WO2011097070A2 - Improved grain milling process - Google Patents
Improved grain milling process Download PDFInfo
- Publication number
- WO2011097070A2 WO2011097070A2 PCT/US2011/021601 US2011021601W WO2011097070A2 WO 2011097070 A2 WO2011097070 A2 WO 2011097070A2 US 2011021601 W US2011021601 W US 2011021601W WO 2011097070 A2 WO2011097070 A2 WO 2011097070A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- ethanol
- mash
- whole grain
- fermentation
- Prior art date
Links
- 238000003801 milling Methods 0.000 title claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000000855 fermentation Methods 0.000 claims abstract description 26
- 230000004151 fermentation Effects 0.000 claims abstract description 26
- 150000007524 organic acids Chemical class 0.000 claims abstract description 24
- 235000020985 whole grains Nutrition 0.000 claims abstract 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 108090000790 Enzymes Proteins 0.000 claims description 13
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 235000013339 cereals Nutrition 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000005985 organic acids Nutrition 0.000 claims description 6
- 108010073178 Glucan 1,4-alpha-Glucosidase Proteins 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004382 Amylase Substances 0.000 claims description 2
- 108010084185 Cellulases Proteins 0.000 claims description 2
- 102000005575 Cellulases Human genes 0.000 claims description 2
- 102100022624 Glucoamylase Human genes 0.000 claims description 2
- 108091005804 Peptidases Proteins 0.000 claims description 2
- 102000035195 Peptidases Human genes 0.000 claims description 2
- 239000004365 Protease Substances 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 108010002430 hemicellulase Proteins 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 3
- 238000000227 grinding Methods 0.000 claims 2
- 101001065065 Aspergillus awamori Feruloyl esterase A Proteins 0.000 claims 1
- 150000001243 acetic acids Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 150000004674 formic acids Chemical class 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 240000008042 Zea mays Species 0.000 abstract description 37
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 37
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 37
- 235000005822 corn Nutrition 0.000 abstract description 37
- 229920002472 Starch Polymers 0.000 abstract description 16
- 235000019698 starch Nutrition 0.000 abstract description 16
- 239000008107 starch Substances 0.000 abstract description 16
- 235000000346 sugar Nutrition 0.000 abstract description 10
- 150000008163 sugars Chemical class 0.000 abstract description 9
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 abstract description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract description 6
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229920002488 Hemicellulose Polymers 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 2
- 238000010411 cooking Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 235000018102 proteins Nutrition 0.000 description 11
- 102000004169 proteins and genes Human genes 0.000 description 11
- 108090000623 proteins and genes Proteins 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000001238 wet grinding Methods 0.000 description 9
- 108010068370 Glutens Proteins 0.000 description 8
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 235000021312 gluten Nutrition 0.000 description 6
- 239000002285 corn oil Substances 0.000 description 5
- 235000005687 corn oil Nutrition 0.000 description 5
- 239000002816 fuel additive Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005360 mashing Methods 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000194 supercritical-fluid extraction Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282849 Ruminantia Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 235000019534 high fructose corn syrup Nutrition 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 240000006162 Chenopodium quinoa Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 240000008620 Fagopyrum esculentum Species 0.000 description 1
- 235000009419 Fagopyrum esculentum Nutrition 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082988 Secale cereale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000019714 Triticale Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012735 amaranth Nutrition 0.000 description 1
- 239000004178 amaranth Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000006053 animal diet Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013000 chemical inhibitor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000011868 grain product Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 241000228158 x Triticosecale Species 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B10/00—Production of sugar juices
- C13B10/003—Production of sugar juices using chemicals other than extracting agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B16/00—Regeneration of cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
-
- 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
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
-
- 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
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- 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
- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- This invention concerns an improved grain milling process, and especially an improved process for the milling of grain, and especially for the milling of corn, for producing ethanol and other value-added products.
- ethanol is produced mainly from corn by either wet milling or dry grind processing. Wet milling plants are capital intensive and use large amounts of process water, but through fractionation of the corn into its germ, fiber, protein and starch components are able to produce a number of value-added coproducts with ethanol, including high fructose corn syrup, corn gluten meal, corn gluten feed, germ meal and corn oil but also including modified starches, maltodextrins and other materials.
