WO2013021966A1 - Système de déshydratation et procédé de déshydratation - Google Patents

Système de déshydratation et procédé de déshydratation Download PDF

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Publication number
WO2013021966A1
WO2013021966A1 PCT/JP2012/069969 JP2012069969W WO2013021966A1 WO 2013021966 A1 WO2013021966 A1 WO 2013021966A1 JP 2012069969 W JP2012069969 W JP 2012069969W WO 2013021966 A1 WO2013021966 A1 WO 2013021966A1
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WIPO (PCT)
Prior art keywords
water separation
separation membrane
water
membrane unit
dehydration
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2012/069969
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English (en)
Japanese (ja)
Inventor
田中　幸男
大空　弘幸
肇 長野
晴章 平山
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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Filing date
Publication date
Application filed by Mitsubishi Heavy Industries Ltd filed Critical Mitsubishi Heavy Industries Ltd
Publication of WO2013021966A1 publication Critical patent/WO2013021966A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/368—Accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/18—Use of gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/32—By heating or pyrolysis

Definitions

  • the present invention relates to a dehydration system and a dehydration method. More specifically, the present invention relates to a dehydration system and a dehydration method capable of efficiently dehydrating a mixture of ethanol, propanol, and water having an azeotropic composition with water, or a mixture of acid and water.
  • Ethanol is attracting attention as a fuel source to replace petroleum fuel, and its market size is predicted to be 115 million kiloliters in 2015.
  • a crude product obtained from a bio raw material such as corn must be purified by distillation and dehydrated to at least 99.5 wt% or more.
  • a dilute ethanol aqueous solution is concentrated in the distillation column to near the azeotropic point of the ethanol / water system and then dehydrated.
  • Patent Document 1 Japanese Patent Laid-Open No. 58-21629.
  • the present invention has been made in view of the above circumstances, and provides a dehydration system and a dehydration method in which the water separation membrane is regenerated and the required number of water separation membranes is reduced while the entire system is in operation.
  • the purpose is to provide.
  • a dehydration system for separating water from a fluid to be treated, comprising at least one water separation membrane unit in operation, and the at least one water separation
  • the membrane unit is configured such that at least one non-operating water separation membrane unit can be installed, and the flow path of the fluid to be treated of the water separation membrane constituting the non-operating water separation membrane unit is heat for regeneration.
  • the water separation membrane can be regenerated by allowing the regeneration hot gas to permeate the water separation membrane in a state where the gas supply path is operated and the dehydration system is in operation. .
  • the dehydration system includes a line for separating water from a fluid to be processed that is processed by the water separation membrane unit in operation, and a water separation membrane unit that is not in operation.
  • the regeneration hot gas can be sucked at an operating pressure for separating water by joining a line for sucking the regeneration hot gas.
  • the present invention is a dehydration method in another aspect, and in the dehydration method of separating water from a fluid to be treated, the dehydration method includes at least one water separation membrane unit in operation, and the at least one water separation membrane unit A dehydration system in which at least one non-operating water separation membrane unit is installed, supplying regeneration hot gas to the flow path of the fluid to be treated of the water separation membrane constituting the non-operating water separation membrane unit; The regeneration hot gas permeates through the water separation membrane and the water separation membrane is regenerated while the dehydration system is in operation.
  • the dehydration method according to the present invention includes a line for separating water from a fluid to be treated that is processed by the water separation membrane unit in operation, and a water separation membrane unit that is not in operation.
  • the regeneration hot gas can be sucked at an operating pressure for separating water by joining a line for sucking the regeneration hot gas.
  • the fluid to be treated is generally an organic aqueous solution.
  • Organic components of the organic aqueous solution include alcohols such as ethanol, propanol, isopropanol and glycol, carboxylic acids such as acetic acid, ethers such as dimethyl ether and diethyl ether, aldehydes such as acetaldehyde, ketones such as acetone and methyl ethyl ketone, and ethyl acetate.
  • One organic component selected from the group consisting of esters, which is soluble in water, can be mentioned.
  • An inert gas is suitable as the regeneration hot gas that can be employed in the present invention.
  • the inert gas include the following. (1) Nitrogen gas If the oxygen concentration increases to the air level, the separation membrane is modified by oxidation, which is not preferable. Accordingly, the oxygen content is preferably less than 10%. In addition, if it is a small amount, the removal by partial combustion of ethanol is advantageous on the contrary, and when aiming at such an effect, oxygen may be contained up to about 5%. (2) Carbon dioxide Nitrogen can be used instead. Carbon dioxide produced as a by-product in the production of ethanol can also be used. (3) Other inert gases It should be noted that an inert gas on the periodic table such as Ar can be used instead of nitrogen.
  • the temperature of the regenerating hot gas is preferably 78 ° C. to 300 ° C., which is an intermediate region between the boiling point of ethanol of 78.3 ° C. and the temperature exceeding 300 ° C. at which carbon starts to precipitate on the film from ethanol. .
