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WO2010098695A1 - Supported liquid membrane and method for recovery of organic compounds from aqueous solutions - Google Patents

Supported liquid membrane and method for recovery of organic compounds from aqueous solutions Download PDF

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Publication number
WO2010098695A1
WO2010098695A1 PCT/RU2010/000054 RU2010000054W WO2010098695A1 WO 2010098695 A1 WO2010098695 A1 WO 2010098695A1 RU 2010000054 W RU2010000054 W RU 2010000054W WO 2010098695 A1 WO2010098695 A1 WO 2010098695A1
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WO
WIPO (PCT)
Prior art keywords
membrane
liquid
organic compounds
recovery
aqueous solutions
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/RU2010/000054
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French (fr)
Inventor
Evgeniy Rubenovich Davidov
Petr Sergeevich Kanygin
Oleg Anatolievich Frakin
Igor Vladimirovich Cheremnov
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
"PROF BUSINESS" LLC
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"PROF BUSINESS" LLC
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 "PROF BUSINESS" LLC filed Critical "PROF BUSINESS" LLC
Publication of WO2010098695A1 publication Critical patent/WO2010098695A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01D61/362—Pervaporation
    • 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
    • B01D61/38—Liquid-membrane separation
    • 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
    • C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the present invention relates to a membrane process for recovery of organic compounds from organic/water solutions. More particularly, it relates to a liquid membrane for separation of alcohols, esters and other organic compounds from water and a method of using such membrane.
  • Pervaporation is a method for the separation of mixtures of liquids by vaporization through a membrane.
  • the membrane acts as a selective barrier between the two phases, the liquid phase feed and the vapor phase permeate. Pervaporation differs from all other membrane processes because of the permeate phase change.
  • the driving force for transport of different components is provided by a chemical potential difference between the liquid feed/retentate and vapor permeate at each side of the membrane.
  • the upstream side of the membrane is at ambient pressure and the downstream side is under vacuum (or by using sweep gas) to allow the evaporation of the selective component after permeation through the membrane.
  • US 5755967 discloses a pervaporation process for the selective removal of acetone and/or butanol from an aqueous solution comprising acetone or butanol, or mixtures thereof.
  • the silicalite, silicalite filled polymer membrane is suited to the removal of acetone and butanol from the aqueous solution.
  • the driving force of the process is a pressure differential across the membrane, it comprises a vacuum on the permeate side of the membrane.
  • EP 0470704 discloses a membrane comprising a porous support and a non-porous separating layer of a polyimine polymer for use in separating water from an aqueous charge mixture of organic oxygenate, for example isopropanol by pervaporation.
  • a polyimine polymer for use in separating water from an aqueous charge mixture of organic oxygenate, for example isopropanol by pervaporation.
  • Various materials can be used as membranes.
  • Polymeric, ceramic, and liquid membranes have been used in the pervaporation process for removing organic compounds.
  • Liquid membrane is a liquid phase existing either in supported or unsupported form that serves as a membrane barrier between two phases (Terminology for membranes and membrane processes (IUPAC Recommendations 1996, page 1486). In supported liquid membranes the organic phase is immobilized in the pores of a porous polymer.
  • the polymeric support usually consists of ultra- or microporous membranes in the form of a sheet or hollow fiber or tube
  • Liquid membranes generally provide high solvent selectivity compared with polymeric membranes and ceramic membranes and it makes liquid membranes an area of significant interest for the recovery of dilute amounts of solvents from aqueous solutions.
  • US 5637224 relates to the removal of volatile organic compounds from aqueous solutions using a hollow fiber contained liquid membrane. Hollow fiber supported liquid membranes and plasma polymerized non-porous silicone coatings are disclosed.
  • WO 0156933 discloses a supported liquid membrane immobilized in a microporous support material, particularly, polypropylene, polytetrafluoroethylene, polyethylene and like for the removal and recovery of one or more target species, for example penicillin, organic acids.
  • liquid membranes have a tendency to degrade rapidly.
  • the instability of liquid membranes presents a major problem and drawback with respect to their use.
  • two significant problems arise because of the instability and degradation of liquid membranes.
  • membrane selectivity significantly decreases, resulting in a permeation of water through the membrane.
  • liquid membrane for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the liquid membrane is a layer of hydrophobic liquid on the surface of the aqueous solution.
  • the hydrophobic liquid is synthetic and/or vegetable oil and/or higher alcohols.
  • the present invention also relates to a method for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the membrane is a layer of hydrophobic liquid on the surface of the aqueous solution.
  • the organic compounds are alcohols
  • the hydrophobic liquid is synthetic and/or vegetable oil and/or higher alcohols.
  • the thickness of the layer of the hydrophobic liquid is about 3-30 mm on the surface of the aqueous solution.
  • the different oils such as synthetic oils, for example silicone oil, paraffin oil; vegetable oils, for example, corn oil, soy oil; some higher alcohols, higher fatty acids are used as the hydrophobic liquid. It is possible to use a mixture of the different oils.
  • the use of the liquid membrane in such process is based on that the molecules of the organic solvents are diphilic, as they consist of hydrophilic (has affinity for polar media - water, for example hydroxyl - group in alcohols) and hydrophobic (has affinity for non-polar media, hydrocarbon radical) units.
  • the diphilic molecules are oriented at the interface in a way that the hydrocarbon parts are in the hydrophobic phase and polar groups are in the aqueous solution.
  • the layer of the hydrophobic liquid is an insuperable barrier for the molecules of water; hence the vapor pressure for water over the layer is negligible as opposed to the vapor pressure for the solvents.
  • the molecules of the organic solvents When vacuum is applied to overhead of the layer of the hydrophobic liquid, the molecules of the organic solvents start to abandon the layer and are directed into a cooling device wherein the solvents are condensed.
  • the difference of solvent concentration in the aqueous solution and gas (vacuum) results in the concentration gradient and the continuous flow of the molecules of the solvents take place from the aqueous solution through the layer into vacuuming overhead space.
  • the advantages of the present invention are in providing a simple and economical, energy efficient method for recovery of organic compounds through the liquid membrane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a liquid membrane for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the liquid membrane is a layer of hydrophobic liquid on the surface of the aqueous solution. Also the invention relates to a method for recovery of organic compounds from aqueous solutions by diffuse evaporation through the liquid membrane by applying vacuum or gas.