- Wet milling ethanol methods conventionally involve five basic processing steps: steeping, germ recovery, fiber recovery, protein recovery and starch washing with subsequent fermentation.
- first step com is steeped in a solution of weak sulfurous acid to hydrate and soften the kernel for subsequent separation/fractionation and to leach solubles (water-soluble amino acids and proteins) from the germ.
- germ and fiber fractions are removed by differences in density and particle size.
- Germ having a lower density than the remaining solid components of the kernel following the steeping step, is removed by a system of hydroclones, then pressed and dried. Where desired, corn oil can be pressed and/or solvent-extracted from the germ and then refined as a further coproduct.
- the fiber fraction, containing the pericarp of the kernel is removed by screening, then contacted with the evaporation- concentrated steepwater from the steeping step. This mixture is then dried to yield a corn gluten feed coproduct.
- the remaining solids are then separated into a starch fraction and a protein fraction, through a system of centrifuges and hydroclones.
- the gluten protein fraction is concentrated using a gluten thickener centrifuge and further dewatered by vacuum belt filtration and drying with rotary steam tube or flash dryers.
- the final dried product, corn gluten meal has a high protein and low fiber content, and is used primarily in nonruminant and companion animal diets.
- the starch recovered by the hydroclone is cooked, liquefied and saccharified to yield glucose, which then undergoes fermentation to the desired primary ethanol product.
- the ethanol is distilled away from the water and residual water-soluble solids.
- the recovered residual solids can be added to the corn gluten feed, while carbon dioxide produced in the fermentation can be marketed to the beverage industry.
- Dry grind ethanol methods also have certain disadvantages, however, as compared to wet milling ethanol methods. Processing the entire kernel, including the non-starch portions of the kernel, is less efficient for producing ethanol. As well, dry grind ethanol processes primarily provide one marketable but relatively lower value coproduct, in the form of distillers' dried grains with solubles (DDGS). The non-fermentable portions in a dry grind ethanol process do contain a fairly high oil content, but recovery is difficult.
- DDGS distillers' dried grains with solubles
- a variation of the typical process first treats the corn with cold water, hot water and/or steam for a time, increasing the moisture content of the corn from 15% to 22%, in order to soften the bran/pericarp and germ and allow their separation from the starchy endosperm tissue of the kernel.
- the corn is sent through an abrasion/degermination step to break the kernels into pericarp, germ and endosperm fractions.
- an aspiration step separates the pericarp from the endosperm, while a gravity table is used to separate the germ fraction from the endosperm.
- the endosperm is then ground and processed in the same way as in a typical dry grind process. While the soaking,
- wet milling ethanol methods offer additional coproduct opportunities as compared to the above-described dry grind methods, but require significant investments of capital and process water resources and involve much greater complexity in operation. Additionally, one of the principal coproducts of wet milling - high fructose corn syrup - has been argued by some to be a significant contributor to obesity. Dry grind methods are simpler and require less capital and water, but produce less value in the way of coproducts and are less efficient generally in terms of extracting full value from the various component parts of the corn kernel.
- An improved milling process for producing fuel additive quality ethanol from a grain such as corn would possess the desirable attributes in both wet milling and dry grind methods, namely, the ability to fractionate and derive value from all parts of the corn kernel that characterizes wet milling, while retaining the simplicity and lower capital and water resource demands of dry grind processing.
- the present invention provides improved methods for the processing of grain and grain products to obtain greater value therefrom in a dry grind ethanol process.
- improved methods for the processing of grain and grain products to obtain greater value therefrom in a dry grind ethanol process.
- the description hereafter will describe such improved methods in the context of preferred embodiments, in processing corn particularly, those skilled in the art will recognize that the methods can be beneficially applied to other grains such as wheat, millet, barley, sorghum, triticale, rice, amaranth, buckwheat, rye, oats and quinoa.
- the present invention provides needed improvements through a simple modification of a typical dry grind process whereby the mash is thermochemically treated, by cooking the mash in the presence of an organic acid.
