mannose.
- the first pretreatment stage provides a percent yield of soluble glucose of from about 10% to about 60%, or an average percent yield of from about 30% to about 45%.
- the percent yield of monomeric glucose from the first stage is from about 0% to about 10%, or an average percent yield of from about 1% to about 4%.
- the first pretreatment stage provides a percent yield of soluble xylose of from about 80% to about 100%, or an average percent yield of from about 93% to about 97%.
- the yield of monomeric xylose from the first stage is from about 0% to about 25%, or an average percent yield of from about 5% to about 10%.
- the first pretreatment stage provides a percent yield of soluble arabinose of from about 85% to about 100%, or an average percent yield of about 95% to about 99%.
- the yield of monomeric arabinose from the first stage is from about 0% to about 95%, or an average percent yield of about 45% to about 60%.
- the first pretreatment stage provides a percent yield of soluble galactose of from about 55% to about 100%, or an average percent yield of about 90% to about 95%.
- the yield of monomeric galactose from the first stage is from about 0% to about 50%, or an average percent yield of about 10% to about 20%.
- the first pretreatment stage provides a percent yield of soluble mannose of from about 30% to about 100%, or an average percent yield of about 75% to about 90%.
- the yield of monomeric mannose from the first stage is from about 0% to about 75%, or an average percent yield of about 10% to about 25%.
- the production of unfermentable compounds that can arise from the degradation of these sugars e.g., furfural and hydroxymethylfurfural from degradation of xylose and glucose, respectively
- the different parameters of this process —residence time, pH, and temperature—combine to influence these outcomes.
- addition of less acid will involve conducting this stage at higher temperature and/or for longer residence time in order to achieve similar results compared to a higher acid concentration. Therefore, in accordance with the present disclosure, the pH of the wet cake and length of the first pretreatment time and the first pretreatment temperature can be selected to achieve desired results.
- the first pretreatment stage can be done by selecting a higher pH (i.e., adding less acid) in combination with a higher first pretreatment temperature, a longer first pretreatment time, or both.
- a lower pH is selected in combination with a lower first pretreatment temperature, a shorter first pretreatment time, or both.
- higher pH and lower first pretreatment temperature can be employed with a longer first pretreatment time.
- a lower pH can be selected in combination with a lower first pretreatment temperature and a longer first pretreatment time.
- One aspect of the pretreatment process is that mixing and the selection of temperature and time can allow for more complete hydrolysis by a given amount of acid added to the wet cake. Therefore, one potential result is a decrease in the amount of acid required to achieve desired yields of fermentable sugars. In one aspect, this provides for more efficient use and less waste of acid.
- the amount of acid can be selected so as to minimize undesired downstream effects. For example, one may seek to decrease the amount of sulfur in dried distillers grains produced by this method by managing the amount of sulfuric acid used in pretreatment.
- preparation of wet cake for acidification can include bringing its solids content to a level of from about 15 wt % to about 40 wt %, or more particularly from about 20 wt % to about 35 wt %.
- acidification can be preceded by washing the wet cake in a washer 406 to remove a portion of the liquid fraction of the wet cake and thereby achieve a desired solids content in the wet cake.
- the washing can also have the benefit of reducing the buffering capacity of the wet cake, or more particularly the liquid fraction of the wet cake. Washing can be done with water or other aqueous liquid.
- liquid reclaimed from other unit processes or a by-product of such processes, such as condensate from evaporation of first thin stillage can be used for this step.
- the liquid fraction removed from the wet cake is substantially replaced by a non-buffering, low pH liquid (the condensate).
- a second pretreatment stage can comprise directing the wet cake to a pretreatment reactor 408 , wherein the wet cake is subjected to a higher temperature and a higher pressure than those employed in the first pretreatment stage.
- the wet cake is heated to a second pretreatment temperature higher than the first pretreatment temperature used in the first stage and held substantially at that temperature for a second pretreatment time.
- the second pretreatment temperature is from about 230° F. to about 330° F.
- the second pretreatment temperature can be from about 245° F. to about 320° F., or from about 250° F.
- the wet cake is also subjected to a second pretreatment pressure that is higher than the first pretreatment pressure. Higher pressures at this stage may be employed to maintain a sufficiently high wet cake temperature.
- Heating at this stage can be accomplished by steam injection, or other heating methods as will be recognized by those of skill in the art with the aid of the present disclosure.
- the wet cake is heated before it is transferred to the pretreatment reactor 408 , for example by steam injection in transit to the pretreatment reactor 408 .
- the acidified wet cake is heated in the pretreatment reactor 408 .
- the results of the second pretreatment stage can be influenced by the particular combination of wet cake pH, second pretreatment temperature, and second pretreatment time.
- the second pretreatment temperature and second pretreatment time can be selected in view of the amount of acid added during acidification so as to enhance the yield of soluble sugars and minimize the creation of degradation products.
- the high yield of soluble sugars in the first pretreatment stage allows operation of the pretreatment reactor 408 at lower temperatures and pressures than might otherwise be required to achieve similar yields of oligomeric and monomeric sugars. In this way the capital cost and energy expenditure of pretreatment may be reduced. Lower pretreatment temperatures also reduce the amount of undesirable sugar degradation products produced, improving the efficiencies of downstream enzymatic hydrolysis and fermentation steps.
- the commencement of hydrolysis in the first stage also allows for a relatively short second pretreatment time. In a particular embodiment, the second pretreatment time can be from about 3 minutes to about 100 minutes.
- the second pretreatment time can be from about 3 minutes to about 50 minutes, or about 30 minutes to about 80 minutes, or from about 5 minutes to about 8 minutes, or from about 20 minutes to about 50 minutes.
- a single pretreatment stage e.g., the second pretreatment stage, can alternatively be relied upon to produce sugars from lignocellulosic material in the wet cake in accordance with the present disclosure.
- a system for pretreating wet cake to produce sugar from lignocellulosic material contained therein can comprise a mixer 402 configured to receive an acid and to receive wet cake, and to mix the acid into the wet cake to produce an acidified wet cake; a pretreatment vessel 404 operably connected to the mixer 402 and configured to receive the acidified wet cake from the mixer 402 and agitate the acidified wet cake at a first pretreatment temperature and a first pretreatment pressure; and a pretreatment reactor 408 operably connected to the pretreatment vessel and configured to receive the acidified wet cake from the pretreatment vessel and react the acidified wet cake at a second pretreatment temperature and a second pretreatment pressure.
- the pretreatment reactor 408 can be a reactor designed to operate at the temperature and pressures discussed above. In a particular embodiment, the reactor is designed so that substantially the entire volume of acidified wet cake is uniformly exposed to the second pretreatment temperature over the second pretreatment time. Possible reactor configurations include one or more continuous stirred reactors in series, one or more batch reactors, or a horizontal or vertical vessel or pipe. In a specific embodiment, the pretreatment reactor 408 is a plug flow reactor. As described above, the pretreatment vessel 404 can be a cone-bottomed tank equipped with an agitator, or a horizontal pipe or vertical pipe.
- the second pretreatment stage provides a percent yield of soluble glucose of from about 10% to about 60%, or an average percent yield of about 35% to about 45%.
- the yield of monomeric glucose from the second stage is from about 0% to about 30%, or an average percent yield of about 5% to about 10%.
- the second pretreatment stage provides a percent yield of soluble xylose of from about 50% to about 100%, or an average percent yield of about 90% to about 95%.
- the yield of monomeric xylose from the second stage is from about 0% to about 65%, or an average percent yield of about 20% to about 30%.
- the second pretreatment stage provides a percent yield of soluble arabinose of from about 40% to about 100%, or an average percent yield of about 85% to about 95%.
- the yield of monomeric arabinose from the second pretreatment stage is from about 20% to about 100%, or an average percent yield of about 65% to about 75%.
- the second pretreatment stage provides a percent yield of soluble galactose of from about 55% to about 100%, or an average percent yield of about 85% to about 95%.
- the yield of monomeric galactose from the second stage is from about 2% to about 100%, or an average percent yield of about 35% to about 45%.
- the second pretreatment stage provides a percent yield of soluble mannose of from about 30% to about 100%, or an average percent yield of about 75% to about 85%.
- the yield of monomeric mannose from the second stage is from about 0% to about 100%, or an average percent yield of about 20% to about 30%.
- Saccharification can then be performed on the pretreated wet cake, comprising using enzymatic hydrolysis to produce further monomeric sugars from oligosaccharides and polysaccharides remaining after the two-stage acid pretreatment process.
- Saccharification can then be performed on the pretreated wet cake, comprising using enzymatic hydrolysis to produce further monomeric sugars from oligosaccharides and polysaccharides remaining after the two-stage acid pretreatment process.
- a method of hydrolyzing lignocellulosic material in wet cake 500 can comprise: feeding 502 wet cake comprising lignocellulosic material into a recycling reactor at a feed rate; enzyme addition 504 , in which at least one enzyme is added to the wet cake; and recycling 506 the wet cake and at least one enzyme through the recycling reactor at a recycle rate and for a residence time to hydrolyze the lignocellulosic material to produce an amount of monomeric sugar in the wet cake.
- the process can comprise feeding the acidified wet cake into a recycling reactor 602 at a feed rate and adding one or more enzymes selected to act upon the oligosaccharides and polysaccharides.
- enzymes known to be effective at breaking up oligosaccharides and lignocellulosic material can be used in this process, and include various cellulases and hemicellulases, as well as amylase and beta-glucosidase. More specifically, hemicellulases can include xylanase, mannase, galactidase, and arabinase.
- the pH of the wet cake can also be increased by the addition of a basic solution, either before or after the wet cake enters the recycling reactor 602 .