Description

SUPPORTED LIQUID MEMBRANE AND METHOD FOR RECOVERY OF ORGANIC COMPOUNDS FROM AQUEOUS SOLUTIONS
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a membrane process for recovery of organic compounds from organic/water solutions. More particularly, it relates to a liquid membrane for separation of alcohols, esters and other organic compounds from water and a method of using such membrane.
BACKGROUND OF THE INVENTION
Recovery of organic compounds from aqueous solutions has traditionally relied on methods such as distillation, liquid-liquid extraction, and adsorption. Recovery processes which involve the use of membranes for separating organic compounds from water have been used increasingly in recent years. Whereas conventional techniques such as distillation, adsorption and extraction are often relatively inadequate and uneconomical, application of membrane technology can save in process costs because energy consumption is low, and raw materials can be recovered and reused. Moreover, the process can be carried out continuously, and disposal problems can be reduced or eliminated. Membrane permeation methods, such as pervaporation, are alternatives which have been studied for recovery of organic compounds from dilute aqueous solutions.
Pervaporation is a method for the separation of mixtures of liquids by vaporization through a membrane. The membrane acts as a selective barrier between the two phases, the liquid phase feed and the vapor phase permeate. Pervaporation differs from all other membrane processes because of the permeate phase change. The driving force for transport of different components is provided by a chemical potential difference between the liquid feed/retentate and vapor permeate at each side of the membrane. Typically, the upstream side of the membrane is at ambient pressure and the downstream side is under vacuum (or by using sweep gas) to allow the evaporation of the selective component after permeation through the membrane.
US 5755967 discloses a pervaporation process for the selective removal of acetone and/or butanol from an aqueous solution comprising acetone or butanol, or mixtures thereof. The silicalite, silicalite filled polymer membrane is suited to the removal of acetone and butanol from the aqueous solution. The driving force of the process is a pressure differential across the membrane, it comprises a vacuum on the permeate side of the membrane.
EP 0470704 discloses a membrane comprising a porous support and a non-porous separating layer of a polyimine polymer for use in separating water from an aqueous charge mixture of organic oxygenate, for example isopropanol by pervaporation. Various materials can be used as membranes. Polymeric, ceramic, and liquid membranes have been used in the pervaporation process for removing organic compounds. Liquid membrane is a liquid phase existing either in supported or unsupported form that serves as a membrane barrier between two phases (Terminology for membranes and membrane processes (IUPAC Recommendations 1996, page 1486). In supported liquid membranes the organic phase is immobilized in the pores of a porous polymer. The polymeric support usually consists of ultra- or microporous membranes in the form of a sheet or hollow fiber or tube.
Liquid membranes generally provide high solvent selectivity compared with polymeric membranes and ceramic membranes and it makes liquid membranes an area of significant interest for the recovery of dilute amounts of solvents from aqueous solutions.
US 5637224 relates to the removal of volatile organic compounds from aqueous solutions using a hollow fiber contained liquid membrane. Hollow fiber supported liquid membranes and plasma polymerized non-porous silicone coatings are disclosed.
WO 0156933 discloses a supported liquid membrane immobilized in a microporous support material, particularly, polypropylene, polytetrafluoroethylene, polyethylene and like for the removal and recovery of one or more target species, for example penicillin, organic acids.
However these membranes and processes using such membranes have the following principal drawbacks:
- difficulties coming from selection of materials for membrane because membranes must have not only high selectivity, performance and mechanical stability, but also withstand the contact with organic compounds at higher temperature;
- the liquid membranes have a tendency to degrade rapidly. The instability of liquid membranes presents a major problem and drawback with respect to their use. In particular, two significant problems arise because of the instability and degradation of liquid membranes. First, membrane selectivity significantly decreases, resulting in a permeation of water through the membrane.
- the membranes themselves are expensive to manufacture and suffer from a short lifetime, often requiring replacement.
Therefore there is a need in a simple and efficient, and economical membrane with low energy requirements for separating volatile organic compounds from water and a method of using such membrane.
BRIEF SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a liquid membrane for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the liquid membrane is a layer of hydrophobic liquid on the surface of the aqueous solution.
The hydrophobic liquid is synthetic and/or vegetable oil and/or higher alcohols.
The present invention also relates to a method for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the membrane is a layer of hydrophobic liquid on the surface of the aqueous solution. In one preferred embodiment the organic compounds are alcohols, hi another preferred embodiment the hydrophobic liquid is synthetic and/or vegetable oil and/or higher alcohols. The thickness of the layer of the hydrophobic liquid is about 3-30 mm on the surface of the aqueous solution.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention the different oils, such as synthetic oils, for example silicone oil, paraffin oil; vegetable oils, for example, corn oil, soy oil; some higher alcohols, higher fatty acids are used as the hydrophobic liquid. It is possible to use a mixture of the different oils.
The use of the liquid membrane in such process is based on that the molecules of the organic solvents are diphilic, as they consist of hydrophilic (has affinity for polar media - water, for example hydroxyl - group in alcohols) and hydrophobic (has affinity for non-polar media, hydrocarbon radical) units. The diphilic molecules are oriented at the interface in a way that the hydrocarbon parts are in the hydrophobic phase and polar groups are in the aqueous solution. The layer of the hydrophobic liquid is an insuperable barrier for the molecules of water; hence the vapor pressure for water over the layer is negligible as opposed to the vapor pressure for the solvents. When vacuum is applied to overhead of the layer of the hydrophobic liquid, the molecules of the organic solvents start to abandon the layer and are directed into a cooling device wherein the solvents are condensed. The difference of solvent concentration in the aqueous solution and gas (vacuum) results in the concentration gradient and the continuous flow of the molecules of the solvents take place from the aqueous solution through the layer into vacuuming overhead space.
The invention may be further understood by the following non-limiting examples.
Example 1
Into a vessel (is maintained under vacuum by a vacuum pump) with 100 ml of 23% aqueous butanol solution, silicone oil was layered on the liquid surface; thickness of layer was 15 mm. Butanol polar hydroxyl groups orient to the water phase with their fatty chains oriented towards the layer of the acid. Then the vacuum pump was started, and the permeate side was evacuated gradually (approximately 5 minutes). The pressure in the vessel was -0.04 atm abs. Then the butanol vapors were condensed, in result 22 ml of condensate was obtained wherein the butanol content was 92%.
Example 2
Into a vessel with 100 ml of 17% aqueous ethyl acetate solution, soy oil was layered on the liquid surface; thickness of layer was 10 mm. Then the vacuum of -0.06 atm abs was applied and the vapors are removed and directed to the vapor condenser. 18 ml of the condensate moisture, contained 89% ethyl acetate was obtained.
The advantages of the present invention are in providing a simple and economical, energy efficient method for recovery of organic compounds through the liquid membrane.