- the organic acid effectively hydrolyzes both the starch and hemicellulosic components in the milled corn to provide fermentable sugars from both the endosperm and other parts of the kernel, without, however, also producing fermentation-inhibiting levels of other known products of the acid hydrolysis of hemicellulosic materials, such as hydroxymethylfurfural (HMF) and furfural.
- HMF hydroxymethylfurfural
- organic acid and "organic acid” will be understood as
- FIGURE 1 depicts an improved grain milling process of the present invention, in one illustrative embodiment.
- a typical dry grind process wherein whole corn is ground, slurried with water, treated with enzymes and cooked to form a liquefied mash, then is treated with additional enzymes, fermented and further processed to yield fuel grade-additive quality ethanol and other products, is modified to incorporate an organic acid such as acetic acid or formic acid (or a combination of these) into the "mashing" step.
- An acid recovery step is optionally but preferably interposed as a further, limited modification, to recover organic acid from the mash prior to the addition of yeast and additional enzymes for carrying out the fermentation of the mash.
- organic acids are not strong acids
- HMF hydroxymethylfurfural
- furfural - both known byproducts of acid hydrolyzing hemicellulosic materials but also both being known inhibitors of enzymatic activity in bioethanol production by fermentation - can be avoided at levels that would tend to undesirably interfere with or inhibit the subsequent fermentation of the C5 and C & sugars to ethanol.
- the amount of chemically labile free sugars or reducing sugars can be kept low, to avoid chemical inhibitors to yeast and sugar loss.
- the organic acids preferably provide additional opportunities to gain value from the proteins and oil present in the corn kernel, too.
- extracting oil from whole corn has to date been an expensive and inefficient proposition because the oil is mainly present in the germ and as a result is present in a low concentration in ground corn as a whole.
- Such high protein solids are desirable for use in animal feeds, but in contrast to the distillers' dried grains which are well-suited only for ruminants, the residual solids provided by our process will in preferred embodiments be suited for use in feeds for non-ruminants such as poultry and hogs.
- FIG. 1 The present invention is illustrated and understood more fully by reference to Figure 1 , in which a modified dry grind ethanol process 10 is shown in a preferred embodiment.
- the embodiment 0 is intended to be illustrative only, and those skilled in the art will readily appreciate that numerous modifications and variations to the embodiment 10 may be made as well as that the present invention may be adapted for use with a variety of existing or known dry grind methods, without departing from the proper scope of the invention as defined more particularly by the claims following hereafter.
- milling may be done by any known method, for example by use of a Fitz mill, Beall degerminator or Satake degerminator.
- Milling step 14 produces a ground corn stream 16, which is a heterogeneous mixture including germ, endosperm, pericarp and fines.
- the fines are primarily starch, and the pericarp is primarily fibrous material.
- Ground corn stream 16 is slurried with water 18, and is cooked into a mash in mashing step 20 in the presence of an organic acid 22 (whether supplied anew or generated largely from optional acid recovery step 28 with makeup acid being supplied anew as needed) and with addition of an enzyme 24 to aid in the liquefaction of fermentable components of the corn.
- an organic acid 22 whether supplied anew or generated largely from optional acid recovery step 28 with makeup acid being supplied anew as needed
- an enzyme 24 to aid in the liquefaction of fermentable components of the corn.
- the ground corn stream 16 is combined with a volume of water 18 having a weight of two to three times the weight of the corn to be mashed, the water 18 usually being supplied in a typical dry grind process in the form of fermentation backset, condensed evaporator water or corn steep liquor.
- the organic acid 22 is preferably acetic acid or formic acid, preferably being supplied with some of the water 18 as a moderate concentration to more highly concentrated aqueous acid solution.
- a preferred concentration range is from 50 percent by weight to 70 percent by weight, while more preferably the acid solution will be closer to 50 percent acid.
- the corn, water and acid mixture is preferably maintained at a temperature between 70 degrees and 90 degrees Celsius (and more preferably at a temperature of from 88 to 90 degrees Celsius) for approximately 30 minutes, after which a-amylase enzyme is added (indicated by stream 24) and the temperature raised to from 105 to 110 degrees Celsius for from 5 to 15 minutes, to aid in the liquefaction of starch and hemicellulose materials from primarily the endosperm and pericarp.
