WO2000014148A1 - Utilisation d'un corps moule en cellulose - Google Patents

Utilisation d'un corps moule en cellulose Download PDF

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Publication number
WO2000014148A1
WO2000014148A1 PCT/AT1999/000212 AT9900212W WO0014148A1 WO 2000014148 A1 WO2000014148 A1 WO 2000014148A1 AT 9900212 W AT9900212 W AT 9900212W WO 0014148 A1 WO0014148 A1 WO 0014148A1
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WO
WIPO (PCT)
Prior art keywords
shaped body
cellulose
substance
treated
membrane
Prior art date
Application number
PCT/AT1999/000212
Other languages
German (de)
English (en)
Inventor
Heinrich Firgo
Peter Gspaltl
Christian Schlossnikl
Original Assignee
Lenzing Aktiengesellschaft
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 Lenzing Aktiengesellschaft filed Critical Lenzing Aktiengesellschaft
Priority to AU54970/99A priority Critical patent/AU5497099A/en
Publication of WO2000014148A1 publication Critical patent/WO2000014148A1/fr

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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
    • B01D71/08—Polysaccharides
    • B01D71/10—Cellulose; Modified cellulose

Definitions

  • the present invention relates to the use of a cellulosic shaped body, in particular a flat film, tubular film or hollow fiber, which was or was produced by the amine oxide process.
  • the present invention further relates to a method for producing a cellulosic membrane.
  • NMMO N-methylmorpholine-N-oxide
  • cellulosic membranes An essential property of cellulosic membranes is their permeability. A distinction is made between “low-flux”, “middle-flux” or “high-flux” membranes.
  • the permeability of the membrane is determined in particular by the pore structure of the membrane.
  • the pore structure and thus the permeability of membranes are primarily determined by process parameters such as stretching, temperature , Precipitation conditions, etc. determined.
  • the use of pore-forming additives such as salts (LiCl, CaCl 2 ) is also known, but is restricted to special applications.
  • the object of the present invention is to increase the permeability of cellulosic membranes which have been produced by the amine oxide process.
  • the object of the present invention is achieved by the use of a cellulosic shaped body, produced by the amine oxide process, which with a Enzyme was treated, which is able to break down cellulose or another substance contained in the molded body as a membrane.
  • a process for treating a flat film or tubular film produced by the amine oxide process using cellulase is known from PCT-WO 98/02046. This document describes that the treatment with cellulase causes the surface of the flat film or tubular film to be roughened. Products modified in this way are particularly suitable as food casings in accordance with PCT-WO 98/02046.
  • a molded article produced by the amine oxide process which has been treated with an enzyme and is capable of breaking down cellulose or another substance contained in the molded article, is outstandingly suitable as a membrane and in particular has very good permeabilities.
  • Flat films, tubular films or hollow fibers are particularly suitable for use as a membrane. If one speaks subsequently of the use of a hollow fiber as a membrane, it is understood by the person skilled in the art that many individual hollow fibers are required to produce a membrane.
  • the permeability of a cellulosic tubular film or flat film produced by the amine oxide process which e.g. without further treatment in the low-flux range, can be increased by the subsequent action of a cellulase on the surface to such an extent that the high-flux range is also reached. Furthermore, it surprisingly turned out that the permeability of the resulting membrane can be controlled in a targeted manner via the concentration of the enzyme acting and via the reaction time.
  • a shaped body is used as the membrane, which has been treated with a cellulase.
  • a shaped body is used as the membrane, which has been treated with a xylanase.
  • a xylanase it is known that the pulps used as starting material for the amine oxide process, in particular hardwood pulps, which were produced by the so-called Kraft process, contain a high proportion of xylans.
  • the term “xylans” is understood by the person skilled in the art not only to be pure xylans, but also, for example, the heteroxylanes and acetylated xylans which occur more frequently in nature.
  • the xylans are distributed in the cellulosic matrix in the finished shaped body, for example the flat film, tubular film or hollow fiber If the molded body is now treated with a xylanase, the distributed xylans are selectively broken down, and the breakdown of the xylans creates additional cavities and pores in the molded body, which increase the permeability of the molded body.
  • xylans Apart from the use of xylans, it is also possible, alone or in addition to the xylans, to provide other substances which can be broken down with an enzyme which cellulose does not degrade or slows down more slowly than these other substances, and thus to influence the pore structure of the membrane. Examples of such other substances are other polysaccharides, e.g. Amylopectin.
  • the permeability can be controlled in a targeted manner by the type and the amount of the substances - if appropriate added - and by the conditions of the enzymatic degradation.
  • the degradation of the enzymatically degradable substances already contained or added can take place completely up to the maximum permeability that can be achieved, or limited by deactivating the enzyme until a desired permeability that is dependent on the concentration and / or residence time is reached.
  • the object of the present invention is also achieved by a method for producing a cellulosic membrane by producing a shaped body from a solution of Cellulose dissolved in an aqueous tertiary amine oxide, which is characterized in that the shaped body contains an enzymatically degradable substance (A) which is different from cellulose and the shaped body is treated with an enzyme which is able to break down the substance (A).