  • the heat of the product fluid obtained from the fluid to be treated can be recovered by a heat exchanger.
  • a dehydration system and a dehydration method in which the water separation membrane is regenerated and the required number of water separation membranes is reduced while the entire system is in operation.
  • FIG. 2A is a plan view and FIG. 2B is a cross-sectional view taken along the line BB of FIG. 2A regarding one embodiment of a water separation membrane that can be employed in the present invention.
  • FIG. 3A is a plan view and FIG. 3B is a cross-sectional view taken along the line CC of FIG. 3A for one embodiment of a water separation membrane that can be employed in the present invention.
  • a dehydration system including a specific number of water separation membrane units will be exemplified, but the present invention is not limited to a specific number of water separation membrane units.
  • a description will be given of a form in which the fluid to be treated is crude ethanol containing water and the regenerating hot gas is a heated nitrogen gas.
  • the present invention is applied based on the technical common sense of those skilled in the art even in the case of using other types of fluids to be treated or hot gas for regeneration.
  • FIG. 1 shows an embodiment of a dehydrating system according to the present invention.
  • the dehydration system according to the present embodiment includes an operating water separation membrane unit 10 and a water separation membrane unit 20 being regenerated.
  • These water separation membrane units 10 and 20 are devices for separating water from the crude ethanol using the water separation membranes 11 and 21 by the pervaporation method.
  • the water separation membrane units 10 and 20 are provided with water separation membranes 11 and 21 having one or more flow paths 12 and 22 extending in the left and right directions through which crude ethanol passes in the main body.
  • a crude ethanol inlet is provided on the left side of the water separation membranes 11 and 21, and a crude ethanol outlet is provided on the right side.
  • Shell portions 13 and 23 are defined on the water permeation side by the outer peripheral surfaces of the water separation membranes 11 and 21 and the inner wall of the unit main body.
  • the valve 15 on the water separation membrane unit 10 side is opened, and the valve 25 on the water separation membrane unit 20 side is closed.
  • the valve 19 on the water separation membrane unit 10 side is opened, and the valve 29 on the water separation membrane unit 20 side is closed.
  • the valve 17 on the water separation membrane unit 10 side is closed, and the valve 27 on the water separation membrane unit 20 side is opened.
  • nitrogen gas heated to 78 ° C. to 300 ° C. is supplied to the water separation membrane unit 20 from the line 26 as a regenerating hot gas via the heat exchanger 32.
  • Nitrogen gas is supplied to the flow path 22 and pushes out the ethanol accumulated in the water separation membrane 21.
  • the extruded nitrogen gas containing ethanol is sucked from the line 33.
  • the water separation membrane 21 is porous, and ethanol molecules are accumulated in the pores.
  • a line 31 for separating water from the crude ethanol treated in the water separation membrane unit 10 and a line 33 for sucking nitrogen gas from the water separation membrane unit 20 are merged to form water. Nitrogen gas is also sucked at an operating pressure [133.22 to 13332.2 Pa (10 to 100 torr)] for reducing the pressure.
  • the water separation membrane unit 20 can be regenerated at an operating pressure for reducing the pressure of the water separation membrane unit 10 in operation. For this reason, another decompression device is not required.
  • the discharge lines 31 and 33 from the shell portions 13 and 23 can be commonly used in both the operation and regeneration states of the water separation membranes 10 and 20, and the number of parts can be reduced.
  • the sucked nitrogen gas contains extruded ethanol. Also, ethanol may be contained in the water that is suction-separated from the water separation membrane unit 10. Therefore, a recovery device for recovering ethanol from the mixture that is joined and discharged by the pump 30 can be provided, and this can be returned to the water separation membrane unit 10 that is operating.
  • FIG. 1 is a simplified conceptual diagram for explanation, and an apparatus not shown can be implemented as a form provided without departing from the spirit of the present invention. . Moreover, it can also implement as a form provided with two or more water separation membrane units in operation. Such a form group is also included in the concept of the present invention, and will be described below as an example.
  • crude ethanol is preferably heated to about 100 to 150 ° C. Therefore, it is general to provide a heater in the lines 14 and 24 in the upstream of the water separation membrane units 10 and 20. As a result, the resulting product ethanol will have heat. This heat can also be imparted to the supplied crude ethanol using a heat exchanger. Furthermore, a part of ethanol obtained from the line 18 can be returned to the line 14 again to separate the water that has not been removed.
  • a plurality of water separation membrane units 10 in operation can be provided in parallel.
  • the ethanol that has passed through the first stage water separation membrane unit is sent to the second stage water separation membrane unit. It is also possible to send ethanol that has passed through the water separation membrane unit at the stage to the water separation membrane unit at the third stage, and finally recover the product ethanol.
  • the water collected from all the water separation membrane units in operation and the water separation membrane unit being regenerated can be collected, and ethanol leaking into the water can be collected by the collection device.
  • the deterioration ratio is a ratio between a water permeation rate at the beginning of the use period and a water permeation rate at that time.
  • the deterioration ratio is set to 0.8.
  • the reason why the deterioration ratio can be set as high as 0.8 is that the water separation membrane unit can be simultaneously regenerated in the operating state.