- a-amylase enzyme is added (indicated by stream 24) and the temperature raised to from 105 to 110 degrees Celsius for from 5 to 15 minutes, to aid in the liquefaction of starch and hemicellulose materials from primarily the endosperm and pericarp.
- the addition of the enzyme combined with heating causes breakdown of the starch to maltooligosaccharides, as in typical dry grind methods.
- the organic acid additionally hydrolyzes (thermochemically treats) the hemicelluloses in the pericarp, previously consigned only to the lower value distillers dried grains coproduct, and provides C 5 sugars which add to the fermentable content of the mash stream 26 proceeding from the mashing step 20.
- the mash 26 then proceeds to an optional acid recovery step 28, wherein the organic acid may be recovered if desired and preferably recycled to provide at least a portion of the acid stream 22.
- the acid recovery step 28 may take various forms, depending, for example, on the organic acid used and on its concentration in the mash stream 26.
- formic acid is known to form an azeotrope with water at concentrations on the order of 50 percent by weight, whereas acetic acid does not, so that either of azeotropic distillation or conventional distillation may be desirably employed dependent on the circurmstances of use.
- those skilled in the art should be well- able to select an economical acid recovery technique for step 28, if acid recovery is considered important.
- the temperature of the mash 30 following the acid recovery step 28 is reduced to between 60 and 75 degrees, and glucoamylase enzyme (shown as stream 32) is added in step 31 to further produce glucose from the starchy endosperm of the corn kernel, while maintaining a temperature of between 60 and 75 degrees over a period of from 1 to 48 hours.
- glucoamylase enzyme shown as stream 32
- the resultant fermentation medium 34 then is fermented in fermentation step 36 with addition of glucoamylase enzyme and of a
- fermentative microorganism which microorganism can be, for example, a yeast (e.g., saccharomyces cerevisiae), bacteria or fungus, such fermentation typically occurring at a temperature of from 30 to 40 degrees Celsius.
- yeast e.g., saccharomyces cerevisiae
- bacteria or fungus such fermentation typically occurring at a temperature of from 30 to 40 degrees Celsius.
- Typical manufacturer-recommended glucoamylase addition levels may be used, for example, on the order of 0.22 units per gram of starch.
- Other enzymes may also be added including hemicellulases, proteases, cellulases, and feruioyl esterases.
- the fermentation results in the production of a carbon dioxide product stream 38, ethanol and various non-fermentable solids and residues, including yeast, gluten proteins, germ and fiber.
- the ethanol and remaining solids are passed (reference number 40) to a distillation step 42, whereby the crude ethanol stream 44 from the fermentation is recovered for further clean-up and purification (not shown) prior to use as a fuel additive.
- the remaining water and solids from the fermentation step 36 undergo a liquids/solids separation as, for example, in a centrifugation step 46, resulting in a solids portion 48 containing the oil-bearing germ and other solids and a thin stillage portion 50 which is preferably concentrated by evaporation in step 52 for being incorporated in a high protein feed product 54.
- the considerable oil content in solids portion 48 is extracted as a crude corn oil coproduct stream 56 for further refining (not shown), by means of oil recovery step 58.
