WO2009123223A1 - Méthode de traitement de purification d'alcool fermenté - Google Patents

Méthode de traitement de purification d'alcool fermenté Download PDF

Info

Publication number
WO2009123223A1
WO2009123223A1 PCT/JP2009/056727 JP2009056727W WO2009123223A1 WO 2009123223 A1 WO2009123223 A1 WO 2009123223A1 JP 2009056727 W JP2009056727 W JP 2009056727W WO 2009123223 A1 WO2009123223 A1 WO 2009123223A1
Authority
WO
WIPO (PCT)
Prior art keywords
alcohol
water
vapor
distillation column
mixed
Prior art date
Application number
PCT/JP2009/056727
Other languages
English (en)
Japanese (ja)
Inventor
政夫 菊地
俊介 中西
Original Assignee
宇部興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Publication of WO2009123223A1 publication Critical patent/WO2009123223A1/fr

Links

Images

Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a fermentation alcohol purification process, particularly a fermentation alcohol purification process that combines a mash tower, a distillation tower (and an evaporator), and a membrane separation device.
  • the present invention relates to a method for purifying alcohol.
  • the alcohol-water mixture solution is separated and concentrated from the fermentation alcohol solution (moromi) by the moromi tower, and then the alcohol-water mixture solution by the concentration tower (distillation tower).
  • the concentration tower distillation tower
  • Patent Document 1 describes a method in which an azeotropic mixture is distilled in a distillation tower, vapor of the azeotropic mixture is supplied to a membrane separation device, and separated by a separation membrane.
  • Patent Document 2 a membrane separation device is used instead of an azeotropic distillation column, and an alcohol-water mixture concentrated to near the azeotropic composition in the distillation column is evaporated by an evaporator and introduced into the membrane separation device for purification. A method of processing is disclosed. Further, it is described that the mixed vapor supplied to the membrane separation apparatus is superheated.
  • Patent Document 3 also discloses the same system as Patent Document 2.
  • a distillation column fraction is introduced into an evaporator and heated, a mixed vapor of alcohol and water having a pressure higher than the operation pressure of the distillation column is generated, and this high pressure vapor is converted into a membrane separator. It is described that the membrane separation apparatus can be operated with high efficiency.
  • JP 2003-93827 A Japanese Unexamined Patent Publication No. 63-258602 WO2004 / 073841
  • a membrane separator is used instead of the azeotropic distillation tower, the equipment can be simplified and the energy efficiency can be improved.
  • the fermentation alcohol is simpler and more energy efficient as a whole process. Sufficient studies have not been conducted on whether or not the product can be purified.
  • the object of the present invention is (Step 1) supplying a fermentation alcohol aqueous solution to a mash tower, heating the fermentation alcohol aqueous solution in the mash tower to distill a distillate containing a mixed vapor of alcohol and water, A distillate or a first condensate obtained by condensing the distillate is supplied to a distillation column. (Step 2) a) The distillate or the first condensate is heated by a distillation column to produce alcohol, water, Or b) a second condensate in which the distillate or the first condensate is heated by a distillation column to distill a mixed vapor of alcohol and water, and the mixed vapor is condensed.
  • Step 4 In the purification method for obtaining anhydrous alcohol that selectively removes water vapor from the mixed vapor of alcohol and water in the membrane separator, the process is simpler and extremely energy efficient as a whole process. It is to provide a well-purified process.
  • the present invention relates to the following matters. 1.
  • a fermentation alcohol aqueous solution is supplied to the mash tower, the fermentation alcohol aqueous solution in the mash tower is heated to distill a distillate containing a mixed vapor of alcohol and water, and this distillate or this distillate. Supplying a first condensate condensed with a product to a distillation column;
  • Step 2) a) a step of heating the distillate or the first condensate by a distillation column to distill a mixed vapor of alcohol and water, or b) the distillate or the first by a distillation column.
  • the condensate is heated to distill the mixed vapor of alcohol and water, the second condensate condensed with the mixed vapor is supplied to the evaporator, and the second condensate in the evaporator is heated.
  • Generating a mixed steam of alcohol and water (Step 3) a step of supplying the mixed vapor distilled from the distillation column in the a) or the mixed vapor generated from the evaporator in the b) to the membrane separator after reducing the pressure; (Step 4)
  • a purification method for obtaining anhydrous alcohol from a fermented alcohol aqueous solution comprising a step of selectively removing water vapor from a mixed steam of alcohol and water by a membrane separator.
  • a fermentation alcohol aqueous solution is supplied to a mash tower, the fermentation alcohol aqueous solution in the mash tower is heated to distill a distillate containing a mixed vapor of alcohol and water.
  • the first condensate obtained by condensing the distillate is supplied to the distillation column, and (2) a) the distillate or the first condensate is heated by the distillation column to distill the mixed vapor of alcohol and water.
  • the solid line indicates the flow of liquid or gas (vapor), and the broken line indicates the connection of the control system.
  • FIG. 1 showing an outline of an example of an embodiment according to the present invention.
  • anhydrous alcohol has a purity of 99.0% by mass or more, preferably 99.5% by mass or more, more preferably 99.7% by mass or more, and particularly preferably 99.8% by mass or more. Means alcohol.
  • the alcohol includes lower alkyl alcohols such as methyl alcohol, propyl alcohol, and butyl alcohol, and is preferably ethanol.
  • the fermented alcohol aqueous solution is not limited.
