WO2008024109A1 - Procédé et dispositif pour produire commercialement de l'éthanol de qualité carburant de moteur - Google Patents

Procédé et dispositif pour produire commercialement de l'éthanol de qualité carburant de moteur Download PDF

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Publication number
WO2008024109A1
WO2008024109A1 PCT/US2006/032830 US2006032830W WO2008024109A1 WO 2008024109 A1 WO2008024109 A1 WO 2008024109A1 US 2006032830 W US2006032830 W US 2006032830W WO 2008024109 A1 WO2008024109 A1 WO 2008024109A1
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Prior art keywords
ethanol
retort
fuel
volume
vacuum
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English (en)
Inventor
Jr. Bennett H. Shelfer
Grant T. Shelfer
Frank A. Shelfer
Park V. Shelfer
Bennett H. Shelfer
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
    • B01D3/002—Processes specially adapted for distillation or rectification of fermented solutions by continuous methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M43/00—Combinations of bioreactors or fermenters with other apparatus
    • C12M43/02—Bioreactors or fermenters combined with devices for liquid fuel extraction; Biorefineries
    • 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 application relates to a commercial, industrial process for malting anhydrous and/or premium quality motor fuel-grade ethanol solely from the feedstock and energy provided by ears of corn including the cob, grain, and shuck. More specifically, the present invention provides a commercial, industrial process for producing at least 99.19 weight % motor fuel-grade ethanol, by distilling a mixture of approximately 95 volume % ethanol and 5 volume % water at very low pressures and at predictable associated minimum boiling point temperatures.
  • Fuel- Grade Ethanol should not typically be below 197 proof (98.5 volume % ethanol, 97.6 weight % ethanol) prior to denaturing.
  • the "beer” containing 10% ethanol by volume is then inserted into a distillation column which is heated with steam so that a precise boiling point is maintained at the top of the column. Therefore, the end result in the distillation column is the emission of nondehydrated ethanol vapor from the top of the column.
  • This nondehydrated ethanol vapor is a mixture of approximately 95 volume % ethanol and 5 volume % water. Since minimum motor fuel-grade ethanol requires at least 98.5 % ethanol by volume (97.6 weight % ethanol), it is necessary to dehydrate the mixture to achieve this percentage of ethanol. [0006] Atmospheric fractional distillation of ethanol/water mixtures produces a minimum boiling-point azeotrope.
  • Azeotropic distillation incorporates hydrocarbon strippers, such as benzene or diethyl ether, which are used to entrain the mixture in a dehydration tower to effectively remove and strip the required amounts of water from the mixture.
  • hydrocarbon strippers such as benzene or diethyl ether
  • Commercial processes of the type described require well over 22,000 BTU's per gallon in the boilers of the distillation columns.
  • drying agents such as benzene and other hydrocarbons, have been deemed hazardous materials by the Environmental Protection Agency, and the use of such materials has been discouraged for fear of contamination of the environment.
  • Molecular Sieves contain Zeolite beads (synthetic, highly ordered aluminosilicates) or corn grits. Like Zeolite beads having very precise pore sizes, corn grits have also been found to be equally adsorptive with respect to the water molecules of the ethanol/water azeotrope.
  • the porous openings are very small void spaces, on the molecular scale, and are usually measured in Angstroms or nanometers. Water molecules have a molecular diameter, which is small enough to allow them to fit into the pore spaces of molecular sieve's packing medium.
  • the molecular diameter of ethanol molecules is larger than that of water molecules, too large in fact for ethanol molecules to fit into the pore spaces of the adsorptive medium of molecular sieves. It is this size-sorting property of the Zeolite beads and corn grits that is responsible for the "sieve" term in the descriptive name, molecular sieve.
  • This basic, separative principle of molecular sieve technologies provides the basis for the dehydration of ethanol in this prior process art form. [0007] As molecular sieve technologies are implemented in commercial production of anhydrous ethanol, two molecular sieves are usually employed in order to provide for a continuous operation of the process.
  • Pressurized, superheated nondehydrated ethanol vapor in a mixture of approximately 95 volume % ethanol and 5 volume % water is forced into a tank containing a bed of molecular sieve adsorbent packing medium.
  • the ethanol water mixture passes over the adsorbent medium and the pressure forces the water into the pores of the adsorbent medium where it is trapped within the internal cavities.
  • the superheated ethanol flow is diverted to a second, dry molecular sieve and the first molecular sieve put under vacuum for regeneration.
  • the pressure drop with the vacuum pulls out the adsorbed water thereby regenerating the packing medium of the molecular sieve so it is dry and ready to pull more water out of additional nondehydrated ethanol vapor.
