WO2000010694A1 - Symplex membrane - Google Patents
Symplex membrane Download PDFInfo
- Publication number
- WO2000010694A1 WO2000010694A1 PCT/EP1999/005737 EP9905737W WO0010694A1 WO 2000010694 A1 WO2000010694 A1 WO 2000010694A1 EP 9905737 W EP9905737 W EP 9905737W WO 0010694 A1 WO0010694 A1 WO 0010694A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulose
- symplex
- water
- membrane
- symplex membrane
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/268—Drying gases or vapours by diffusion
-
- 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
Definitions
- the invention relates to an improved symplex membrane which contains polyanions formed from at least one cellulose ether containing sulfoalkyl groups as the anionic component and to the use of this symplex membrane for separating water or water vapor from organic substances and substance mixtures.
- Symplex membranes are understood to mean sheet-like associations of at least one polyelectrolyte (polyanions or polycations) and a low-molecular or polymeric counterion, in which the positively or negatively charged groups of the polyelectrolyte are crosslinked with the opposite charge of the corresponding counterions via a salt bridge.
- Non-porous membranes are used especially for material separation processes using pervaporation or ultrafiltration in the vacuum range.
- organic solvents such as alcohols.
- Ketones and aldehydes are described in principle suitable membranes in US Pat. No. 3,546,142, US Pat. No. 3,549,016, DE-PS 3526 755, DE-PS 3518871, EP-PS 96339.
- the quality of a membrane basically depends on the separation factor, the filtrate flow density to be achieved, the mechanical and chemical stability.
- the systems described are characterized either by a high separation factor or by a high filtrate flow density, but not a combination of these properties that meets practical requirements. Improvements in the direction of a high filtrate current density and a high separation factor have been achieved by using hydrophilic polyelectrolytes, for example based on ion complexes (J. Membrane Science, 32 (1987) 207). However, these membranes always had good water solubility and therefore insufficient resistance.
- the invention is therefore based on the object of providing an improved symplex membrane which has a high mechanical and chemical stability, consists of material which is available in sufficient quantity and quality, allows simple and reproducible production of membranes and achieves the desired separation performance.
- a symplex membrane which contains polyanions formed from at least one cellulose ether containing sulfoalkyl groups as the anionic component.
- Cellulose ethers containing sulfoalkyl groups preferably sulfoethyl cellulose, sulfo- propyl cellulose or mixed ethers of cellulose, which are etherified with sulfoethyl and sulfopropyl groups.
- the use of sulfoethyl cellulose is particularly preferred.
- derivatives of sulfoethyl cellulose or sulfopropyl cellulose can be used as the cellulose ethers containing sulfoalkyl groups, which derivatives are additionally substituted by carboxymethyl,
- Methyl, hydroxyethyl, ethyl or hydroxypropyl groups with a molar degree of substitution MS ⁇ 1 are substituted.
- the cellulose ether solution containing anionic sulfoalkyl groups preferably sulfoethyl cellulose solution.
- applied in a uniform layer thickness to a polymeric support and surrounded with the cationic crosslinking agent for example by spreading the cellulose ether solution with a doctor on the polymeric support and then spreading the cationic crosslinking agent with a second doctor over the first layer.
- a polymeric carrier is passed sequentially through the cellulose ether solution and the cationic crosslinking agent.
- the cationic crosslinking agent penetrates the cellulose ether solution from the outside.
- the symplex membrane is applied to a liquid-permeable carrier for practical use to further improve the mechanical stability.
- the usual materials in particular polyacrylonitrile, polyetherimide, polyvinylidene fluoride, polysulfone, polyhydrogenation as porous membrane or polyester, polypropylene as fleece can be used as polymeric carrier for the symplex membrane according to the invention.
- filter paper is also used instead of a polymeric carrier.
- the cellulose ether solution is applied in a uniform layer to a degreased glass plate.
- the coated glass plate is then immersed in the crosslinking bath in which the symplex membrane is formed. After removal from the crosslinking bath and thorough rinsing with water, the symplex membrane is transferred from the glass plate to a polymeric support or also to a PE film as an intermediate support.
- the symplex membranes according to the invention can be produced with good mechanical stability, are stable with respect to aqueous systems and organic solvents, and are notable for a high separation factor combined with a high filtrate flow density.
- the charge density of the samples which can be used to calculate average degrees of substitution (DS value), was determined using polyelectrolyte titration.
- An oppositely charged polyelectrolyte with a known charge density is added to the solution of the polyelectrolyte.
