WO2000014148A1 - Use of a cellulosic moulded part - Google Patents

Use of a cellulosic moulded part 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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Prior art keywords
shaped body
cellulose
substance
treated
membrane
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PCT/AT1999/000212
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German (de)
French (fr)
Inventor
Heinrich Firgo
Peter Gspaltl
Christian Schlossnikl
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Lenzing Aktiengesellschaft
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Priority to AU54970/99A priority Critical patent/AU5497099A/en
Publication of WO2000014148A1 publication Critical patent/WO2000014148A1/en

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    • 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.

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

Abstract

The invention relates to the use of a cellulosic moulded part produced by the amine oxide method and treated with an enzyme capable of breaking down cellulose or another substance contained in said moulded part, as a membrane. The invention further relates to a method for producing a cellulosic membrane by producing a moulded part from a solution of cellulose in an aqueous tertiary amine oxide. Said method is characterized in that the moulded part contains a substance (A) which differs from cellulose and can be broken down by enzymes and in that said moulded part is treated with an enzyme capable of breaking down said substance (A).

Description

Verwendung eines cellulosischen FormkörpersUse of a cellulosic molding
Die vorliegende Erfindung betrifft die Verwendung eines cellulosischen Formkörpers, insbesondere einer Flachfolie, Schlauchfolie oder Hohlfaser, welcher bzw. welche nach dem Aminoxidverfahren hergestellt wurde. Die vorliegende Erfindung betrifft weiters ein Verfahren zur Herstellung einer cellulosischen Membran.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.
Verfahren zur Herstellung von cellulosischen Formkörpern aus Lösungen der Cellulose in einem wässerigen tertiären Aminoxid (insbesondere N-Methylmorpholin-N-oxid, im folgenden „NMMO" genannt) sind bekannt und werden z.B. in der US-A 4,246,221 sowie der PCT-WO 93/19230 beschrieben. Dieses bekannte Verfahren wird im folgenden als „Aminoxidverfahren" bezeichnet. Es ist bekannt, nach dem Aminoxidverfahren Flachfolien, Schlauchfolien oder Hohlfasern herzustellen. Aus der EP-A 0 807 460 ist auch bekannt, nach dem Aminoxidverfahren hergestellte Flachfolien, Schlauchfolien oder Hohlfasern als Membranen einzusetzen.Processes for producing cellulosic molded articles from solutions of cellulose in an aqueous tertiary amine oxide (in particular N-methylmorpholine-N-oxide, hereinafter referred to as “NMMO”) are known and are described, for example, in US Pat. No. 4,246,221 and PCT-WO 93 / 19230. This known process is hereinafter referred to as the "amine oxide process". It is known to produce flat films, tubular films or hollow fibers by the amine oxide process. It is also known from EP-A 0 807 460 to use flat films, tubular films or hollow fibers produced by the amine oxide process as membranes.
Eine wesentliche Eigenschaft cellulosischer Membranen ist deren Permeabilität. Dabei unterscheidet man zwischen „low-flux", „middle-flux" oder „high-flux"-Membranen. Die Permeabilität der Membran wird dabei insbesondere durch die Porenstruktur der Membran bestimmt.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.
Die Porenstruktur sowie damit die Permeabilität von Membranen wird je nach Art des Herstellungsverfahrens wie z.B. dem Naßspinnverfahren, dem Trocken/Naßspinnverfahren, dem Extrusionsverfahren usw. und des Materials (z.B. Cellulose, Celluloseacetat, Polyolefine usw.) in erster Linie durch Prozeßparameter wie Verstreckung, Temperatur, Fällungsbedingungen usw. bestimmt. Der Einsatz von porenbildenden Additiva wie Salzen (LiCl, CaCl2) ist ebenso bekannt, aber auf spezielle Anwendungen beschränkt.The pore structure and thus the permeability of membranes, depending on the type of manufacturing process such as the wet spinning process, the dry / wet spinning process, the extrusion process etc. and the material (e.g. cellulose, cellulose acetate, polyolefins etc.) 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.