- Oil recovery step 58 can use any conventional technique for extracting the oil value in the solids portion 48, including, for example, chemical extraction, expeller extraction, hydraulic press extraction, carbon dioxide assisted extraction and supercritical fluid extraction. Expeller extraction is preferred. Where supercritical fluid extraction is used, a preferred supercritical fluid is carbon dioxide with or without co-solvents such as propane and/or ethanol. Suitable methods of supercritical fluid extraction are set forth, for example, in U.S. Pat. No. 4,495,207 to Christianson et al., which is incorporated by reference herein.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Processing Of Solid Wastes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2012008944A MX2012008944A (en) | 2010-02-03 | 2011-01-19 | Improved grain milling process. |
CN201180007787.9A CN102770548B (en) | 2010-02-03 | 2011-01-19 | Improved grain milling process |
EP11740178.6A EP2531605A4 (en) | 2010-02-03 | 2011-01-19 | Improved grain milling process |
US13/521,365 US9096911B2 (en) | 2010-02-03 | 2011-01-19 | Grain milling process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US30085310P | 2010-02-03 | 2010-02-03 | |
US61/300,853 | 2010-02-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2011097070A2 true WO2011097070A2 (en) | 2011-08-11 |
WO2011097070A3 WO2011097070A3 (en) | 2011-11-24 |
Family
ID=44356034
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/021518 WO2011097065A2 (en) | 2010-02-03 | 2011-01-18 | Method of producing sugars using a combination of acids to selectively hydrolyze hemicellulosic and cellulosic materials |
PCT/US2011/021601 WO2011097070A2 (en) | 2010-02-03 | 2011-01-19 | Improved grain milling process |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/021518 WO2011097065A2 (en) | 2010-02-03 | 2011-01-18 | Method of producing sugars using a combination of acids to selectively hydrolyze hemicellulosic and cellulosic materials |
Country Status (13)
Country | Link |
---|---|
US (2) | US20130130331A1 (en) |
EP (2) | EP2531528B1 (en) |
JP (1) | JP2013518972A (en) |
KR (1) | KR20120120394A (en) |
CN (2) | CN102822203A (en) |
AU (1) | AU2011213271B2 (en) |
BR (1) | BR112012019121A2 (en) |
CA (1) | CA2788329C (en) |
DK (1) | DK2531528T3 (en) |
ES (1) | ES2538669T3 (en) |
MX (2) | MX2012008946A (en) |
RU (1) | RU2012134274A (en) |
WO (2) | WO2011097065A2 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8926794B2 (en) * | 2011-07-07 | 2015-01-06 | Tate & Lyle Ingredients Americas Llc | Process of extraction of hemicellulose from corn fiber |
EP2766491A4 (en) * | 2011-09-23 | 2015-04-29 | Archer Daniels Midland Co | C1-c2 organic acid treatment of lignocellulosic biomass to produce acylated cellulose pulp, hemicellulose, lignin and sugars and fermentation of the sugars |
CN103987664B (en) | 2011-12-06 | 2017-03-08 | 德尔塔阀门公司 | Ozone distribution in tap |
JP6148720B2 (en) | 2012-03-12 | 2017-06-14 | アーチャー−ダニエルズ−ミッドランド カンパニー | Process for producing sugar and / or sugar alcohol dehydrate |
BR112014026267A2 (en) * | 2012-04-26 | 2017-06-27 | Archer Daniels Midland Co | method for processing lignocellulosic biomass; composition; and composition obtained by the method |
US20130295628A1 (en) * | 2012-05-02 | 2013-11-07 | Api Intellectual Property Holdings, Llc | Processes for producing energy-dense biomass and sugars or sugar derivatives, by integrated hydrolysis and torrefaction |
US8715765B2 (en) * | 2012-06-18 | 2014-05-06 | Randal Myers | Process of treating biomass |
US9695484B2 (en) | 2012-09-28 | 2017-07-04 | Industrial Technology Research Institute | Sugar products and fabrication method thereof |
US20140186903A1 (en) * | 2012-12-28 | 2014-07-03 | Api Intellectual Property Holdings, Llc | Processes and apparatus for producing furfural, levulinic acid, and other sugar-derived products from biomass |