  • the dehydration system according to the present invention can be realized as a multistage dehydration system having more than three stages, and the number of water separation membrane units to be regenerated is limited to one. is not.
  • a concentration meter for monitoring the concentration of ethanol taken out from each water separation membrane unit can be installed in each water separation membrane unit. As a result, the deterioration ratio can be monitored. Furthermore, a thermometer for monitoring the temperature of the product fluid taken out from each water separation membrane unit may be provided.
  • FIG. 1 An alternative form that is possible in the form of employing one operating water separation membrane unit as shown in FIG. 1 is also adopted in a form having two or more working water separation membrane units unless contrary to the object of the present invention. can do.
  • Water separation membranes used in water separation membrane units such as the water separation membrane units 10, 20 etc. separate crude ethanol into anhydride and water.
  • Such water separation membranes are known in various forms and are commercially available.
  • a monolith type and a tubular type water separation membrane can be used.
  • FIG. 2B is a cross section taken along line BB of FIG. 2A.
  • the monolith-type water separation membrane 110 is provided with a plurality of crude ethanol flow paths 110 that are one or more hollow portions extending vertically to pass crude ethanol through a cylindrical water separation membrane 110.
  • the crude ethanol flow path 110c inside the water separation membrane is called the primary side or supply side of the membrane, and the outside of the water separation membrane 110 is the secondary side of the membrane, or It is called the transmission side.
  • the water separation membrane 110 is arranged such that the flow path direction is parallel to the vertical direction as shown in FIG. It can also be installed. Then, while reducing the permeation side of the water separation membrane 110, the crude ethanol is supplied from the inlet 110a on the lower side in the vertical direction, flows in the direction opposite to the gravity, and is discharged from the outlet 110b on the upper side in the vertical direction. By this operation, the water in the crude ethanol becomes water vapor and is extracted from the side surface of the cylindrical water separation membrane 110 to the permeate side. As a result, the crude ethanol recovered from the water separation membrane part outlet 110b is dehydrated.
  • the illustrated monolith-type water separation membrane 110 is schematic, but as an example, a columnar water separation membrane with a diameter of 30 mm is provided with 30 holes with a diameter of 3 mm. Can do. As another example, a water separation membrane having a diameter of 150 to 200 mm and having 200 holes having a diameter of 2 mm can be used.
  • the length of the water separation membrane can be appropriately determined by those skilled in the art according to the desired membrane performance, but as an example, a length of 150 mm to 1 m can be used.
  • the tubular water separation membrane 210 has a tubular shape in which only one crude ethanol passage 210c is provided.
  • the tubular-type water separation membrane 210 has the same installation mode and effect as the monolith-type water separation membrane.
  • the tubular water separation membrane one having an outer diameter of 10 mm and an inner diameter of 7 mm can be used, and as another example, one having an outer diameter of 30 mm and an inner diameter of 22 mm can be used.
  • a length of 150 mm to 1 m can be used.
  • a microporous membrane having a nano-order or smaller pore size precisely controlled with an inorganic material can be used as a material for the water separation membrane.
  • the microporous membrane exhibits a molecular sieving effect that allows a gas with a small molecular diameter to pass through and excludes a gas with a large molecular diameter, and shows a behavior of activated diffusion in which the permeability coefficient increases with increasing temperature.
  • the microporous membrane include a carbon membrane, a silica membrane, and a zeolite membrane.
  • a carbon-based inorganic water separation membrane having a pore diameter of 10 angstroms or less is suitable as the water separation membrane.
  • an inorganic water separation membrane described in Japanese Patent No. 2808479 can be applied.
  • the inorganic water separation membrane of Patent No. 2808479 is an acid-resistant composite separation obtained by supporting silica gel obtained through hydrolysis of an alkoxysilane containing an ethoxy group or a methoxy group in the pores of an inorganic porous body. It is a membrane.
  • the form, size, and material of the water separation membrane can be appropriately selected by those skilled in the art according to the purpose of use.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un système de déshydratation et un procédé de déshydratation, ledit système de déshydratation conduisant une régénération de membranes de séparation d'eau tandis que le système dans son ensemble est en fonctionnement et est constitué de sorte que le nombre de membranes de séparation d'eau requis soit réduit. Le système de déshydratation a au moins une unité de membrane de séparation d'eau (10) en fonctionnement et est configuré de sorte que pour l'au moins une unité de membrane de séparation d'eau (10) en fonctionnement, il peut exister au moins une unité de membrane de séparation d'eau (20) non en fonctionnement. Du gaz chauffé pour régénération est fourni à un trajet d'écoulement (22) pour un fluide à traiter avec une membrane de séparation d'eau (21) de l'unité de membrane de séparation d'eau (20) non en fonctionnement, et dans un état dans lequel le système de déshydratation est en fonctionnement, la membrane de séparation d'eau (21) peut être régénérée par le gaz chauffé pour régénération traversant la membrane de séparation d'eau (21).
PCT/JP2012/069969 2011-08-10 2012-08-06 Système de déshydratation et procédé de déshydratation Ceased WO2013021966A1 (fr)