Die vorliegende Erfindung stellt sich zur Aufgabe, die Permeabilität von cellulosischen Membranen, welche nach dem Aminoxidverfahren hergestellt wurden, zu erhöhen.The object of the present invention is to increase the permeability of cellulosic membranes which have been produced by the amine oxide process.
Die Aufgabe der vorliegenden Erfindung wird gelöst durch die Verwendung eines cellulosischen Formkörpers, hergestellt nach dem Aminoxidverfahren, welcher mit einem Enzym behandelt wurde, das in der Lage ist, Cellulose oder eine andere im Formkörper enthaltene Substanz abzubauen, als Membran.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.
Ein Verfahren zur Behandlung einer nach dem Aminoxidverfahren hergestellten Flachfolie oder Schlauchfolie mittels Cellulase ist aus der PCT-WO 98/02046 bekannt. In diesem Dokument wird beschrieben, daß durch die Behandlung mit Cellulase eine Aufrauhung der Oberfläche der Flachfolie bzw. Schlauchfolie erreicht wird. Solcherart modifizierte Produkte eignen sich gemäß der PCT-WO 98/02046 besonders als Nahrungsmittelhülle.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.
Es hat sich nun überraschenderweise gezeigt, daß ein nach dem Aminoxidverfahren hergestellter Formkörper, welcher mit einem Enzym behandelt wurde, das in der Lage ist, Cellulose oder eine andere im Formkörper enthaltene Substanz abzubauen, sich hervorragend als Membran eignet und insbesondere sehr gute Permeabilitäten aufweist.It has now surprisingly been found that 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.
Zur Verwendung als Membran eignen sich insbesondere Flachfolien, Schlauchfolien oder Hohlfasern. Wenn in der Folge von der Verwendung einer Hohlfaser als Membran gesprochen wird, so versteht sich für den Fachmann, daß zur Herstellung einer Membran viele einzelne Hohlfasern benötigt werden.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.
So kann die Permeabilität einer nach dem Aminoxidverfahren hergestellten cellulosischen Schlauchfolie oder Flachfolie, welche z.B. ohne weitere Behandlung im low-flux-Bereich liegt, durch die nachträgliche Einwirkung einer Cellulase auf die Oberfläche soweit erhöht werden, daß auch der high-flux-B ereich erreicht wird. Weiters stellte sich überraschenderweise heraus, daß über die Konzentration des einwirkenden Enzyms sowie über die Einwirkzeit die Permeabilität der resultierenden Membran gezielt gesteuert werden kann.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.
In einer bevorzugten Ausführungsform der Erfindung wird ein Formkörper als Membran verwendet, welcher mit einer Cellulase behandelt wurde.In a preferred embodiment of the invention, a shaped body is used as the membrane, which has been treated with a cellulase.
In einer weiteren bevorzugten Ausführungsform der Erfindung wird ein Formkörper als Membran verwendet, welcher mit einer Xylanase behandelt wurde. Es ist bekannt, daß die als Ausgangsmaterial des Aminoxidverfahrens eingesetzten Zellstoffe, insbesondere Laubholzzellstoffe, welche nach dem sogenannten Kraftverfahren hergestellt wurden, einen hohen Anteil an Xylanen enthalten. Unter dem Begriff „Xylane" versteht der Fachmann nicht nur reine Xylane, sondern auch z.B. die in der Natur häufiger vorkommenden Heteroxylane sowie acetylierte Xylane. Die Xylane befinden sich im fertigen Formkörper, z.B. der Flachfolie, Schlauchfolie oder Hohlfaser verteilt in der cellulosischen Matrix. Wird der Formkörper nunmehr mit einer Xylanase behandelt, so werden die verteilten Xylane selektiv abgebaut. Durch den Abbau der Xylane entstehen im Formkörper zusätzliche Hohlräume und Poren, welche die Permeabilität des Formkörpers erhöhen.In a further preferred embodiment of the invention, a shaped body is used as the membrane, which has been treated with 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.