CN103966367B (en) | 2013-02-01 | 2016-01-20 | 财团法人工业技术研究院 | Process for the preparation of saccharides |
JP2014193977A (en) * | 2013-03-29 | 2014-10-09 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg including the resin composition, laminate sheet, and molding material |
US9315750B2 (en) * | 2013-06-27 | 2016-04-19 | Api Intellectual Property Holdings, Llc | Processes for producing biomass pellets and sugars |
KR101918731B1 (en) * | 2015-09-25 | 2018-11-14 | 씨제이제일제당 주식회사 | Method for concentrating protein in grain powder |
EP3170900A1 (en) * | 2015-11-19 | 2017-05-24 | Reliance Industries Limited | A process for conversion of biomass to organic compound(s) |
US10837029B2 (en) * | 2015-11-25 | 2020-11-17 | Flint Hills Resources, Lp | Methods and systems for grinding corn and making ethanol therefrom |
CN108463437B (en) | 2015-12-21 | 2022-07-08 | 德尔塔阀门公司 | Fluid delivery system comprising a disinfection device |
JP2018000114A (en) * | 2016-07-04 | 2018-01-11 | 国立大学法人東京工業大学 | Method for producing monosaccharide or oligosaccharide from material containing cellulose and lignin |
BE1025161B1 (en) * | 2017-04-20 | 2018-11-26 | Galactic S.A. | PROCESS FOR THE SIMULTANEOUS PRODUCTION OF LACTIC ACID AND ALCOHOL OR BIOGAS FROM CEREALS |
IT201700123012A1 (en) * | 2017-10-30 | 2019-04-30 | Versalis Spa | PROCEDURE FOR THE PRODUCTION OF BIOMASS SUGARS DERIVING FROM PLANTS OF GUAYULE |
FI129229B (en) * | 2019-02-07 | 2021-09-30 | Fazer Ab Oy Karl | Method for utilizing biomasses |
CN111087491B (en) * | 2019-12-13 | 2021-09-21 | 华南理工大学 | Method for preparing hemicellulose, carboxylated cellulose nano crystal, fibril and citrate multi-component product from fiber by using citric acid |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5366558A (en) * | 1979-03-23 | 1994-11-22 | Brink David L | Method of treating biomass material |
US6333181B1 (en) * | 1997-04-07 | 2001-12-25 | University Of Florida Research Foundation, Inc. | Ethanol production from lignocellulose |
US7452425B1 (en) * | 2003-03-25 | 2008-11-18 | Langhauser Associates, Inc. | Corn refining process |
US7101691B2 (en) * | 2003-08-29 | 2006-09-05 | Ultraforce Technology Llc | Alcohol production using sonication |
US7504245B2 (en) * | 2003-10-03 | 2009-03-17 | Fcstone Carbon, Llc | Biomass conversion to alcohol using ultrasonic energy |
KR20060114323A (en) * | 2003-10-31 | 2006-11-06 | 가부시키가이샤 에바라 세이사꾸쇼 | Method of separating and recovering acid/sugar solution and lignophenol derivative from lignocellulosic substance |
MXPA06013600A (en) * | 2004-05-27 | 2007-03-15 | Genencor Int | Acid-stable alpha amylases having granular starch hydrolyzing activity and enzyme compositions. |
BRPI0500534A (en) * | 2005-02-15 | 2006-10-10 | Oxiteno Sa Ind E Comercio | acid hydrolysis process of cellulosic and lignocellulosic materials, digestion vessel and hydrolysis reactor |
CN101506372A (en) * | 2005-03-17 | 2009-08-12 | 诺维信北美公司 | Processes for producing fermentation products |
WO2007100897A2 (en) * | 2006-02-27 | 2007-09-07 | Edenspace System Corporation | Energy crops for improved biofuel feedstocks |
CN101240297A (en) * | 2007-02-07 | 2008-08-13 | 徐佳珊 | Production of ethanol from agronomic crop fibre castoff |
CN101765663B (en) * | 2007-03-14 | 2014-11-05 | 托莱多大学 | Biomass pretreatment |
FI121885B (en) * | 2007-11-09 | 2011-05-31 | Chempolis Oy | A process for making a sugar product |
CN100564667C (en) * | 2008-02-28 | 2009-12-02 | 中国石油化工股份有限公司 | Combined pretreatment method and system for lignocellulose |
-
2011
- 2011-01-18 US US13/521,462 patent/US20130130331A1/en not_active Abandoned
- 2011-01-18 RU RU2012134274/05A patent/RU2012134274A/en not_active Application Discontinuation
- 2011-01-18 EP EP11740173.7A patent/EP2531528B1/en not_active Not-in-force
- 2011-01-18 ES ES11740173.7T patent/ES2538669T3/en active Active
- 2011-01-18 KR KR1020127022807A patent/KR20120120394A/en active IP Right Grant