  • it is a fermented alcohol aqueous solution obtained by fermenting raw materials such as saccharides, starches, and celluloses. These materials are fermented in a fermenter to form a fermented alcohol aqueous solution.
  • the alcohol concentration of the aqueous fermentation alcohol solution is usually about 5 to 12% by mass.
  • this fermented alcohol aqueous solution includes alcohols such as yeast, fungus, methanol, fatty acids such as formic acid, acetic acid, succinic acid, lactic acid, butyric acid, aldehydes such as acetaldehyde, formaldehyde, Esters such as ethyl acetate and butyl acetate, acetals such as diethyl acetal, ketones such as acetone and methyl ethyl ketone, amines such as pyridine, picoline, 3-methylamine and 4-methylpyridine, and higher alcohols and fatty acid esters It contains various by-produced compounds such as so-called fusel oil which is a mixture. Moreover, normally, unfermented raw material components and the like remain as insoluble components to form a slurry.
  • alcohols such as yeast, fungus, methanol
  • fatty acids such as formic acid, acetic acid, succinic acid, lactic acid, butyric acid
  • This aqueous fermented alcohol solution is directly supplied from the fermenter or temporarily stored in a tank and then indirectly supplied to the mash tower 10. It is preferable that a large insoluble component is removed from the fermentation alcohol aqueous solution by rough filtration before being supplied to the mash tower.
  • the fermented alcohol aqueous solution after fermenting in the fermenter may have a pH of about 3 to 5 depending on by-product fatty acids. For this reason, it is preferable to neutralize the acid component contained in the fermentation alcohol aqueous solution by adding an alkali component or the like. By performing this neutralization treatment, it is possible to reliably prevent the acid from being mixed into the purified anhydrous alcohol.
  • Suitable examples of the alkali component to be added include water-soluble alkali compounds such as sodium hydroxide, potassium hydroxide, and potassium permanganate.
  • the aqueous fermentation alcohol solution is heated to distill a distillate containing a mixture of alcohol and water, and a condensate obtained by condensing the distillate is supplied to the distillation tower 20.
  • the distillate containing a mixture of alcohol and water is preferably a mixed vapor of alcohol and water (in a gaseous state), but a mixture containing droplets of a fermented alcohol aqueous solution in a mixed vapor of alcohol and water ( It may be a gas-liquid mixed state).
  • the main role of the moromi tower 10 is to suppress the discharge (loss) of alcohol outside the system as much as possible from the aqueous solution of fermentation alcohol, insoluble components such as unfermented raw material components, and high-boiling components such as fusel oil. Is preferably separated and removed together with low-boiling by-product components and water.
  • the moromi tower is not particularly limited, and a conventionally known type can be suitably used. Simple distillation or continuous distillation may be used. The number of distillation stages is preferably about several stages. For example, a tray-type tray such as a mountain-cap tray or a baffle tray with little scale adhesion can be suitably used. Furthermore, it may be a single distillation type such as flash distillation or a combination of a plurality of them.
  • the operating pressure of the moromi tower is preferably reduced pressure or atmospheric pressure.
  • the raw fermentation alcohol aqueous solution is introduced into the tower from a feed port relatively close to the top of the moromi tower 10.
  • steam steam
  • This water vapor rises in the tower while exchanging heat and materials with the liquid flowing down the tower.
  • the steam component at the bottom of the tower is almost water, and the alcohol concentration in the steam increases near the top of the tower.
  • water containing almost no alcohol is discharged from the bottom of the tower together with insoluble components as a bottom liquid.
  • the distillate containing a mixture of alcohol and water taken from the top of the moromi tower 10 or the concentration stage is sent to the condenser 11 and condensed. A part of this condensate is refluxed to the mash column, and the remaining condensate is supplied to the distillation column 20.
  • the alcohol concentration of the alcohol aqueous solution of the condensate supplied from the mash tower 10 to the distillation tower 20 can be controlled by changing the ratio of the condensate refluxed to the mash tower 10 and the number of stages of the distillation tower 20.
  • the distillate containing a mixed vapor of alcohol and water taken out from the top of the mash tower 10 or the concentration stage is not condensed and is in a gaseous state or a gas-liquid mixture. It can also be supplied to the distillation column 20 in a state.
  • a part of the distillate containing a mixed vapor of alcohol and water was supplied to the distillation column 20 and the remaining distillate was condensed by a condenser. The entire amount of the condensate can be refluxed to the mash tower.
  • the alcohol concentration of the distillate supplied from the mash column 10 to the distillation column 20 can be controlled by the ratio of the distillate supplied to the condenser.
  • the top of the mash column 10 is used to protect the separation membrane.
  • the steam mixed with alcohol and water extracted from the water is partially condensed (some low-boiling components remain as steam, and the other steam-water mixture is condensed), and low-boiling components such as aldehydes are mixed with alcohol. It is preferable to separate from the mixed vapor with water and remove it out of the system.
  • the alcohol concentration of the alcohol aqueous solution of the condensate supplied from the mash tower 10 to the distillation tower 20 is (of course fermented alcohol aqueous solution) in order to improve the energy efficiency in the entire process from the mash tower to the membrane separator.
  • the concentration is less than 50% by mass, preferably 12% by mass or more and less than 50% by mass, more preferably 20% by mass or more and less than 50% by mass, and further preferably 30% by mass or more and less than 50% by mass. Be controlled.