Abgesehen von der Verwendung von Xylanen ist es auch möglich, alleine oder zusätzlich zu den Xylanen andere Substanzen, welche mit einem Enzym abgebaut werden können, welches Cellulose nicht oder langsamer als diese anderen Substanzen abbaut, vorzusehen und damit die Porenstruktur der Membran zu beeinflussen. Beispiele für solche andere Substanzen sind andere Polysaccharide, z.B. Amylopektin.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.
In diesem Zusammenhang ist es weiters möglich, enzymatisch abbaubare Substanzen, die unter den Bedingungen des Aminoxidverfahrens stabil sind und aufgrund ihrer Löslichkeitseigenschaften nicht vor dem Ausfällen der Celluloselösung zum Formkörper aus dem Verfahren ausgeschleust werden, dem Aminoxidverfahren an einer beliebigen Stufe zuzugeben und in die Cellulosematrix des Formkörpers zu inkorporieren.In this context, it is also possible to add enzymatically degradable substances, which are stable under the conditions of the amine oxide process and, because of their solubility properties, are not removed from the process before the cellulose solution precipitates out of the molding, to the amine oxide process at any stage and into the cellulose matrix of the Incorporate molded body.
Die Permeabilität kann durch die Art und die Menge der - gegebenenfalls zugegebenen - Substanzen sowie durch die Bedingungen des enzymatischen Abbaus gezielt gesteuert werden.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.
Der Abbau der bereits enthaltenen bzw. zugesetzten enzymatisch abbaubaren Substanzen kann dabei vollständig bis zur maximal erreichbaren Permeabilität oder begrenzt durch eine Deaktivierung des Enzyms bis zum Erreichen einer von der Konzentration und/oder Verweilzeit abhängigen gewünschten Permeabilität erfolgen.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.
Die Aufgabe der vorliegenden Erfindung wird auch durch ein Verfahren zur Herstellung einer cellulosischen Membran mittels Herstellung eines Formkörpers aus einer Lösung von Cellulose in einem wässerigen tertiären Aminoxid gelöst, welches dadurch gekennzeichnet ist, daß der Formkörper eine von Cellulose verschiedene enzymatisch abbaubare Substanz (A) enthält und der Formkörper mit einem Enzym behandelt wird, welches in der Lage ist, die Substanz (A) abzubauen.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).
Das erfindungsgemäße Verfahren beruht auf dem Prinzip, im aus der Cellulose gebildeten Formkörper bzw. an dessen Oberfläche eine vorzugsweise gleichmäßig verteilt vorliegende enzymatisch abbaubare Substanz (A) vorzusehen. Wenn man nun diesen Formkörper mit einem Enzym behandelt, welches die Substanz (A) abbauen kann, wird innerhalb der Matrix der Cellulose selektiv die Substanz (A) abgebaut. Dadurch entstehen an den Stellen, an welchen die Substanz (A) vorliegt, Hohlräume bzw. Poren, wodurch die Permeabilität des Formkörpers bzw. der aus dem Formkörper bestehenden Membran erhöht wird.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.
Unter einer „Lösung von Cellulose" wird dabei eine Lösung aus cellulosischem Material verstanden, wobei als cellulosisches Material Zellstoff, Zellstoffmischungen aber auch Cellulosederivate eingesetzt werden können. Die Lösung kann weiters gegebenenfalls noch Zusätze wie Stabilisatoren, Weichmacher, Porenbilder und dergleichen enthalten.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.
Als „enzymatisch abbaubare Substanz (A)" werden Substanzen verstanden, welche von Cellulose verschieden sind und welche mit Enzymen abgebaut werden können, welche die Cellulose nicht oder langsamer als die Substanz (A) abbauen. Darunter fallen z.B. andere Polysaccharide, aber auch z.B. Hemicellulosen. Geeignete Substanzen (A) können anhand ihrer Löslichkeitseigenschaften bzw. ihrer Stabilität gegenüber den chemischen und physikalischen Bedingungen des Aminoxidverfahrens ausgewählt werden.“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.
