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    • 专利摘要:
    OIL COMPOSITION AND METHOD FOR PRODUCTION THEREOF.The present invention relates to a corn oil composition comprising unrefined corn oil having a free fatty acid content of less than approximately 5 weight percent and methods for producing the same.
    公开号:BR112013005449A2
    申请号:R112013005449-2
    申请日:2011-09-07
    公开日:2020-08-25
    发明作者:Jason Bootsma
    申请人:Poet Research, Inc.；
    IPC主号:
    专利说明:

    Descriptive Report of the Patent of Invention for "OIL COMPOSITION AND METHOD FOR PRODUCTION THEREOF". . FIELD | The present invention relates to corn oil compositions and, in particular, corn oil compositions which contain a free severe acid content of less than 5 percent by weight as well as methods for producing the same.
    FUNDAMENTALS : - Ethanol can be produced starting from grain-based raw materials (eg corn, sorghum/millet, barley, wheat, soy, etc.), starting from . sugar (eg sugar cane, sugar beets etc.) or starting from biomass (eg lignocellulosic raw materials such as Pa- nicum virgatum, corn cobs and fodder, wood or other plant material).
    In a conventional ethanol plant, corn is used as a stock and ethanol is produced from the starch contained in the corn. Corn kernels are cleaned and ground to prepare the starch-containing material for processing. Corn kernels can also be fractionated to separate material containing starch (eg, endosperm) from other matter (such as fiber and germ). The material containing the starch is suspended with water and liquefied to facilitate saccharification, when the starch is converted to sugar (e.g., glucose) and fermentation, when the sugar is converted by an ethanol producer (e.g., yeast). ) in ethanol. The product of fermentation is beer, which comprises a liquid component, including ethanol, water, and soluble components, and a solid component, including unfermented particulate matter (among other things). The fermentation product is sent to a distillation system where the fermentation product is distilled and dehydrated to ethanol. Residual matter (e.g., whole grain residues after alcohol extraction) comprises water, soluble components, oil, and unfermented solids (e.g., the solid components of beer with substantially all of the alcohol removed, which can be dried into dry grains of destination
    (DDG) and marketed, for example, as an animal feed product). Other co-products (eg syrup and oil contained in syrup) - can also be recovered from whole grain residues after alcohol extraction.
    The water removed from the fermentation product in the distillation can be treated for reuse in the plant.
    Various processes for recovering oil from a fermentation product are currently known in the art.
    Such processes, however, can be costly, ineffective or even dangerous.
    For example, some processes, such as the one disclosed in WO 2008/039859 , use a solvent extraction technique which in turn requires the use of volatile organic compounds such as hexane.
    Other processes, such as the one set forth in the U.S. Patent Application Publication.
    No. ' 2007/0238891, use large amounts of heat.
    Still other conventional processes, such as that set forth in the U.S. Patent Application Publication.
    No. 2006/0041152 and 2006/0041153 simply apply centrifugal force to a fermented product in an attempt to separate an oily product.
    Conventional processes to recover oil from a fermentation product can sacrifice oil quality such that the oil contains a high level of free fatty acids.
    The presence of a high level of acids | Free fatty acids can impair the production of end products such as, for example, the yield and quality of any biodiesel eventually produced with oil as a raw material.
    Processes for producing ethanol, such as the Process presented in WO 2004/081 193, produce fermentation by-products that contain higher levels of oils while maintaining a low level of free fatty acids.
    However, by applying centrifugal force to the fermented product, it can | an emulsion is formed that holds the valuable oil within the emulsion. | Thus, there is a problem in that both conventional and new processes alike cannot effectively, efficiently, or safely separate or "break" quality oil from a product. fermented.
    SUMMARY OF THE INVENTION This invention relates to a corn oil composition which comprises unrefined corn oil with corn oil having a free fatty acid content of less than approximately 5 weight percent and a moisture content of from approximately 0.2 to approximately 1 weight percent, wherein the moisture content comprises an alkali metal ion and/or an alkali metal ion content greater than 10 ppm. o... This invention also relates to a method of providing a corn oil composition from a fermentation residue. corn production comprising the steps of a) adjusting the pH of the corn fermentation residue to provide a corn oil layer and an aqueous layer and b) separating the corn oil layer from the aqueous layer to provide the oil composition of corn.
    This invention also relates to a method for providing a corn oil composition from a corn fermentation residue comprising the steps of a) adjusting the pH of the corn fermentation residue with a depleted alkaline wash solution to providing a corn oil layer and an aqueous layer and (b) separating the corn oil layer from the aqueous layer to provide the corn oil composition.
    This invention also relates to a raw material for the production of biodiesel, wherein the raw material comprises a corn oil composition comprising unrefined corn oil having | a free fatty acid content of less than approximately 5 percent in | Weight; a moisture content of from approximately 0.2 to approximately 1 weight percent; wherein the moisture content comprises an alkali metal ion and/or an alkali metal ion content greater than 10 ppm. In another embodiment, the amount of fatty acid content is less than 4 percent by weight.
    This invention also relates to a still dry grain comprising approximately 4% or less fat.
    BRIEF DESCRIPTION OF THE DRAWINGS Figure 1A is a perspective view of a biorefinery - comprising a cellulosic ethanol production facility. Figure 1B is a perspective view of a biorefinery comprising a cellulosic ethanol production facility and a corn-based ethanol production facility.
    Figure 2 is a schematic block flow diagram of a method for producing ethanol from corn. 2 - Figure 3 is a schematic flow diagram of a method pa- =| for the production of ethanol from corn. . Figure 4A shows the components removed (e.g., whole grain residues after alcohol extraction), which comprise water, soluble components, oil, and unfermented solids (e.g., the beer solids component with substantially all of the ethanol removed), can be dried into still dry grain (DDG) and marketed, for example, as an animal feed product.
    Figure 4B shows the treatment system that can comprise a separation (to produce fine grain residues after alcohol extraction and wet grains), a second treatment system and a dryer and produces an oily composition and dry grains. of more soluble distillers.
    Figures 5A and 5B show the second treatment system (ie the oil separation system).
    Figures 6A and 6B show the treatment system.
    Figure 7 shows the effect of pH on the fatty acid content of the oil composition.
    Figure 8 shows the effect of pH on the separation of oil from the emulsion.
    Figure 9A shows the fatty acid content of the oil samples. | Figure 9B shows the insolubles content of the oil samples. | |
    Figure 9C shows the moisture content of the oil samples. ] Figure 9D shows the phospholipid content of the . oil. Figure 10 shows the peroxide value of oils stored at 40ºC in the dark. Figure 11 shows the hexanal content of oils stored at 40°C in the dark. Figure 12 shows the CS-2 oil peroxide value during 2nd storage at 20°C. . o " o : - - - Figure 13 shows an example flow diagram of the method. Figures 14A, 14B, 14C, 14D and 14E show various flow diagrams for delivering the oily composition and dry beans from distillers of the invention.
    DETAILED DESCRIPTION OF THE INVENTION This invention relates to a corn oil composition and a method for producing the same. It is understood that this invention is not limited to the particular embodiments described, as such may, of course, vary. It is also understood that the terminology used in this case is for the purpose of describing only particular embodiments and is not intended to be limiting, as the scope of this invention will be limited only by the appended claims. It needs to be noted that as used in this case and the appended claims, the singular forms "a", "a", and "the, a" include plural references unless the context clearly dictates otherwise. Thus, for example, the reference to "an alkali metal ion" includes a large number of alkali metal ions.
    1. Definitions Unless defined otherwise, all technical and scientific terms used in this case have the same meaning as commonly | understood by one skilled in the art to which this invention pertains.
    As used in this case the following terms have the following meanings.
    - As used in this case, the term "comprising" or "comprises" is intended to mean that the compositions and methods include the aforementioned elements, but do not exclude others. "Consisting essentially of" when used to define compositions and methods, will mean the exclusion of other elements of any significance essential to the combination for the purpose cited. Thus, a composition that — essentially consists of the elements as defined in this case would not exclude other materials or steps that do not materially affect the new (s) and . basic feature(s) of the claimed invention. "Consists essentially of" must mean more than trace elements of other ingredients and substantial steps in the method. The defined modalities | for each of these transition terms are within the scope of this invention! dog.
    As used in this case, the term "approximately" when used before a numerical designation, e.g. temperature, time, amount and concentration, including range, indicates approximations that may vary by (+) or (-) 10 %, 5% or 1%.