  • the above-mentioned role of the mash tower insoluble components such as unfermented raw material components and high-boiling components such as fusel oil are preferably added to the low-boiling side while suppressing the discharge of alcohol as much as possible.
  • the role of concentrating the alcohol is excessively added, so that it is necessary to further increase the concentration stage above the supply port of the fermentation alcohol aqueous solution of the mash tower 10 Therefore, the size and complexity of the device cannot be avoided.
  • the alcohol concentration of the distillate supplied to the distillation column 20 or the condensate of this distillate is less than 50% by mass, preferably 12% by mass or more and less than 50% by mass, more preferably 20% by mass or more and less than 50% by mass, Preferably, 30% by mass or more and less than 50% by mass can be easily achieved by a simple apparatus having about several distillation stages or less, and a part of the mixed steam of alcohol and water distilled from the distillation column. This is because, even when the water is condensed or refluxed to the mash tower, the rate of reflux can be made extremely low, so that rapid processing becomes possible and energy consumption can be suppressed.
  • the ratio of the condensate refluxed in the moromi tower is preferably 20% or less, more preferably 10% or less.
  • the role of the distillation column 20 is that the distillate from the mash column is 150 kPa (absolute pressure) or more, preferably 150 to 700 kPa (absolute pressure), more preferably 200 to 600 kPa (absolute pressure), and even more preferably 200 to 500 kPa.
  • Distilling at an operating pressure of (absolute pressure) is to concentrate the alcohol concentration to 55% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more. Although it may concentrate to near azeotropic composition here, it is preferred to concentrate to 90 mass% or less, more preferably 80 mass% or less.
  • the burden on the membrane separator increases, so the membrane separator becomes large and the fermentation alcohol is more convenient and extremely energy efficient as a whole process. This is not preferable because it cannot be purified to obtain anhydrous alcohol. On the other hand, it is not limited to make the alcohol concentration too high, but it is not preferable because the fermentation alcohol cannot be purified and processed in an extremely energy efficient manner as the whole process, so that anhydrous alcohol cannot be obtained.
  • a part of the mixed vapor of alcohol and water distilled in the distillation column 20 is condensed and refluxed as a condensate to the distillation column.
  • the remaining mixed vapor is reduced in pressure by a pressure reducing means while maintaining the vapor temperature. Then, it is supplied to the membrane separator 40.
  • the pressure reducing means is not particularly limited, but a pressure regulating valve having a throttle valve is preferably used. In addition, it is important that this depressurization results in the condensation temperature of the mixed steam of alcohol and water being lower than the temperature of the mixed steam.
  • the pressure is reduced to about 5 kPa or more, preferably 10 kPa or more, more preferably 10 to 500 kPa, and still more preferably about 10 to 300 kPa.
  • One of the features of the present invention is that after a mixed vapor of alcohol and water is generated by a distillation tower, the pressure is reduced by a pressure reducing means while maintaining the vapor temperature, and then supplied to the membrane separator.
  • the purpose of reducing the pressure is to sufficiently reduce the condensation temperature of the mixed vapor to be lower than the temperature of the mixed vapor so that the saturated mixed vapor does not condense in the membrane separator.
  • the condensation temperature of the mixed steam is 3 ° C. or more, preferably 5 ° C. or less lower than the temperature of the mixed steam. In addition, it is 10 degrees C or less normally.
  • reducing the pressure of the mixed steam once heated to a high pressure is poor in energy efficiency only in the process, but it is possible to improve the energy efficiency in the whole process.
  • the operating pressure of the distillation column 20 is set to 150 kPa (absolute pressure) or more, preferably 150 to 700 kPa (absolute pressure), because the pressure of the mixed vapor of alcohol and water supplied to the membrane separator is increased to increase the separation efficiency ( This is to improve the purification efficiency.
  • a pressure of less than 150 kPa (absolute pressure) is not preferable because the pressure of the mixed vapor supplied to the membrane separation device 40 becomes too low and the separation efficiency is lowered.
  • the pressure exceeds 700 kPa (absolute pressure) the separation efficiency in the membrane separation apparatus is improved, but the pressure resistance performance of the distillation apparatus and the membrane separation apparatus is excessively required, and there is a problem that the apparatus is enlarged. Since it occurs, it is not necessarily preferable.
  • the distillation column 20 is not particularly limited as long as it is suitable for a normal high-pressure distillation operation, such as a plate type or a packed column.
  • a supply unit for supplying an aqueous alcohol solution is disposed in the middle stage of the distillation column.
  • a part of the column bottom liquid is heated by the reboiler 21 to become vapor, and rises in the column while exchanging heat and materials with the liquid flowing down in the column.
  • steam of alcohol and water with which the alcohol concentration was concentrated distills from a tower top or a concentration stage.
  • a part of the mixed vapor of alcohol and water distilled by the distillation column 20 is cooled by the condenser 22 to become a condensate, and passes through the condensate tank 23 by, for example, a condensate pump. Alternatively, it is refluxed to the concentration stage.
  • the remainder of the mixed steam of alcohol and water distilled by the distillation tower 20 is decompressed by the decompression means 24 and then supplied to the membrane separation device 40.
  • the reboiler 21 that heats the bottom liquid of the distillation column 20 can also use the condensation heat of steam supplied from the outside.