Solche Substanzen können, wie im Fall von Hemicellulosen, z.B. Xylanen, bereits im Rohstoff für das Aminoxidverfahren enthalten sein. Die Substanz (A) kann im fertigen Formkörper innerhalb der cellulosischen Matrix verteilt sein. Die Substanz (A) kann aber auch im wesentlichen an der Oberfläche des Formkörpers vorliegen.Such substances, as in the case of hemicelluloses, e.g. Xylans, already contained in the raw material for the amine oxide process. The 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird die Substanz (A) dem Formkörper bzw. der Lösung der Cellulose und/oder deren Vorprodukten vor der Behandlung des Formkörpers mit dem Enzym zugegeben. Als Vorprodukte der Lösung sind z.B. der Zellstoff selbst oder eine Suspension von Cellulose im tertiären Aminoxid, aus welcher in bekannter Weise die Lösung hergestellt wird, zu verstehen. Auch eine Zugabe zum Formkörper im Gelzustand, d.h. während des Ausfällens im Fällbad ist möglich. In diesem Fall kann z.B. das Fällbad die Substanz (A) enthalten, welche dann vom frisch ausgefällten Formkörper aufgenommen wird.In a preferred embodiment of the process according to the invention, 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. As 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. An addition to the shaped body in the gel state, ie during the precipitation in the precipitation bath, is also possible. In this case, the precipitation bath can contain substance (A), for example, which is then taken up by the freshly precipitated shaped body.
Eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß als Substanz (A) Xylane eingesetzt werden und der Formkörper mit einer Xylanase behandelt wird. Die Xylane sind dabei zumeist bereits im Zellstoff, dem Rohstoff des Aminoxidverfahrens enthalten. Es können aber weitere Xylanmengen während des Aminoxidverfahrens zugegeben werden.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.
Die enzymatische Behandlung des Formkörpers findet am fertigen Formkörper, z.B nach dessen Wäsche statt. Nach der Behandlung des Formkörpers mit dem Enzym wird das Enzym dauerhaft inaktiviert. Die Behandlung kann einseitig, beidseitig bzw. beidseitig mit auf den beiden Seiten unterschiedlichen Bedingungen durchgeführt werden. Bei einer einseitigen Behandlung oder einer beidseitigen Behandlung unter unterschiedlichen Bedingungen resultieren asymmetrische Membranen.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.
Die Methoden, eine geeignete Substanz (A) aufzufinden und in geeigneter Menge in den cellulosischen Formkörper zu inkorporieren, die Verfahren zur enzymatischen Behandlung eines Formkörpers, sowie die Möglichkeiten, dieses Verfahren zu steuern, sind dem Fachmann bekannt.Those skilled in the art are familiar with the methods of finding a suitable substance (A) and incorporating it in a suitable amount into the cellulosic shaped body, the processes for the enzymatic treatment of a shaped body and the possibilities for controlling this process.
Es ist natürlich auch möglich, verschiedene enzymatisch abbaubare Substanzen vorzusehen und den Formkörper mit verschiedenen Enzymen zu behandeln. Weiters ist es möglich, nicht nur die Substanz (A) mittels des entsprechenden Enzyms, sondern auch gleichzeitig oder in einem separaten Schritt zumindest einen Teil der Cellulosematrix mittels Cellulase abzubauen.It is of course also possible to provide various enzymatically degradable substances and to treat the shaped body with different enzymes. Furthermore, it is possible not only to break down the substance (A) by means of the corresponding enzyme, but also at the same time or in a separate step at least part of the cellulose matrix using cellulase.
Als Formkörper eignen sich insbesondere Flachfolien, Schlauchfolien oder Hohlfasern. Die vorliegende Erfindung betrifft auch eine cellulosische Membran, welche durch das erfindungsgemäße Verfahren erhältlich ist. Im Unterschied zu einer cellulosischen Membran, welche durch das Behandeln eines Formkörpers mit Cellulase erhältlich ist, sind die erfindungsgemäßen Membranen nur an jenen Stellen modifiziert, an welchen in der cellulosischen Matrix die Substanz (A) eingelagert ist. Dabei resultieren neuartige Membranen mit gezielt steuerbaren Membraneigenschaften.Flat films, tubular films or hollow fibers are particularly suitable as shaped articles. The present invention also relates to a cellulosic membrane which can be obtained by the process according to the invention. In contrast to 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.