- Bases that can be used in this step include, without limitation, ammonia, aqua ammonia, sodium hydroxide, sodium bicarbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, and magnesium hydroxide. Other suitable bases for use in this step will be apparent to those of skill in the art having the benefit of this disclosure.
- the wet cake can first be cooled if needed to bring it to a temperature at which the selected enzyme(s) will have the desired level of activity. As illustrated in FIG.
- cooling can be performed by flashing a vapor off of the wet cake in a flash drum 604 .
- flashing can be performed by flashing a vapor off of the wet cake in a flash drum 604 .
- other approaches and equipment suitable for cooling wet cake can be employed in addition or in alternative to flashing, including without limitation, multiple flash steps and passing the wet cake through one or more heat exchangers.
- the process can continue with recycling the wet cake repeatedly through the recycling reactor 602 for a selected residence time, during which the enzyme(s) is mixed substantially uniformly throughout the volume of wet cake and begins to hydrolyze the oligosaccharides and lignocellulosic material.
- the recycling reactor 602 is operated at a recycle rate that is higher than the mass flow rate at which the wet cake is fed into the recycling reactor 602 .
- the recycle rate is from about 1 to about 10 times the feed rate.
- the recycle rate is from about 5 to about 10 times the feed rate.
- the recycle rate is from about 3 to about 6 times the feed rate.
- the recycle rate is from about 1 to about 5 times the feed rate.
- Outcomes from recycling the wet cake include, but are not limited to, reducing the viscosity of the wet cake entering the recycling reactor 602 due to dilution; 2) aiding reduction of the temperature of the wet cake to a target temperature for enzymatic activity; and 3) effective mixing of the enzyme(s) into the wet cake.
- the wet cake has a viscosity from 250 cp to 3000 cp upon exiting the recycling reactor 602 .
- the wet cake has a viscosity of from 500 cp to 2000 cp.
- the effective mixing allows for using cost-effective amounts of enzymes.
- the residence time during which a volume of wet cake and enzyme(s) is present in the reactor can be selected to be sufficient to achieve the above objectives.
- the residence time is from about 6 hours to about 15 hours.
- the residence time is from about 10 hours to about 13 hours, or from about 12 hours to about 15 hours, or more particularly from about 11 hours to about 13 hours.
- the enzymatic hydrolysis process is a flow-through process, where the feed rate, recycle rate, and residence time are selected so that each unit volume of wet cake entering the reactor undergoes substantially similar processing conditions.
- a system 600 for saccharification of lignocellulosic material in wet cake can comprise a recycling reactor 602 configured to receive wet cake, such as from the flash drum 604 , and at least one enzyme and allow for reaction between the same.
- the recycling reactor 602 can be further configured to receive a recycle stream of the wet cake and enzyme(s) at a recycle rate that is greater than the feed rate.
- the recycle rate is from about 1 to 10 times the feed rate.
- the recycle rate is from 1 to 3 times the feed rate.
- the recycle rate is from 2 to 4 times the feed rate.
- the system 600 can include a pump operably connected to the recycling reactor 602 that provides circulation of the recycle stream at the recycle rate.
- the recycling reactor 602 can be further configured to receive a base and to combine the base and the wet cake.
- the residence time may be sufficient for enzymatic hydrolysis to begin, yet it need not be long enough to complete said hydrolysis. Rather, after initial hydrolysis the wet cake and enzymes may be transferred to a fermentation tank 606 where further hydrolysis occurs prior to starting fermentation. Prior to starting fermentation, the temperature of the wet cake is reduced from the hydrolysis temperature (typically in the range of about 120° F. to 150° F.) to the optimum fermentation temperature (typically about 95° F.). Hydrolysis continues at a slower rate during fermentation.
- the pretreated wet cake is transferred to one of a plurality of saccharification tanks.
- the wet cake can first be cooled if needed to bring it to a temperature at which the selected enzyme(s) will have the desired level of activity.
- the pH in the saccharification tank is adjusted if needed and enzymes are added.
- the plurality of saccharification tanks are functionally connected in series to perform saccharification in a serial manner, wherein enzymatic hydrolysis is allowed to proceed for a time in the first saccharification tank, after which the wet cake is transferred to another saccharification tank in the series for further enzymatic hydrolysis.
- the series can include the recycling reactor 602 , into which the pretreated wet cake is transferred and in which enzymatic hydrolysis begins before the wet cake is transferred to the first saccharification tank.
- the size and number of saccharification tanks can be adjusted to provide a desired total residence time. In a specific embodiment, the total residence time is from about 35 hours to about 55 hours. In a more specific embodiment, the total residence time is about 40 hours.
- the plurality of saccharification tanks are configured in parallel to perform saccharification in a batch manner, wherein a batch of pretreated wet cake is transferred to one of the saccharification tanks in which the pH is adjusted if needed, enzymes are added, and enzymatic hydrolysis proceeds for a residence time, and then the wet cake and enzymes are transferred to the fermentation tank 606 .
- Another batch of pretreated wet cake can be transferred into another one of the saccharification tanks to undergo the same or a similar process.
- saccharification comprises using at least three saccharification tanks cycling at intervals, for example where one or more saccharification tanks are holding wet cake undergoing hydrolysis, while one or more of the other saccharification tanks are being filled with pretreated wet cake, and one or more of the remaining saccharification tanks are transferring wet cake and enzymes to the fermentation tank 606 .
- each saccharification tank can be sized so as to hold the wet cake and enzymes for a desired residence time.
- the residence time is from about 35 hours to about 55 hours. In a more specific embodiment, the residence time is about 40 hours.
- Fermentation creates cellulosic ethanol and carbon dioxide from the sugars in the wet cake.
- an ethanol-producing microbe is added to the wet cake.
- any ethanol-producing microbes including native and genetically modified microbes, may be used, such as Zymomonas mobilis, Saccharomyces cerevisiae, Escherichia coli, Bacillus subtilis , and Pichia pastoris .
- enzymatic hydrolysis of remaining polysaccharides and oligosaccharides begun in the previous step may continue in the fermentation tank 606 .
- the contemporaneous fermentation of sugars in the wet cake may promote more complete hydrolysis of the polysaccharides by decreasing end-product inhibition of the hydrolysis reactions.
- hydrolysis and fermentation of wet cake exiting the recycling reactor 602 may be done in batches among a number of tanks so that adjacent processes can operate continuously, if desired.
- a batch of beer produced in fermentation tank 606 can be collected in a beer well 608 .
- Carbon dioxide and other vapor streams may be collected from the fermentation tank(s) and the beer well 608 and scrubbed using techniques known in the art to remove ethanol and other components entrained in the vapor.
- Ethanol can be recovered from the beer using any number of techniques and equipment known in the art to be suitable for this purpose. More particularly, typical techniques, generally termed distillation, involve separating the liquid and solid components by initiating the transition of the liquid component to vapor, which is then condensed and collected. Typically, the initial output of this process is a mixture of ethanol, water, and other volatile components. Further steps can be performed on this mixture to separate ethanol from the other components, typically by making use of differences in their respective volatilities. A cellulosic ethanol production process is illustrated in FIG.
- the beer produced by fermentation is transferred from the beer well 608 to a distillation column 702 to produce a cellulosic ethanol stream and also a whole stillage by-product, referred to herein as “second whole stillage”, comprising the non-volatile components of the beer.
- the second whole stillage is collected into a whole stillage tank 706 .
- the whole stillage tank 706 can be equipped with an agitator.
- the cellulosic ethanol stream can be directed to a dehydration system 604 to remove water and other non-ethanol volatile components.
- dehydration can comprise sending the cellulosic ethanol stream through either or both of a rectification column, and one or more molecular sieves.
- dehydration can comprise sending the cellulosic ethanol stream through a membrane separation system, in which a pervaporation membrane is used to separate water and ethanol through differential permeation.
- the second whole stillage can exhibit particular characteristics that distinguish it from the first whole stillage produced by primary ethanol production.
- the second whole stillage by-product of the present disclosure comprises low weight percentages of residual fiber, starch, and cellulose and a high percentage weight of crude protein.
- the second whole stillage has a percent by weight of crude protein from about 40% to about 55%.
- crude protein content of the second whole stillage is from about 40 wt % to about 50 wt %, or from about 35 wt % to about 55 wt %, or from about 35 wt % to about 50 wt %.
- protein is filtered from the first whole stillage in the screener 202 into a filtrate stream as described above and the filtrate stream is combined with the second whole stillage in the whole stillage tank 706 . Agitation can be employed in the whole stillage tank 706 to provide thorough mixing of the filtrate into the second whole stillage.
- co-product production from the second whole stillage can comprise separating the second whole stillage into its liquid and solid components. Separation techniques and equipment suitable for this process are well-known in the art.
- the second whole stillage can be processed using the same or similar approaches as are used in primary ethanol production plants.
- the second whole stillage can be fed from the whole stillage tank 706 into a centrifuge 902 , such as a decanter centrifuge, which separates the second whole stillage into a semi-solid low-fiber slurry and a thin stillage (termed hereinafter as “second thin stillage”).
- a dryer 904 can be used to remove residual moisture from the resulting low-fiber slurry, thereby producing a dried distillers grains (DDG) having a high protein content.
- DDG dried distillers grains
- Dried distillers grains with solubles can be made by recombining syrup (produced from the evaporation of first thin stillage) with wet distillers grains before drying. Accordingly, it is contemplated that syrup produced from the evaporation of both first thin stillage and second thin stillage can be combined with the low-fiber slurry in making DDGS in accordance with the present disclosure.
- the inventors have surprisingly found that a higher quality DDGS may be attainable when the low-fiber slurry of the present disclosure is dried without the addition of the second thin stillage.