  • the operating pressure of the distillation column 20 is suitably controlled by adjusting (limiting) the flow rate of steam for heating the bottom liquid of the distillation column.
  • the distillation column 20 by adjusting the ratio of the mixed vapor of alcohol and water distilled from the top of the column or the concentration stage to the distillation column 20 as a condensate and the number of stages of the distillation column,
  • the alcohol concentration of the mixed steam of alcohol and water to be distilled can be suitably controlled.
  • the ratio of the condensed liquid to be refluxed is relatively low. Is preferred. Preferably it is less than 50% of the condensate, more preferably less than 40%, even more preferably less than 20%, particularly preferably less than 10%.
  • the alcohol concentration of the mixed vapor of alcohol and water distilled from the top of the column or from the concentrating stage is not particularly limited.
  • any alcohol concentration from 50% by mass to azeotropic composition (or 96% by mass) can be used.
  • it is more preferably 55% to 90% by weight, further preferably 60% to 90% by weight, and particularly preferably 65% to 85% by weight. is there.
  • the condensation heat of the condenser 22 is preferably recovered by using the preheating of the aqueous alcohol solution supplied to the distillation column 20 or the reboiler heating of the mash column 10 and the necessary amount of reflux liquid cannot be condensed. It is preferable to add an auxiliary condenser and condense with cooling water.
  • the aqueous alcohol solution supplied to the distillation column 20 is preferably preheated to near its boiling point. At that time, it is preferable to effectively use the heat of the anhydrous alcohol purified by the reflux liquid of the distillation column 20 or the membrane separation device 40.
  • the mixed vapor of alcohol and water supplied to the membrane separation device 40 flows while in contact with the selectively permeable separation membrane. At that time, since the water vapor selectively permeates the separation membrane, the mixed vapor having a reduced alcohol concentration mainly composed of water vapor is recovered on the permeation side of the separation membrane.
  • the alcohol concentration of the mixed steam is about several to several mass% (for example, 20 mass% of alcohol), and is preferably circulated and supplied to the distillation column 20 in order to increase the alcohol recovery rate.
  • water vapor is removed on the non-permeating side of the separation membrane, high-purity anhydrous alcohol can be recovered.
  • the permeation amount of water vapor that permeates the separation membrane is proportional to the partial pressure difference between the water vapors on both sides of the membrane. For this reason, separation efficiency (purification efficiency) can be increased by increasing the partial pressure difference between the water vapors on both sides of the membrane.
  • a high-pressure mixed vapor of alcohol and water of 150 kPa (absolute pressure) or higher, preferably 150 to 700 kPa (absolute pressure) is supplied to the membrane separator. At the same time, it is also preferable to reduce the pressure on the permeate side of the separation membrane.
  • the space on the permeate side of the separation membrane is connected to a vacuum pump 42 via a heat exchanger (condenser) 41 to reduce the pressure, and the permeated vapor that has permeated the separation membrane is condensed in the condenser to be condensed.
  • This condensate is preferably stored in the condensate tank 43 and then circulated and supplied to the distillation column 20.
  • the membrane separation device 40 is not limited as long as it can separate water vapor from the mixed vapor of water vapor and ethanol vapor with a separation membrane.
  • the separation membrane is not particularly limited as long as it selectively permeates water vapor with respect to alcohol vapor. It may be made of a polymer such as polyimide, polyetherimide, polycarbonate, polysulfone or high molecular weight polyvinyl alcohol, or may be made of an inorganic material such as zeolite or zirconia.
  • the form of the membrane separation device is also a hollow fiber separation membrane module made of, for example, an asymmetric polyimide hollow fiber membrane, a shell-and-tube module comprising a tubular separation membrane element in which a zeolite is formed on a porous tubular support, etc.
  • the conventionally known ones can be suitably used. Examples of these include, but are not limited to, Japanese Unexamined Patent Application Publication Nos. 2000-262828 and 2001-62257 using polyimide hollow fiber membranes, and Japanese Unexamined Patent Application Publication No. 2003-93844 using zeolite membranes. Preferred examples include those described in JP-A-2006-263574, JP-A-2007-203210 and the like.
  • the water vapor transmission rate (P ′ H 2 O 2 ) is preferably 0.5 ⁇ 10 ⁇ 3 cm 3 (STP) / cm 2 ⁇ sec ⁇ cm Hg or more, more preferably 1.0 in use.
  • ⁇ 10 ⁇ 3 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg or more, ratio of water vapor transmission rate (P ′ H 2 O ) to alcohol transmission rate (P ′ alcohol ) (P ′ H 2 O / P ′ alcohol ) Is preferably 50 or more, more preferably 100 or more.
  • FIG. 2 showing an outline of an example of another embodiment according to the present invention.
  • the role of the distillation column in FIG. 1 is that an aqueous alcohol solution having an alcohol concentration of less than 50% by mass from the mash column is distilled under pressure to concentrate the alcohol, and at the same time, the high-pressure alcohol of 150 kPa (absolute pressure) or higher and water It was to produce mixed steam.
  • the embodiment shown in FIG. 2 is characterized in that the distillation column is operated at a low pressure of about 50 to 150 kPa, preferably at atmospheric pressure, and the condensate obtained by condensing the mixed vapor of alcohol and water obtained here is evaporated. To generate a mixed vapor of alcohol and water having a high pressure of 150 kPa (absolute pressure) or higher.
  • the distillation tower and the evaporator which are the features of FIG. 2 will be described. The other points are as described with reference to FIG.