  • the method according to the invention is based on the principle of providing a preferably evenly distributed enzymatically degradable substance (A) in the molded body formed from the cellulose or on the surface thereof. If one now treats this shaped body with an enzyme which can degrade the substance (A), the substance (A) is selectively degraded within the matrix of the cellulose. This creates cavities or pores at the points at which the substance (A) is present, as a result of which the permeability of the shaped body or of the membrane consisting of the shaped body is increased.
  • a “solution of cellulose” is understood to mean a solution made of cellulosic material, cellulose, cellulose mixtures but also cellulose derivatives being able to be used as the cellulosic material.
  • the solution may also contain additives such as stabilizers, plasticizers, pore formers and the like.
  • Enzymatically degradable substance (A) is understood to mean substances which are different from cellulose and which can be broken down with enzymes which do not break down the cellulose or break it down more slowly than substance (A). These include, for example, other polysaccharides, but also, for example, hemicelluloses Suitable substances (A) can be selected on the basis of their solubility properties or their stability to the chemical and physical conditions of the amine oxide process.
  • substance (A) can be distributed in the finished molded body within the cellulosic matrix. However, substance (A) can also be present essentially on the surface of the molded body.
  • substance (A) is added to the shaped body or the solution of cellulose and / or its precursors before the shaped body is treated with the enzyme.
  • precursors to the solution eg the pulp itself or a suspension of cellulose in the tertiary amine oxide, from which the solution is prepared in a known manner.
  • the precipitation bath can contain substance (A), for example, which is then taken up by the freshly precipitated shaped body.
  • a particularly preferred embodiment of the process according to the invention is characterized in that xylans are used as substance (A) and the shaped body is treated with a xylanase.
  • the xylans are usually already contained in the pulp, the raw material of the amine oxide process. However, further amounts of xylan can be added during the amine oxide process.
  • the enzymatic treatment of the shaped body takes place on the finished shaped body, e.g. after it has been washed. After the shaped body has been treated with the enzyme, the enzyme is permanently inactivated.
  • the treatment can be carried out on one side, on both sides or on both sides with different conditions on the two sides. With a one-sided treatment or a bilateral treatment under different conditions, asymmetrical membranes result.
  • the present invention also relates to a cellulosic membrane which can be obtained by the process according to the invention.
  • a cellulosic membrane which can be obtained by treating a shaped body with cellulase
  • the membranes according to the invention are modified only at those locations where substance (A) is embedded in the cellulosic matrix. This results in novel membranes with specifically controllable membrane properties.
  • the ultrafiltration rate given in the following examples is defined as the water volume passing through the membrane wall per unit of time, based on the membrane surface and the test pressure.
  • A membrane area [m 2 ]
  • P test pressure [mm Hg]
  • a cellulose solution with a temperature of 100 ° C. containing 13% by mass of cellulose, 77.1% by mass of NMMO and 9.9% by mass of H 2 O was made using a flat die which had an extrusion gap with a length of 40 cm and a width of 300 ⁇ m, with a throughput of 37.8 kg / h through an air gap of 2 cm in length vertically down into a precipitation bath consisting of 80 mass% water and 20 mass% NMMO.
  • the exit speed was 4.2 m / min and the film was pulled off at three times the exit speed.
  • the film was then immersed in a solution consisting of 150 g / l glycerol and water for 10 s and dried.
  • the film obtained had the following properties:
  • a film produced according to Example 1 was subsequently dissolved in a solution containing 25 g / 1 cellulase (Cellusoft L from Novo Nordisk A / S, Bagsvaerd, Denmark) and water, a pH of 4.5 to 5.5 and a temperature from 50 ° C to 60 ° C, immersed. The residence time was 10 minutes. The water adhering to the surface was then stripped off and the film was immersed in a boiling aqueous solution with a pH of 10 for 20 s to deactivate the enzyme, and the UFR was then determined.
  • 25 g / 1 cellulase Cellusoft L from Novo Nordisk A / S, Bagsvaerd, Denmark
  • the residence time was 10 minutes.
  • the water adhering to the surface was then stripped off and the film was immersed in a boiling aqueous solution with a pH of 10 for 20 s to deactivate the enzyme, and the UFR was then determined.
  • the ultrafiltration rate UFR of the film treated in this way was 1.13 ml / m 2 / h / mm Hg.
  • the ultrafiltration rate UFR was 6.08 ml / m 2 / h / mm Hg
  • the ultrafiltration rate UFR was 41.69 ml / m 2 / h / mm Hg
  • the ultrafiltration rate UFR was 126.55 ml / m 2 / h / mm Hg
  • Example 5 The procedure was analogous to Example 5, except that the enzyme content of the treatment solution was 100 g / l.
  • the ultrafiltration rate UFR was 1000.55 ml / m 2 / h mm Hg
  • the films treated with enzymes according to Examples 2 to 6 are outstandingly suitable for use as a membrane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne l'utilisation comme membrane d'un corps moulé en cellulose, fabriqué selon le procédé à l'oxyde d'amine, qui a été traité par une enzyme capable de dégrader la cellulose ou une autre substance qu'il contient. Elle concerne également un procédé qui permet de fabriquer une membrane cellulosique par fabrication d'un corps moulé à partir d'une solution de cellulose dans un oxyde d'amine tertiaire aqueux. Le procédé est caractérisé par le fait que le corps moulé contient une substance (A) enzymatiquement dégradable, autre que la cellulose, et qu'on le traite par une enzyme capable de dégrader ladite substance (A).
PCT/AT1999/000212 1998-09-03 1999-09-03 Utilisation d'un corps moule en cellulose WO2000014148A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54970/99A AU5497099A (en) 1998-09-03 1999-09-03 Use of a cellulosic moulded part