- syrup produced from the first thin stillage from the primary ethanol production plant evaporator 118 is still mixed with the low-fiber slurry prior to drying, but without inclusion of the second thin stillage or syrup produced therefrom.
- the DDGS in accordance with the present disclosure has a total protein content of from about 40 wt % to about 70 wt %. In a more particular embodiment, the DDGS has a total protein content of from about 50 wt % to about 65 wt %. In other particular embodiments the total protein content can be from about 45 wt % to about 55 wt %, or from about 40 wt % to about 60 wt %, or from about 50 wt % to about 70 wt %.
- the DDGS also has a low fiber content due to the extent of breakdown and conversion of the fiber in the wet cake feedstock by the two-stage acid pretreatment process and the enzymatic hydrolysis process of the present disclosure.
- the DDGS comprises fiber in an amount from about 0.5 wt % to about 2 wt %.
- the DDGS in accordance with the present disclosure can also include particular nutrients of interest in animal health.
- the DDGS contains glutamic acid in an amount from about 6 wt % to about 10 wt %, or more specifically from about 7 wt % to about 9 wt %.
- the DDGS contains aspartic acid in an amount from about 1 wt % to about 5 wt % or more specifically from about 2 wt % to about 4 wt %. In another aspect, the DDGS contains alanine in an amount from about 2 wt % to about 5 wt % or more specifically from about 3 wt % to about 4 wt %. In another aspect, the DDGS contains vitamin A in an amount from about 800 I.U./kg and about 1200 I.U./kg, or more specifically from about 900 I.U./kg to about 1100 I.U./kg. In another aspect, the DDGS contains vitamin E in an amount from about 450 I.U./kg and about 650 I.U./kg, or more specifically from about 400 I.U./kg to about 600 I.U./kg.
- a low fiber content in the DDGS of the present disclosure gives it enhanced digestibility and digestible energy.
- the DDGS has a digestible energy content of at least 1500 kcal/lb.
- digestible energy content is from 1500 kcal/lb to about 2000 kcal/lb.
- low fiber content imparts particular physical characteristics, such as a fine consistency and higher density.
- the DDGS has a density of from about 30 lbs/ft 3 to about 40 lbs/ft 3 , or more specifically from about 34 lbs/ft 3 to about 38 lbs/ft 3 , or from about 30 lbs/ft 3 to about 35 lbs/ft 3 , or from about 34 lbs/ft 3 to about 40 lbs/ft 3 .
- the second thin stillage can be directed to other uses.
- the second thin stillage can be directed to an evaporator, where evaporation of water from the second thin stillage can proceed until the second thin stillage becomes a syrup, or further to produce a substantially solid material, either of which can be used as an animal feed additive.
- the second thin stillage stream is combined with the first thin stillage stream for evaporation in the same evaporator, e.g., evaporator 118 .
- evaporator 118 e.g., evaporator 118
- the second thin stillage can be directed to an anaerobic digester 906 , where anaerobic digestion can be performed on the second thin stillage to produce a biogas which can be scrubbed and added to existing natural gas pipelines or the biogas can be used in the primary ethanol plant's boiler.
- This approach may be undertaken as an effective way to remove the chemical oxygen demand of the second thin stillage.
- Another aspect of the present disclosure with respect to corn-based ethanol production processes is that with less fiber to bind corn oil contained in the second whole stillage by-product, more of the corn oil is decanted off into the second thin stillage. Accordingly, in one embodiment a distillers corn oil stream can be obtained from the second thin stillage. In a particular embodiment, the second thin stillage is combined with the first thin stillage for further processing, e.g., evaporation to produce a syrup from which distillers corn oil is extracted. Recovery of corn oil from thin stillage can be achieved by extraction systems and methods known in the art, including evaporation, centrifugation, and solvent extraction.
- the second thin stillage provides an additional yield of DCO of from about 0.1 to 0.5 lbs per bushel of corn feedstock. In another specific embodiment, the additional yield of DCO is from about 0.1 lbs to about 0.7 lbs per pound of wet cake solids.
- a method for increasing ethanol production associated with an existing ethanol production plant 100 can comprise feeding wet cake resulting from separation of first whole stillage into a cellulosic ethanol production process 1002 , which can comprise any of the steps and processes described above. As illustrated in FIG. 10 (a portion of which is shown in FIG. 1 ) which shows an enhanced ethanol production plant 1000 in accordance with the present disclosure, a method for increasing ethanol production associated with an existing ethanol production plant 100 can comprise feeding wet cake resulting from separation of first whole stillage into a cellulosic ethanol production process 1002 , which can comprise any of the steps and processes described above. As illustrated in FIG.
- equipment for this added process can comprise, without limitation, a washer 406 for the step of washing the wet cake; a mixer 402 for the step of acidification by mixing acid into the wet cake; a pretreatment vessel 404 for the step of agitating the acidified wet cake; a pretreatment reactor 408 for performing the second pretreatment stage; a recycling reactor 602 in which the wet cake is recycled with enzymes to initiate enzymatic hydrolysis; a fermentation tank 606 for furthering the hydrolysis of the wet cake and fermenting sugars produced in the foregoing processes; and a distillation column 702 to recover a stream of cellulosic ethanol and produce a by-product of second whole stillage.
- a washer 406 for the step of washing the wet cake
- a mixer 402 for the step of acidification by mixing acid into the wet cake
- a pretreatment vessel 404 for the step of agitating the acidified wet cake
- a pretreatment reactor 408 for performing the second pretreatment stage
- the cellulosic ethanol stream can be directed to an existing dehydration system 114 system in the existing ethanol production plant 100 .
- first whole stillage from the distillation system 112 can be filtered in a screener 202 and the resulting filtrate combined with second whole stillage in a whole stillage tank 706 , wherein protein contained in the filtrate bypasses the intervening stages.
- a modification of existing corn-based ethanol production provides an increased yield of distillers corn oil.
- a method for increasing distillers corn oil production associated with an existing ethanol production plant 100 is also provided by feeding wet cake resulting from centrifuge 116 of first whole stillage into a cellulosic ethanol production process 1002 .
- the second whole stillage by-product from the distillation column 702 is separated with a centrifuge 902 into a low-fiber slurry and second thin stillage.
- the second thin stillage is combined with the first thin stillage for evaporation to produce a syrup from which distillers corn oil is extracted.
- the syrup from the existing ethanol plant's evaporator and the low-fiber slurry can then be directed to a dryer 904 for preparation of a DDGS in accordance with the present disclosure.
- the dryer 904 may be dedicated to drying of the low-fiber slurry and syrup, due to all of the wet cake from the existing ethanol production plant being directed to the added cellulosic ethanol production.
- the second thin stillage can be directed to an anaerobic digester 906 , where anaerobic digestion can be performed on the second thin stillage to produce a biogas which can be scrubbed and added to existing natural gas pipelines or the biogas can be used in the primary ethanol plant's boiler.
- This approach may be undertaken as an effective way to remove the chemical oxygen demand of the second thin stillage.
- Corn wet cake from primary ethanol production was subjected to the following cellulosic ethanol production process to produce a dried distillers grains with solubles. Steps 1-5 were performed at an ethanol plant modified according to embodiments herein. Steps 6-9 were performed at a research center according to embodiments herein.
- Second Pretreatment % Acid Temp Time Yield of Total Soluble Sugars Stage Added (° F.) (min) Glucose Xylose Galactose Arabinose Mannose Average 3.8 268 32 41.2% 92.8% 91.6% 90.9% 81.0% MIN 2.0 244 3 16.4% 54.0% 63.5% 46.2% 0.0% MAX 6.2 320 205 52.4% 100.0% 100.0% 100.0% 100.0% Std Dev 1.0 15 28 6.1% 7.7% 10.1% 8.8% 21.1%
- Second Pretreatment % Acid Temp Time Yield of Monomeric Sugars Stage Added (° F.) (min) Glucose Xylose Galactose Arabinose Mannose Average 3.8 268 32 7.6% 25.3% 40.6% 70.4% 23.4% MIN 2.0 244 3 0.0% 2.8% 5.6% 22.1% 0.0% MAX 6.2 320 205 20.4% 60.0% 99.3% 96.4% 119.8% Std Dev 1.0 15 28 5.5% 13.8% 20.3% 10.8% 26.8%
Abstract
Description
- This application claims the benefit of U.S. Provisional Patent Application No. 62/989,423 filed Mar. 13, 2020 and entitled “ENHANCING PRODUCT STREAMS FROM ETHANOL PRODUCTION,” the entire contents of which are hereby incorporated herein by reference.
- The present disclosure relates generally to energy production from biomass sources. More specifically, the present disclosure relates to enhancing product and co-product yield from ethanol production processes.
- The production of ethanol from biomass involves a number of unit processes, each having various inputs and losses. Whole stillage as a by-product of distillation represents a considerable process loss, particularly for ethanol production from feedstocks containing significant amounts of starch and lignocellulosic material. Whole stillage can contain unrecovered ethanol and unfermentable carbohydrates, the latter of which represent an unrealized potential yield of ethanol. The fiber content of stillage solids can also make desirable co-products of ethanol production (e.g., distillers corn oil (DCO) from corn-based ethanol production) less accessible for recovery. There is considerable interest in seizing the opportunities presented by ethanol production by-products for additional product and co-product yield. However, challenges remain in that utilization of this material to this end requires more intensive mechanical and chemical treatment, and therefore increased inputs of material resources and energy.