    As used in this case, the term "unrefined corn oil" refers to corn oil that has not been subjected to a refining process, such as alkali refining or physical refining (i.e., distillation, deodorization, bleaching etc.).
    As used in this case, the term "free fatty acid" refers to an unesterified fatty acid, or more specifically, a fatty acid that has a carboxylic acid head group and a non-saturated or unsaturated (group) end. branched from 4 to 28 carbons. The term "aliphatic" has a generally recognized meaning and refers to a group containing only carbon and hydrogen atoms that is straight-chain, branched-chain, cyclic, saturated or unsaturated, but not aromatic.
    As used herein, the term "moisture content" refers to an amount of water and other soluble components in the oil composition. The moisture in the corn oil composition contains the alkali or and/or alkali metal and may contain other soluble components such as volatile material including hexane, ethanol, methane! and the like.
    As used in this case, the term "an alkali metal ion" refers to one or more metal ions from Group 1 of the periodic table (e.g., lithium (Li), sodium (Na), potassium ( K*) etc.).
    As used in this case, the term "an alkali metal ion" refers to a Group 2 metal ion of the periodic table (e.g. magnesium (Mg *), calcium (Ca **) etc. .). 7 As used in this case, the term "insoluble" refers to a material in the oil that is not solvated by the water, the oil, or the moisture content within the oil. As used herein, the term "non-saponifiables" refers to components of the oil that do not form soaps when mixed with a base and include any variety of possible non-triglyceride materials. This material can act as contaminants during biodiesel production. The unsaponifiable material can significantly reduce the final product yields of the oily composition and can, in turn, reduce the final product yields of the methods disclosed herein.
    As used in this case, the term "peroxide value" refers to the amount of oxygen peroxide (in millimoles) per 1 kilogram of fat or oil and is a test of the oxidation of double bonds in oils. The peroxide value is determined by measuring an amount of iodine (|) by means of colorimetry which is formed by the reaction of peroxides (ROOH) formed in the oil with iodide by the following equation: 2 | + HO + ROOH > ROH + 20H + |2. As used in this case, the term "oxidative stability index value" refers to the period of time over which the oil resists oxidation at a given temperature. Typically, oil oxidation is slow, until natural resistance is overcome (due to degree of saturation, natural or added antioxidants, etc.), at which point oxidation is accelerated and becomes very rapid. The measure of this time period is the value of the oxidative stability index. . As used herein, the term "corn fermentation residue" refers to the residual components of a corn fermentation process after ethanol is recovered, typically through distillation. Typically, the corn fermentation residue comprises water, some residual starch, enzymes, etc. As used in this case, the term "syrup" refers to the composition | ... viscous tion that is provided by the evaporation of fine-grained residues = after alcohol extraction. As used herein, the term "base" refers to a compound or composition that raises the pH of an aqueous solution. Suitable bases for use in this invention include, but are not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide or depleted alkali solution for washing.
    As used in this case, the term "alkali wash solution" refers to the basic solution that is used to disinfect the fermenter after the fermentation process is complete. The alkali wash solution typically comprises sodium hydroxide.
    2. Embodiments This invention relates generally to oily compositions recovered from a fermentation by-product. The oil compositions contain low levels of free fatty acids which makes them valuable for use in biodiesel, edibles and nutraceuticals applications. This invention also relates to methods of recovering such oily compositions from a fermentation process.
    The corn oil of this invention is provided by fermenting corn in the production of ethanol. Referring to Figures 2 and 3, in a typical example of an ethanol production process, corn can be prepared for further treatment in a preparation system. As seen in Figure 3, the preparation system may comprise a cleaning or sieving step to remove foreign material such as stones,
    dust, sand, pieces of corn cobs and stalks and other material do not ! , fermentable.
    After cleaning/sieving, the particle size of mi- | “It can be reduced by milling to facilitate further processing.
    Corn kernels can also be fractionated into endosperm which contains starch and fiber and germ.
    The ground corn or endosperm is then suspended with water, enzymes, and agents to facilitate the conversion of starch to J-sugar (eg, glucose). The sugar can then be converted to ethanol by | an ethanol producer (eg yeast) in a fermentation system | -..... dog.
    In one embodiment, fermentation is carried out without creating a hot suspension (ie, without cooking). In such an embodiment, the fermentation includes the step of saccharifying the starch composition with an enzyme composition to form a saccharified composition (e.g., without cooking). In one embodiment the starch composition comprises water and from 5% to 60% dry solid granular starch, based on the total weight of the starch composition.
    In another embodiment, the starch composition comprises 10% to 50% dry solid granular starch or 15% to 40% dry solid granular starch or 20% to 25% dry solid granular starch, based on the total weight of the composition. of starch.
    The fermentation product is beer, which comprises ethanol, water, oil, additional soluble components, unfermented particulate matter, etc.
    The fermentation product can then be distilled to yield ethanol, leaving the remaining components as whole grain residues after alcohol extraction.
    Whole grain residues after alcohol extraction can then be separated to provide a liquid component (ie, fine grain residues after alcohol extraction) and a solid component.
    The solid component can be dried to provide the dry grain from the distillers of this invention, while the fine-grain residue after alcohol extraction can be obtained to provide the oily compositions of this invention.
    Corn Oil Composition One aspect of this invention provides an unrefined corn oil composition comprising having a free fatty acid content of less than approximately 5 percent by weight; a moisture content of from approximately 0.2 to approximately 1 weight percent and an alkali metal ion and/or alkali metal ion content greater than 10 ppm. The unrefined corn oil of this invention has not been subjected to a refining process. Such refining processes include alkali refining and/or physical refining (ie distillation, deodorization, bleaching, etc.) and are used to decrease the free fatty acid content, the | moisture, the content of insolubles and/or the content of unsaponifiable products. ] o... The free fatty acid content of the present unrefined corn oil composition is less than approximately 5 percent by weight. The oil composition described in this case has a level of free fatty acid content that can reduce the amount of refining or front-end processing for use in producing biodiesel. The fuel properties of biodiesel are determined by the amounts of each fatty acid is a raw material used to produce the fatty acid methyl esters. In some embodiments, the free fatty acid content comprises at least one fatty acid selected from the group consisting of C;16 palmitic, Cig stearic, Cig.1 oleic, C18.2 linoleic, and C18.3 linolenic (where the number after "-" reflects the number of unsaturation points.) In some embodiments, the free fatty acid content is less than 5 percent in For example, in some embodiments, the free fatty acid content is less than approximately 4 weight percent or alternatively, less than approximately 3 weight percent or alternatively, less than approximately 2 weight percent or there alternatively, less than approximately 1 percent by weight.
    Keeping moisture levels low is advantageous as moisture can result in the formation of free fatty acids. The unrefined corn oil composition of this invention has a moisture content of less than approximately 1 percent by weight. The moisture in the present corn oil composition may comprise water along with other soluble components such as one or more alkali and/or alkali metal and may also contain other soluble components such as volatile material which includes hexane, ethanol, methanol and the like.
    The pH of the water consisting of the moisture content is generally alkaline (ie >7) and comprises one or more alkali and/or alkali metals.
    In some embodiments, the moisture content of the unrefined corn oil composition is from approximately 0.2 to approximately 1 weight percent, or alternatively, approximately or less than approximately 0.8 weight percent. or alternatively approximately or less than approximately 0.6 weight percent or alternatively approximately or less than approximately 0.4 weight percent or alternatively approximately 0.2 weight percent Weight.
    In certain embodiments, the metal ion concentration of the moisture content is approximately 2000 ppm.
    Accordingly, an unrefined corn oil composition having from approximately 0.2 to approximately 1 weight percent would have a metal ion concentration of from approximately 4 ppm to approximately 20 ppm.
    Typically, the moisture content of the unrefined corn oil composition is approximately 0.5 percent by weight having a metal ion concentration of approximately 2000 Ppm, which results in an ion concentration in the oil composition of approximately 10 ppm. .
    In some embodiments, the unrefined corn oil composition has a metal ion concentration greater than approximately 0.4 ppm or greater than approximately 0.5 ppm! or greater than approximately 0.6 ppm or greater than approximately 0.7 ppm or greater than approximately 0.8 ppm or 20 ppm.
    As stated earlier, the moisture content is generally alkaline (ie >7). Accordingly, the water content in the oil comprises an alkali metal ion and/or alkali metal ion content of or greater than approximately 10 ppm.
    The alkali metal ion present in the composition may be any alkali and/or any alkali metal ion and is, in some embodiments, any combination of lithium (Li'), sodium (Na"), "magnesium (Mg ”), potassium (K*) and/or calcium (Ca *). In some embodiments, the alkaline moisture content may comprise an organic base, such as ammonia and/or ammonium ions.