  • the operating pressure of the distillation column 20 is preferably in the range of 50 to 150 kPa, and is usually atmospheric pressure.
  • the reboiler 21 that heats the bottom liquid of the distillation column 20 can use the condensation heat of steam supplied from the outside, but the condensation heat of the non-permeated vapor of the membrane separation device 40 can be suitably used as preheating, for example. it can.
  • the condenser 22 cools the mixed vapor of alcohol and water distilled from the top of the distillation column 20 or the concentration stage to form a condensate.
  • the condensate may be temporarily stored in the condensate tank 23. A part of this condensate is refluxed to the top of the column or the concentration stage by, for example, a condensate pump, and the remainder is sent to the evaporator 30.
  • the alcohol concentration of the mixed vapor of alcohol and water obtained at the top of the distillation column or at the concentration stage can be suitably controlled by the ratio of the condensate refluxed to the distillation column 20 and the number of stages of the distillation column.
  • the alcohol concentration of the mixed steam of alcohol and water obtained at the top of the distillation column 20 or at the concentration stage is controlled to be 55% by mass or more.
  • the ratio of the condensed liquid to be refluxed is relatively low. Is preferred. Preferably it is less than 50% of the condensate, more preferably less than 35%, even more preferably less than 20%, particularly preferably less than 10%.
  • the condensation heat of the condenser 22 may be used for preheating the aqueous alcohol solution supplied to the distillation column.
  • the supplied aqueous alcohol solution is preferably preheated to near its boiling point. At that time, it is preferable that the steam that cannot be condensed by the condenser 22 is condensed by cooling water by the auxiliary condenser.
  • an aqueous alcohol solution having an alcohol concentration of 55% by mass or more is supplied from the distillation column 20 through the condenser 22 to the evaporator 30.
  • the role of the evaporator 30 is to heat the alcohol aqueous solution to evaporate the whole amount and supply it to the membrane separation device 40 as a mixed vapor of alcohol and water.
  • the evaporator 30 is provided with a sufficient heating function, and can be operated at a relatively high pressure of 150 kPa (absolute pressure) or higher, preferably 200 kPa (absolute pressure) or higher, in the pressure of the mixed alcohol and water vapor obtained. .
  • the upper limit of the pressure is usually about 700 kPa (absolute pressure) or less.
  • the operating pressure of the evaporator 30 is controlled by the amount of heat (steam amount) applied to the evaporator, but at that time, the flow rate of the mixed vapor distilled from the evaporator may be controlled. Further, the pressure of the mixed vapor can be suitably adjusted by adjusting (restricting) the flow rate of the vapor flowing through the pressure reducing means between the evaporator and the membrane separator and the non-permeate side of the membrane separator 40. And it is preferable to adjust the pressure in an evaporator so that the evaporation temperature in the evaporator 30 may become about 5 degreeC or more higher than the temperature of the tower bottom of the distillation column 20. FIG. This makes it possible to use the non-permeate vapor of the membrane separator 40 as a heat source for the reboiler of the distillation column 20.
  • the total amount of the mixed vapor of alcohol and water obtained in the evaporator 30 is reduced in pressure by the decompression means, and then supplied to the membrane separation device 40 for purification.
  • the pressure reducing means is not particularly limited, but a pressure regulating valve having a throttle valve is preferably used.
  • the pressure is reduced to about 5 kPa or more, preferably 10 kPa or more, more preferably 10 to 500 kPa, and still more preferably about 10 to 300 kPa.
  • one of the features of the present invention is that after the high-pressure alcohol / water mixed vapor is generated by the evaporator, the pressure of the mixed vapor is maintained while maintaining the temperature of the mixed vapor. It is to supply to the membrane separator after decompressing.
  • the purpose of reducing the pressure is to sufficiently reduce the condensation temperature of the mixed vapor to be lower than the temperature of the mixed vapor so that the saturated mixed vapor does not condense in the membrane separator.
  • the condensation temperature of the mixed steam is 3 ° C. or more, preferably 5 ° C. or more lower than the temperature of the mixed steam. In addition, it is 10 degrees C or less normally.
  • reducing the pressure of the mixed steam once heated to a high pressure is poor in energy efficiency only in the process, but it is possible to improve the energy efficiency in the whole process.
  • FIG. 3 shows an outline of another example of the embodiment according to the present invention which is basically the same as FIG.
  • the bottom liquid discharged from the mash tower 10 is used for preheating the aqueous fermentation alcohol solution supplied to the mash tower 10, and the reflux steam of the distillation tower 20 is obtained by condensing the permeate condensate of the membrane separation apparatus 40.
  • the non-permeated vapor (anhydrous alcohol vapor) of the membrane separation device 40 is preheated when the condensed liquid of the permeated vapor of the membrane separation device 40 is circulated and supplied to the distillation column 20.
  • a portion of the bottom liquid of the moromi tower 10 is used for heating the bottom liquid when it is circulated to the mash tower, and each is suitably heat-recovered.
  • the thermal energy of the mixed steam generated in the mash column, distillation column (and evaporator) and membrane separation apparatus is preferably recovered in another process in the system as described above. It may be recovered in a completely different heating process.
  • Example 1 The fermented ethanol aqueous solution with the ethanol concentration of 7.3 mass% obtained in the fermenter was refined using 72.7 tons per hour using the apparatus schematically shown in Fig. 3, and 99.8 mass% absolute ethanol was purified. An attempt was made to obtain 5 tons per hour.