- The embodiments disclosed herein will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. These drawings depict only typical embodiments, which will be described with additional specificity and detail through use of the accompanying drawings in which:
-
FIG. 1 illustrates anethanol production plant 100 representative of current approaches used in the art. -
FIG. 2 illustrates a part of a primary ethanol production plant modified according to an embodiment. -
FIG. 3 illustrates a method for producing a sugar from lignocellulosic material in wet cake, in accordance with an embodiment. -
FIG. 4 illustrates a process for pretreatment of wet cake in accordance with the embodiment ofFIG. 3 . -
FIG. 5 illustrates a method for hydrolyzing lignocellulosic material in wet cake, in accordance with one embodiment. -
FIG. 6 illustrates a process for enzymatic hydrolysis in accordance with the embodiment ofFIG. 5 . -
FIG. 7 illustrates an exemplary process for recovering cellulosic ethanol in accordance with an embodiment. -
FIG. 8 illustrates an exemplary process for recovering cellulosic ethanol modified in accordance with the embodiment shown inFIG. 2 . -
FIG. 9 illustrates a process for co-product production from fermented wet cake in accordance with an embodiment. -
FIG. 10 illustrates an enhanced ethanol production plant and associated methods in accordance with particular embodiments. -
FIG. 11 illustrates an enhanced ethanol production plant and associated methods in accordance with particular embodiments. - Reaping the potential benefits of utilizing ethanol production by-products can depend to a significant extent on the ability to recover additional ethanol and co-products from them in a cost- and resource-effective manner. In one aspect, this can involve accomplishing extra treatment steps in a more efficient manner, so that good results are achieved with a judicious use of resources. Another aspect can include increasing the useful qualities of such products and co-products. In another aspect, resource-effectiveness can be enhanced by coupling these additional recovery processes with existing production processes so as to take advantage of reusable inputs and by-products.
- Processes are described herein for realizing an enhanced yield of ethanol and quality of co-products from the by-products (e.g., stillage) of existing ethanol production processes, particularly processes for producing ethanol from starch-based biomass such as corn, or other biomass comprising lignocellulosic material. Also described herein are product outputs of these processes having new and useful properties.
- Reference throughout this specification to “an embodiment,” “the embodiment,” “particular embodiments,” or “certain embodiments” means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the quoted phrases, or variations thereof, as recited throughout this specification are not necessarily all referring to the same embodiment.
- The phrase “operably connected to” refers to any form of interaction between two or more entities, including mechanical, electrical, magnetic, electromagnetic, fluid, and thermal interaction. Two entities may interact with each other even though they are not in direct contact with each other. For example, two entities may interact with each other through an intermediate entity.
- As shown in
FIG. 1 presenting corn-based ethanol production by way of example, anethanol production plant 100 can comprise a plurality of unit operations and processes as follows. A corn feedstock is ground by amill 102 to reduce the corn to particles of a selected size. In a particular embodiment, themill 102 can employ a dry-milling process, i.e., employing mechanical means of breaking or crushing the corn kernels into smaller pieces without the addition of any liquid. Dry-milling techniques include, by way of non-limiting example, hammer milling, roller milling, and ball-milling. The fractionated corn undergoes further processes designed to make available fermentable sugars from the carbohydrates (primarily starch) in the corn. These processes can include slurrying performed in aslurrying tank 104, cooking in acook tank 106, and liquefaction in aliquefaction tank 108. The resulting mash is transferred to afermentation tank 110, where simple sugars produced by these processes undergo fermentation to produce ethanol. The resulting mixture of corn solids, water and ethanol, termed beer, is then sent to adistillation system 112, which strips the ethanol from the beer, yielding an ethanol solution product stream and whole stillage—mostly non-fermentable solids and water—as a by-product. Residual water is removed from the ethanol solution in one or more steps in adehydration system 114. - The whole stillage can be further treated to recover co-products. Typically, this involves using separation equipment such as a
centrifuge 116 to separate the whole stillage into its solid and liquid fractions, respectively termed hereinafter as “wet cake” and “first thin stillage” or “centrate.” The wet cake can be combined with syrup produced by evaporating the thin stillage, and then dried to produce dried distillers grains with solubles (DDGS), commonly utilized in animal feed. Distillers corn oil can be extracted from the syrup produced by evaporating water from the first thin stillage, for example by usingevaporator 118. - The whole stillage by-product of typical ethanol production processes, referred to herein as “first whole stillage”, can contain significant amounts of polysaccharides that exited those processes in a still unfermented or unfermentable state. For example, a considerable fraction of the lignocellulosic material (cellulose, hemicellulose, and lignin) and residual starch found in corn—much of it from corn fiber—may be found in first whole stillage from corn-based ethanol production. First whole stillage, or more particularly the solid fraction thereof, can therefore be used as a feedstock for processes designed to convert these materials into sugars that can be fermented to produce an additional ethanol stream, i.e., cellulosic ethanol. The extent to which this is accomplished determines not only the additional ethanol yield from the initial feedstock, but also the characteristics of the stillage by-product of this second-generation process, which in turn influences the quality and characteristics of co-products. Other processes exist by which fermentable solids may be separated or concentrated from the by-products of primary ethanol production. It is contemplated that any such material, which can be generally termed “fermentation residual material”, can be used as a feedstock for processes described herein. Therefore while the term “wet cake” is used herein by way of non-limiting example to refer to such feedstock, the discussion is intended to apply generally to fermentation residual materials.
- According to the present disclosure, a method comprising a two-stage acid pretreatment process can operate on a feedstock of wet cake from primary ethanol production to effectively break up a fraction of the lignocellulosic material contained therein and convert the starch, cellulose and hemicellulose in that fraction into oligomeric and monomeric sugars.
- In an embodiment, the composition of wet cake entering the process is modified by treating the first whole stillage stream. More specifically, protein contained in the first whole stillage is removed therefrom so as to lower the protein content of the wet cake before further processing. In accordance with the embodiment, the first whole stillage is directed to equipment configured to remove a portion of the protein contained in the first whole stillage.
FIG. 2 shows part of the primary ethanol production plant illustrated inFIG. 1 modified in accordance with a particular embodiment, in which the first whole stillage from thedistillation system 112 is passed—optionally with wash water—through ascreener 202 configured to filter the first whole stillage so that a filtrate stream containing a portion of the protein is separated from the first whole stillage before the filtered first whole stillage enters thecentrifuge 116. Equipment suitable for this purpose are known to those of skill in the art with the aid of the present disclosure. These include pressure screen devices, paddle screen devices and centrifuges with screens to allow protein to be separated which employ pressure, paddles or centrifugal force, respectively to bring a material to be filtered into contact with one or more screens by which liquid and constituents dissolved or suspended therein are separated from solids. Washing may be used to aid in the separation of protein from the whole stillage. In a specific embodiment, thescreener 202 includes one or more screens each having a mesh size selected so as to separate liquid from the first whole stillage and thereby separate some of the protein from the solids. In a more specific embodiment, the screener includes a screen having a mesh size of from 100 openings/in2 to 500 openings/in2, or more specifically any one of 100, 150, 200, 250, 300, 350, 400, 450, or 500 openings/in2. In a particular embodiment, the screener includes a plurality of stages through which the first whole stillage passes sequentially, where the plurality of stages may comprise screens of different mesh sizes. - After exiting the screener, the filtered first whole stillage is then separated by the
centrifuge 116 into first thin stillage and wet cake, and the wet cake is subjected to processes such as the two-stage acid pretreatment process described below. In an aspect of these embodiments, the protein in the filtrate bypasses the two-stage acid pretreatment process and can be recovered in a downstream stage. - In an embodiment as illustrated in
FIG. 3 , a method for producing sugar from lignocellulosic material inwet cake 300 can comprise a step of washing 302 the wet cake to remove a liquid fraction from the wet cake. The washing step can be accomplished in the screening step described above or employed in addition to or in alternative to the screening described above. In anacidification 304 step, an amount of an acid is mixed into the wet cake. Two stages of pretreatment are included in the embodiment, where afirst pretreatment stage 306, comprises agitating the wet cake and the acid for a first pretreatment time at a first pretreatment temperature. Asecond pretreatment stage 308 comprises pretreating the wet cake with the acid in a pretreatment reactor for a second pretreatment time at a second pretreatment temperature. - This embodiment is illustrated further by way of example in
FIG. 4 . According to the embodiment, the method can comprise mixing an amount of an acid into the wet cake. The acid is added in an amount so that the concentration of the acid in the wet cake is from about 0.5 wt % to about 7 wt %. The acid may be added in an amount so as to achieve a pH of the wet cake of from about 1.5 to about 2.5. The acid can be added to the wet cake and mixed therewith using mechanical systems to achieve thorough mixing. In one embodiment, as illustrated inFIG. 4 , amixer 402 designed for mixing high viscosity fluids, also known as a pug mill mixer or mingler, can be used for this purpose. By way of non-limiting example, the acid used can be a mineral acid such as sulfuric, phosphoric, hydrochloric, hydrofluoric, formic, or nitric acid, or a mixture thereof, or an organic acid such as maleic, oxalic, acetic, or fumaric acid, or a mixture thereof. As would be apparent to those having skill in the art with the aid of the present disclosure, other acids may be used to decrease the pH of the wet cake in accordance with present embodiment. - In accordance with the embodiment, the first pretreatment stage can comprise heating and agitating the acidified wet cake to begin hydrolysis of the lignocellulosic material in the wet cake. Heating may not be necessary if the wet cake is already at a sufficiently high temperature. In a particular embodiment, the acidified wet cake can be transferred to a
pretreatment vessel 304 for this purpose. In a more particular embodiment, this vessel is a cone-bottomed tank equipped with an agitator, where agitation of the material is performed for a first pretreatment time. In other embodiments, a horizontal or vertical pipe could be used for this step. In a particular embodiment, the acidified wet cake is heated before it is transferred to thepretreatment vessel 404, for example while it is in themixer 402. In another embodiment, the acidified wet cake is heated in thepretreatment vessel 404. - In a particular aspect of the two-stage acid pretreatment process, this first pretreatment stage is accomplished without employing high pressures. In a particular embodiment, the first stage is conducted with the acidified wet cake at a first pretreatment pressure that is from slightly negative (about −1 psig) to about 10 psig. According to more specific embodiments, the first pretreatment pressure can be from about −1 psig to about 5 psig, or from 0 psig to about 6 psig, or from 0 psig to about 10 psig.