  • the present invention provides a system for the commercial, industrial production of dehydrated ethanol of premium quality fuel-grade to anhydrous quality by vacuum dehydration which will overcome the above-stated disadvantages and other historically perceived obstacles.
  • the present invention provides a system for commercially and industrially producing premium quality motor fuel-grade ethanol containing, at least 99.5 % ethanol by volume (99.19 weight % ethanol), which utilizes substantially less energy than conventional industrial process equipment.
  • the present invention provides a commercial and industrial process for producing ethanol which may be fueled utilizing only the shuck and cob of the ears of corn from which the grain is derived for the feedstock of the process.
  • the present invention provides a method of commercially, and industrially producing fuel-grade to anhydrous ethanol wherein the dehydration of ethanol/water mixtures requires no dehydrating agent such as benzene which may have harmful effects on the environment.
  • the present invention provides a system for continuously maintaining the proper operating parameters for commercially, and industrially distilling an ethanol mixture at low pressures in order to dehydrate or remove undesired quantities of water.
  • the present invention provides a vacuum dehydration unit for commercially, and industrially producing fuel-grade dehydrated ethanol which eliminates the use of plates and packing material while, at the same time, achieving particularly good vapor-liquid contact resulting in a vapor-liquid equilibrium throughout the retort so as to produce industrial flow rates of fuel-grade to anhydrous ethanol.
  • the present invention provides a vacuum dehydration unit for commercially, and industrially producing fuel-grade to anhydrous ethanol without the need for or the use of molecular sieve technologies.
  • the present invention provides a vacuum dehydration unit for commercially and industrially producing fuel-grade to anhydrous ethanol which requires less capital expense, less operating energy and is easier and safer to operate and maintain than conventional industrial process equipment.
  • the foregoing and other embodiments of the present invention are accomplished, generally speaking, by providing a vacuum dehydration retort into which approximately a 95 volume % and 5 volume % mixture of ethanol and water, respectively, is introduced. The mixture is distilled in this vacuum retort at sufficiently low pressures, and at minimum boiling point temperatures, so as to produce the desired percentage of ethanol required in the final product which is removed from the top of the vacuum retort as a vapor.
  • the vapor-liquid equilibrium and retort temperatures are regulated thermodynamically via computer process-quality control.
  • Sufficient heat input is supplied to the liquid reflux in the base of the vacuum retort to insure vapor boil-up rates necessary to produce vapor product flow rates consistent with yielding desired industrial production volume flow rates of fuel-grade to anhydrous ethanol.
  • a heat-removal unit, positioned within the vacuum retort as a fine tube coil serves to maintain a carefully controlled thermal gradient from the surface of the reflux in the retort to the head of the retort and from the feed entry point into the retort to the head of the retort.
  • the present invention achieves particularly good vapor-liquid contact resulting in a vapor-liquid equilibrium from the bottom to the top of the retort without using plates of any kind. There is little or no pressure drop within the retort due to the fact that there is no packing material or plates to obstruct the ascending vapor and descending liquid reflux.
  • the vacuum dehydration technique for dewatering ethanol mixtures according to the present invention requires much less energy to fuel the conversion process than required in hydrocarbon stripper or molecular sieve processes which are now commercially used.
  • a BTU analysis of the energy requirements of the process of the present invention confirms that, if one snaps a single ear of corn from the stalk for conversion into ethanol, the BTU' s contained in the shuck and cob alone will fuel the entire conversion process of the associated corn kernels for that ear with a 40% overage of energy.
  • corn stover exclusive of the stalks, to fuel the entire industrial process of making fuel-grade to anhydrous ethanol.
  • prior art hydrocarbon stripping processes require a minimum of 22,000 BTU' s per gallon of energy for their operation
  • prior art molecular sieve technologies require at least 16,000 BTU's per gallon of energy for operation
  • the vacuum dehydration process of the present invention requires just over 14,000 BTU's per gallon.
  • the dehydration section of the prior art hydrocarbon stripping processes require at least four (4) times as many BTU's per gallon as the vacuum dehydration section of the present invention.
  • the prior art molecular sieve technologies require a minimum of almost two (2) times as many BTU's per gallon as the vacuum dehydration section of the present invention.