  • Process 1 A fermented ethanol aqueous solution having an ethanol concentration of 7.3% by mass is preheated with a preheater, and is fed at a flow rate of 72.7 t / hour to a mash tower having a theoretical plate number equivalent to 5 with a liquid feed pump.
  • Water vapor (steam 1) necessary for carrying out a distillation process by evaporating the supplied aqueous solution of fermentation ethanol is directly blown into the bottom of the mash column.
  • the distillate containing the mixed vapor of ethanol and water produced in the moromi tower and sent from the top of the tower is condensed by the condenser.
  • a part of the condensate is refluxed to the mash column, and the remaining condensate is supplied to the distillation column.
  • the reflux amount is adjusted so that the ethanol concentration at the top of the mash column is 39% by mass.
  • the temperature of the mixed vapor of ethanol and water distilled from the distillation tower and sent from the top of the tower is adjusted to 135 ° C. by adjusting the heating amount of the distillation tower.
  • a part of the mixed vapor is condensed by a condenser and refluxed to the distillation column.
  • the reflux amount By adjusting the reflux amount, the ethanol concentration of the mixed vapor of ethanol and water at the top of the distillation column is adjusted to 75% by mass.
  • Process 3 The remaining mixed vapor of ethanol and water that has not been condensed is reduced from 551 kPa to 300 kPa (gauge pressure) by a pressure adjusting valve (throttle valve) while maintaining the vapor temperature, and supplied to the membrane separation device.
  • the mixed vapor of ethanol and water supplied to the membrane separator is 10.4 t per hour.
  • the membrane separation device is a module as described in Japanese Patent Application Laid-Open No. 2000-262838, and has a water vapor transmission rate (P ′ H2O ) at 135 ° C. of 1.2 ⁇ 10 ⁇ 3 cm 3 (STP) / cm.
  • a vacuum pump is provided via a condenser, and the pressure is reduced to 12 kPa (absolute pressure).
  • the vapor that has permeated the separation membrane is completely condensed by a condenser so that the degree of vacuum on the permeate side of the separation membrane is maintained.
  • a part of the non-permeated vapor discharged from the membrane separation device is configured to be supplied to the permeation side of the membrane separation device as a purge gas for increasing the separation efficiency of the membrane separation device.
  • Vapor recovered from the permeation side of the separation membrane of the membrane separation apparatus (permeated vapor and vapor supplied as purge gas) is condensed, preheated with non-permeated vapor, and circulated and supplied to the distillation column. Further, the non-permeate vapor recovered from the non-permeate side of the separation membrane of the membrane separator is used for heating the bottom liquid when circulating the low column liquid of the mash tower to the mash tower in addition to the preliminary heating. After being recovered by heat, it is cooled and recovered as absolute ethanol having an ethanol concentration of 99.8% by mass in a product tank at 5 tons per hour.
  • Table 1 shows the results when the same operation as in the example was performed except that the operation in the step 2 was changed as follows in the example 1.
  • Process 2 An ethanol aqueous solution having an ethanol concentration of 13.3 t per hour and an ethanol concentration of 39% by mass is supplied to a distillation column corresponding to 6 theoretical plates by a liquid feed pump.
  • a reboiler is provided at the bottom of the distillation column, and the bottom liquid extracted from the bottom is converted to a mixed vapor by the reboiler supplied with steam 2 and circulated and supplied to the distillation column.
  • the column bottom liquid extracted from the column bottom is circulated and supplied to the mash column at a flow rate of 8.3 t per hour.
  • the column bottom liquid is kept at an ethanol concentration of about 2.5% by mass or less.
  • the mixed vapor of ethanol and water sent from the top of the distillation column in the distillation column is adjusted by adjusting the flow rate at which the non-permeate side vapor of the membrane separation device 40 is discharged from the outlet of the membrane separation membrane device. Is adjusted to 300 kPa (gauge pressure).
  • a part of the mixed vapor is condensed by a condenser and refluxed to the distillation column.
  • the reflux amount By adjusting the reflux amount, the ethanol concentration of the mixed vapor of ethanol and water at the top of the distillation column is adjusted to 75% by mass.
  • the remaining mixed vapor of ethanol and water that has not been condensed is heated to 135 ° C. by a superheater (steam 3) and supplied to the membrane separation apparatus.
  • the mixed steam of ethanol and water supplied to the membrane separator is 10.4 t per hour.
  • Examples 2 to 7 Except that the conditions shown in Table 1 were adopted, an attempt was made to obtain 9 tons of absolute ethanol at 5 t / hour by the same operation as in Example 1.
  • Table 1 shows the results when operating in the same manner as in Reference Example 1 except that the conditions shown in Table 1 were adopted.
  • a fermentation alcohol aqueous solution is supplied to a mash tower, the fermentation alcohol aqueous solution in the mash tower is heated to distill a distillate containing a mixed vapor of alcohol and water.
  • the first condensate obtained by condensing the distillate is supplied to the distillation column, and (2) a) the distillate or the first condensate is heated by the distillation column to distill the mixed vapor of alcohol and water.
  • the distillate or the first condensate is heated by a distillation column to distill a mixed vapor of alcohol and water, and the second condensate obtained by condensing the mixed vapor is supplied to an evaporator.
  • the second condensate in the evaporator is heated to generate a mixed vapor of alcohol and water and supplied to the membrane separator.
  • the purification process method for obtaining anhydrous alcohol is simpler and extremely A method for energy efficient purification can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