    Accordingly, in one embodiment, this invention is directed to an unrefined corn oil composition comprising . having a free fatty acid content of less than approximately 5 weight percent; a moisture content of from approximately 0.2 to approximately 1 weight percent and an ammonia and/or ammonium ion content greater than approximately 10 ppm or from approximately- | 4 ppm up to approximately 20 ppm.
    In some embodiments, unrefined corn oil has | — ...an insoluble content of less than approximately 1 percent by weight. The insoluble content is not solvated by the aqueous part, the oil, or the moisture within the oil and may include material such as residual solids (eg, corn fiber).
    In some embodiments, the unrefined corn oil has a unsaponifiables content of less than approximately 3 weight percent or less than approximately 2 weight percent or less than approximately 1 weight percent. The unsaponifiable matter can significantly reduce the final product yields of the oily composition and can in turn reduce the product yields of the methods disclosed herein. The unsaponifiables content of the oil does not form soaps when mixed with the base and includes any variety of possible non-triglyceride materials that act as contaminants during biodiesel production. The unrefined corn oil of this invention may also comprise various other oil-soluble components. It is considered that the amount of such components would not be so great that the composition of unrefined corn oil would need refining before being used as a biodiesel, for example. Such components may include, for example, one or more of lutein, cis-lutein, zeaxanthin, alpha-cryptoxanthin, beta-cryptoxanthin, alpha-carotene, beta-carotene, cis-beta-carotene, alpha-tocopherol, beta-tocopherol, delta-tocopherol or gamma-tocopherol, alpha-tocotrienol, beta-tocotrienol, gamma-tocotrienol and/or delta-tocotrienol. In some modalities, the unrefined corn oil composition has a tocol content.
    ferol less than approximately 1 mg/g.
    In some embodiments, the unrefined corn oil composition has a me-tocotrienol content. nor than approximately 1.3 mg/g.
    In some embodiments, the unrefined corn oil composition has a beta-carotene content greater than approximately 2 µg/g.
    Such components are known antioxidants and can thus provide oxidative stability to the unrefined corn oil composition. | Unrefined corn oil composition of this invention exhibits | — higher level of oxidative stability than turbocharged corn oils = by conventional methods.
    This may be due to any combination of factors such as the degree of saturation of the oil, natural antioxidants and the like and can be readily determined using methods well known in the art.
    In some embodiments, the oxidative stability of the unrefined corn oil composition is greater than approximately 4 hours at a temperature of approximately 110°C (See Example 4). In addition, oxidative stability can be evaluated using its peroxide value.
    In some embodiments, the unrefined corn oil composition exhibits a peroxide value of less than approximately 2 parts per million or less than 1 part per million.
    Methods One aspect of this invention is directed to a method for providing a corn oil composition starting from a corn fermentation residue comprising the steps of: b) adjusting the pH of the corn fermentation residue to provide a layer of corn oil and an aqueous layer and c) separating the corn oil layer from the aqueous layer to provide the corn oil composition.
    One aspect of this invention is directed to a method of providing a corn oil composition starting from a corn fermentation residue which comprises the steps of: a) separating the corn fermentation residue to provide an emulsion layer and a first aqueous layer;
    b) adjusting the pH of the emulsion layer to provide a layer of corn oil and a second aqueous layer e.g. c) separating the corn oil layer from the second aqueous layer to provide the corn oil composition.
    In some embodiments, the corn fermentation residue of this invention comprises whole grain residues after alcohol extraction. In one fermentation method, the whole grain residue after alcohol extraction is the components left over from the fermenter after the ethanol has been distilled. Whole grain residues after alcohol extraction comprise a solid component and a liquid component. The "liquid component of whole grain residues after alcohol extraction is called in this case fine grain residues after alcohol extraction (Figure 4A). In one embodiment, the whole grain residues after alcohol extraction can be subjected to further processing steps to produce fine grain residues after alcohol extraction. The fine grain residues after alcohol extraction can be recovered from the solid component of the whole grain residues after alcohol extraction by phase separation and decanting, or can be accelerated using methods such as centrifugation. In one embodiment, the solid component of the whole grain residue after alcohol extraction can be subjected to drying to provide dry grain from the distillers and marketed as a animal feed product. In some embodiments, the corn fermentation residue comprises fine grain residues after alcohol extraction. In one embodiment, moisture may be removed from the fine grain waste after alcohol extraction to create a concentrated fermented product, here called syrup. Moisture can be removed in a variety of ways such as, for example, by evaporation under vacuum. cuo which, in turn, can prevent dirt accumulation. Consequently, | in some embodiments, the corn fermentation residue comprises syrup. In some embodiments, the corn fermentation residue has a moisture content of between approximately 95% and approximately 60% weight percent. In some embodiments, fermentation residue | corn production has a moisture content of approximately 95% or ! approximately 90%> or approximately 85% or approximately . 80% or approximately 75% or approximately 70% or approximately 65% or approximately 60% weight percent. The method of this invention optionally comprises a step of separating the corn fermentation residue (whole grain residues after alcohol extraction, fine grain residues after alcohol or syrup extraction) to provide an emulsion layer and a first - aqueous layer. The separation step can be carried out simply: - allowing phase separation to occur over time and the oil layer decanted or using a centrifuge or a combination thereof, which includes, but does not is limited to, for example, a | ' press, an extruder, a decanter centrifuge, a centrifuge with | disc stack, a sieve centrifuge, or a combination thereof. In some embodiments, the separation does not comprise heating. In one embodiment, a continuous flow is maintained at approximately 4000
    9. One skilled in the art will appreciate that the speed or amount of centrifugal force applied will depend on various factors such as sample size and can be adjusted accordingly depending on such factors. Suitable separators and centrifuges are available from various manufacturers, such as, for example, Seital from Vicenza, Italy, Westfalia from Oelde, Germany or Alfa Laval from Lund, Sweden. In one embodiment, the resulting emulsion layer contains from approximately 20% w/w to approximately 70% w/w of oil. In another embodiment, the emulsion layer contains | from approximately 30%> weight/weight to approximately 60%> weight/weight of oil. In yet another embodiment, the emulsion layer contains from approximately 40% by weight/weight to approximately 50% by weight/weight of oil. The oil fraction may also comprise — varying amounts of the overall volume of the fermentation residue. In one embodiment, the emulsion layer comprises approximately 20% w/w of the initial volume of the fermented product.
    In one embodiment, the corn fermentation residue separation step is performed shortly after the initial ethanol production. To maintain the quality of the oily composition and avoid exposure to heat and oxygen, which are contributors to the formation of free fatty acids.
    The emulsion layer, which comprises the oil composition of this invention, is preferably separated from the first aqueous layer.
    All or a fraction of the first aqueous layer can be further processed or applied to solids, such as, for example, still dry grain. the... — In a preferred mode, once separated from the first "
    aqueous layer, the pH of the emulsion layer is adjusted such that the emulsion is sufficiently disrupted, thereby providing the oily composition of this invention and a second aqueous layer.
    The pH adjustment allows for the selective separation of the highest quality oil while leaving the free fatty acids in an aqueous fraction by saponifying the fatty acids thereby making them more soluble in water.
    In this way, some of the free fatty acid is removed resulting in oil that contains low levels of free fatty acid.
    The age of the fermented product and the organic acid content of the fermented product can affect the optimal pH for separation, however, the oil fraction is treated at the highest possible pH to reduce the overall free fatty acid content in the separated oil. without sacrificing oil quality.
    Typically, in the range of suitable pH's of from approximately 7.5 to approximately 10. The mixture of the free oil composition and the
    oil can be removed for further processing.
    In another embodiment, the first aqueous layer is not removed from the emulsion layer, but instead is subjected to base treatment to form the oil layer and the second aqueous layer comprising both the first aqueous layer and the resulting water. of the breakage of the emulsion.
    The oil layer is then separated from the second aqueous layer.
    Accordingly, in some embodiments, the method comprises the steps of a) adjusting the pH of the corn fermentation residue to provide a layer of corn oil and a second aqueous layer and b) separating the corn oil layer from the second aqueous layer to provide the corn oil composition.
    In some embodiments, the separation steps do not include heating. . In some embodiments, the pH of the emulsion layer is lowered by the addition of an acid.
    In such an embodiment, the pH can be adjusted low by approximately 1 pH unit or approximately 2 pH units or approximately 3 pH units.