Beispiele:Examples:
Die in den folgenden Beispielen angegebene Ultrafiltrationsrate ist definiert als das pro Zeiteinheit durch die Membranwand durchtretende Wasservolumen bezogen auf die Membranfläche und den Prüfdruck.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.
mlml
UFR = t.A.p h.m .mmHgUFR = t.A.p h.m .mmHg
V = Flüssigkeitsvolumen t = Zeit [h]V = liquid volume t = time [h]
A = Membranfläche [m2] P = Prüfdruck [mm Hg]A = membrane area [m 2 ] P = test pressure [mm Hg]
Beispiel 1 (Vergleichsbeispiel)Example 1 (comparative example)
Eine Celluloselösung mit einer Temperatur von 100 °C enthaltend 13 Masse-% Cellulose, 77,1 Masse% NMMO und 9,9 Masseprozent H2O, wurde mittels einer Flachdüse, welche einen Extrusionsspalt mit einer Länge von 40 cm und eine Breite von 300 μm aufwies, mit einem Durchsatz von 37,8 kg/h durch einen Luftspalt von 2 cm Länge senkrecht nach unten in ein Fällbad, bestehend aus 80 Masse% Wasser und 20 Masse% NMMO, extrudiert.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 μm, 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.
Die Austrittsgeschwindigkeit betrug 4,2 m/min und die Folie wurde mit dem Dreifachen der Austrittsgeschwindigkeit abgezogen. Die Folie wurde anschließend für 10 s in eine Lösung bestehend aus 150g/l Glycerin und Wasser getaucht und getrocknet.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.
Die erhaltene Folie hatte folgende Eigenschaften:The film obtained had the following properties:
Dicke (trocken) 29 μmThickness (dry) 29 μm
UFR 0,68 ml/m2/h/mm HgUFR 0.68 ml / m 2 / h / mm Hg
Beispiel 2Example 2
Eine Folie hergestellt nach Beispiel 1 wurde nachträglich in eine Lösung, die 25 g/1 Cellulase (Cellusoft L der Novo Nordisk A/S, Bagsvaerd, Dänemark) und Wasser enthielt, einen pH Wert von 4,5 bis 5,5 und eine Temperatur von 50°C bis 60°C aufwies, getaucht. Die Verweilzeit betrug 10 min. Danach wurde das an der Oberfläche anhaftende Wasser abgestreift und die Folie zur Deaktivierung des Enzyms für 20 s in eine kochende wäßrige Lösung mit einem pH- Wert von 10 getaucht und anschließend der UFR Wert bestimmt.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.
Die Ultrafiltrationsrate UFR der so behandelten Folie betrug 1,13 ml/m2/h/mm Hg.The ultrafiltration rate UFR of the film treated in this way was 1.13 ml / m 2 / h / mm Hg.
Beispiel 3Example 3
Es wurde analog zu Beispiel 2 vorgegangen, nur betrug die Verweilzeit der Folie in der Lösung des Enzyms 40 min.The procedure was analogous to Example 2, but the residence time of the film in the solution of the enzyme was 40 min.
Die Ultrafiltrationsrate UFR betrug 6,08 ml/m2/h/mm HgThe ultrafiltration rate UFR was 6.08 ml / m 2 / h / mm Hg
Beispiel 4Example 4
Es wurde analog zu Beispiel 2 vorgegangen, nur betrug die Verweilzeit der Folie in der Lösung des Enzyms 80 min.The procedure was analogous to Example 2, but the residence time of the film in the solution of the enzyme was 80 min.
Die Ultrafiltrationsrate UFR betrug 41,69 ml/m2/h/mm Hg Beispiel 5The ultrafiltration rate UFR was 41.69 ml / m 2 / h / mm Hg Example 5
Es wurde analog zu Beispiel 2 vorgegangen, nur betrug die Verweilzeit der Folie in der Lösung des Enzyms 120 min.The procedure was analogous to Example 2, but the residence time of the film in the solution of the enzyme was 120 min.