- The wet cake is heated to a first pretreatment temperature for the first stage of pretreatment. This can be done during acidification in the
mixer 402 or during agitation in thepretreatment vessel 404. Alternatively, the wet cake may be hot (e.g., 170° F. or above) as it exits from the first whole stillage decanter and therefore may not need to be heated further. In a particular embodiment, the first pretreatment temperature is from about 170° F. to about 225° F. According to more specific embodiments, the first pretreatment temperature is from about 180° F. to about 215° F., or from about 190° F. to about 200° F., or from about 170° F. to about 200° F., or from about 180° F. to about 225° F. In a particular embodiment, the first pretreatment pressure is at atmospheric pressure and the boiling temperature of pure water at the elevation at which this step is conducted is the upper limit for the first pretreatment temperature. - The first pretreatment time can be selected so as to achieve thorough mixing of the acid and wet cake based on the mass of wet cake resident in this step. In a particular embodiment, the first pretreatment time can be from about 10 minutes to about 300 minutes. In more specific embodiments, the first pretreatment time can be from about 30 minutes to about 180 minutes, or about 20 minutes to about 120 minutes, or from about 5 minutes to about 90 minutes, or from about 15 minutes to about 60 minutes.
- The inventors have surprisingly found that, despite employing relatively low pressure and temperature, the first pretreatment stage achieves effective hydrolysis of cellulose and hemicellulose to a desired yield of soluble sugars (e.g., glucose, xylose, galactose, arabinose, and mannose). In an embodiment, the first pretreatment stage provides a percent yield of soluble glucose of from about 10% to about 60%, or an average percent yield of from about 30% to about 45%. In a more particular embodiment, the percent yield of monomeric glucose from the first stage is from about 0% to about 10%, or an average percent yield of from about 1% to about 4%. In another embodiment, the first pretreatment stage provides a percent yield of soluble xylose of from about 80% to about 100%, or an average percent yield of from about 93% to about 97%. In a more particular embodiment, the yield of monomeric xylose from the first stage is from about 0% to about 25%, or an average percent yield of from about 5% to about 10%. In another embodiment, the first pretreatment stage provides a percent yield of soluble arabinose of from about 85% to about 100%, or an average percent yield of about 95% to about 99%. In a more particular embodiment, the yield of monomeric arabinose from the first stage is from about 0% to about 95%, or an average percent yield of about 45% to about 60%. In still another embodiment, the first pretreatment stage provides a percent yield of soluble galactose of from about 55% to about 100%, or an average percent yield of about 90% to about 95%. In a more particular embodiment, the yield of monomeric galactose from the first stage is from about 0% to about 50%, or an average percent yield of about 10% to about 20%. In still another embodiment, the first pretreatment stage provides a percent yield of soluble mannose of from about 30% to about 100%, or an average percent yield of about 75% to about 90%. In a more particular embodiment, the yield of monomeric mannose from the first stage is from about 0% to about 75%, or an average percent yield of about 10% to about 25%.
- In another aspect of the two-stage acid pretreatment process, in addition to effective conversion of lignocellulosic material to sugars, the production of unfermentable compounds that can arise from the degradation of these sugars (e.g., furfural and hydroxymethylfurfural from degradation of xylose and glucose, respectively) is minimized. The different parameters of this process—residence time, pH, and temperature—combine to influence these outcomes. Generally, addition of less acid will involve conducting this stage at higher temperature and/or for longer residence time in order to achieve similar results compared to a higher acid concentration. Therefore, in accordance with the present disclosure, the pH of the wet cake and length of the first pretreatment time and the first pretreatment temperature can be selected to achieve desired results. In one example, the first pretreatment stage can be done by selecting a higher pH (i.e., adding less acid) in combination with a higher first pretreatment temperature, a longer first pretreatment time, or both. In another example, a lower pH is selected in combination with a lower first pretreatment temperature, a shorter first pretreatment time, or both. In still another example, higher pH and lower first pretreatment temperature can be employed with a longer first pretreatment time. In another example, a lower pH can be selected in combination with a lower first pretreatment temperature and a longer first pretreatment time.
- One aspect of the pretreatment process is that mixing and the selection of temperature and time can allow for more complete hydrolysis by a given amount of acid added to the wet cake. Therefore, one potential result is a decrease in the amount of acid required to achieve desired yields of fermentable sugars. In one aspect, this provides for more efficient use and less waste of acid. The amount of acid can be selected so as to minimize undesired downstream effects. For example, one may seek to decrease the amount of sulfur in dried distillers grains produced by this method by managing the amount of sulfuric acid used in pretreatment.
- The content of solids and liquids in wet cake can influence the effectiveness of acid in pretreatment. That is, a higher liquid content may dilute or buffer the added acid or otherwise reduce the amount of interaction between the acid and the lignocellulosic material in the wet cake. In a particular embodiment, preparation of wet cake for acidification can include bringing its solids content to a level of from about 15 wt % to about 40 wt %, or more particularly from about 20 wt % to about 35 wt %. In a specific embodiment, acidification can be preceded by washing the wet cake in a
washer 406 to remove a portion of the liquid fraction of the wet cake and thereby achieve a desired solids content in the wet cake. The washing can also have the benefit of reducing the buffering capacity of the wet cake, or more particularly the liquid fraction of the wet cake. Washing can be done with water or other aqueous liquid. In a specific embodiment, liquid reclaimed from other unit processes or a by-product of such processes, such as condensate from evaporation of first thin stillage, can be used for this step. In an aspect of this embodiment, the liquid fraction removed from the wet cake is substantially replaced by a non-buffering, low pH liquid (the condensate). - To facilitate further hydrolysis of cellulose and hemicellulose to fermentable sugars, after the first pretreatment time has concluded a second pretreatment stage can comprise directing the wet cake to a
pretreatment reactor 408, wherein the wet cake is subjected to a higher temperature and a higher pressure than those employed in the first pretreatment stage. In a particular embodiment, the wet cake is heated to a second pretreatment temperature higher than the first pretreatment temperature used in the first stage and held substantially at that temperature for a second pretreatment time. In a particular embodiment, the second pretreatment temperature is from about 230° F. to about 330° F. According to more specific embodiments, the second pretreatment temperature can be from about 245° F. to about 320° F., or from about 250° F. to about 300° F., or from about 270° F. to about 300° F., or from about 230° F. to about 310° F. In a more particular embodiment, the wet cake is also subjected to a second pretreatment pressure that is higher than the first pretreatment pressure. Higher pressures at this stage may be employed to maintain a sufficiently high wet cake temperature. - Heating at this stage can be accomplished by steam injection, or other heating methods as will be recognized by those of skill in the art with the aid of the present disclosure. In a particular embodiment, the wet cake is heated before it is transferred to the
pretreatment reactor 408, for example by steam injection in transit to thepretreatment reactor 408. In another embodiment, the acidified wet cake is heated in thepretreatment reactor 408. As with the first stage, the results of the second pretreatment stage can be influenced by the particular combination of wet cake pH, second pretreatment temperature, and second pretreatment time. As such, the second pretreatment temperature and second pretreatment time can be selected in view of the amount of acid added during acidification so as to enhance the yield of soluble sugars and minimize the creation of degradation products. - The high yield of soluble sugars in the first pretreatment stage allows operation of the
pretreatment reactor 408 at lower temperatures and pressures than might otherwise be required to achieve similar yields of oligomeric and monomeric sugars. In this way the capital cost and energy expenditure of pretreatment may be reduced. Lower pretreatment temperatures also reduce the amount of undesirable sugar degradation products produced, improving the efficiencies of downstream enzymatic hydrolysis and fermentation steps. The commencement of hydrolysis in the first stage also allows for a relatively short second pretreatment time. In a particular embodiment, the second pretreatment time can be from about 3 minutes to about 100 minutes. According to more specific embodiments, the second pretreatment time can be from about 3 minutes to about 50 minutes, or about 30 minutes to about 80 minutes, or from about 5 minutes to about 8 minutes, or from about 20 minutes to about 50 minutes. However, it will be understood that a single pretreatment stage, e.g., the second pretreatment stage, can alternatively be relied upon to produce sugars from lignocellulosic material in the wet cake in accordance with the present disclosure. - From the present disclosure and the illustration in
FIG. 4 , it will be appreciated that a system for pretreating wet cake to produce sugar from lignocellulosic material contained therein can comprise amixer 402 configured to receive an acid and to receive wet cake, and to mix the acid into the wet cake to produce an acidified wet cake; apretreatment vessel 404 operably connected to themixer 402 and configured to receive the acidified wet cake from themixer 402 and agitate the acidified wet cake at a first pretreatment temperature and a first pretreatment pressure; and apretreatment reactor 408 operably connected to the pretreatment vessel and configured to receive the acidified wet cake from the pretreatment vessel and react the acidified wet cake at a second pretreatment temperature and a second pretreatment pressure. Thepretreatment reactor 408 can be a reactor designed to operate at the temperature and pressures discussed above. In a particular embodiment, the reactor is designed so that substantially the entire volume of acidified wet cake is uniformly exposed to the second pretreatment temperature over the second pretreatment time. Possible reactor configurations include one or more continuous stirred reactors in series, one or more batch reactors, or a horizontal or vertical vessel or pipe. In a specific embodiment, thepretreatment reactor 408 is a plug flow reactor. As described above, thepretreatment vessel 404 can be a cone-bottomed tank equipped with an agitator, or a horizontal pipe or vertical pipe. - In the second pretreatment stage additional polysaccharides in the acidified wet cake are converted to oligomers and monomers, and oligomeric sugars entering this stage are converted to monomers and smaller oligomers. In an embodiment, the second pretreatment stage provides a percent yield of soluble glucose of from about 10% to about 60%, or an average percent yield of about 35% to about 45%. In a more particular embodiment, the yield of monomeric glucose from the second stage is from about 0% to about 30%, or an average percent yield of about 5% to about 10%. In another embodiment, the second pretreatment stage provides a percent yield of soluble xylose of from about 50% to about 100%, or an average percent yield of about 90% to about 95%. In a more particular embodiment, the yield of monomeric xylose from the second stage is from about 0% to about 65%, or an average percent yield of about 20% to about 30%. In another embodiment, the second pretreatment stage provides a percent yield of soluble arabinose of from about 40% to about 100%, or an average percent yield of about 85% to about 95%. In a more particular embodiment, the yield of monomeric arabinose from the second pretreatment stage is from about 20% to about 100%, or an average percent yield of about 65% to about 75%. In still another embodiment, the second pretreatment stage provides a percent yield of soluble galactose of from about 55% to about 100%, or an average percent yield of about 85% to about 95%. In a more particular embodiment, the yield of monomeric galactose from the second stage is from about 2% to about 100%, or an average percent yield of about 35% to about 45%. In still another embodiment, the second pretreatment stage provides a percent yield of soluble mannose of from about 30% to about 100%, or an average percent yield of about 75% to about 85%. In a more particular embodiment, the yield of monomeric mannose from the second stage is from about 0% to about 100%, or an average percent yield of about 20% to about 30%.