L’invention concerne une méthode de traitement de purification destinée à produire un alcool absolu à partir d'une solution aqueuse d'alcool fermenté. La méthode consiste à réduire la pression d'un mélange de vapeur d'alcool et d'eau distillé dans une colonne de distillation; et à introduire le mélange de vapeur dans une unité de séparation membranaire. Cette méthode permet de réaliser un traitement de purification par un procédé globalement plus pratique et avec un rendement énergétique extrêmement élevé.
PCT/JP2009/056727 2008-03-31 2009-03-31 Méthode de traitement de purification d'alcool fermenté WO2009123223A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-092076 2008-03-31
JP2008092076 2008-03-31

Publications (1)

Publication Number Publication Date
WO2009123223A1 true WO2009123223A1 (fr) 2009-10-08

Family

ID=41135591

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/056727 WO2009123223A1 (fr) 2008-03-31 2009-03-31 Méthode de traitement de purification d'alcool fermenté

Country Status (2)

Country Link
JP (1) JP2009263356A (fr)
WO (1) WO2009123223A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014171417A (ja) * 2013-03-07 2014-09-22 Mitsui Eng & Shipbuild Co Ltd バイオエタノールの回収方法及び回収システム
US9120724B2 (en) 2011-09-09 2015-09-01 Takara Shuzo Co., Ltd. Method for producing absolute alcohol and absolute alcohol
CN108905259A (zh) * 2018-07-18 2018-11-30 芜湖青悠静谧环保科技有限公司 一种新型制备燃料乙醇的工艺装置
JP2019509324A (ja) * 2016-11-14 2019-04-04 エルジー・ケム・リミテッド フェノールの精製方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8859827B2 (en) 2011-11-18 2014-10-14 Celanese International Corporation Esterifying acetic acid to produce ester feed for hydrogenolysis
US20120010445A1 (en) * 2010-07-09 2012-01-12 Celanese International Corporation Low Energy Alcohol Recovery Processes
US8748675B2 (en) 2011-06-16 2014-06-10 Celanese International Corporation Extractive distillation of crude alcohol product
US8802901B2 (en) 2011-11-18 2014-08-12 Celanese International Corporation Continuous ethyl acetate production and hydrogenolysis thereof
US9024089B2 (en) 2011-11-18 2015-05-05 Celanese International Corporation Esterification process using extractive separation to produce feed for hydrogenolysis
US8748673B2 (en) 2011-11-18 2014-06-10 Celanese International Corporation Process of recovery of ethanol from hydrogenolysis process
US8853468B2 (en) 2011-11-18 2014-10-07 Celanese International Corporation Vapor esterification method to produce ester feed for hydrogenolysis
US8829251B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Liquid esterification method to produce ester feed for hydrogenolysis
US8829249B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Integrated esterification and hydrogenolysis process for producing ethanol
CN103946200A (zh) 2011-11-22 2014-07-23 国际人造丝公司 使乙醇和乙酸混合物酯化以生产用于氢解的酯进料
US9029614B2 (en) 2011-12-14 2015-05-12 Celanese International Corporation Phasing reactor product from hydrogenating acetic acid into ethyl acetate feed to produce ethanol
US8907139B2 (en) 2011-12-28 2014-12-09 Celanese International Corporation Process for acetal removal in the purification of a crude ethanol product
US9024086B2 (en) 2012-01-06 2015-05-05 Celanese International Corporation Hydrogenation catalysts with acidic sites