  • the operating parameters of the present invention relating to the vacuum retort of the dehydration section can be predetermined with satisfactory accuracy. For example, by analyzing the results of both actual and projected test data and determining the mathematical relationship between all operating parameters, it has been determined that the following operating parameters for producing a premium quality 99.19 wt. % motor fuel-grade ethanol, up to 100% by weight of ethanol, are as follows:
  • thermodynamic and operational characteristics of the vacuum dehydration process of the present invention and the attendant advantages thereof shall become more readily apparent by using an example production volume of 10,000 gallons per day of premium quality motor fuel-grade ethanol, having a product liquid composition of 98.73 Mole % ethanol and 1.27 Mole % water (99.5 wt. % and 0.5 wt. %), to calculate mass and heat balance figures made reference to in the drawings contained herein.
  • production volumes of the process of the present invention may be scaled up or down, in relation to the example, 10,000 gallons per day production volume, without significantly changing or altering the advantages of the thermodynamic and operational efficiencies of the process.
  • Figure 1 is a schematic diagram illustrating the process of the present invention for producing motor fuel-grade to anhydrous ethanol
  • Figure 2 is a graph of weight % ethanol versus pressure relating to the vacuum retort
  • Figure 3 is a graph of weight % ethanol versus temperature relating to the vacuum retort
  • Figure 4 is a graph of temperature versus pressure relating to the vacuum retort
  • Figure 5 is a graph of pressure versus temperature versus composition ethanol in the vapor product relating to the vacuum retort;
  • Figure 6 is a preferred embodiment of a grain receiving, milling, and storage area to be utilized with the system of Figure 1 ;
  • Figures 7A and 7B present a diagrammatic heat and mass balance across the vacuum dehydration process of the present invention to be used in conjunction with Figure 8;
  • Figure 8 is a tabulation of enthalpy data relating to the vacuum retort and to be utilized in reference by the heat and mass balances of Figures 7 A and 7B;
  • Figure 9 is a diagrammatic representation illustrating rigid-transformation and rotation of axes performed during mathematical modeling and equation development.
  • FIG. 1 there is illustrated a schematic diagram of a system for incorporating the process of the present invention, generally indicated 20.
  • "Beer” from fermented corn grain, in a fermentation area, having approximately 10% to 12% by weight ethanol is pumped from that fermentation area through condenser preheater 12, and condenser preheater 24 into a prior art stripping and rectifying fractional distillation column 14.
  • Process steam (from the extraction port of a co-generation turbogenerator) is supplied to the stripping and rectification distillation area at Reboiler 16.
  • the process steam flows through Reboiler 16 where it transfers (no live steam comes in contact with the "beer") enough heat to maintain a column head (of distillation column 14) temperature at approximately 87.8°C.
  • the vacuum retort maintained at the preferred reduced pressure, is herein equipped with a heat-removal system (internal cooling coil).
  • the purpose of the heat-removal system is to maintain a carefully controlled temperature gradient from the surface of the liquid reflux in the bottom of the retort 20 (51°C or higher as necessary) to the head of the retort (33.4°C) such that the head temperature is maintained equal to the appropriate minimum boiling point temperature, and from the feed entry point into the retort (77.8°C) to the retort head (33.4°C).
  • Computer process-quality control of the removal of heat from the vacuum dehydration unit provides an internal temperature gradient so that sufficient heat-input, supplied to liquid reflux in the base of the vacuum retort, insures vapor boil-up rates, causing vapor product flow rates, consistent with producing industrial volumes of fuel-grade to anhydrous ethanol.
  • the cooling medium for the heat-removal system within the vacuum retort is herein represented as chilled water. However, any suitable coolant may be utilized such as carbon dioxide, especially if CO 2 is being captured during a fermentation process.
  • the liquid reflux in the bottom of the retort 20 is returned to the prior art stripping and rectification column 14 at approximately 2.8 pounds (0.33 gallons) per minute, at a point 14R appropriate for its composition.
  • a vacuum pump 36 is provided in series with a condenser 32. Also provided in the bottom of vacuum retort 20 is a recirculating pump 38 which recirculates out of the bottom of the vacuum retort 20 liquid which is a reflux mixture made up predominantly of water with some residual ethanol. This reflux in the bottom of retort 20 is pumped back to the stripping and rectification column 14 at approximately 2.8 pounds (0.33 gallons) per minute, at a point 14R appropriate for its composition. In a preferred embodiment the pressure within the vacuum retort 20 is maintained at approximately 95.0 m.m. of mercury, or 0.125 atmospheres.
  • the temperature gradient within the vacuum retort 20 maintains a bottom temperature within the retort of 51.0 0 C and a head temperature within the vacuum retort 20 equal to the corresponding minimum boiling point of 33.4°C.
  • a bottom temperature within the retort of 51.0 0 C
  • a head temperature within the vacuum retort 20 equal to the corresponding minimum boiling point of 33.4°C.