Die Ultrafiltrationsrate UFR betrug 126,55 ml/m2/h/mm HgThe ultrafiltration rate UFR was 126.55 ml / m 2 / h / mm Hg
Beispiel 6Example 6
Es wurde analog Beispiel 5 vorgegangen, nur betrug der Enzymgehalt der Behandlungslösung 100 g/1.The procedure was analogous to Example 5, except that the enzyme content of the treatment solution was 100 g / l.
Die Ultrafiltrationsrate UFR betrug 1000,55 ml/m2/h mm HgThe ultrafiltration rate UFR was 1000.55 ml / m 2 / h mm Hg
Die mit Enzymen behandelten Folien gemäß den Beispielen 2 bis 6 eignen sich hervorragend zum Einsatz als Membran. The films treated with enzymes according to Examples 2 to 6 are outstandingly suitable for use as a membrane.

Claims

Patentansprüche: Claims:
1. Verwendung eines cellulosischen Formkörpers, hergestellt nach dem Aminoxidverfahren, welcher mit einem Enzym behandelt wurde, das in der Lage ist, Cellulose oder eine andere im Formkörper enthaltene Substanz abzubauen, als Membran.1. Use of a cellulosic shaped body, produced by the amine oxide process, which has been treated with an enzyme which is capable of breaking down cellulose or another substance contained in the shaped body, as a membrane.
2. Verwendung gemäß Anspruch 1, dadurch gekennzeichnet, daß der Formkörper eine Flachfolie, Schlauchfolie oder Hohlfaser ist.2. Use according to claim 1, characterized in that the shaped body is a flat film, tubular film or hollow fiber.
3. Verwendung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Formkörper mit einer Cellulase behandelt wurde.3. Use according to claim 1 or 2, characterized in that the shaped body has been treated with a cellulase.
4. Verwendung gemäß Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß der Formkörper mit einer Xylanase behandelt wurde.4. Use according to claim 1, 2 or 3, characterized in that the shaped body has been treated with a xylanase.
5. Verfahren zur Herstellung einer cellulosischen Membran mittels Herstellung eines Formkörpers aus einer Lösung von Cellulose in einem wässerigen tertiären Aminoxid, dadurch gekennzeichnet, daß der Forrnkörper eine von Cellulose verschiedene enzymatisch abbaubare Substanz (A) enthält und der Forrnkörper mit einem Enzym behandelt wird, welches in der Lage ist, die Substanz (A) abzubauen.5. A process for the production of a cellulosic membrane by producing a shaped body from a solution of cellulose in an aqueous tertiary amine oxide, characterized in that the shaped body contains an enzymatically degradable substance (A) other than cellulose and the shaped body is treated with an enzyme which is able to degrade substance (A).
6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß die Substanz (A) dem Formkörper bzw. der Lösung der Cellulose und/oder deren Vorprodukten vor der Behandlung des Formkörpers mit dem Enzym zugegeben wird.6. The method according to claim 5, characterized in that the substance (A) is added to the shaped body or the solution of cellulose and / or its precursors before the treatment of the shaped body with the enzyme.
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß als Substanz (A) Xylane eingesetzt werden und der Formkörper mit einer Xylanase behandelt wird.7. The method according to claim 5 or 6, characterized in that xylans are used as substance (A) and the shaped body is treated with a xylanase.
8. Verfahren gemäß einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß als Formkörper eine Flachfolie, Schlauchfolie oder Hohlfaser hergestellt wird.8. The method according to any one of claims 5 to 7, characterized in that a flat film, tubular film or hollow fiber is produced as the shaped body.
9. Cellulosische Membran, erhältlich nach einem Verfahren gemäß einem der Patentansprüche 5 bis 8. 9. Cellulosic membrane, obtainable by a process according to one of claims 5 to 8.
PCT/AT1999/000212 1998-09-03 1999-09-03 Use of a cellulosic moulded part WO2000014148A1 (en)

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