- the charges of the titrant neutralize the charges of the sample, the charge zero point denotes the end point of the titration. It was detected using a particle charge detector (PCD).
- PCD particle charge detector
- the average molar masses of the samples used were determined by means of size exclusion chromatography (GPC). It is a chromatographic method in which the particles are separated according to their hydrodynamic volume, which is roughly related to their molecular weight. There is a connection between the time of elution and the molecular weight.
- the molecular weights were determined in part by means of relative and absolute GPC.
- the relative GPC a calibration line was created on the basis of pullulin standard samples of known molar mass.
- the absolute GPC there is no need to determine one
- the limit viscosity number measurements were carried out in a 0.1 M NaNO 3 solution as solvent at 25 ° C. using an Ubbelohde capillary viscometer. A series of dilutions was made and the flow time through the capillary of each solution and the solvent was determined. The evaluation was made according to the Huggins equation.
- the thickness of the symplex membranes is decisive for the manageability. It was measured with a mechanical thickness measuring device (Ikon from Zeiss, Jena). The measurements were taken ten times at different locations in the
- the symplex membranes swell to different extents in different solvents.
- the degree of swelling SD was determined from the mass of the symplex membrane before and after the swelling process using the following equation:
- the stability of the symplex membranes in different solvents or salt solutions was tested.
- the masses of the symplex membrane were related to each other before and after a storage period in the corresponding solvent.
- Density measurements (DMA 48, company Paar KG, Austria) determined.
- the average molar mass of the sample used was 1.2-10 6 g / mol.
- a 4% solution of a PDADMAC sample with an average molecular weight of 100,000 g / mol was prepared under the same conditions.
- the sulfoethyl cellulose solution was applied to a glass plate at a layer height of 500 ⁇ m and the entire glass plate was then placed in the PDADMAC solution. After 1 hour, the symplex membrane formed was removed from the solution, rinsed thoroughly with water, transferred to a PE film and dried at room temperature.
- the symplex membrane When dry, the symplex membrane is slightly cloudy. It is very stable and can be handled well without tearing. An elastic modulus of 3733 MPa with an elongation at break of 3.6% was determined for the mechanical stability.
- the symplex membrane formed can be described with the following parameters:
- the thickness of the symplex membrane was 12 ⁇ m, the degree of swelling was 289%. In the cleaning phase, excess polycation components of approx. 12% by weight are flushed out of the symplex membrane, and then there are no more changes in weight. Analogous behavior was observed in CaCl- > and NaCl solutions.
- the separation performance of the symplex membrane in relation to the separation of isopropanol / water is one
- a 4% solution of a PDADMAC sample was prepared under the same conditions.
- the sample used has an average molecular weight of 100,000 g / mol.
- the sulfoethyl cellulose solution was spread on a glass plate in a layer thickness of 500 ⁇ m and the entire glass plate was placed in the PDADMAC solution. After 1 hour, the symplex membrane formed was removed from the solution, rinsed thoroughly with water, transferred to a PE film and added
- the symplex membrane When dry, the symplex membrane is slightly cloudy. It is very stable and can be handled well without tearing.
- the symplex membrane formed can be described with the following parameters:
- the thickness of the symplex membrane was 20 ⁇ m, the degree of swelling was 139%. In the cleaning phase, excess polycation components of approx. 6% by weight are flushed out of the symplex membrane, and then there is no change in weight. Analogous behavior was observed in CaCl 2 and NaCl solutions.
- the separation performance of the symplex membrane in relation to the separation of isopropanol / water is one
- the sulfoethyl cellulose solution was applied in a layer height of 500 ⁇ m on a glass plate and the glass plate was then placed in the PDADMAC solution. After 1 hour, the one that had formed in the meantime
- Symplex membrane removed from the solution, rinsed thoroughly with deionized water, transferred to a PE film and dried at room temperature.
- the symplex membrane When dried, the symplex membrane is slightly cloudy. It is very stable and can be handled well without tearing.
- the symplex membrane formed can be described with the following parameters:
- the thickness of the symplex membrane was 19 ⁇ m, the degree of swelling was 152%.
- excess polycation components of approx. 8% by weight flushed out of the symplex membrane, then no change in weight occurs. Analogous behavior was observed in CaCl2 and NaCl solutions.
- Example 3 Instead of the 4% sulfoethyl cellulose solution, a 3% sulfoethyl cellulose solution was used.