    It is envisaged that any mineral or inorganic acid can be used to adjust the pH of the emulsion layer. : : : In some embodiments, the pH of the emulsion layer is increased by addition of base.
    In such an embodiment, the pH can be adjusted upwards by approximately 1 pH unit or approximately | 2 pH units or approx. 3 pH units or approx. 4 pH units or approx. 5 pH units or approx. 6 pH units.
    In some embodiments, the pH of the emulsion layer is less than about 4 or about 3.5, prior to the emulsion layer pH adjustment step.
    It is considered that any inorganic or mineral base can be used to adjust the pH of the emulsion layer.
    Suitable bases include, but are not limited to, a base selected from the group consisting of sodium hydroxide, me- | 20 sodium oxide, potassium hydroxide, calcium hydroxide or spent alkali solution for washing.
    In some embodiments, the base may be an organic base, such as ammonia.
    Efficient phase separation of the emulsion layer can be achieved by adjusting the pH of the emulsion layer to approximately 7.5 to approximately 10 or from approximately 8 to approximately 9 or to a pH of approximately 8.2. Once the emulsion has sufficiently broken down, a layer of corn oil and a second aqueous layer are provided (Figures 5A and 5B). The corn oil layer comprises unrefined corn oil as disclosed in this case.
    In some cases, an interface layer may be present between the oil layer and the aqueous layer, which is known in the art as a rag layer.
    The interface layer may comprise oil, water, phospholipids, free fatty acids, solids, etc.
    In some mo- | Finally, the interface layer is substantially removed from the layer. of oil with the aqueous layer.
    However, as the interface layer may comprise a significant amount of oil, it may be advantageous to extract oil from the interface layer.
    Consequently, in some embodiments, the interface layer is maintained with the oil layer and subjected to the pH adjustment step.
    The volume of the interface layer can be reduced by approximately 50% or more by using a larger volume of ... . Aqueous solution compared to the volume of the oil layer.
    Therefore, it may be advantageous to use a larger volume of aqueous solution by adding water | , and/or by using spent alkali solution for washing.
    Such methods I . can provide an oil that has a lower concentration of phospholipid.
    Consequently, unrefined corn oil as disclosed in this case can be provided by separating the corn oil layer from the second aqueous layer.
    The step of separating the corn oil layer from the second aqueous layer can be carried out simply by allowing phase separation to take place over time and the oil layer decanted or by using a centrifuge or a combination including, but not limited to, for example a press, an extruder, a decanter centrifuge, a disc stack centrifuge, a sieve centrifuge or a combination thereof. (Figures 6A and 6B). In some embodiments, separation does not include heating.
    In one embodiment, a continuous flow is maintained at approximately 4000 g.
    One skilled in the art will appreciate that the speed or amount of centrifugal force applied will depend on various factors such as sample size and can be adjusted appropriately depending on such factors.
    Suitable separators and centrifuges are available from various manufacturers, such as, for example, Seital from Vicenza, Italy, Westfalia from Oelde, Germany or Alfa Laval from Lund, Sweden.
    In one embodiment, the second aqueous part comprises 60% to 80% moisture, based on the total weight of the second aqueous part.
    In one embodiment, the second aqueous part comprises 10% to 40% protein, based on the total weight of the second aqueous part.
    In a modality. The second aqueous part comprises up to 50% oil, based on the total weight of the second aqueous part.
    The remainder of the second aqueous part typically comprises starch, neutral detergent fiber and the like.
    The second aqueous part can be used to treat still dry grain or other solids where a higher level of these components is desirable.
    One aspect of this invention is directed to a method for providing a corn fermentation oil composition from a corn fermentation residue comprising the steps of: a) adjusting the pH of the corn fermentation residue with a | spent alkaline washing solution to provide a layer of corn oil and an aqueous layer and b) separating the corn oil layer from the aqueous layer to provide the corn oil composition.
    Distillers Dry Grains As shown in Figure 4B, the treatment system may comprise a separator (which produces fine grain residues after alcohol and wet grain extraction), a second treatment system and a dryer and produces an oily composition and grains. still dry.
    The aqueous components removed from the first and/or second separation stages can be added over wet beans in the dryer and dried to provide dry distillers beans with soluble products.
    Accordingly, in one embodiment, this invention provides a distillers dry grain that comprises approximately 4% or less fat or approximately 3% or less fat or approximately 2% or less fat.
    In some embodiments, the stills dry grain also comprises approximately 20% protein or approximately 25% protein or approximately 30% protein, approximately 35% protein or approximately 40% protein.
    Uses The oil composition of this invention can be used in a wide variety of applications. Such application examples include the areas of oily chemical compounds, feed (e.g. animal feed). as well as oils suitable for human consumption and/or biodiesel. Accordingly, one embodiment of this invention is a biodiesel comprising an unrefined corn oil composition as described in this case. Another embodiment of this invention is a raw material for the production of biodiesel which comprises the composition of unrefined corn oil as described in this case. - , — Oily chemical compounds include raw material chemicals that are suitable for the production of biodiesel (fatty acid methyl esters). Industrial oily chemical compounds are useful in the production of soaps, detergents, wire insulation, industrial lubricants, leather treatments, cutting oils, mining agents for oil well drilling, paint removal, plastic stabilizers, and in rubber production. Other industrial applications include waxes, shampoos, personal care and food emulsifiers or additives.
    One embodiment of this invention is directed to a still dry bean that comprises approximately 4% or less fat.
    In some embodiments, the distillers' dry grain also comprises approximately 30% protein.
    The corn oil of this invention can also be used for human consumption. Products for human consumption include edible oils that meet GRAS crude oil standards, as well as carriers for drug molecules in pharmaceutical preparations. These products that are adapted for human consumption also include nutraceutical applications. The oil compositions as described in this case contain higher than average levels of various nutraceuticals such as, for example, tocopherols, tocotrienols and phytosterols. In one embodiment, and while not intended to be bound by a particular theory, levels of the oil composition higher than average levels of various nutraceuticals can be attributed to the removal of corn oil directly from the whole grain simply as opposed to the corn germ itself. The nutraceuticals in the present oily composition can also be processed - for inclusion in various applications such as health foods (foods grown with natural fertilizers and free of additives), dietary supplements, food supplements and fortifying food products.
    EXAMPLES A series of examples were conducted according to an example system modality (as shown in the Figures) in an effort to determine the proper apparatus and operating conditions for the separation of pre-treated biomass. , Example 1 The pH level capable of providing an oily composition that contains a low level of free fatty acid was determined (Figure 7). First, an oil fraction as an emulsion separate from the fermented product was adjusted to pH levels of 7.7, 7.9, 8.0, 8.1, 8.2, and 8.3. The samples were then centrifuged to separate the oily composition and the oily composition was analyzed for free fatty acid content. This experiment was conducted twice. The results of each experiment, Experiment 1 and Experiment 2, are shown in Table 1. In summary, those samples tested at a lower pH (ie, less than 8.0) exhibited free fatty acid contents above 3.5 % w/w while those tested at a pH above 8.1 exhibited a free fatty acid content of less than 2% w/w. | TABLE 1 Í e HU 7.7 79 80 81 82 83 free leaves (percent) 35 22 20 22 20 18 Free fatty acids (percent) 48 35 31 22 20 18 Example 2 Experiments were conducted to determine the amount of free oil present after adjusting the oil fraction at various pH levels (Figure 8). A series of oil fractions, in the form of emulsion samples
    Previously separated by a first application of centrifugal force was treated with NaOH to adjust the pH to various levels as shown. seated in Table 2. Each sample contained the same amount of oil before adjusting the pH.
    After adjusting the pH to the target value, the volume of free oil was measured.
    In summary, the optimum pH at approximately 8.2 was obtained as evidence for the highest value of free oil volume.
    It has been shown that the volume of free oil increases to this value and then deteriorates thereafter.
    Thus, there is an optimal pH for the separation for each "oil defraction" sample. Experiments were conducted to demonstrate that the combination of pH adjustment and application of centrifugal force resulted in (a) higher quality corn oil compositions and (b) higher yield of corn oil composition compared to those oily compositions obtained by applying centrifugal force alone (Figures 9A, 9B, 9C and 9D) It has been shown that the free fatty acid content is reduced by up to 3% by pH adjustment in combination with centrifugal force as opposed to centrifugal force alone .
    The yield of the separated oily composition was increased by 140%. The experiment was carried out for approximately 30 days and included 3 daily samples.
    An analysis of the composition of the products obtained was carried out | of a system modality.