- Saccharification can then be performed on the pretreated wet cake, comprising using enzymatic hydrolysis to produce further monomeric sugars from oligosaccharides and polysaccharides remaining after the two-stage acid pretreatment process. In an embodiment as shown in
FIG. 5 , a method of hydrolyzing lignocellulosic material inwet cake 500 can comprise: feeding 502 wet cake comprising lignocellulosic material into a recycling reactor at a feed rate;enzyme addition 504, in which at least one enzyme is added to the wet cake; andrecycling 506 the wet cake and at least one enzyme through the recycling reactor at a recycle rate and for a residence time to hydrolyze the lignocellulosic material to produce an amount of monomeric sugar in the wet cake. - The embodiment as illustrated further by way of example in
FIG. 6 . According to the embodiment, the process can comprise feeding the acidified wet cake into arecycling reactor 602 at a feed rate and adding one or more enzymes selected to act upon the oligosaccharides and polysaccharides. As will be appreciated by those of skill in the art with the aid of this disclosure, enzymes known to be effective at breaking up oligosaccharides and lignocellulosic material can be used in this process, and include various cellulases and hemicellulases, as well as amylase and beta-glucosidase. More specifically, hemicellulases can include xylanase, mannase, galactidase, and arabinase. To facilitate activity of the enzyme(s), the pH of the wet cake can also be increased by the addition of a basic solution, either before or after the wet cake enters therecycling reactor 602. Bases that can be used in this step include, without limitation, ammonia, aqua ammonia, sodium hydroxide, sodium bicarbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, and magnesium hydroxide. Other suitable bases for use in this step will be apparent to those of skill in the art having the benefit of this disclosure. The wet cake can first be cooled if needed to bring it to a temperature at which the selected enzyme(s) will have the desired level of activity. As illustrated inFIG. 6 , cooling can be performed by flashing a vapor off of the wet cake in aflash drum 604. As will be appreciated by those of skill in the art with the aid of this disclosure, other approaches and equipment suitable for cooling wet cake can be employed in addition or in alternative to flashing, including without limitation, multiple flash steps and passing the wet cake through one or more heat exchangers. - The process can continue with recycling the wet cake repeatedly through the
recycling reactor 602 for a selected residence time, during which the enzyme(s) is mixed substantially uniformly throughout the volume of wet cake and begins to hydrolyze the oligosaccharides and lignocellulosic material. In a particular embodiment, therecycling reactor 602 is operated at a recycle rate that is higher than the mass flow rate at which the wet cake is fed into therecycling reactor 602. In an embodiment, the recycle rate is from about 1 to about 10 times the feed rate. In a more specific embodiment, the recycle rate is from about 5 to about 10 times the feed rate. In a still more specific embodiment, the recycle rate is from about 3 to about 6 times the feed rate. In another specific embodiment, the recycle rate is from about 1 to about 5 times the feed rate. - Outcomes from recycling the wet cake include, but are not limited to, reducing the viscosity of the wet cake entering the
recycling reactor 602 due to dilution; 2) aiding reduction of the temperature of the wet cake to a target temperature for enzymatic activity; and 3) effective mixing of the enzyme(s) into the wet cake. In a particular embodiment, the wet cake has a viscosity from 250 cp to 3000 cp upon exiting therecycling reactor 602. In a more specific embodiment, the wet cake has a viscosity of from 500 cp to 2000 cp. In one aspect, the effective mixing allows for using cost-effective amounts of enzymes. - The residence time during which a volume of wet cake and enzyme(s) is present in the reactor can be selected to be sufficient to achieve the above objectives. In a particular embodiment, the residence time is from about 6 hours to about 15 hours. In more particular embodiments, the residence time is from about 10 hours to about 13 hours, or from about 12 hours to about 15 hours, or more particularly from about 11 hours to about 13 hours. In a particular embodiment, the enzymatic hydrolysis process is a flow-through process, where the feed rate, recycle rate, and residence time are selected so that each unit volume of wet cake entering the reactor undergoes substantially similar processing conditions.
- From the present disclosure and the illustration in
FIG. 6 , it will be appreciated that asystem 600 for saccharification of lignocellulosic material in wet cake can comprise arecycling reactor 602 configured to receive wet cake, such as from theflash drum 604, and at least one enzyme and allow for reaction between the same. Therecycling reactor 602 can be further configured to receive a recycle stream of the wet cake and enzyme(s) at a recycle rate that is greater than the feed rate. In a particular embodiment, the recycle rate is from about 1 to 10 times the feed rate. In a more specific embodiment, the recycle rate is from 1 to 3 times the feed rate. In a still more specific embodiment, the recycle rate is from 2 to 4 times the feed rate. Thesystem 600 can include a pump operably connected to therecycling reactor 602 that provides circulation of the recycle stream at the recycle rate. Therecycling reactor 602 can be further configured to receive a base and to combine the base and the wet cake. - The residence time may be sufficient for enzymatic hydrolysis to begin, yet it need not be long enough to complete said hydrolysis. Rather, after initial hydrolysis the wet cake and enzymes may be transferred to a
fermentation tank 606 where further hydrolysis occurs prior to starting fermentation. Prior to starting fermentation, the temperature of the wet cake is reduced from the hydrolysis temperature (typically in the range of about 120° F. to 150° F.) to the optimum fermentation temperature (typically about 95° F.). Hydrolysis continues at a slower rate during fermentation. - In some embodiments, the pretreated wet cake is transferred to one of a plurality of saccharification tanks. The wet cake can first be cooled if needed to bring it to a temperature at which the selected enzyme(s) will have the desired level of activity. The pH in the saccharification tank is adjusted if needed and enzymes are added. In a particular embodiment, the plurality of saccharification tanks are functionally connected in series to perform saccharification in a serial manner, wherein enzymatic hydrolysis is allowed to proceed for a time in the first saccharification tank, after which the wet cake is transferred to another saccharification tank in the series for further enzymatic hydrolysis. This transferring step is repeated with the remaining saccharification tanks in the series, after which the wet cake and enzymes are transferred to the
fermentation tank 606. In a specific embodiment, the series can include therecycling reactor 602, into which the pretreated wet cake is transferred and in which enzymatic hydrolysis begins before the wet cake is transferred to the first saccharification tank. In an aspect, the size and number of saccharification tanks can be adjusted to provide a desired total residence time. In a specific embodiment, the total residence time is from about 35 hours to about 55 hours. In a more specific embodiment, the total residence time is about 40 hours. - In another particular embodiment, the plurality of saccharification tanks are configured in parallel to perform saccharification in a batch manner, wherein a batch of pretreated wet cake is transferred to one of the saccharification tanks in which the pH is adjusted if needed, enzymes are added, and enzymatic hydrolysis proceeds for a residence time, and then the wet cake and enzymes are transferred to the
fermentation tank 606. Another batch of pretreated wet cake can be transferred into another one of the saccharification tanks to undergo the same or a similar process. In a more particular embodiment, saccharification comprises using at least three saccharification tanks cycling at intervals, for example where one or more saccharification tanks are holding wet cake undergoing hydrolysis, while one or more of the other saccharification tanks are being filled with pretreated wet cake, and one or more of the remaining saccharification tanks are transferring wet cake and enzymes to thefermentation tank 606. In an aspect, each saccharification tank can be sized so as to hold the wet cake and enzymes for a desired residence time. In a specific embodiment, the residence time is from about 35 hours to about 55 hours. In a more specific embodiment, the residence time is about 40 hours. - Fermentation creates cellulosic ethanol and carbon dioxide from the sugars in the wet cake. To commence this step, an ethanol-producing microbe is added to the wet cake. It will be appreciated by those skilled in the art in view of the present disclosure that one or more of any ethanol-producing microbes, including native and genetically modified microbes, may be used, such as Zymomonas mobilis, Saccharomyces cerevisiae, Escherichia coli, Bacillus subtilis, and Pichia pastoris. As indicated above, enzymatic hydrolysis of remaining polysaccharides and oligosaccharides begun in the previous step may continue in the
fermentation tank 606. In an aspect of the embodiment, the contemporaneous fermentation of sugars in the wet cake may promote more complete hydrolysis of the polysaccharides by decreasing end-product inhibition of the hydrolysis reactions. - According to one embodiment, hydrolysis and fermentation of wet cake exiting the