CN104039448B (zh) 2012-01-06 2016-11-16 国际人造丝公司 具有钴改性载体的加氢催化剂
US8957262B2 (en) 2012-11-20 2015-02-17 Celanese International Corporation Olefin hydration for hydrogenation processes
US9000237B2 (en) 2012-12-20 2015-04-07 Celanese International Corporation Ethanol refining process using intermediate reboiler
US8975451B2 (en) 2013-03-15 2015-03-10 Celanese International Corporation Single phase ester feed for hydrogenolysis
US8926718B2 (en) 2013-03-15 2015-01-06 Celanese International Corporation Thermochemically produced ethanol compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5830301A (ja) * 1981-08-13 1983-02-22 Kuraray Co Ltd 液体混合物の分離方法
JP2003093827A (ja) * 2001-09-26 2003-04-02 Tsukishima Kikai Co Ltd 共沸混合物の分離方法、共沸物の分離装置および蒸留塔
WO2004073841A1 (fr) * 2003-02-21 2004-09-02 Bussan Nanotech Research Institute, Inc. Procede de concentration d'un materiau organique soluble dans l'eau
JP2006263561A (ja) * 2005-03-23 2006-10-05 Mitsui Eng & Shipbuild Co Ltd 蒸留−膜分離ハイブリッド装置、および蒸留と膜分離を組み合わせた分離方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5830301A (ja) * 1981-08-13 1983-02-22 Kuraray Co Ltd 液体混合物の分離方法
JP2003093827A (ja) * 2001-09-26 2003-04-02 Tsukishima Kikai Co Ltd 共沸混合物の分離方法、共沸物の分離装置および蒸留塔
WO2004073841A1 (fr) * 2003-02-21 2004-09-02 Bussan Nanotech Research Institute, Inc. Procede de concentration d'un materiau organique soluble dans l'eau
JP2006263561A (ja) * 2005-03-23 2006-10-05 Mitsui Eng & Shipbuild Co Ltd 蒸留−膜分離ハイブリッド装置、および蒸留と膜分離を組み合わせた分離方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9120724B2 (en) 2011-09-09 2015-09-01 Takara Shuzo Co., Ltd. Method for producing absolute alcohol and absolute alcohol
JP2014171417A (ja) * 2013-03-07 2014-09-22 Mitsui Eng & Shipbuild Co Ltd バイオエタノールの回収方法及び回収システム
JP2019509324A (ja) * 2016-11-14 2019-04-04 エルジー・ケム・リミテッド フェノールの精製方法
US10532968B2 (en) 2016-11-14 2020-01-14 Lg Chem, Ltd. Method for purifying phenol
CN108905259A (zh) * 2018-07-18 2018-11-30 芜湖青悠静谧环保科技有限公司 一种新型制备燃料乙醇的工艺装置

Also Published As

Publication number Publication date
JP2009263356A (ja) 2009-11-12

Similar Documents

Publication Publication Date Title
WO2009123223A1 (fr) Méthode de traitement de purification d'alcool fermenté
JP5593629B2 (ja) 醗酵アルコールの精製処理方法
JP5369765B2 (ja) 醗酵アルコールの精製処理方法
JP4414922B2 (ja) 蒸留−膜分離ハイブリッド装置、および蒸留と膜分離を組み合わせた分離方法
JP3764894B2 (ja) 水溶性有機物の濃縮方法
US8128787B2 (en) Membrane-augmented distillation with pressure change to separate solvents from water
US20130015052A1 (en) Liquid Separation by membrane assisted vapor stripping process
JP6196807B2 (ja) 水溶性有機物の濃縮方法及び水溶性有機物の濃縮装置
JP4831934B2 (ja) 水溶性有機物濃縮装置
JP2007275690A (ja) 有機液体水溶液からの有機液体分離回収方法
JPH0463110A (ja) アルコール含有反応液の分離精製法
WO2018168651A1 (fr) Procédé de production d'alcool
JP4360194B2 (ja) 水溶性有機物の濃縮方法及び濃縮装置
JPS63175602A (ja) 有機物水溶液の濃縮方法
JP2009045573A (ja) 醗酵エタノールの精製処理方法およびそのシステム
JPS63278522A (ja) 揮発性混合物の分離方法
KR20180018955A (ko) 아세트산 정제 공정 및 장치
CN113543869A (zh) 使用优化的渗透蒸发法进行的具有高水含量的含二醇混合物的脱水
JPS63258602A (ja) 揮発性混合物の分離方法
JPH0533978B2 (fr)
JPH025441B2 (fr)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09727442

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09727442

Country of ref document: EP

Kind code of ref document: A1