    The results are summarized in Table 3. To the syrup fraction obtained by the ethane production process! it was centrifuged to be separated into a light fraction (emulsified oil) and a heavy fraction (stickwater). The syrup obtained was mostly oil-free.
    The heavy fraction was returned to the normal process to be evaporated further and added to the wet and dry cake.
    The pH of the light fraction was increased to approximately 8.2 from a pH of approximately 3.5. The pH-adjusted emulsified material was fed to a second centrifuge stage.
    The heavy fraction (soap stock) from the second centrifuge stage had a high content of soaps and proteins and was mixed with stickwater and added to the wet and dry cake.
    The light fraction from and from the second centrifuge was the oil.
    The oil exhibited a high quality and low content of free fatty acids (see Figure 9A), insolubles (see Figure 9B), moisture (see Figure 9C), phospholipids (see Figure 9D) and unsaponifiables.
    The oil provided an excellent raw material for the production of biodiesel and could be used in food applications with additional refining.
    The distiller's dry grain composition designed to result from the combination of wet cake, soap stock, and low-fat syrup exhibited lower fat and higher protein content than typical for the distillers' dry grain.
    TABLE 3 Fat Protein Moisture Other (percent. percent percent percent)*** Starting Material 5th to First Fraction Light 35 3.6 | ss Emulsified Oil)* First Fraction Weigh- 35 4.2 83 10 da (Stickwater)* Oily Composition)* Second Fraction Weigh- 5.9 77 11 da (Soap Stock)* Low Fat DDGS 8.7 57 ** * = Sampled, ** = Engineered, *** = Includes fiber, ash, starch, etc.
    Example 4 In a conventional process for dry milled ethanol, whole corn is milled into a flour, mixed with water and cooked at a high temperature to gelatinize the starch and make it more available for liquefaction and subsequent saccharification by enzymes. .
    The cooked pasta is then cooled to facilitate the fermentation of the sugars into ethanol.
    The resulting beer includes both soluble and insoluble components such as protein, oil, fiber, residual starch and glycerol.
    The beer is separated into ethanol and remains
    whole grain duos after alcohol extraction in the distillation. Whole grain residues after alcohol extraction can be dehydrated to produce wet cake by removing a component from the fine grain residues after alcohol extraction by centrifugation. The oil is fairly evenly divided by weight between the fine grain residue after alcohol extraction and the wet cake. The fine grain residue after alcohol extraction is typically further evaporated into syrup, which can be added back to the wet cake during a drying process that produces still dry grains with solubles (i.e. DDGS). Corn oil.
    can be recovered from the syrup by a simple centrifuge step," as described, for example, in a US patent to GS Cleantech: Corporation (US patent serial number 7,601,858). Ethanol uses a modified dry-milling process known as raw starch ethanol production. In these facilities, corn is ground to fine flour, mixed with water and enzymes, and fermented to beer containing ethanol in a simultaneous saccharification and ethanol reaction. fermentation.The rest of the starch process with raw starch is similar to the conventional process.
    However, in the crude starch process the oil cannot be separated from the syrup by a simple centrifuge step, but requires an additional treatment step (pH adjustment) and a second centrifuge step to recover the oil. Globally, producing ethanol from raw starch requires less energy and water cooling.
    Oil extracted from corn DDGS using solvents and oil extracted by centrifuge from fine grain residues after alcohol extraction were characterized. These oils have similar or slightly lower concentrations of tocopherols than germ oil, but have higher concentrations of phytosterols, tocotrienols and stearyl ferulates than corn germ oil. However, oils also tend to have a high free fatty acid composition, which is detrimental to biodiesel production as well as to oxidative stability.
    go.
    The ethanol plants that supply the distillers' beans for oil extraction in the aforementioned studies were all working. with the conventional dry milling process for ethanol.
    To our knowledge, the oil extracted from the distillers grains of the raw starch ethanol process has not been characterized.
    The oxidative stability of corn oil post-fermentation was also not studied.
    The present example provides the following: 1. To compare the fatty acid and phytochemical composition of oils extracted from corn germ, ' — fine grain residues after alcohol and DDGS extraction; 2. Evaluate and =. : - compare the oxidative stability of these oils; and 3. Determine the oxidative stability of oil extracted from fine-grain residues after alcohol extraction at room temperature.
    Materials and Methods: Chemical Substances Í Chemical Substances (ACS grade or higher) were obtained from Sigma-Supelco (St.
    Louis, MO) unless otherwise noted in the cited methods.
    Solvents were HPLC grade and were obtained from Fisher (Fairlawn, NJ). Oils The five oils that were characterized included extracts made with hexane in a corn germ Soxhlet apparatus (CG) and DDGS (DDGS) three oils that were extracted by centrifugation from the ethanol production facilities with dry milling (CS -1, CS-2, CS-3). Corn germ was obtained in an ethanol production facility that operates a dry fractionation process in which corn kernels are separated into germ, fiber and endosperm fractions prior to fermentation.
    Corn DDGS were obtained from a raw starch ethanol production facility operated by POET, LLC (Sioux Falls, SD). CG and DDGS were extracted overnight (approx. 20 hours) by Soxhlet extraction using hexane.
    Four Soxhlet extractors in parallel with -100 glcartridge were used for several days in a row and the extracts were combined to obtain sufficient germ oil and DDGS for analysis.
    and storage studies.
    The hexane was removed by rotary evaporation at 40°C, the oil was then stirred for 4 hours under a high vacuum. to remove some excess hexane, after which the oil was poured into several amber bottles, with argon on top to prevent lipid oxidation | and frozen at -20C until used for analysis.
    Got CS-1 from a ! conventional plant from dry milled material to ethanol.
    CS-2 and CS-3 were obtained from two different production runs with a facility for the production of ethanol from raw starch operated by POET.
    CS- o... 41,CS-2,eCS-3 were transported overnight on dry ice to the research location and immediately transferred to glass vials, with argon inlet on top and frozen (-20°C) until they are used for analysis.
    Oil Analysis Acid Value The Acid Value was determined by titration using the official AOCS method Cd 3d-63 (AOCS, 1998). The acid value was used to calculate the percent free fatty acid (FFA) as percent oleic acid by dividing the acid value by 1.99 as quoted in the Method.
    Each oil was analyzed in triplicate for Acid Value and the average is shown.
    Fatty Acid Composition and Sludge Value Oily triacylglycerols were transesterified using the method described by Ichihara (1996). Fatty acid methyl esters were analyzed in triplicate by GC as previously described (Winkler and Warner, 2008). Sludge values were calculated based on fatty acid composition according to the AOCS Cd Ic-85 Method (AOCS, 1998). Analysis of Tocopherols, Phytosterols and Steryl Ferulate The levels of tocopherols, tocotrienols and steryl ferulates were analyzed in triplicate in the crude oils by HPLC with a combination of UV and fluorescence detection as described above (Winkler and others, 2007). To analyze the total content and composition of phytosterols, the oils were saponified and the phytosterols were extracted and derived.
    analyzed as described above (Winkler et al., 2007). Phytosterols were quantitatively evaluated by GC as described by Winkler and Vaughn (2009). The identity of phytosterol peaks was confirmed by GC-MS analysis performed on an Agilent (Santa Clara, CA, USA) 6890 GC-MS equipped with an HP-SMS capillary column (30 m 9 0.25 mm 9 0.25 Im), a 5973 selective mass detector and a 7683 autosampler. The GC to MSD transfer line was set to 280°C.
    The injector and oven temperature programs were the same as described above for the instrument: — GC-FID instrument.
    The MSD parameters were as follows: === scan mode, 50-600 amu, ionization voltage, 70 eV and EM voltage, 1.823"V.
    Mass spectral identification was performed using the Wiley MS database combined with comparison to literature values for relative RT (compared to B-sitosterol) and mass spectra (Beveridge et al., 2002). ! Carotenoid Analysis The carotenoid analysis and quantitative evaluation were conducted by HPLC as described by Winkler and Vaughn (2009). Oxidative Stability Index The OSI at 110°C was determined in triplicate following the Official AOCS Method Cd 12b-92 (AOCS, 1998). Metrmoh (Herisau, Switzerland) 743 Rancimat with air flow control computer program and temperature automatically controlled and calculated OSI values based on induction time.
    Accelerated Storage Study The study protocol followed AOCS Recommended Practice Cg 5-97 (AOCS, 1998). Oil samples (5 g) were weighed into small 40 ml amber vials that were loosely capped.
    For each treatment and day, small vials were prepared in triplicate.