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA1494/98 1998-09-03
AT149498A AT406738B (de) 1998-09-03 1998-09-03 Verwendung eines cellulosischen formkörpers

Publications (1)

Publication Number Publication Date
WO2000014148A1 true WO2000014148A1 (fr) 2000-03-16

Family

ID=3515094

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1999/000212 WO2000014148A1 (fr) 1998-09-03 1999-09-03 Utilisation d'un corps moule en cellulose

Country Status (3)

Country Link
AT (1) AT406738B (fr)
AU (1) AU5497099A (fr)
WO (1) WO2000014148A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112934000A (zh) * 2021-03-09 2021-06-11 宁波大学 一种pvdf微滤膜的改性方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61274682A (ja) * 1985-05-31 1986-12-04 Nok Corp 酵素固定化膜の製造法
KR910008554B1 (ko) * 1989-06-09 1991-10-19 재단법인 한국화학연구소 생물학적 방법에 의한 다공질체의 제조방법
WO1996018761A1 (fr) * 1994-12-15 1996-06-20 Akzo Nobel Nv Procede de fabrication d'articles moules cellulosiques
EP0807460A1 (fr) * 1996-05-15 1997-11-19 Akzo Nobel N.V. Membrane cellulosique pour dialyse

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD151179A1 (de) * 1978-05-16 1981-10-08 Vazgen Jacopian Verfahren zur kontrollierten veraenderung der morphologie von polymerformkoerpern
DD244696A1 (de) * 1985-12-24 1987-04-15 Akad Wissenschaften Ddr Verfahren zur herstellung von kapillarhohlmembranen aus regeneratcellulose
JPS638401A (ja) * 1986-06-30 1988-01-14 Asahi Chem Ind Co Ltd セルロ−スのアルカリ性ド−プ
JP3464053B2 (ja) * 1994-09-28 2003-11-05 ユニチカ株式会社 セルロース系繊維布帛の退色化加工方法
DE19628232A1 (de) * 1996-07-15 1998-01-22 Kalle Nalo Gmbh Cellulosehydrat-Formkörper mit enzymatisch modifizierter Oberfläche

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61274682A (ja) * 1985-05-31 1986-12-04 Nok Corp 酵素固定化膜の製造法
KR910008554B1 (ko) * 1989-06-09 1991-10-19 재단법인 한국화학연구소 생물학적 방법에 의한 다공질체의 제조방법
WO1996018761A1 (fr) * 1994-12-15 1996-06-20 Akzo Nobel Nv Procede de fabrication d'articles moules cellulosiques
EP0807460A1 (fr) * 1996-05-15 1997-11-19 Akzo Nobel N.V. Membrane cellulosique pour dialyse

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199249, Derwent World Patents Index; Class A35, AN 1992-405152, XP002121093 *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 136 (C - 419) 30 April 1987 (1987-04-30) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112934000A (zh) * 2021-03-09 2021-06-11 宁波大学 一种pvdf微滤膜的改性方法
CN112934000B (zh) * 2021-03-09 2022-03-25 宁波大学 一种pvdf微滤膜的改性方法

Also Published As

Publication number Publication date
AT406738B (de) 2000-08-25
AU5497099A (en) 2000-03-27
ATA149498A (de) 2000-01-15

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