- the symplex membrane formed can be described with the following parameters'
- the thickness of the symplex membrane was 13 ⁇ m, the degree of swelling was 183%.
- excess polycation components of approx. 10% by weight are flushed out of the symplex membrane, and then there is no change in weight. Analogous behavior was observed in CaCl 2 and NaCl solutions.
- Example 3 Instead of the 4% sulfoethyl cellulose solution, a 5% sulfoethyl cellulose solution was used.
- the symplex membrane formed can be described with the following parameters:
- the thickness of the symplex membrane was 25 ⁇ m, the degree of swelling was 139%.
- excess polycation components of approx. 6% by weight are flushed out of the symplex membrane, and then there is no change in weight. Analogous behavior was observed in CaCl 2 and NaCl solutions.
- the casting solution had a concentration of 2%.
- Molar mass of the sample used was 5.5-10 5 g / mol.
- a 20% solution of a PDADMAC sample with an average molecular weight of 100,000 g / mol was prepared with stirring at room temperature in deionized water and used for crosslinking.
- the separation performance of the symplex membrane in relation to the separation of isopropanol / water is one
- Range of V2 5 - 40,000 mPas with stirring at room temperature dissolved in deionized water so that 1 - 10% solutions were formed.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU55117/99A AU5511799A (en) | 1998-08-20 | 1999-08-09 | Symplex membrane |
EP99941541A EP1115475A1 (en) | 1998-08-20 | 1999-08-09 | Symplex membrane |
JP2000566006A JP2002523527A (en) | 1998-08-20 | 1999-08-09 | Simplex thin film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19837673.1 | 1998-08-20 | ||
DE19837673A DE19837673A1 (en) | 1998-08-20 | 1998-08-20 | Simplex membrane, for separation of water from organic materials, contains at least one sulfoalkyl group containing cellulose ether polyanion as anionic component |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000010694A1 true WO2000010694A1 (en) | 2000-03-02 |
Family
ID=7878060
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/005737 WO2000010694A1 (en) | 1998-08-20 | 1999-08-09 | Symplex membrane |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1115475A1 (en) |
JP (1) | JP2002523527A (en) |
AU (1) | AU5511799A (en) |
DE (1) | DE19837673A1 (en) |
WO (1) | WO2000010694A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD270012A1 (en) * | 1988-03-16 | 1989-07-19 | Horst Dautzenberg | METHOD FOR PRODUCING MEMBRANES FROM POLYELECTROLYTE COMPLEXES |
US4871461A (en) * | 1987-01-22 | 1989-10-03 | The General Director Of The Agency Of Industrial Science And Technology | Polymer composite membrane |
DD292846A5 (en) * | 1989-10-11 | 1991-08-14 | Akad Wissenschaften Ddr | USE OF SYMPLEXMEMBRANES FOR PERVAPORATION |
EP0587071A1 (en) * | 1992-09-08 | 1994-03-16 | Gkss-Forschungszentrum Geesthacht Gmbh | Polyelectrolyte composite membrane |
-
1998
- 1998-08-20 DE DE19837673A patent/DE19837673A1/en not_active Withdrawn
-
1999
- 1999-08-09 EP EP99941541A patent/EP1115475A1/en not_active Withdrawn
- 1999-08-09 JP JP2000566006A patent/JP2002523527A/en active Pending
- 1999-08-09 AU AU55117/99A patent/AU5511799A/en not_active Abandoned
- 1999-08-09 WO PCT/EP1999/005737 patent/WO2000010694A1/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4871461A (en) * | 1987-01-22 | 1989-10-03 | The General Director Of The Agency Of Industrial Science And Technology | Polymer composite membrane |
DD270012A1 (en) * | 1988-03-16 | 1989-07-19 | Horst Dautzenberg | METHOD FOR PRODUCING MEMBRANES FROM POLYELECTROLYTE COMPLEXES |
DD292846A5 (en) * | 1989-10-11 | 1991-08-14 | Akad Wissenschaften Ddr | USE OF SYMPLEXMEMBRANES FOR PERVAPORATION |
EP0587071A1 (en) * | 1992-09-08 | 1994-03-16 | Gkss-Forschungszentrum Geesthacht Gmbh | Polyelectrolyte composite membrane |
Also Published As
Publication number | Publication date |
---|---|
JP2002523527A (en) | 2002-07-30 |
EP1115475A1 (en) | 2001-07-18 |
AU5511799A (en) | 2000-03-14 |
DE19837673A1 (en) | 2000-02-24 |
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