    The small vials were stored in completely randomized order in a “dark oven maintained at 40 + 1°C.
    For each oil, three small vials were removed on days one through six and on day eight.
    CG oil samples were also removed on days 10 and 12. However, as the study progressed, it was determined that DDGS and CS-2 oils were oxidizing more slowly than CG oil, so samples were removed on - days 12 and 14 to extend its storage for two more days.
    After removal from the oven, the small vials were immediately placed on top of argon, tightly capped and frozen (-20°C) until analysis, as until analysis.
    Analyzes were conducted on the same day or within 2 days of removal from the oven.
    Peroxide values were determined using the method described by Shantha and Decker (1994). Each replica of o... from storage studies was analyzed in duplicate.
    Hexanal in the main oil space of each replica was quantitatively evaluated in duplicate by solid phase micro extraction (SPME) and GC analysis as described by Winkler and Vaughn (2009). Room Temperature Storage Study CS-Oil 2 was placed inside three 4L amber bottles.
    Each bottle was filled to the same volume of 3.4 L.
    The amount of headspace above the oil samples was equivalent to 0.9 L.
    Bottles were tightly capped and stored in the dark at 20°C + 3°C, temperature was monitored daily and high and low temperatures were recorded.
    Samples were taken once a week for 13 weeks.
    For sampling, the bottles were first gently shaken for 30 s to mix the contents.
    Then a glass pipette was inserted into the center of the bottle and 5 mL of oil was taken out and placed in a bottle with a screw cap, covered with argon and frozen (-20°C) until analysis.
    Peroxide value and hexanal headspace analysis were performed on the oil samples as described above and were typically run on the same day or within 1-2 days of sampling.
    Results Composition of Fatty Acids and Free Fatty Acids | 30 The fatty acid compositions (Table 4) of all five oils were typical for corn oil.
    Sludge values ranged from 122.4 to 124.3. These results agree with other reports that the composition
    The fatty acid content of oil extracted from DDGS and fine-grain residues after alcohol extraction are similar to that of corn oil.
    The two oils - (CS-1 and CS-2) that were centrifuged from syrup from raw ethanol starch production facilities had the lowest % FFA (2.03% and 2.48%, respectively). Oil recovered by centrifuging syrup from the ethanol production plant with traditional dry crushing had the highest Acid Value at 10.1% FFA.
    Other studies have reported the FFA content of oil recovered by centrifugation of: fine grain residues after alcohol extraction ranging from 11.2-16.4%. - These results indicate that the elimination of the cooking step in the pro- ' Crude starch production reduces FFA production.
    Oil extracted from DDGS: using hexane had the second highest acid value (7.42% FFA). | Winkler-Moser and Vaughn (J.
    love
    Oil Chem.
    Soc, 2009, 86, 1073-1082) rela- ! found an FFA content of 6.8% (w/w) in DDGS oil extracted with Soxhlet hexane, while Moreau et al. (J.
    love
    Oil Chem.
    Soc, 2010b, In Press) reported an FFA content ranging from 8-12% in DDGS that was extracted with hexane using accelerated solvent extraction.
    The FFA content of DDGS extracts was shown to vary widely depending on the extraction method and conditions and solvent used.
    The DDGS used in this study also came from a raw ethanol starch plant, so it could be expected to have a lower FFA.
    However, the high temperatures used to dry the wet grains may have contributed to the increase in FFA.
    In one experiment, Moreau and others (J.
    love
    Oil Chem.
    Soc, 2010b, In Press) demonstrated that oil extracted from fine-grain residues after extraction of alcohol and dry grains from distillers (prior to blending the grains with the syrup) had a high content of FFA that was carried through of the DDGS.
    The FFA content of hexane extracted from corn germ was 3.8%, which is slightly higher than the average 2.5% FFA typically found in crude corn germ oil.
    For biodiesel production, oil with an Acid Value greater than one requires pretreatment because free fatty acids form soaps during base-catalyzed esterification, which interferes with the separation of glycerol from methyl esters of fatty acid. Thus, crude oils with lower free fatty acids will have less oil loss due to pretreatment. . Free fatty acids decrease the oxidative stability of oils and can also precipitate at ambient temperatures, both of which can have a negative impact on fuel performance.
    Table 4. Acid Value, Fatty Acid Composition and Calculated Sludge Value of oils extracted from corn germ (GC), distillers dry grains with solubles (DDGS) and extracted through a slurry centrifuge from fine grain residues after alcohol extraction (CS-1, CS-2,CS-3). cG DDGS cs-1 cs-2 cs-3 Acid Value (mg of 10.7+0.07 20.8+0.56 28.3+0.32 5.70+0/13 6.88+0, 09. KOH/g) FFA(%deacid -3.80+0.03 7.42+013 10.1+0.11 2.03+0.05 2.48+0.05 oleic). Fatty Acid Composition (%) 16:0 131 12.9 11.5 12.2 12.9 16:1 0.0 o1 o1 01 01 | 18:0 1.5 18 17 18 1.5 181 29.2 28.1 29.3 28.3 27.5 18:2 55.0 55.5 55.6 55.3 55.9 20:0 0 .2 0.3 0.3 0.4 0.3 18:3 1.0 12 117 12 12 20:1 0.0 0.0 0.2 0.3 0.2 Value of sludge Cal- 122.4 123.1 124.3 123.7 124.1 Theore composition of tocopherols, tocotrienols, and carotenoids Tocopherols are common in vegetable oils and are primary antioxidants that protect most oils. With corn and other plants, the tocopherol and tocotrienol content will vary based on factors including hybrids, growing conditions, post-harvest and processing conditions, as well as the type of solvent used for extraction. Therefore, little can be concluded in this study regarding how processing practices affected tocopherol levels since each production facility and even each production run will have started with different batches of whole corn. Gamma- and alpha-tocopherols were the most prominent homologues detected in all five oils (Table 5), along with a small amount of delta-tocopherol, which is the typical tocopherol profile for corn oil. CG oil had the highest total concentration of tocopherols
    (1433.6 ug/g oil) followed by DDGS extracted from hexane (1104.2). Levels in DDGS oil are similar to what was previously reported in . DDGS extracted from hexane from a conventional dry crushing production facility. The tocopherols in corn are located in the germ portion of the kernel, so the rest of the corn kernel contributes little to the tocopherol content. CS-1, CS-2, and CS-3 all had less alpha-tocopherol compared to CG and DDGS oils, but were similar to the levels reported in centrifuge-extracted oil from fine-grained residues after extraction. alcohol (Moreau et al., J. Am. Oil Chem. Soc, 2010a, In - : À Press).
    ' Table 5. Tocol and carotenoid content and the Oxidative Stability Index (OSI) at 110ºC, for oils extracted from corn germ (GC), distillers dry grains with solubles (DDGS) and fine grain residue syrup after extraction of alcohol extracted by centrifuge (CS-1, CS-2,CS-3) cG6 DDGS Ccs-1 Ccs-2 Ccs-3 Total Tocopherols (vg/9) 1433.6 1104.2 1056.9 931 .3 783.4 Alpha-tocopherol 213.8 295.6 164.5 160.4 123.2 1185.4 760.8 852.7 742.0 640.0 Gamma-tocopherol Delta-tocopherol 34.3 47.8 39.7 28.8 20.2 Total Tocotrienols (vg/9) 235.6 1762.3 1419.6 1224.4 1175.2 Alpha-tocotrienol — 21.9 471.9 328.5 243.6 269.4 Gamma-tocotrienol 165.6 1210.0 1063.6 963.4 880 Delta-tocotrienol 48.1 80.3 27.5 17.3 25.8 Total Carotenoids — 1.33 75.02 129.48 61.1 85 .0 (vg/9) Lutein — 0.37 46.69 75.69 38.13 53.7 Zeaxantna — 0.4 24.16 45.58 16.78 23.7 Beta-cryptoxanthin 0.56 3.31 7.35 412 5.1 Beta-carotene — NO. 0.86 0.86 2.07 25 OSI(h) 391 6.62 4.45 4.52 5.27 Not detected Tocotrienols are common in rice bran oil and palm oil, but not abundant in most commercial vegetable oils. Their antioxidant activity is similar to that of tocopherols in bulk oil systems, but they also appear to have hypocholesterolemic, anticancer, and neuroprotective properties. Post-fermentation corn oils (DDGS, CS-1, CS-2, and CS-3) had a higher concentration of tocotrienol compared to CG oil, because tocotrienols are found in the endosperm fractions, which are mainly removed during fractionation of - corn germ.