  • additional heat input is required for the production of industrial product flow rates during the dehydration phase of distillation.
  • the mixture flashes upon entrance to the vacuum retort.
  • the less volatile component water
  • condenses allowing the rising vapors to become enriched in the more volatile component (ethanol).
  • the quantity of heat supplied to the liquid in the bottom of the vacuum retort is modified sufficiently to insure a vapor boil-up rate consistent with the desired industrial product flow rates.
  • the necessary vapor boil-up rate and the predetermined and carefully controlled thermal balance throughout the vacuum retort the refluxing condensate literally rains down inside the vacuum retort in intimate contact with the ascending vapor.
  • these are considered to be optimum operating parameters, although other parameters may be utilized at acceptable operating ranges.
  • vapor having a composition of approximately 99.5 weight % ethanol and 0.5 weight % water is removed from the top of the vacuum retort 20 and flows through the product condenser cooler 32, and is quick-cooled to a temperature of about 12.8 0 C. From there it passes at the rate of approximately 6.82 gallons per minute (45.34 pounds per minute) into an "anhydrous" ethanol storage area.
  • the effectiveness of the vacuum dehydration unit herein described is realized as a result of computer process-quality control of the heat-removal system which produces, maintains, and allows for the necessary thermodynamic heat balance which further allows the vapor-liquid equilibrium to exist at the system vacuum pressure without plates or packing.
  • the system of the present invention also contemplates the reuse of products of the distillation process by providing reboilers, condensers, and similar recirculation loops for reclaiming heat to and from the process respectively.
  • a vent condenser 22 is provided adjacent condenser preheater 12 for receiving vapor vented there from, and recirculating the same into the system.
  • flash drum 26 is coupled to condenser 24 for recirculating excess heat through the system.
  • a series of pumps 38, 40, 42, and 44 are appropriately provided for causing the aforementioned recirculation of fluids.
  • the present invention also provides for the determination of the preferred operating ranges or parameters associated with vacuum retort 20 to maintain a thermodynamic balance, based not only on test results but also on projections of preferred operating parameters from a discovered mathematical relationship between the various operating parameters. For example, it has been determined, as part of the present invention that, for achieving premium quality 99.19% by weight motor fuel-grade ethanol, the optimum minimum boiling point temperature within the head of vacuum retort 20 should be 34.28°C and the associated operating pressure within the retort should be 0.145 atmospheres.
  • the optimum minimum boiling point temperature within the head of retort 20 is 33.4°C, and a preferred associated operating pressure within the retort 20 is 0.125 atmospheres.
  • 100% by weight, anhydrous, ethanol can be optimally achieved by maintaining a 32.24°C minimum boiling point temperature within the head of retort 20 and an associated operating pressure within the retort of 0.110 atmospheres.
  • FIG. 2 there is represented a graph of vapor component weight % ethanol versus pressure (P).
  • the z n or vapor component weight % ethanol axis has its origin at
  • Figure 3 represents a plot of Z n or z n - 95 versus Temperature [T n ) , wherein
  • FIG. 5 Combining the three graphic illustrations displays a three-dimensional plot of vapor component weight % ethanol versus temperature versus pressure, which is represented as Figure 5.
  • This 2-D graphic relationship provides a visual representation of the three variables composition, pressure, and temperature.
  • the relationship between pressure and temperature, depicted in Figure 4 is represented as visually seen from atop the Z n axis, looking down on the plane of the X n and T n axes.
  • Z n must equal 4.5 , which equals, ⁇ z n — 95) ; refer to Table 4.
  • log (z n -95) 1Og[C 113 +b n3 (ln(y n -30))] .
  • logx ⁇ log ⁇ 2 +6 2 log (ln(j/ n -30)-/ ⁇ )(cosl80 o ) ⁇
  • the operating parameters i.e., composition, temperature, and pressure
  • the operating parameters are determined from the system of equations developed above which mathematically models the process and when implemented appropriately provides a rapid and accurate means of computing the required conditions of interest, from 95.2 weight % ethanol to 100 weight % ethanol, through real-time computer process-quality control.
  • the system of the present invention is designed to accept a 95 volume % ethanol feed, the system concept allows it to be engineered to dehydrate any suitable beer feed stream.
  • the grain receiving, milling and storage area of the system of the present invention is illustrated generally as 50 in Figure 6.
  • This area of the plant 50 will receive the ears of corn including the grain, cob, and shucks to be utilized with the process of the present invention.
  • the shucks and cobs will be utilized to fuel the system of Figure 1, while the corn kernels (60.84% starch) are utilized as the primary ethanol production feed stock from which the "beer" is derived.