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JP2011-175009 2011-08-10
JP2011175009A JP2013034969A (ja) 2011-08-10 2011-08-10 脱水システム及び脱水方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109999674A (zh) * 2018-12-06 2019-07-12 曾杰 基于微波处理的过滤器的清洗干燥工艺及装置
US12427482B2 (en) 2019-12-10 2025-09-30 Nanosized Sweden Ab Membrane distiller and operation method therefore

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015181965A (ja) * 2014-03-20 2015-10-22 日本碍子株式会社 再生方法及び再生装置
JP6626736B2 (ja) * 2016-02-25 2019-12-25 日立造船株式会社 ゼオライト膜複合体の再生方法
WO2018207343A1 (fr) 2017-05-12 2018-11-15 日揮株式会社 Dispositif de séparation de gaz

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62250907A (ja) * 1986-04-25 1987-10-31 Shin Etsu Chem Co Ltd 分離膜の性能回復方法
JPS6316006A (ja) * 1986-07-04 1988-01-23 Sasakura Eng Co Ltd パ−ベ−パレ−シヨン蒸溜装置の運転方法
JPH04243527A (ja) * 1991-01-24 1992-08-31 Nitto Denko Corp パーベーパレーション膜装置の運転方法
JPH05103957A (ja) * 1991-03-06 1993-04-27 Mitsui Eng & Shipbuild Co Ltd 有機物選択透過性パーベーパレーシヨン膜の性能回復方法
JPH1157415A (ja) * 1997-08-28 1999-03-02 Kurita Water Ind Ltd 膜脱気装置の運転方法及び膜脱気装置
JP2010509034A (ja) * 2006-11-08 2010-03-25 日本碍子株式会社 セラミックフィルタ及びその再生方法
JP2011083694A (ja) * 2009-10-15 2011-04-28 Mitsubishi Heavy Ind Ltd 脱水装置の運転方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62250907A (ja) * 1986-04-25 1987-10-31 Shin Etsu Chem Co Ltd 分離膜の性能回復方法
JPS6316006A (ja) * 1986-07-04 1988-01-23 Sasakura Eng Co Ltd パ−ベ−パレ−シヨン蒸溜装置の運転方法
JPH04243527A (ja) * 1991-01-24 1992-08-31 Nitto Denko Corp パーベーパレーション膜装置の運転方法
JPH05103957A (ja) * 1991-03-06 1993-04-27 Mitsui Eng & Shipbuild Co Ltd 有機物選択透過性パーベーパレーシヨン膜の性能回復方法
JPH1157415A (ja) * 1997-08-28 1999-03-02 Kurita Water Ind Ltd 膜脱気装置の運転方法及び膜脱気装置
JP2010509034A (ja) * 2006-11-08 2010-03-25 日本碍子株式会社 セラミックフィルタ及びその再生方法
JP2011083694A (ja) * 2009-10-15 2011-04-28 Mitsubishi Heavy Ind Ltd 脱水装置の運転方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109999674A (zh) * 2018-12-06 2019-07-12 曾杰 基于微波处理的过滤器的清洗干燥工艺及装置
CN109999674B (zh) * 2018-12-06 2021-09-10 曾杰 基于微波处理的过滤器的清洗干燥工艺及装置
US12427482B2 (en) 2019-12-10 2025-09-30 Nanosized Sweden Ab Membrane distiller and operation method therefore

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