Claims

1. A liquid membrane for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the liquid membrane is a layer of hydrophobic liquid on the surface of the aqueous solution.
2. The liquid membrane of Claim 1 wherein the hydrophobic liquid is synthetic and/or vegetable oil and/or higher alcohols.
3. A method for recovery of organic compounds from aqueous solutions by diffuse evaporation through membrane by applying vacuum or gas wherein the membrane is a layer of hydrophobic liquid on the surface of the aqueous solution.
4. The method of Claim 3 wherein the organic compounds are alcohols.
5. The method of Claim 3 wherein the hydrophobic liquid is synthetic and/or vegetable oil and/or higher alcohols.
6. The method of Claim 3 wherein the thickness of the layer of the hydrophobic liquid is about 3-30 mm on the surface of the aqueous solution.
PCT/RU2010/000054 2009-02-25 2010-02-09 Supported liquid membrane and method for recovery of organic compounds from aqueous solutions Ceased WO2010098695A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2009106236 2009-02-25
RU2009106236/05A RU2409414C2 (en) 2009-02-25 2009-02-25 Liquid membrane to extract alcohols or ethers from water solutions, and method of releasing alcohols or ethers

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WO2010098695A1 true WO2010098695A1 (en) 2010-09-02

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5013447A (en) * 1989-07-19 1991-05-07 Sepracor Process of treating alcoholic beverages by vapor-arbitrated pervaporation
WO2008143704A2 (en) * 2006-12-01 2008-11-27 Gevo, Inc. Engineered microorganisms for producing n-butanol and related methods

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CA2040798A1 (en) * 1990-05-25 1991-11-26 Dean T. Tsou Facilitated liquid membranes for olefin/paraffin gas separations and related process
RU2080162C1 (en) * 1994-04-27 1997-05-27 Акционерное общество открытого типа "Научно-исследовательский и проектный институт азотной промышленности и продуктов органического синтеза" Apparatus for liquid membrane-mediated separation of substances
RU2144075C1 (en) * 1997-10-21 2000-01-10 Закрытое акционерное общество "Проектно-строительное предприятие ИНСЕРВ" Method for production of alcoholic beverages
WO2001056933A2 (en) * 2000-02-04 2001-08-09 Commodore Separation Technologies, Inc. Combined supported liquid membrane/strip dispersion processes and extractants
US6485650B1 (en) * 2000-08-28 2002-11-26 Facilichem, Inc. Liquid membrane separation of enantiomers
RU2270487C1 (en) * 2004-06-11 2006-02-20 Российская Федерация в лице Министерства Российской Федерации по атомной энергии Method for recovering liquid radioactive wastes involving extraction of radionuclides
RU2297975C1 (en) * 2005-08-25 2007-04-27 Институт нефтехимического синтеза им. А.В. Топчиева РАН (ИНХС РАН) Method of the nanofiltration separation of the liquid organic mixtures

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5013447A (en) * 1989-07-19 1991-05-07 Sepracor Process of treating alcoholic beverages by vapor-arbitrated pervaporation
WO2008143704A2 (en) * 2006-12-01 2008-11-27 Gevo, Inc. Engineered microorganisms for producing n-butanol and related methods

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
MATSUMURA: "Energy saving effect of pervaporation using oleyl alcohol liquid membrane in butanol purification", BIOPROCESS ENGINEERING, SPRINGER VERLAG, DE, vol. 3, 1 January 1988 (1988-01-01), pages 93 - 100, XP009135942, ISSN: 0178-515X *
TERMINOLOGY FOR MEMBRANES AND MEMBRANE PROCESSES (IUPAC RECOMMENDATIONS, 1996, pages 1486
WEILNHAMMER ET AL: "Continuous fermentation with product recovery by in-situ extraction", CHEMICAL ENGINEERING AND TECHNOLOGY, WEINHEIM, DE, vol. 17, no. 6, 1 January 1994 (1994-01-01), pages 365 - 373, XP009135992, ISSN: 0930-7516 *
ZHONGPING SHI ET AL: "Performance evaluation of acetone-butanol continuous flash extractive fermentation process", BIOPROCESS AND BIOSYSTEMS ENGINEERING, SPRINGER, BERLIN, DE LNKD- DOI:10.1007/S00449-004-0396-7, vol. 27, no. 3, 1 May 2005 (2005-05-01), pages 175 - 183, XP019347336, ISSN: 1615-7605 *

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Publication number Publication date
RU2009106236A (en) 2010-08-27
RU2409414C2 (en) 2011-01-20

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