recycling reactor 602 may be done in batches among a number of tanks so that adjacent processes can operate continuously, if desired. To accommodate the beer output stream from thefermentation tank 606 and to facilitate controlled delivery to subsequent processes, a batch of beer produced infermentation tank 606 can be collected in abeer well 608. Carbon dioxide and other vapor streams may be collected from the fermentation tank(s) and the beer well 608 and scrubbed using techniques known in the art to remove ethanol and other components entrained in the vapor. - Ethanol can be recovered from the beer using any number of techniques and equipment known in the art to be suitable for this purpose. More particularly, typical techniques, generally termed distillation, involve separating the liquid and solid components by initiating the transition of the liquid component to vapor, which is then condensed and collected. Typically, the initial output of this process is a mixture of ethanol, water, and other volatile components. Further steps can be performed on this mixture to separate ethanol from the other components, typically by making use of differences in their respective volatilities. A cellulosic ethanol production process is illustrated in
FIG. 7 , in which the beer produced by fermentation is transferred from the beer well 608 to adistillation column 702 to produce a cellulosic ethanol stream and also a whole stillage by-product, referred to herein as “second whole stillage”, comprising the non-volatile components of the beer. In a particular embodiment, the second whole stillage is collected into awhole stillage tank 706. In an aspect of the embodiment, thewhole stillage tank 706 can be equipped with an agitator. - As will be appreciated by those having skill in the art, the percentage of ethanol and water in the cellulosic ethanol stream after a single distillation will depend upon many variables, including the type, length, efficiency, and pressure of the column. The cellulosic ethanol stream can be directed to a
dehydration system 604 to remove water and other non-ethanol volatile components. In a particular embodiment, dehydration can comprise sending the cellulosic ethanol stream through either or both of a rectification column, and one or more molecular sieves. In another embodiment, dehydration can comprise sending the cellulosic ethanol stream through a membrane separation system, in which a pervaporation membrane is used to separate water and ethanol through differential permeation. - The second whole stillage can exhibit particular characteristics that distinguish it from the first whole stillage produced by primary ethanol production. In one embodiment, as a result of the pretreatment and saccharification processes of the present disclosure, most or all of the carbohydrates in the lignocellulosic material in the wet cake feedstock is converted to fermentable sugars, which are then converted to ethanol in fermentation. Therefore, the second whole stillage by-product of the present disclosure comprises low weight percentages of residual fiber, starch, and cellulose and a high percentage weight of crude protein. In a particular embodiment, the second whole stillage has a percent by weight of crude protein from about 40% to about 55%. In more specific embodiments, crude protein content of the second whole stillage is from about 40 wt % to about 50 wt %, or from about 35 wt % to about 55 wt %, or from about 35 wt % to about 50 wt %. In another particular embodiment as shown in
FIG. 8 , protein is filtered from the first whole stillage in thescreener 202 into a filtrate stream as described above and the filtrate stream is combined with the second whole stillage in thewhole stillage tank 706. Agitation can be employed in thewhole stillage tank 706 to provide thorough mixing of the filtrate into the second whole stillage. One result of the processes described herein is that protein (both plant protein and yeast or other microbes) will constitute a significant percentage of the total mass of the second whole stillage, making it a good source material for production of high-protein dried distillers grains and other products derived therefrom. - In accordance with the present disclosure, co-product production from the second whole stillage can comprise separating the second whole stillage into its liquid and solid components. Separation techniques and equipment suitable for this process are well-known in the art. In one embodiment, the second whole stillage can be processed using the same or similar approaches as are used in primary ethanol production plants. In an exemplary embodiment as shown in
FIG. 9 , the second whole stillage can be fed from thewhole stillage tank 706 into acentrifuge 902, such as a decanter centrifuge, which separates the second whole stillage into a semi-solid low-fiber slurry and a thin stillage (termed hereinafter as “second thin stillage”). Adryer 904 can be used to remove residual moisture from the resulting low-fiber slurry, thereby producing a dried distillers grains (DDG) having a high protein content. - Dried distillers grains with solubles (DDGS) can be made by recombining syrup (produced from the evaporation of first thin stillage) with wet distillers grains before drying. Accordingly, it is contemplated that syrup produced from the evaporation of both first thin stillage and second thin stillage can be combined with the low-fiber slurry in making DDGS in accordance with the present disclosure. However, the inventors have surprisingly found that a higher quality DDGS may be attainable when the low-fiber slurry of the present disclosure is dried without the addition of the second thin stillage. In this embodiment, syrup produced from the first thin stillage from the primary ethanol
production plant evaporator 118 is still mixed with the low-fiber slurry prior to drying, but without inclusion of the second thin stillage or syrup produced therefrom. - In certain embodiments, the DDGS in accordance with the present disclosure has a total protein content of from about 40 wt % to about 70 wt %. In a more particular embodiment, the DDGS has a total protein content of from about 50 wt % to about 65 wt %. In other particular embodiments the total protein content can be from about 45 wt % to about 55 wt %, or from about 40 wt % to about 60 wt %, or from about 50 wt % to about 70 wt %. In an aspect of these embodiments, the DDGS also has a low fiber content due to the extent of breakdown and conversion of the fiber in the wet cake feedstock by the two-stage acid pretreatment process and the enzymatic hydrolysis process of the present disclosure. In a more specific aspect, the DDGS comprises fiber in an amount from about 0.5 wt % to about 2 wt %. The DDGS in accordance with the present disclosure can also include particular nutrients of interest in animal health. In one aspect, the DDGS contains glutamic acid in an amount from about 6 wt % to about 10 wt %, or more specifically from about 7 wt % to about 9 wt %. In another aspect, the DDGS contains aspartic acid in an amount from about 1 wt % to about 5 wt % or more specifically from about 2 wt % to about 4 wt %. In another aspect, the DDGS contains alanine in an amount from about 2 wt % to about 5 wt % or more specifically from about 3 wt % to about 4 wt %. In another aspect, the DDGS contains vitamin A in an amount from about 800 I.U./kg and about 1200 I.U./kg, or more specifically from about 900 I.U./kg to about 1100 I.U./kg. In another aspect, the DDGS contains vitamin E in an amount from about 450 I.U./kg and about 650 I.U./kg, or more specifically from about 400 I.U./kg to about 600 I.U./kg.
- In another aspect, a low fiber content in the DDGS of the present disclosure gives it enhanced digestibility and digestible energy. In a particular aspect, the DDGS has a digestible energy content of at least 1500 kcal/lb. In a more specific aspect, digestible energy content is from 1500 kcal/lb to about 2000 kcal/lb. In another aspect, low fiber content imparts particular physical characteristics, such as a fine consistency and higher density. In a particular embodiment the DDGS has a density of from about 30 lbs/ft3 to about 40 lbs/ft3, or more specifically from about 34 lbs/ft3 to about 38 lbs/ft3, or from about 30 lbs/ft3 to about 35 lbs/ft3, or from about 34 lbs/ft3 to about 40 lbs/ft3.
- As noted above, rather than recombination with the low-fiber slurry to produce DDGS for animal feed, the second thin stillage can be directed to other uses. In co-product production, the second thin stillage can be directed to an evaporator, where evaporation of water from the second thin stillage can proceed until the second thin stillage becomes a syrup, or further to produce a substantially solid material, either of which can be used as an animal feed additive. In a particular embodiment, the second thin stillage stream is combined with the first thin stillage stream for evaporation in the same evaporator, e.g.,
evaporator 118. Alternatively, as shown inFIG. 9 , the second thin stillage can be directed to ananaerobic digester 906, where anaerobic digestion can be performed on the second thin stillage to produce a biogas which can be scrubbed and added to existing natural gas pipelines or the biogas can be used in the primary ethanol plant's boiler. This approach may be undertaken as an effective way to remove the chemical oxygen demand of the second thin stillage. - Another aspect of the present disclosure with respect to corn-based ethanol production processes is that with less fiber to bind corn oil contained in the second whole stillage by-product, more of the corn oil is decanted off into the second thin stillage. Accordingly, in one embodiment a distillers corn oil stream can be obtained from the second thin stillage. In a particular embodiment, the second thin stillage is combined with the first thin stillage for further processing, e.g., evaporation to produce a syrup from which distillers corn oil is extracted. Recovery of corn oil from thin stillage can be achieved by extraction systems and methods known in the art, including evaporation, centrifugation, and solvent extraction. In a specific embodiment, the second thin stillage provides an additional yield of DCO of from about 0.1 to 0.5 lbs per bushel of corn feedstock. In another specific embodiment, the additional yield of DCO is from about 0.1 lbs to about 0.7 lbs per pound of wet cake solids.