  • the ears of corn, in the shuck can be received via rail or truck, weighed for payment and inventory, and dumped into the respective unload hoppers 52, illustrated in Figure 6. From these hoppers 52, the ears are screw conveyed into a bucket elevator 54 into a corn shelter 56. The kernels from shelter 56 are then dropped into a kernel corn silo 62 for storage. The shucks, cobs, and trash are conveyed to a fuel storage area by belt conveyor 58, where all boiler fuel is stored until needed. Dirt and other nonflammable material is discharged from the corn shelter 56.
  • the ears of corn may be transported by belt conveyor 60 to storage and, when needed, back through a second run of the conveyor to the corn shelter 56, when the latter is once again available for use.
  • Kernels of corn from the kernel corn silo are screw conveyed from the bottom of the silo 62 to the entrance of a hammer-mill 63 where they are crushed into meal, and then elevated via a bucket elevator 64 to a meal silo 66 for storage. As needed in the process illustrated in Figure 1, the meal is removed from the silo 66 and air conveyed, if desired, to the fermentation area for conversion to "beer".

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Abstract

La présente invention concerne un procédé de production d'éthanol de qualité carburant dans lequel un mélange d'approximativement 95 % en volume d'éthanol et 5 % en volume est distillé dans une cornue sous vide dans une plage de pression allant de 0,145 atmosphères à 0,110 atmosphères, tandis que la température du point d'ébullition minimum de l'azéotrope est contrôlé dans la plage allant de 34,28 °C à 32,34 °C. Le procédé de la présente invention présente de très faibles besoins en énergie par comparaison aux procédés commercialement connus pour produire l'éthanol de qualité carburant. Par conséquent, la tige de maïs provenant uniquement de la rafle et des bogues de l'épi de maïs associé fournit non seulement la quantité d'énergie nécessaire pour convertir le grain de chaque épi en un éthanol de qualité carburant mais également au moins 33 % en plus d'énergie que ce qui est nécessaire pour les besoins en énergie de l'ensemble du procédé. Grâce à la cogénération, l'énergie additionnelle ou en excès fournie par la rafle et les bogues de chaque épi pourrait être utilisée pour produire de l'électricité co-produite pour la vente à une grille électrique d'utilité commerciale. Ainsi, l'ensemble du système pour produire de l'éthanol de qualité carburant décrit ici est autonome.
PCT/US2006/032830 2006-08-22 2006-08-22 Procédé et dispositif pour produire commercialement de l'éthanol de qualité carburant de moteur Ceased WO2008024109A1 (fr)

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CN101381279B (zh) * 2008-10-15 2011-06-01 天津大学 燃料乙醇脱水的装置和方法
CN101525272B (zh) * 2009-04-07 2012-05-30 天津大学 乙醇蒸馏脱水节能工艺及设备
CN102126920B (zh) * 2010-01-13 2013-09-25 中国石油化工集团公司 三塔三效差压热集成制取共沸乙醇的方法
WO2016061262A1 (fr) * 2014-10-14 2016-04-21 Gevo, Inc. Procédés de conversion d'éthanol en hydrocarbures inférieurs fonctionnalisés et hydrocarbures en aval
CN106495988A (zh) * 2016-09-27 2017-03-15 广西罗城科潮基业科技发展有限公司 一种优级醇无水酒精的加工方法
US10350511B1 (en) * 2016-07-15 2019-07-16 Bioleap, Inc. Distillation reflux reduction
US10633320B2 (en) 2018-01-04 2020-04-28 Gevo, Inc. Upgrading fusel oil mixtures over heterogeneous catalysts to higher value renewable chemicals

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US4345973A (en) * 1980-08-25 1982-08-24 Purdue Research Foundation Vapor phase dehydration of aqueous alcohol mixtures
US4746610A (en) * 1983-02-02 1988-05-24 Douglas W. Wills Efficient use of thermal energy from an internal combustion engine in ethanol production

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US2440925A (en) * 1944-04-27 1948-05-04 Chemprotin Producs Fermenting method
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US4308106A (en) * 1980-08-01 1981-12-29 Mannfeld Robert L Process for removing substantially all water from an alcohol-containing solution for use as a motor fuel or motor fuel additive
US4345973A (en) * 1980-08-25 1982-08-24 Purdue Research Foundation Vapor phase dehydration of aqueous alcohol mixtures
US4746610A (en) * 1983-02-02 1988-05-24 Douglas W. Wills Efficient use of thermal energy from an internal combustion engine in ethanol production

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