    Thus, despite having a lower concentration of tocopherol, all post-fermentation oils had a higher concentration of toco! total compared to CG oil.
    The post-fermentation corn oils had much more carotenoids than the extracted corn germ oil as well.
    However, the concentration of carotenoids was substantially lower than that of tocols in the five oils (Table 5). As with tocotrienols, carotenoids -4 are located in the endosperm fraction of corn kernels.
    The main carotenoids in the oils were lutein and zeaxanthin, as well as minor amounts of beta-cryptoxanthin and beta-carotene.
    The content and composition of carotenoids were similar to amounts found in DDGS oil in a previous study, however, Moreau et al (J.
    love
    Oil Chem.
    Soc, 2010a, Ih Press) reported carotenoid content in oil from fine-grain residues after extraction of centrifuge-extracted alcohol ranging | from 295 to 405 pg/g oil.
    Carotenoids are substantially affected by corn hybrids, which may explain the discrepancy.
    Beta-carotene and beta-cryptoxanthin are both precursors of Vitamin A, while lutein and zeaxanthin are both protective against age-related macular degeneration and cataracts.
    Carotenoids have been shown to have a number of beneficial physiological actions other than the activity of Vitamin A, including antioxidant activity, enhanced immune response, and chemoprotective activity against various types of cancer.
    Phytosterol composition content The total phytosterol content in the three oils ranged from 1.5-2.0% (w/w) (Table 6). Post-fermentation corn oils had more total phytosterols compared to GC oil because they include phytosterols and phytosterol ferulate esters from the bran and pericarp, in addition to the phytosterols from the corn kernel portion.
    The phytosterol composition is also different between GC oil and post-fermentation corn oils.
    DDGS and CS-1, CS-2, and CS-3 oils had similar concentrations of the phyto-
    common sterols campesterol, stigmasterol|, and sitosterol compared with CG oil.
    However, they had a much higher concentration of the two phytosterols - saturated (phytostanols), campestanol and sitostanol.
    The high content of these phytostanols is due to their preferential esterification in maize to steryl ferulates, the content of which is also shown in Table 6. Steryl ferulates are found in the inner pericarp of maize and other grains.
    The presence of a small amount of these compounds in corn germ oil indicates that there may be some contamination of the germ by some pe-ee tissue 2——— — — —Icarp internal, since it has been established that these compounds are unique — the 02. cos of the aleurone layer of the pericarp.
    Phytosterols are highly valued as ingredients in functional foods because of their ability to lower blood cholesterol by blocking cholesterol resorption from the intestines.
    Steryl ferulates have been shown to maintain the cholesterol-lowering capacity of phytosterols and still have antioxidant activity due to the ferulic acid cluster.
    Table 6. Phytosterol content and composition in oils extracted from corn germ (GC), distillers dry grains with solubles (DDGS) and fine grain residue syrup after extraction of alcohol extracted through centrifuge (CS-1 , CS-2, CS-3). ce DDGS cs1 Ccs-2 Ccs-3 mg/g % mgog % mg % mgg % mg % Total Phytosterols 14.9 21.7 18.7 20.1 20.2 Campesterol 3.08 20.7 297 137 2/74 14/77 2.74 136 3.0 14.7 Campestanol 0.25 1.7 135 62 140 7.5 1.80 65 14 6.7 Stigmasterol 0.98 66 1.10 5.1 0.76 41 091 45 0.89 44 Sitosterol 9.04 60.9 103 475 877 469 936 465 93 461 Sitostan! Ethylene ND o 034 17 0.30 1.5 Cycloarthane| cG6 DDGS cs-1 Ccs-2 Ccs-3 mg/g %º mg/g % mg/g % mg/g % mg/g % Citrostadiene! ND O 031 14 ND O 031 16 036 18 Steril ferulates 0.58 / 3.9 342 1577 315 16.8 3.38 168 3.35 166 ryl (mg/g) The weight percentage of total phytosterols "Not Detected Oxidative Stability Index (OS!) | The oxidative stability of oils is affected by many factors, including | the fatty acid composition, the concentration and stability | of antioxidants in the oil, and the presence of pro-oxidant compounds, such as free fatty acids, lipid peroxides or pro-oxidant metals.
    The Rancadat is an accelerated test (which takes from several hours to a day, depending on the oil and test temperature) used to establish the relative oxidative stability of oils, which is measured by the induction time (called the an oxidative stability index, OSI) for an oil to begin oxidation under controlled temperature and airflow conditions.
    The OSI of CG oil was the lowest, while that of DDGS oil was stable. highest quality (Table 5), which corresponds to the lowest and highest concentration of antioxidant tocopherols.
    CS-1 had a slightly smaller OSI. than CS-2 and CS-3 despite having a higher concentration of tocols; this can be explained by its higher FFA content and initial peroxide value | higher.
    Accelerated Storage Study Although OSI is a rapid method for determining the relative stability of various oils, it is often recommended that oil stability be measured at lower temperatures as well, as oxidation mechanisms change at higher temperatures.
    The peroxide value is an indicator of the primary stage of lipid oxidation in which lipid radicals are attacked by oxygen to form lipid hydroperoxides.
    At temperatures below 100°C, lipid peroxides accumulate until they begin to break down to form secondary oxidation products including volatile aldehydes (eg, hexanal), ketones and esters.
    GC oil exhibited the highest rate of increase in peroxides when stored at 40°C, indicating that it was the most susceptible to oxidation (Figure 10). CS-1 and CS-2 were more stable than CG oil, but CS-2 was slightly more stable than CS-1. As a point of comparison, GC took 2-3 days to reach a peroxide value of 10 mEq/kg, 5 days for CS-1 and between 6-8 days for CS-2. The DDGS oil extracted from hexane was more stable and did not show any increase in the peroxide value during the first 8 days of storage, after which it increased at a slow rate and did not even reach a value of 5 mEq/kg by the end of the storage period. study. i Trends in relative oxidative stability were the same as . predicted by the OSI values, however, the OSI values did not demonstrate as clearly the differences in the stability of the four oils as was observed in this evaluation at a lower temperature.
    As lipid hydroperoxides break down, they form volatile compounds that can be measured in the headspace as indicators of secondary lipid oxidation. Hexanal is produced by splitting the... do13-hydroperoxide of linoleic acid and is therefore often used — as a reliable indicator of secondary lipid oxidation in oils that have a high content of linoleic acid. On day O of the study, CG and :DDGS oils had very low hexanal content, while CS-1 and CS-2 had approximately 1-1.4 ug/g of hexanal in the oil (Figure 11). Since CG and DDGS oils were treated via rotary evaporation to remove hexane after extraction, there may be residual levels of hexanal (and other volatile compounds) in these oils as well as those that were removed via rotoevaporation. Hexanal content increased to 4 v9g/g in GC, but stabilized after day 8. In CS-1 and CS-2, hexanal levels increased to 3 pg/g and 4 ug/g, respectively, and also stabilized in around 6 days of storage. Hexanal increased at a slower rate in DDGS oil, to a final level of 3 pug/g. The total hexanal content remained relatively low in all oils throughout the storage study, perhaps indicating that the hexanal formed during this time period came from the breakdown of residual lipid peroxides already present in the three oils and that the process of accelerated peroxide breakdown and aldehyde formation had not yet taken place. laughed. This was supported by the fact that the peroxide values had not yet balanced out or decreased, as is often observed in storage studies where the oil is in the secondary stages of lipid oxidation. Room Temperature Storage Study Although OSI and accelerated storage studies are useful for determining the relative stability of oils with different fatty acid compositions or antioxidant levels, these still cannot be used to predict stability at room temperature. shelf under real life conditions.
    Accelerated storage studies would need to be performed at at least three different temperatures and the induction periods would have to be plotted in order to predict the induction period at a certain temperature.
    In order for the oil derived from the ethanol production process to be used in applications such as the production of - biodiesel, it is interesting to predict its stability during storage. — -
    Larger volumes of CS-2 oil were stored in the dark at room temperature and PV and the hexanal content determined weekly to determine the induction time under these conditions.
    It was not enough for the other oils to include the same in this part of the study.
    The peroxide value remained in a lag stage for 6 weeks, after which period | After this time it started to slowly increase (Figure 12). However, | at 13 weeks of storage, it was still below a peroxide value of 2.0 mEq/kg oil.
    Headspace hexanal content was also measured weekly, but the content remained the same throughout the study indicating that the oil was still in the primary stages of lipid oxidation until the end of the study.
    Regression analysis of the PV of the oil based on the rate of increase after the lag phase ended (weeks 7 to 13) predicted that it would reach a PV of 10 mEq/kg after approximately 58 weeks of storage under these same conditions. .
    This study could not be used to predict oil stability under commercial production conditions where factors such as the surface area to volume ratio, the use of inert gas in the headspace, and fluctuations in temperature would all have an impact on the rate of lipid oxidation.
    However, the results indicate that under ideal conditions of a low surface area to volume ratio, ambient temperature and limited exposure to light, crude oil from fine-grain residues after alcohol extraction would likely remain oxidatively. stable for several months or more.
    This is an important issue
    Used for storing and transporting crude oil from fine-grain residues after alcohol extraction prior to further processing - for biodiesel or other uses.
    Conclusions This Example compared the composition and oxidative stability of oils extracted from corn germ, distillers dried corn kernels and fine grain residues after alcohol extraction from a conventional dry mill ethanol production facility as well. as well as a raw ethanol starch production facility.
    The fatty acid compositions of all five oils were typical for corn oil.
    Oil extracted from fine-grained residues after alcohol extraction. in a raw starch production facility it has a lower FFA than fine grain residues after the extraction of alcohol from an ethanol production facility with conventional dry crushing.
    This is likely due to the lower processing temperatures used in the raw starch process where the cooking stage is eliminated.
    Í All post-fermentation oils had higher concentrations of tocotrienols, carotenoids, phytosterols and phytosterol ferulate esters compared | with corn germ oil.
    The higher concentrations of the antioxidant carotenoid tocotrienols and steryl ferulates are probably responsible for their greater stability compared to that of corn germ oil.
    Soybean oil is the most common raw material for biodiesel, but this study indicates that from the point of view of fatty acid composition and oxidative stability, oil extracted from fine grain residues after alcohol extraction would be an economical alternative. .
    Considering that over 25 million metric tons of DDGS with approximately 10% oil are produced from the ethanol industry each year, enough oil could be recovered to offset a substantial amount of the soybean oil that is directed to the production of biodiesel.
    This would result in two fuels, ethanol! and biodiesel, produced from a single raw material.
    RR Mi MORRO ANA, A UNOS Reino meeeo aeee O ÁÂÁSR A Aço MSN N2ºH=AÚ < ,... 2..1PIW-P" .“ »--Fer ÔÊ A/»ÓÔÔÓ Ó P CS, MM 38/38 The embodiments that are disclosed and described in the patent application (including the Figures and Examples) are intended to be illustrative - and explanatory - of this invention.
    Modifications and variations of the disclosed modalities, for example, of the equipment and processes used (or that will be used) as well as the compositions and treatments used (or that will be used), are possible; all such modifications and variations are intended to be within the scope of this invention.
    权利要求:
    Claims (28)
    [1]
    1. Corn oil composition comprising - unrefined corn oil having a free fatty acid content of less than approximately 5 weight percent and a moisture content of from approximately 0.2 to approximately 1 weight percent, wherein the moisture content comprises an alkali metal ion and/or an alkali metal ion content greater than 10 ppm. : —
    [2]
    A corn oil composition as claimed in claim. 1, wherein the unrefined corn oil has an insoluble content of less than approximately 1 percent by weight.
    .
    [3]
    The corn oil composition of claim 1, wherein the free fatty acid content is less than approximately 3 weight percent. |
    [4]
    The corn oil composition of claim 1, wherein the free fatty acid content is less than approximately 2 weight percent.
    [5]
    The corn oil composition of claim 1, wherein the free fatty acid content comprises at least one fatty acid selected from the group consisting of C16 palmitic, C18 stearic, C18-1 oleic, C18-2 linoleic and C 18-3 linolenic.
    [6]
    The corn oil composition of claim 1, wherein the unrefined corn oil has a non-saponifiables content of less than approximately 3 weight percent.
    [7]
    A corn oil composition as claimed in claim | 1, wherein the unrefined corn oil also comprises one or more components selected from the group consisting of lutein, cis-lutein, zeaxanthin, alpha-cryptoxanthin, Dbeta-cryptoxanthin, alpha-carotene, beta-carotene, cis-beta- carotene, alpha-tocopherol, beta-tocopherol, delta-tocopherol or gamma-tocopherol, alpha-tocotrienol, beta-tocotrienol, gamma-tocotrienol and delta-tocotrienol.
    [8]
    8. Corn oil composition according to claim
    [9]
    1, wherein the unrefined corn oil has a tocopherol content of less than approximately 1 mg/g. The corn oil composition of claim 1, wherein the unrefined corn oil has a tocotrienol content of less than approximately 1.3 mg/g.
    [10]
    The corn oil composition of claim 1, wherein the unrefined corn oil has a beta-carotene content greater than approximately 2 upg/g.
    [11]
    A corn oil composition as claimed in claim.
    1, wherein unrefined corn oil exhibits a peroxide value of less than approximately 2 parts per million.
    .
    [12]
    The corn oil composition of claim 1, wherein the unrefined corn oil exhibits an oxidative stability of greater than approximately 4 hours at a temperature of approximately 110°C.
    [13]
    13. A method for providing the corn oil composition from a corn fermentation residue comprising the steps of: a) adjusting the pH of the corn fermentation residue to provide a layer of corn oil and an aqueous layer and b) separating the corn oil layer from the aqueous layer to provide the corn oil composition.
    [14]
    A method as claimed in claim 13, wherein the corn fermentation residue has a moisture content of between approximately 60% and approximately 95%.
    [15]
    A method as claimed in claim 13, wherein the corn fermentation residue comprises fine grain residue after alcohol extraction.
    [16]
    A method as claimed in claim 15, also comprising a step of evaporating the fine grain residue after alcohol extraction prior to the step of adjusting the pH of the corn fermentation residue.
    [17]
    A method according to claim 13, wherein the residue | of corn fermentation comprises syrup. .
    [18]
    The method of claim 13, wherein the step of adjusting the pH comprises adding a base.
    [19]
    The method of claim 13, wherein the step of adjusting the pH comprises adding a base selected from the group consisting of ammonia, sodium hydroxide, sodium methoxide, potassium hydroxide, calcium hydroxide and spent solution. of alkali for washing.
    [20]
    A method according to claim 13, wherein the pH of . - corn fermentation residue is less than approximately 4' before the corn fermentation residue pH adjustment step.
    [21]
    The method of claim 13, wherein the pH of the corn fermentation residue is approximately 3.5 prior to the step of adjusting the pH of the corn fermentation residue.
    [22]
    The method of claim 13, wherein the pH of the corn fermentation residue is adjusted from approximately 7.5 to approximately 10.
    [23]
    The method of claim 13, wherein the pH of the corn fermentation residue is adjusted from approximately 8 to approximately 9.
    [24]
    The method of claim 13, wherein the pH of the corn fermentation residue is adjusted to approximately 8.2.
    [25]
    A method according to claim 13, wherein the step of separating the corn fermentation residue comprises a centrifuge.
    [26]
    26. Raw material for the production of biodiesel, wherein the raw material comprises a corn oil composition according to claim 1.
    [27]
    The raw material of claim 26, wherein the amount of fatty acid content in the corn oil composition is less than 4 percent by weight.
    [28]
    28. A method for providing the corn oil composition of a corn fermentation residue comprising the steps of: a) adjusting the pH of the corn fermentation residue with a | . spent alkaline wash solution to provide a corn oil layer and an aqueous layer; and b) separating the corn oil layer from the aqueous layer to provide the corn oil composition.
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    同族专利:
    公开号 | 公开日
    US20130109873A1|2013-05-02|
    HUE030986T2|2017-06-28|
    US20150291923A1|2015-10-15|
    EP2613642B1|2016-08-10|
    CN103153079A|2013-06-12|
    EP2613642A1|2013-07-17|
    US9061987B2|2015-06-23|
    MX343362B|2016-11-03|
    US20110086149A1|2011-04-14|
    MX2013002603A|2013-05-17|
    WO2012033843A1|2012-03-15|
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    法律状态:
    2020-09-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-26| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-04-20| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-07-27| B09B| Patent application refused [chapter 9.2 patent gazette]|
    2021-10-05| B12B| Appeal against refusal [chapter 12.2 patent gazette]|
    2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US12/877,987|US9061987B2|2008-09-10|2010-09-08|Oil composition and method for producing the same|
    US12/877,987|2010-09-08|
    PCT/US2011/050705|WO2012033843A1|2010-09-08|2011-09-07|Oil composition and method for producing the same|
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