- It is contemplated that particular benefits may arise from adding one or more of the processes described above to an existing corn-based ethanol production process. In one aspect, this can provide additional ethanol production in the form of a cellulosic ethanol stream. As illustrated in
FIG. 10 (a portion of which is shown inFIG. 1 ) which shows an enhancedethanol production plant 1000 in accordance with the present disclosure, a method for increasing ethanol production associated with an existingethanol production plant 100 can comprise feeding wet cake resulting from separation of first whole stillage into a cellulosicethanol production process 1002, which can comprise any of the steps and processes described above. As illustrated inFIG. 10 , equipment for this added process can comprise, without limitation, awasher 406 for the step of washing the wet cake; amixer 402 for the step of acidification by mixing acid into the wet cake; apretreatment vessel 404 for the step of agitating the acidified wet cake; apretreatment reactor 408 for performing the second pretreatment stage; arecycling reactor 602 in which the wet cake is recycled with enzymes to initiate enzymatic hydrolysis; afermentation tank 606 for furthering the hydrolysis of the wet cake and fermenting sugars produced in the foregoing processes; and adistillation column 702 to recover a stream of cellulosic ethanol and produce a by-product of second whole stillage. In a particular example as shown inFIG. 10 , the cellulosic ethanol stream can be directed to an existingdehydration system 114 system in the existingethanol production plant 100. In another particular example as shown inFIG. 10 , first whole stillage from thedistillation system 112 can be filtered in ascreener 202 and the resulting filtrate combined with second whole stillage in awhole stillage tank 706, wherein protein contained in the filtrate bypasses the intervening stages. - In another aspect, a modification of existing corn-based ethanol production provides an increased yield of distillers corn oil. As illustrated in
FIG. 10 , a method for increasing distillers corn oil production associated with an existingethanol production plant 100 is also provided by feeding wet cake resulting fromcentrifuge 116 of first whole stillage into a cellulosicethanol production process 1002. The second whole stillage by-product from thedistillation column 702 is separated with acentrifuge 902 into a low-fiber slurry and second thin stillage. In a particular embodiment as shown inFIG. 10 , the second thin stillage is combined with the first thin stillage for evaporation to produce a syrup from which distillers corn oil is extracted. The syrup from the existing ethanol plant's evaporator and the low-fiber slurry can then be directed to adryer 904 for preparation of a DDGS in accordance with the present disclosure. Thedryer 904 may be dedicated to drying of the low-fiber slurry and syrup, due to all of the wet cake from the existing ethanol production plant being directed to the added cellulosic ethanol production. - In an alternative embodiment of an enhanced
ethanol production plant 1100 as shown inFIG. 11 , the second thin stillage can be directed to ananaerobic digester 906, where anaerobic digestion can be performed on the second thin stillage to produce a biogas which can be scrubbed and added to existing natural gas pipelines or the biogas can be used in the primary ethanol plant's boiler. This approach may be undertaken as an effective way to remove the chemical oxygen demand of the second thin stillage. - It will be appreciated from the foregoing that energy expenditures and costs associated with the added processes can be offset to a degree, not only by the added value of increased product and co-product streams, but also by directing process outputs back into appropriate units of the existing plant. In addition, resources and by-products associated with individual processes can be re-used or re-purposed. For example, steam generated from flashing steps can be used for heating in other steps such as acidification and pretreatment, as well as for driving beer through distillation columns. In addition, the enhanced production provided by the processes described herein allow existing ethanol production plants to forego resource-intensive corn milling techniques (e.g., wet milling) in preparing the corn feedstock for use.
- Corn wet cake from primary ethanol production was subjected to the following cellulosic ethanol production process to produce a dried distillers grains with solubles. Steps 1-5 were performed at an ethanol plant modified according to embodiments herein. Steps 6-9 were performed at a research center according to embodiments herein.
-
- 1. The corn wet cake (3,473 lbs, 32% solids) was mixed in an agitated cone bottom tank with 135 gallons of process condensate (water) and 85 lbs of 40 wt % sulfuric acid;
- 2. The acidified wet cake was heated with direct steam injection to about 190° F. and held at that temperature for one hour (i.e., first pretreatment);
- 3. The wet cake was pumped through a horizontal plug flow reactor at about 280° F. with a residence time of 25 minutes (i.e., second pretreatment);
- 4. Wet cake was continuously discharged from the reactor to the flash tank and then to the enzymatic hydrolysis tank. The temperature of the wet cake was lowered to 140° F. and the pH was adjusted to 4.5 with aqueous ammonia, and cellulase and hemicellulase enzymes were added;
- 5. Hydrolysis proceeded for about 50 hours; the temperature was lowered to 95° F. followed by addition of a GMO saccharomyces yeast and fermentation for about 50 hours;
- 6. The resulting beer was distilled in a beer column;
- 7. The whole stillage was decanted in a centrifuge to produce a second wet cake and thin stillage (i.e., second thin stillage);
- 8. The thin stillage was evaporated to produce syrup;
- 9. The syrup was combined with the second wet cake and dried in a ring dryer to produce DDGS having the following properties:
-
TABLE 1 Chemical and Physical properties of typical dried distillers grains with solubles (DDGS) produced from the cellulosic ethanol process described above. The DDGS exhibited a typical density of 35-37 lbs/ft3. Chemical and Physical Properties Min Max Moisture % — 13.0 Total Protein, % 40.0 — Fiber (crude), % — 2.0 Fat (crude), % 1 — Ash, % 8.0 -
TABLE 2 Energy analysis of the dried distillers grains with solubles. Energy Typical, d.b. Kcal/lb kcal/kg Digestible Energy 1600 3530 Metabolizable Energy 1100 2425 Net Energy Gain 600 1320 Net Energy Maintenance 900 1985 Net Energy Lactation 800 1765 Total Digestible Nutrients, % 88 -
TABLE 3 Nutritional content of the dried distillers grains with solubles. Nutrients Typical, % DM Protein 45 Fat 1.5 Fiber 1.5 ADF 3.5 NDF 4 Ash 8 Alanine 3.6 Arginine 1.5 Aspartic Aid 2.8 Cystine 0.8 Glutamic Acid 8.9 Glycine 1.7 Histidine 1 Isoleucine 1.7 Leucine 5.6 Lysine 1 Methionine 1 Phenylalanine 2.3 Proline 3.9 Serine 2.4 Threonine 1.7 Tryptophan 0.3 Tyrosine 1.7 Valine 2.2 Vitamins Vitamin A, IU/100 g 107.2 Vitamin E IU/kg 535 Niacin mg/kg 19.6 Inositol mg/100 G 2020 Folic Acid mg/kg 0.89 Protein-Ruminants Estimated RUP, % CP 69 Rumen, % CP 41 Intestine, % CP 42 Total digested, % CP 74 Minerals Typical, as is Magnesium, % 0.5 Phosphorus, % 1.7 Potassium, % 1.7 Chloride, % 0.2 Sulfur, % 1.7 Calcium, ppm 300 Sodium, ppm 400 Copper, ppm 8.6 Iron, ppm 795 Manganese, ppm 25 Selenium, ppm 0.2 Zinc, ppm 79 - The effect of three parameters (% acid added, temperature, and residence time) were measured in forty-three trials in which corn wet cake was subjected to a two-stage pretreatment process similar to Steps 1-2 (first pretreatment stage) and Step 3 (second pretreatment stage) in Example 1. The yields of soluble sugars and monomeric sugars resulting from each stage are shown below.
-
TABLE 4 Percent yields of five soluble sugars produced in the first pretreatment stage. First Pretreatment % Acid Temp Time Yield of Total Soluble Sugars Stage Added (° F.) (min) Glucose Xylose Galactose Arabinose Mannose Average 3.7 188 64 39.0% 96.8% 94.7% 98.4% 83.4% MIN 2.0 162 10 19.3% 87.3% 64.6% 91.2% 0.0% MAX 6.2 196 307 51.3% 100.0% 100.0% 100.0% 100.0% Std Dev 0.9 8.6 67 6.2% 3.5% 8.2% 2.4% 22.6% -
TABLE 5 Percent yields of five monomeric sugars produced in the first pretreatment stage. First Pretreatment % Acid Temp Time Yield of Monomeric Sugars Stage Added (° F.) (min) Glucose Xylose Galactose Arabinose Mannose Average 3.7 188 64 1.7% 7.1% 11.6% 52.0% 16.1% MIN 2.0 162 10 0.0% 0.7% 3.0% 2.3% 0.0% MAX 6.2 196 307 7.9% 20.4% 42.1% 89.8% 69.4% Std Dev 0.9 8.6 67 2.3% 4.4% 7.9% 16.1% 17.1% -
TABLE 6 Percent yields of five soluble sugars produced in the second pretreatment stage. Second Pretreatment % Acid Temp Time Yield of Total Soluble Sugars Stage Added (° F.) (min) Glucose Xylose Galactose Arabinose Mannose Average 3.8 268 32 41.2% 92.8% 91.6% 90.9% 81.0% MIN 2.0 244 3 16.4% 54.0% 63.5% 46.2% 0.0% MAX 6.2 320 205 52.4% 100.0% 100.0% 100.0% 100.0% Std Dev 1.0 15 28 6.1% 7.7% 10.1% 8.8% 21.1% -
TABLE 7 Percent yields of five monomeric sugars produced in the second pretreatment stage. Second Pretreatment % Acid Temp Time Yield of Monomeric Sugars Stage Added (° F.) (min) Glucose Xylose Galactose Arabinose Mannose Average 3.8 268 32 7.6% 25.3% 40.6% 70.4% 23.4% MIN 2.0 244 3 0.0% 2.8% 5.6% 22.1% 0.0% MAX 6.2 320 205 20.4% 60.0% 99.3% 96.4% 119.8% Std Dev 1.0 15 28 5.5% 13.8% 20.3% 10.8% 26.8% - The above yields were determined by liquid chromatography. It is believed that the results reported for mannose, particularly the minimum percent yields (“MIN”), may reflect interference from other compounds in the samples.
- While specific embodiments and applications have been illustrated and described, it is to be understood that the invention is not limited to the precise configuration and components disclosed herein. Various modifications, changes, and variations which will be apparent to those skilled in the art may be made in the arrangement, operation, and details of the methods and systems of the present invention disclosed herein without departing from the spirit and scope of the invention.
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