- 2011-01-18 WO PCT/US2011/021518 patent/WO2011097065A2/en active Application Filing
- 2011-01-18 DK DK11740173.7T patent/DK2531528T3/en active
- 2011-01-18 CN CN201180015103XA patent/CN102822203A/en active Pending
- 2011-01-18 CA CA2788329A patent/CA2788329C/en not_active Expired - Fee Related
- 2011-01-18 AU AU2011213271A patent/AU2011213271B2/en not_active Ceased
- 2011-01-18 JP JP2012551990A patent/JP2013518972A/en active Pending
- 2011-01-18 BR BR112012019121A patent/BR112012019121A2/en not_active Application Discontinuation
- 2011-01-18 MX MX2012008946A patent/MX2012008946A/en active IP Right Grant
- 2011-01-19 CN CN201180007787.9A patent/CN102770548B/en active Active
- 2011-01-19 WO PCT/US2011/021601 patent/WO2011097070A2/en active Application Filing
- 2011-01-19 US US13/521,365 patent/US9096911B2/en active Active
- 2011-01-19 EP EP11740178.6A patent/EP2531605A4/en not_active Withdrawn
- 2011-01-19 MX MX2012008944A patent/MX2012008944A/en unknown
Non-Patent Citations (1)
Title |
---|
See references of EP2531605A4 * |
Also Published As
Publication number | Publication date |
---|---|
MX2012008944A (en) | 2012-11-30 |
RU2012134274A (en) | 2014-03-10 |
JP2013518972A (en) | 2013-05-23 |
MX2012008946A (en) | 2012-12-05 |
WO2011097065A3 (en) | 2011-11-17 |
EP2531605A4 (en) | 2014-03-19 |
US20130130331A1 (en) | 2013-05-23 |
WO2011097070A3 (en) | 2011-11-24 |
CN102770548A (en) | 2012-11-07 |
CN102822203A (en) | 2012-12-12 |
EP2531528B1 (en) | 2015-03-18 |
ES2538669T3 (en) | 2015-06-23 |
CA2788329A1 (en) | 2011-08-11 |
EP2531528A4 (en) | 2014-04-02 |
AU2011213271B2 (en) | 2014-05-22 |
US20130102045A1 (en) | 2013-04-25 |
AU2011213271A1 (en) | 2012-08-09 |
US9096911B2 (en) | 2015-08-04 |
CA2788329C (en) | 2017-08-01 |
CN102770548B (en) | 2015-07-08 |
EP2531605A2 (en) | 2012-12-12 |
WO2011097065A2 (en) | 2011-08-11 |
BR112012019121A2 (en) | 2016-06-28 |
DK2531528T3 (en) | 2015-05-26 |
KR20120120394A (en) | 2012-11-01 |
EP2531528A2 (en) | 2012-12-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9096911B2 (en) | Grain milling process | |
EP3121258B1 (en) | Systems and methods for producing a sugar stream or biofuel and/or biochemicals | |
US9732302B2 (en) | System and method for separating high value by-products from grains used for alcohol production | |
US11053522B2 (en) | Methods and systems for obtaining oil from a stillage composition | |
US7488390B2 (en) | Corn and fiber refining | |
CA2846489C (en) | Process for producing cellulosic biofuel | |
US10480038B2 (en) | System and method for producing a sugar stream | |
US20130288376A1 (en) | System for and method of separating germ from grains used for alcohol production | |
US20230079475A1 (en) | System and method for producing a sugar stream with front end oil separation | |
US20240060148A1 (en) | System and method for producing a sugar stream | |
US20090238918A1 (en) | Corn Wet Milling Process | |
WO2006104504A2 (en) | Integrated fermentation product recycling | |
WO2012036857A2 (en) | Improved milling process with oil recovery | |
EP2997144B1 (en) | Enzyme compositions for the improvement of fermentation processes and by-products | |
US20150087039A1 (en) | Methods for enhancing the recovery of oil during biofuel production | |
EP3134507A1 (en) | Integrated cellulosic ethanol production process | |
WO2023148756A1 (en) | An integrated process for the production of ethanol and protein from rice distillery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180007787.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11740178 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13521365 Country of ref document: US |
|
REEP | Request for entry into the european phase |
Ref document number: 2011740178 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011740178 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2012/008944 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |