EP0374700B1 - Process for preparing mechanical pulp and for paper containing said pulp - Google Patents

Process for preparing mechanical pulp and for paper containing said pulp Download PDF

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Publication number
EP0374700B1
EP0374700B1 EP89122946A EP89122946A EP0374700B1 EP 0374700 B1 EP0374700 B1 EP 0374700B1 EP 89122946 A EP89122946 A EP 89122946A EP 89122946 A EP89122946 A EP 89122946A EP 0374700 B1 EP0374700 B1 EP 0374700B1
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EP
European Patent Office
Prior art keywords
resin
pulp
paper
lipase
amount
Prior art date
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Expired - Lifetime
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EP89122946A
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German (de)
French (fr)
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EP0374700A2 (en
EP0374700A3 (en
Inventor
Yuko Central Research Laboratory Irie
Motoo Central Research Laboratory Matsukura
Kunio Central Research Laboratory Hata
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Nippon Paper Industries Co Ltd
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Priority to AT89122946T priority Critical patent/ATE102667T1/en
Publication of EP0374700A2 publication Critical patent/EP0374700A2/en
Publication of EP0374700A3 publication Critical patent/EP0374700A3/en
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Publication of EP0374700B1 publication Critical patent/EP0374700B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control

Definitions

  • This invention relates to a process for the manufacture of mechanical wood pulp (such as wood pulp, refiner wood pulp, etc.) and paper containing this wood pulp.
  • mechanical wood pulp such as wood pulp, refiner wood pulp, etc.
  • Mechanical wood pulp such as wood pulp
  • wood pulp is made by mechanically treating logs or wood chips, e.g. grinds with a wood sander or refiner.
  • the wood pulp obtained which has the disadvantage of a lower strength, is obtained in a higher yield, is cheaper and results in a more opaque paper compared to pulp which is produced using chemicals such as alkali, etc.
  • the resin components of the mechanical pulp remain unchanged due to the mechanical grinding.
  • the wood contains about 1-10% resin components in addition to the main wood components, cellulose, hemicellulose and lignin.
  • the softwood a main raw material of mechanical pulp, contains a large amount of resin components such as fatty acids, resin acids, glycerides, etc.
  • a part of the resin components is excreted from the wood pulp, so that the resins are suspended in water or adsorbed on the fiber surface. That is, they change from a state fixed on the fiber to an excreted (free) state.
  • the precipitated resin floating in the backwater which is referred to as "colloidal resin" consists of resin particles of approximately 0.2-2 ⁇ m in size.
  • paper is produced by treating the paper raw materials produced by various processes by sorting processes, adding various additives and forming a sheet by a paper-making machine.
  • the separated resin or the resin adsorbed on the fiber is deposited on tubes, laid paper, sieves, rollers, etc., so that resin difficulty - paper soiling, scrap, etc. - occurs.
  • the resin problems often occur with paper containing a large amount of mechanical pulp.
  • GB-A-1 189 604 describes a method which enables the duration of the "seasoning” to be shortened without cellulose degradation by prior treatment of the wood chips with lipase-producing fungi. Neither this method, which is based on “seasoning” under difficult to control conditions, nor the Addition of the surfactants, which leads to the dispersion of the resin microparticles and the removal of the resin deposit, is sufficient to avoid the resin problems.
  • the object of the invention is therefore to provide an improved process for the production of mechanical wood pulp or of paper which contains this wood pulp. Resin difficulties in particular should be reduced.
  • the inventors examined both the wood components extracted from Japanese red pine, a typical wood for mechanical wood pulp, and the resin components used in the production of the mechanical wood pulp from Japanese Red pine or the paper containing the mechanical wood pulp has been deposited. It has been found that the major constituent of the resin deposited is the same as the resin constituent in the original wood and is rich in triglycerides, fatty acids, resin acids and their metal salts. In particular, the deposited resin always contains a large amount of triglycerides. Therefore, it is believed that triglycerides mainly cause resin problems. This finding confirms the teaching contained in GB-A-1 189 604.
  • the invention relates to a method for producing mechanical pulp and / or paper containing mechanical pulp and is characterized in that that the paper raw material and / or the backwater is treated with an acylglycerol lipase, optionally in immobilized form.
  • the acylglycerol lipase used is preferably that which is produced by at least one microorganism from the group Aspergillus niger, Pseudomonas fluorescenz, Pseudomonas fragi, Geotrichum candidum and Candida cylindracea.
  • the acylglycerol lipase according to the invention is an enzyme for the hydrolysis of the triglycerides, a main component of the resin.
  • suitable acylglycerol lipases are not particularly limited.
  • z. B. Use the following: Aspergillus niger, Pseudomonas fluorescens, Pseudumonas fragi, Geotrichum candidum and Candida cylindracea, Mucor javanicus, Rhizopus javanicus, Rhizopus delemar, Rhizopus niveus and fungal strains of the genus Rhizopus.
  • the purer the acylglycerol lipase according to the invention the better the effect.
  • the acylglycerol lipases used according to the invention can be used alone or in a mixture, and they can also be used with good success in combination with other decomposition enzymes, such as cellulases, hemicellulases, proteases, etc.
  • the acylglycerol lipase according to the invention is added in an amount of 0.1-10000 ppm, based on the weight of the mechanical wood pulp, to the sludge of the paper stock which contains the mechanical wood pulp produced during the sanding of the wood.
  • the sludge obtained is then stirred or left to stand, the temperature preferably being 10-70 ° C., particularly preferably 35-55 ° C.
  • the enzyme according to the invention acts weakly and slowly.
  • the enzyme of the invention loses its activity.
  • the pH is preferably adjusted to 3-11. Outside this pH range, the activity of the enzyme is reduced. A large amount of water is used in the manufacture of the paper stock and the paper, a large part of which is circulated and reused.
  • the use of the acylglycerol lipase according to the invention leads to the avoidance of resin problems with this backwater, with a direct addition of an acylglycerol lipase to the backwater, or the addition of a so-called immobilized acylglycerol lipase or a so-called immobilized microorganism. which extracellularly produces the acylglycerol lipase, is used with a good effect.
  • the Immobilization of the enzyme or the microorganism can be carried out in a known manner by connection with a carrier, crosslinking, entrapping process, etc. Because the process according to the invention is very selective and mild, it has the advantages that the treated paper raw materials remain unchanged and the usual process is not influenced.
  • the cause of the resin difficulties is unclear, but it is believed that the resin difficulties depend on the resin concentration, substance concentration, pH, temperature, metal ion concentration and type.
  • the adhesion to the solid surface is attributed to Van der Waal's forces that fix the substances on the solid surface.
  • the interaction between the substances is based, among other things, on a hydrophobic bond or a dipole moment effect.
  • a hydrophobic or non-polar molecule or such a part of the molecule is attracted to a hydrophobic or non-polar surface.
  • a hydrophilic or polar molecule is attracted to a hydrophilic or polar surface.
  • the triglycerides appear to play the following role in depositing the resin in a process for making paper stock and paper.
  • the triglyceride, a non-polar component of the colloidal resin adheres to a hydrophobic or non-polar surface such as the metal surface of tubes, the surface of press rolls in a papermaking process, etc. due to Van der Waal's forces.
  • the adhesive portion acts as a core to which hydrophobic or non-polar molecules or parts of molecules adhere, the resin deposits being formed.
  • acylglycerol lipase acts on the non-polar triglyceride, which has high adhesiveness to a hydrophobic and non-polar surface, and which is present in the resin on the surface of the mechanical pulp or in the backwater resin and and colloidal resin.
  • the triglycerides are hydrolyzed to water-soluble glycerols and polar fatty acids, which prevents adhesion to hydrophobic metal tubes, laid walls, rollers, etc. Thus, since the adhesion of the resin is prevented from the beginning, no resin deposits are formed, so that the resin trouble is avoided.
  • the process of the present invention has the advantages that the deposition of the resin components in the manufacture of the mechanical pulp or the paper containing the mechanical pulp is prevented, and defects such as resin stains and holes in a paper sheet, etc. caused by the resin, be avoided.
  • the method of the invention has no adverse impact on paper quality and practical production, and is simple and can be used in the previous pulp and paper making process.
  • Fresh Japanese red pine chips were extracted with methanol using a Soxhlet extractor. 10 g of the extract was dissolved in a mixed solution of 100 ml of isopropanol, 60 ml of acetone and 5 ml of water to obtain a resin solution.
  • the prepared resin dispersion was adjusted to pH 7 using hydrochloric acid and / or sodium hydroxide.
  • the acylglycerol lipases were added at different concentrations and temperatures, as in Table 1 is shown and stirred for 4 hours to prepare the treated solution.
  • the treated solution was adjusted to pH 4 with aluminum sulfate and hydrochloric acid.
  • 2.5 cm of a 22 cm wide and 7 cm long polyethylene board were immersed in the solution.
  • the adjusted solution was stirred for 30 minutes using a vibromixer (linitator manufactured by US Heidon Co.).
  • the polyethylene board was extracted and dried.
  • the amount of adhesive resin was calculated and expressed as a percentage based on the amount of adhesive resin in the untreated sample.
  • Example 2 The resin dispersion prepared in Example 1 was adjusted to a pH of 7 using hydrochloric acid and / or sodium hydroxide.
  • the acylglycerol lipase was added in an amount of 500 ppm based on the resin weight and stirred at 40 ° C.
  • the amount of adhesive resin was calculated in the same manner as in Example 1; it is shown in Table 2.
  • Table 2 enzyme time Art concentration 2 hours. 4 hours 8 hours Untreated - 105 mg (100%) 101 mg (100%) 107 mg (100%) Li. OF 500 ppm 67 mg (63.8%) 31 mg (30.7%) 31 mg (24.4%) Li. GC-5 5) 500 ppm 85 mg (81.0%) 70 mg (69.3%) 59 mg (55.1%) (Note 5) Li. GC-5; Trade name: Lipase GC-5 (manufactured by Amano Seiyaku Co.) produced by Geotrichum candidum.
  • Example 4 The same sample as in Example 3 was used.
  • the enzyme according to the invention was added to the sample in an amount of 50 ppm, based on the weight of the wood pulp, and treated at different temperatures for different periods.
  • the amount of adhesive resin was measured and is shown in Table 4.
  • Table 4 enzyme pH Treatment time temperature 20 ° C 40 ° C 60 ° C Untreated - 115 mg (100%) 102 mg (100%) 117 mg (100%) Li. OF 7 2 hours. - 44 mg (53.9%) - 4 hours 64 mg (55.7%) 29 mg (28.4%) 100 mg (85.5%) 8 hours - 27 mg (26.5%) - Untreated 9 - 128 mg (100%) 121 mg (100%) 134 mg (100%) Li.
  • the enzyme according to the invention was added in an amount of 0.5 ppm, based on the weight of the return water, treated at 40 ° C. for 2 hours and stirred with a vibromixer for 120 minutes.
  • Newsprint with a basis weight of approximately 46 g / m2 was produced by the Bel-Baie-Former multi-dryer machine with a width of 5080 mm and a speed of 830 m / min, the paper raw material being made from 30% wood pulp, 45% old newspaper paper stock (without printer's ink), 10% Softwood sulfate pulp and 15% thermomechanical pulp existed.
  • the wood pulp was made from red pine, adjusted to a grinding level of 60-70 ml CSF by the post-refiner, stored as a pulp for some time, optionally mixed with other pulps and auxiliaries, stored again and finally subjected to a paper manufacturing process. It takes 90 minutes from the refiner through the laid paper and containers to the paper machine.
  • the enzyme according to the invention was added to the wood pulp sludge of 3.8% concentration before the post-refiner so that the lipase OF had a concentration of 3 ppm. This enzyme was continuously added to the wood pulp for two weeks. The amount of resin adhering to the wire and press parts and the time interval between the cleaning operations required to remove the resin adhering to the center roller were determined. The output of this machine was about 200 tons per day.
  • a light-weight printing paper with a basis weight of 34 g / m 2 was produced according to Example 7, the paper stock consisting of 20% wood pulp, 50% old newspaper paper stock (without printing ink), 15% softwood sulfate pulp and 15% thermomechanical wood pulp.
  • the Lipase OF was added to the pulp in an amount of 3 ppm.
  • the output of this machine was about 200 tons per day.
  • the amount of resin adhering in the wire and press parts and the resin holes in the paper due to the resin adhering to the fiberizing roller were determined. The results obtained were compared to those of the "untreated" method and are shown in Table 8.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
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  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Abstract

A process for preparing mechanical pulp and/or paper containing the mechanical pulp is described, wherein an acylglycerol lipase is used. The process according to the invention avoids the problems caused by the resins in the preparation of mechanical pulp and/or paper containing said pulp.

Description

Diese Erfindung betrifft ein Verfahren zur Herstellung von mechanischem Holzstoff (wie Holzschliff, Refiner-Holzschliff usw.) und von Papier, das diesen Holzstoff enthält.This invention relates to a process for the manufacture of mechanical wood pulp (such as wood pulp, refiner wood pulp, etc.) and paper containing this wood pulp.

Mechanischer Holzstoff, wie Holzschliff, wird hergestellt, indem man Stammholz oder Hackschnitzel mechanisch behandelt, z.B. mit einem Holzschleifer oder Refiner schleift. Der erhaltene Holzstoff, der als Nachteil eine geringere Festigkeit aufweist, fällt aber in höherer Ausbeute an, ist billiger und ergibt im Vergleich zu Zellstoff, der unter Verwendung von Chemikalien, wie Alkali usw. hergestellt wird, ein undurchsichtigeres Papier. Weiter bleiben die Harzbestandteile des mechanischen Holzstoffs wegen des mechanischen Schleifens unverändert. Im allgemeinen enthält das Holz etwa 1-10 % Harzbestandteile neben den Hauptholzbestandteilen, Zellulose, Hemizellulose und Lignin.Mechanical wood pulp, such as wood pulp, is made by mechanically treating logs or wood chips, e.g. grinds with a wood sander or refiner. The wood pulp obtained, which has the disadvantage of a lower strength, is obtained in a higher yield, is cheaper and results in a more opaque paper compared to pulp which is produced using chemicals such as alkali, etc. Furthermore, the resin components of the mechanical pulp remain unchanged due to the mechanical grinding. Generally, the wood contains about 1-10% resin components in addition to the main wood components, cellulose, hemicellulose and lignin.

Diese Harzbestandteile sind je nach Holzart qualitativ und quantitativ verschieden. Das Nadelholz, ein Hauptausgangsmaterial des mechanischen Holzstoffs, enthält eine große Menge von Harzbestandteilen, wie Fettsäuren, Harzsäuren, Glyceriden usw. Ein Teil der Harzbestandteile wird vom Holzstoff ausgeschieden, so daß die Harze im Wasser schwebend oder auf der Faseroberfläche adsorbiert vorhanden sind. D.h., sie gehen von einem auf der Faser fixierten Zustand in einen ausgeschiedenen (freien) Zustand über. Das ausgeschiedene, im Rückwasser schwebende Harz, das als "kolloidales Harz" bezeichnet wird, besteht aus Harzteilchen von etwa 0,2-2 µm Größe.These resin components differ qualitatively and quantitatively depending on the type of wood. The softwood, a main raw material of mechanical pulp, contains a large amount of resin components such as fatty acids, resin acids, glycerides, etc. A part of the resin components is excreted from the wood pulp, so that the resins are suspended in water or adsorbed on the fiber surface. That is, they change from a state fixed on the fiber to an excreted (free) state. The precipitated resin floating in the backwater, which is referred to as "colloidal resin", consists of resin particles of approximately 0.2-2 μm in size.

Im allgemeinen wird Papier hergestellt, indem man die durch verschiedene Verfahren erzeugten Papierrohstoffe durch Sortierprozesse behandelt, verschiedene Additive zugibt und durch eine Papierherstellungsmaschine ein Blatt formiert.In general, paper is produced by treating the paper raw materials produced by various processes by sorting processes, adding various additives and forming a sheet by a paper-making machine.

In einer Reihe von Herstellungsprozessen wird das ausgeschiedene Harz oder das auf der Faser adsorbierte Harz auf Röhren, Bütten, Sieben, Walzen usw. abgelagert, so daß Harzschwierigkeit - Papierverschmutzung, Papierausschuß usw. - auftreten. Insbesondere treten die Harzschwierigkeiten oft bei Papier auf, das eine große Menge von mechanischem Holzstoff enthält.In a number of manufacturing processes, the separated resin or the resin adsorbed on the fiber is deposited on tubes, laid paper, sieves, rollers, etc., so that resin difficulty - paper soiling, scrap, etc. - occurs. In particular, the resin problems often occur with paper containing a large amount of mechanical pulp.

Zur Vermeidung der Harzschwierigkeiten dient das sog. "Seasoning", bei dem das Holz im Freien längere Zeit gelagert wird. Zur Vermeidung der Harzschwierigkeiten kann man auch oberflächenaktive Mittel verwenden, wie polyoxyethylenierte Alkyläther mit unterschiedlichem Polyoxyethylenierungsgrad, Alkylphenylderivate und Mittel, die diese als Hauptbestandteil enthalten, wie es in der JP-A-50-22606 beschrieben wurde.So-called "seasoning", in which the wood is stored outdoors for a long time, is used to avoid resin problems. To avoid resin problems, you can also use surfactants such as polyoxyethylenated alkyl ethers with different degrees of polyoxyethylenation, alkylphenyl derivatives and agents containing them as the main component as described in JP-A-50-22606.

Das erwähnte "Seasoning", das zur Abnahme der Menge an Harzbestandteilen im Holz aufgrund der Veränderung des Harzes durch Luftoxidation führt, hat die Nachteile, daß große Flächen und eine lange Zeit, wie 3-6 oder mehr Monate, benötigt werden. Daher ist es schwierig, nur durch das "Seasoning" die Harzschwierigkeiten zu vermeiden. In der GB-A-1 189 604 wird ein Verfahren beschrieben, das eine Kürzung der Dauer des "Seasonings" ohne Celluloseabbau durch vorherige Behandlung der Holzspäne mit Lipase-produzierenden Pilzen ermöglicht. Weder dieses Verfahren, das auf "Seasoning" unter schwer Kontrollierbaren Bedingungen beruht, noch die Zugabe der oberflächenaktiven Mittel, die zur Dispergierung der Harzmikroteilchen und zur Beseitigung der Harzablagerung führt, ist ausreichend, um die Harzschwierigkeiten zu vermeiden.The mentioned "seasoning", which leads to a decrease in the amount of resin components in the wood due to the change of the resin by air oxidation, has the disadvantages that large areas and a long time, such as 3-6 or more months, are required. It is therefore difficult to avoid the resin difficulties only by "seasoning". GB-A-1 189 604 describes a method which enables the duration of the "seasoning" to be shortened without cellulose degradation by prior treatment of the wood chips with lipase-producing fungi. Neither this method, which is based on "seasoning" under difficult to control conditions, nor the Addition of the surfactants, which leads to the dispersion of the resin microparticles and the removal of the resin deposit, is sufficient to avoid the resin problems.

Der Erfindung liegt daher die Aufgabe zugrunde, ein verbessertes Verfahren zur Gewinnung von mechanischem Holzstoff oder von Papier, das diesen Holzstoff enthält, zur Verfügung zu stellen. Dabei sollen insbesondere die Harzschwierigkeiten verringert werden.The object of the invention is therefore to provide an improved process for the production of mechanical wood pulp or of paper which contains this wood pulp. Resin difficulties in particular should be reduced.

Um ein wirksames Verfahren zur Vermeidung der Harzschwierigkeiten zu finden, haben die Erfinder sowohl die Holzbestandteile, die aus japanischer Rotkiefer, einer typischen Holzart für den mechanischen Holzstoff, extrahiert worden waren, als auch die Harzbestandteile untersucht, die bei der Herstellung des mechanischen Holzstoffs aus japanischer Rotkiefer oder des den mechanischen Holzstoff enthaltenden Papiers abgelagert wurden. Es hat sich gezeigt, daß der Hauptbestandteil des abgelagerten Harzes dem Harzbestandteil im ursprünglichen Holz gleich ist, und daß er reich an Triglyceriden, Fettsäuren, Harzsäuren und ihren Metallsalzen ist. Insbesondere enthält das abgelagerte Harz immer eine große Menge an Triglyceriden. Daher vermutet man, daß zur Hauptsache Triglyceride die Harzschwierigkeiten verursachen. Dieser Befund bestätigt die in der GB-A-1 189 604 enthaltenen Lehre.In order to find an effective method for avoiding the resin trouble, the inventors examined both the wood components extracted from Japanese red pine, a typical wood for mechanical wood pulp, and the resin components used in the production of the mechanical wood pulp from Japanese Red pine or the paper containing the mechanical wood pulp has been deposited. It has been found that the major constituent of the resin deposited is the same as the resin constituent in the original wood and is rich in triglycerides, fatty acids, resin acids and their metal salts. In particular, the deposited resin always contains a large amount of triglycerides. Therefore, it is believed that triglycerides mainly cause resin problems. This finding confirms the teaching contained in GB-A-1 189 604.

Während die Zersetzung der Triglyceride nach dem in der GB-A-1 189 604 beschriebenen Verfahren mehrere Tage in Anspruch nimmt, wurde nun folgendes gefunden:
Die Anwendung einer Acylglycerin-Lipase bewirkt die Zersetzung der Triglyceride, so daß Harzablagerungen vermieden werden, ohne die Stoff- und Papierqualität und die Operationsbedingungen nachteilig zu beeinflussen.While the decomposition of the triglycerides takes several days according to the process described in GB-A-1 189 604, the following has now been found:
The use of an acylglycerol lipase causes the triglycerides to decompose, so that resin deposits are avoided without adversely affecting the fabric and paper quality and the operating conditions.

Die Erfindung betrifft ein Verfahren zur Herstellung von mechanischem Holzstoff und/oder von den mechanischen Holzstoff enthaltenden Papier und ist dadurch gekennzeichnet, daß man den Papierrohstoff und/oder das Rückwasser mit einer Acylglycerin-Lipase, gegebenenfalls in immobilisierter Form, behandelt.
Vorzugsweise verwendet man als Acylglycerin-Lipase diejenige, die von mindestens einem Mikroorganismus aus der Gruppe Aspergillus niger, Pseudomonas fluorescenz, Pseudomonas fragi, Geotrichum candidum und Candida cylindracea produziert wird.The invention relates to a method for producing mechanical pulp and / or paper containing mechanical pulp and is characterized in that that the paper raw material and / or the backwater is treated with an acylglycerol lipase, optionally in immobilized form.
The acylglycerol lipase used is preferably that which is produced by at least one microorganism from the group Aspergillus niger, Pseudomonas fluorescenz, Pseudomonas fragi, Geotrichum candidum and Candida cylindracea.

Die erfindungsgemäße Acylglycerin-Lipase ist ein Enzym zur Hydrolyse der Triglyceride, eines Hauptbestandteils des Harzes. Beispiele für geeignete Acylglycerin-Lipasen unterliegen keinen besonderen Beschränkungen. Als Mikroorganismus, die das erfindungsgemäß zur Anwendung kommende Enzym produzieren, kann man z. B. folgende verwenden:
Aspergillus niger, Pseudomonas fluorescens, Pseudumonas fragi, Geotrichum candidum und Candida cylindracea, Mucor javanicus, Rhizopus javanicus, Rhizopus delemar, Rhizopus niveus und Pilzstämme der Gattung Rhizopus.The acylglycerol lipase according to the invention is an enzyme for the hydrolysis of the triglycerides, a main component of the resin. Examples of suitable acylglycerol lipases are not particularly limited. As a microorganism that produce the enzyme to be used according to the invention, z. B. Use the following:
Aspergillus niger, Pseudomonas fluorescens, Pseudumonas fragi, Geotrichum candidum and Candida cylindracea, Mucor javanicus, Rhizopus javanicus, Rhizopus delemar, Rhizopus niveus and fungal strains of the genus Rhizopus.

Je reiner die erfindungsgemäße Acylglycerin-Lipase ist, desto besser ist der Effekt. Man kann die erfindungsgemäß verwendeten Acylglycerin-Lipasen allein oder im Gemisch einsetzen, und sie können auch in Kombination mit anderen Zersetzungsenzymen, wie Cellulasen, Hemicellulasen, Proteasen usw. mit gutem Erfolg angewendet werden.The purer the acylglycerol lipase according to the invention, the better the effect. The acylglycerol lipases used according to the invention can be used alone or in a mixture, and they can also be used with good success in combination with other decomposition enzymes, such as cellulases, hemicellulases, proteases, etc.

Bei der Herstellung des mechanischen Holzstoffs oder des den mechanischen Holzstoff enthaltenden Papiers wird die erfindungsgemäße Acylglycerin-Lipase in einer Menge von 0,1-10000 ppm, bezogen auf das Gewicht des mechanischen Holzstoffs, zum Schlamm des Papierrohstoffs zugegeben, der den beim Schleifen des Holzes erzeugten mechanischen Holzstoff enthält. Dann wird der erhaltene Schlamm gerührt oder stehen gelassen, wobei die Temperatur bevorzugt bei 10-70 °C, insbesondere bevorzugt bei 35-55 °C liegt. Bei einer Temperatur unter 10 °C wirkt das erfindungsgemäße Enzym schwach und langsam. Bei einer Temperatur über 70 °C verliert das erfindungsgemäße Enzym seine Aktivität. Je mehr zugegeben wird, umso weniger Zeit wird für die Spaltung benötigt, wobei 0,1 ppm des Enzyms, bezogen auf das Gewicht des Triglycerides, ausreichend sind, und eine Menge über 10 000 ppm wirtschaftlich ungünstig ist. Weiter wird der pH-Wert vorzugsweise auf 3-11 eingestellt. Außerhalb dieses pH-Bereichs wird die Aktivität des Enzyms erniedrigt. Bei der Herstellung des Papierrohstoffs und des Papiers wird eine große Menge Wasser verwendet, wobei ein großer Teil davon umläuft und wiederverwendet wird. Weil dieses Rückwasser Holzbestandteile enthält, führt die Anwendung der erfindungsgemäßen Acylglycerin-Lipase bei diesem Rückwasser zur Vermeidung der Harzschwierigkeiten, wobei eine unmittelbare Zugabe einer Acylglycerin-Lipase zum Rückwasser, oder die Zugabe einer sog. immobilisierten Acylglycerin-Lipase oder eines sog. immobilisierten Mikroorganismus, der extrazellulär die Acylglycerin-Lipase erzeugt, mit gutem Effekt angewandt wird. In diesem Fall kann die Immobilisierung des Enzyms oder des Mikroorganismus auf bekannte Weise durch Verbindung mit einem Träger-, Vernetzungs-, Entrapmentverfahren usw., durchgeführt werden. Weil das erfindungsgemäße Verfahren sehr selektiv und mild verläuft, hat es die Vorteile, daß die behandelten Papierrohstoffe unverändert bleiben und der übliche Prozeß nicht beeinflußt wird.In the manufacture of mechanical wood pulp or of the paper containing the mechanical wood pulp, the acylglycerol lipase according to the invention is added in an amount of 0.1-10000 ppm, based on the weight of the mechanical wood pulp, to the sludge of the paper stock which contains the mechanical wood pulp produced during the sanding of the wood. The sludge obtained is then stirred or left to stand, the temperature preferably being 10-70 ° C., particularly preferably 35-55 ° C. At a temperature below 10 ° C, the enzyme according to the invention acts weakly and slowly. At a temperature above 70 ° C, the enzyme of the invention loses its activity. The more that is added, the less time is required for the cleavage, 0.1 ppm of the enzyme, based on the weight of the triglyceride, being sufficient, and an amount in excess of 10,000 ppm being economically disadvantageous. Furthermore, the pH is preferably adjusted to 3-11. Outside this pH range, the activity of the enzyme is reduced. A large amount of water is used in the manufacture of the paper stock and the paper, a large part of which is circulated and reused. Because this backwater contains wood components, the use of the acylglycerol lipase according to the invention leads to the avoidance of resin problems with this backwater, with a direct addition of an acylglycerol lipase to the backwater, or the addition of a so-called immobilized acylglycerol lipase or a so-called immobilized microorganism. which extracellularly produces the acylglycerol lipase, is used with a good effect. In this case, the Immobilization of the enzyme or the microorganism can be carried out in a known manner by connection with a carrier, crosslinking, entrapping process, etc. Because the process according to the invention is very selective and mild, it has the advantages that the treated paper raw materials remain unchanged and the usual process is not influenced.

Die Harzschwierigkeiten treten in einem komplizierten System auf, bei dem Stoffasern, Harze, Metallionen, Füllstoffe usw. im Gemisch vorliegen. Die Ursache für die Harzschwierigkeiten ist unklar, man vermutet jedoch, daß die Harzschwierigkeiten von der Harzkonzentration, Stoffkonzentration, dem pH-Wert, der Temperatur, Metallionenkonzentration und -art abhängen. Im allgemeinen wird die Adhäsion an der Feststoffoberfläche auf van-der-Waal'sche Kräfte zurückgeführt, die die Substanzen auf der Feststoffoberfläche fixieren. Die Wechselwirkung zwischen den Substanzen beruht u.a. auf einer hydrophoben Bindung oder einer Dipolmomentwirkung. Ein hydrophobes oder nichtpolares Molekül oder ein solcher Molekülteil wird von einer hydrophoben oder nichtpolaren Oberfläche angezogen. Ein hydrophiles oder polares Molekül wird dagegen von einer hydrophilen oder polaren Oberfläche angezogen. Bei der Ablagerung des Harzes in einem Prozeß zur Herstellung von Papierrohstoff und Papier scheinen die Triglyceride die folgende Rolle zu spielen. Das Triglycerid, ein nichtpolarer Bestandteil des kolloidalen Harzes, haftet an einer hydrophoben oder nichtpolaren Oberfläche, wie der Metalloberfläche von Röhren, der Oberfläche von Preßwalzen in einem Papierherstellungsprozeß usw. aufgrund der Van-der-Waal'schen Kräfte.Resin difficulties arise in a complex system in which fibers, resins, metal ions, fillers, etc. are mixed. The cause of the resin difficulties is unclear, but it is believed that the resin difficulties depend on the resin concentration, substance concentration, pH, temperature, metal ion concentration and type. In general, the adhesion to the solid surface is attributed to Van der Waal's forces that fix the substances on the solid surface. The interaction between the substances is based, among other things, on a hydrophobic bond or a dipole moment effect. A hydrophobic or non-polar molecule or such a part of the molecule is attracted to a hydrophobic or non-polar surface. A hydrophilic or polar molecule, on the other hand, is attracted to a hydrophilic or polar surface. The triglycerides appear to play the following role in depositing the resin in a process for making paper stock and paper. The triglyceride, a non-polar component of the colloidal resin, adheres to a hydrophobic or non-polar surface such as the metal surface of tubes, the surface of press rolls in a papermaking process, etc. due to Van der Waal's forces.

Der haftende Anteil wirkt als Kern, an dem hydrophobe oder nichtpolare Moleküle oder Molekülteile haften, wobei die Harzablagerungen gebildet werden.The adhesive portion acts as a core to which hydrophobic or non-polar molecules or parts of molecules adhere, the resin deposits being formed.

Die Wirkung der Acylglycerin-Lipase besteht darin, daß sie auf das nichtpolare Triglycerid einwirkt, das eine hohe Haftfähigkeit an einer hydrophoben und nichtpolaren Oberfläche besitzt und das in dem Harz an der Oberfläche des mechanischen Holzstoffs oder in dem Rückwasserharz und und kolloidalen Harz vorliegt. Die Triglyceride werden dabei zu wasserlöslichen Glycerolen und polaren Fettsäuren hydrolysiert, wodurch die Haftung an hydrophoben Metallröhren, Büttenwänden, Walzen usw. verhindert wird. Weil somit die Haftung des Harzes von Anfang an verhindert wird, bilden sich keine Harzablagerungen, so daß die Harzschwierigkeiten vermieden werden.The action of acylglycerol lipase is that it acts on the non-polar triglyceride, which has high adhesiveness to a hydrophobic and non-polar surface, and which is present in the resin on the surface of the mechanical pulp or in the backwater resin and and colloidal resin. The triglycerides are hydrolyzed to water-soluble glycerols and polar fatty acids, which prevents adhesion to hydrophobic metal tubes, laid walls, rollers, etc. Thus, since the adhesion of the resin is prevented from the beginning, no resin deposits are formed, so that the resin trouble is avoided.

Das erfindungsgemäße Verfahren hat die Vorteile, daß die Ablagerung der Harzbestandteile bei der Herstellung des mechanischen Holzstoffs oder des den mechanischen Holzstoff enthaltenden Papiers verhindert wird, und daß Mängel, wie Harzflecke und -löcher in einem Papierblatt usw., die durch das Harz verursacht werden, vermieden werden.The process of the present invention has the advantages that the deposition of the resin components in the manufacture of the mechanical pulp or the paper containing the mechanical pulp is prevented, and defects such as resin stains and holes in a paper sheet, etc. caused by the resin, be avoided.

Das erfindungsgemäße Verfahren hat keinen nachteiligen Einfluß auf die Papierqualität und die praktische Produktion, und es ist einfach und kann beim bisherigen Holzstoff- und Papierherstellungsprozeß angewendet werden.The method of the invention has no adverse impact on paper quality and practical production, and is simple and can be used in the previous pulp and paper making process.

Diese Erfindung wird durch folgende Beispiele erläutert. In den Beispielen wird die nicht mit dem erfindungsgemäßen Enzym behandelte Probe als "unbehandelt" bezeichnet.This invention is illustrated by the following examples. In the examples, the sample not treated with the enzyme according to the invention is referred to as "untreated".

Beispiel 1example 1

Frische japanische Rotkieferhackschnitzel wurden mit Methanol unter Verwendung eines Soxhlet-Extraktors extrahiert. 10 g des Extrakts wurden in einer Mischlösung von 100 ml Isopropanol, 60 ml Aceton und 5 ml Wasser aufgelöst, um eine Harzlösung zu erhalten.Fresh Japanese red pine chips were extracted with methanol using a Soxhlet extractor. 10 g of the extract was dissolved in a mixed solution of 100 ml of isopropanol, 60 ml of acetone and 5 ml of water to obtain a resin solution.

10 ml der Harzlösung und 0,6 g Aluminiumsulfat (als Feststoff) wurden in einen 1 l Wasser enthaltenden Becher eingeleitet und unter starken Rühren dispergiert, um eine Harzdispersion zu bilden. In diesem Fall beträgt die Ausbeute des mit Methanol extrahierten Harzes 4,7 %, bezogen auf das trockene Hackschnitzelgewicht, wobei dieses Harz 37,8 % Triglyceride enthält.10 ml of the resin solution and 0.6 g of aluminum sulfate (as a solid) were introduced into a 1-liter beaker and dispersed with vigorous stirring to form a resin dispersion. In this case the yield of the resin extracted with methanol is 4.7%, based on the dry wood chip weight, this resin containing 37.8% triglycerides.

Dann wurde die zubereitete Harzdispersion unter Verwendung von Salzsäure und/oder Natriumhydroxid auf einen pH-Wert von 7 eingestellt. Die Acylglycerin-Lipasen wurden dazu bei unterschiedlicher Konzentration und verschiedenen Temperaturen zugegeben, wie in Tabelle 1 gezeigt wird, und es wurde 4 Stunden gerührt, um die behandelte Lösung herzustellen.
Die behandelte Lösung wurde mit Aluminiumsulfat und Salzsäure auf einen pH-Wert von 4 eingestellt. Um die haftende Harzmenge gemäß Tapping Routine Control Method RC-324 zu bestimmen, wurden 2,5 cm eines Polyäthylenbrettes von 22 cm Breite und 7 cm Länge in die Lösung getaucht. Die eingestellte Lösung wurde 30 Minuten unter Verwendung eines Vibromischers (Linitator, hergestellt von U.S. Heidon Co.) gerührt. Dann wurde das Polyäthylenbrett extrahiert und getrocknet. Die haftende Harzmenge wurde berechnet und in Prozent , bezogen auf die haftende Harzmenge der unbehandelten Probe, angegeben.

Figure imgb0001
Figure imgb0002
 Then the prepared resin dispersion was adjusted to pH 7 using hydrochloric acid and / or sodium hydroxide. The acylglycerol lipases were added at different concentrations and temperatures, as in Table 1 is shown and stirred for 4 hours to prepare the treated solution.
The treated solution was adjusted to pH 4 with aluminum sulfate and hydrochloric acid. In order to determine the amount of resin adhering according to the Tapping Routine Control Method RC-324, 2.5 cm of a 22 cm wide and 7 cm long polyethylene board were immersed in the solution. The adjusted solution was stirred for 30 minutes using a vibromixer (linitator manufactured by US Heidon Co.). Then the polyethylene board was extracted and dried. The amount of adhesive resin was calculated and expressed as a percentage based on the amount of adhesive resin in the untreated sample.
Figure imgb0001
Figure imgb0002

Beispiel 2Example 2

Die in Beispiel 1 zubereitete Harzdispersion wurde unter Verwendung von Salzsäure und/oder Natriumhydroxid auf einen pH-Wert von 7 eingestellt. Die Acylglycerin-Lipase wurde in einer Menge von 500 ppm, bezogen auf das Harzgewicht, zugegeben und bei 40 °C gerührt. Nach der angegebenen Zeit wurde die haftende Harzmenge in gleicher Weise wie im Beispiel 1 berechnet; sie ist in Tabelle 2 gezeigt. Tabelle 2 Enzym Zeit Art Konzentration 2 Std. 4 Std. 8 Std. Unbehandelt - 105 mg (100 %) 101 mg (100 %) 107 mg (100 %) Li. OF 500 ppm 67 mg (63.8 %) 31 mg (30.7 %) 31 mg (24.4 %) Li. GC-55) 500 ppm 85 mg (81,0 %) 70 mg (69,3 %) 59 mg (55,1 %) (Anmerkung 5) Li. GC-5; Handelsname: Lipase GC-5 (hergestellt von Amano Seiyaku Co.), produziert von Geotrichum candidum. The resin dispersion prepared in Example 1 was adjusted to a pH of 7 using hydrochloric acid and / or sodium hydroxide. The acylglycerol lipase was added in an amount of 500 ppm based on the resin weight and stirred at 40 ° C. After the specified time, the amount of adhesive resin was calculated in the same manner as in Example 1; it is shown in Table 2. Table 2 enzyme time Art concentration 2 hours. 4 hours 8 hours Untreated - 105 mg (100%) 101 mg (100%) 107 mg (100%) Li. OF 500 ppm 67 mg (63.8%) 31 mg (30.7%) 31 mg (24.4%) Li. GC-5 5) 500 ppm 85 mg (81.0%) 70 mg (69.3%) 59 mg (55.1%) (Note 5) Li. GC-5; Trade name: Lipase GC-5 (manufactured by Amano Seiyaku Co.) produced by Geotrichum candidum.

Beispiel 3Example 3

1000 ml Schlamm, der 10 g Holzschliff von 63 ml CSF (Canadian Standard Freeness) enthielt, wurden aus japanischer Rotkiefer hergestellt. Die Acylglycerin-Lipasen wurden dazu in verschiedenen Konzentrationen zugegeben und bei verschiedenen pH-Werten in der gleichen Weise wie im Beispiel 1 behandelt. Die am Polyäthylenbrett haftende Harzmenge wurde wie im Beispiel 1 gemessen und wird in Tabelle 3 gezeigt. Tabelle 3 Enzym pH Art Konzentration7) 3 5 7 9 Unbehandelt 115 mg (100 %) 112 mg (100 %) 102 mg (100 %) 121 mg (100 %) Li. OF 10 ppm - - 90 mg (88,2 %) - 50 ppm 80 mg (67,8 %) 58 mg (51,8 %) 28 mg (27,5 %) 62 mg (51,2 %) 250 ppm - - 21 mg (20,6 %) - Li. B6) 10 ppm - - - 96 mg (79,3 %) 50 ppm 95 mg (80,5 %) 65 mg (58,3 %) 42 mg (41,2 %) 27 mg (22,3 %) 250 ppm - - - 24 mg (19,8 %) Li. A 50 ppm 84 mg (71,2 %) 66 mg (58,9 %) 49 mg (48,0 %) 88 mg (72,7 %) 40 °C, Behandlungszeit: 4 Stunden (Anmerkung 6) Li. B; Handelsname: Lipase B (hergestellt von Sapporo Breweries Limited.), produziert von Pseudomonas fragi 22-39B (Anmerkung 7) Konzentration: Enzymzugabekonzentration 1000 ml of sludge containing 10 g of wood pulp from 63 ml of CSF (Canadian Standard Freeness) was made from Japanese red pine. The acylglycerol lipases were added in different concentrations and treated at different pH values in the same way as in Example 1. The amount of resin adhered to the polyethylene board was measured as in Example 1 and is shown in Table 3. Table 3 enzyme pH Art Concentration 7) 3rd 5 7 9 Untreated 115 mg (100%) 112 mg (100%) 102 mg (100%) 121 mg (100%) Li. OF 10 ppm - - 90 mg (88.2%) - 50 ppm 80 mg (67.8%) 58 mg (51.8%) 28 mg (27.5%) 62 mg (51.2%) 250 ppm - - 21 mg (20.6%) - Li. B 6) 10 ppm - - - 96 mg (79.3%) 50 ppm 95 mg (80.5%) 65 mg (58.3%) 42 mg (41.2%) 27 mg (22.3%) 250 ppm - - - 24 mg (19.8%) Li. A 50 ppm 84 mg (71.2%) 66 mg (58.9%) 49 mg (48.0%) 88 mg (72.7%) 40 ° C, treatment time: 4 hours (Note 6) Li. B; Trade name: Lipase B (manufactured by Sapporo Breweries Limited.), Produced by Pseudomonas fragi 22-39B (Note 7) Concentration: enzyme addition concentration

Beispiel 4Example 4

Die gleiche Probe wie in Beispiel 3 wurde verwendet. Das erfindungsgemäße Enzym wurde zur Probe in einer Menge von 50 ppm, bezogen auf das Holzstoffgewicht, zugegeben und während unterschiedlicher Dauer bei verschiedenen Temperaturen behandelt.
Die haftende Harzmenge wurde gemessen und wird in Tabelle 4 gezeigt. Tabelle 4 Enzym pH Behandlungszeit Temperatur 20 °C 40 °C 60 °C Unbehandelt - 115 mg (100 %) 102 mg (100 %) 117 mg (100 %) Li. OF 7 2 Std. - 44 mg (53,9 %) - 4 Std. 64 mg (55,7 %) 29 mg (28,4 %) 100 mg (85,5 %) 8 Std. - 27 mg (26,5 %) - Unbehandelt 9 - 128 mg (100 %) 121 mg (100 %) 134 mg (100 %) Li. B 2 Std. - - 43 mg (32,3 %) 4 Std. 97 mg (75,8 %) 27 mg (22,3 %) 26 mg (19,4 %) 8 Std. - - 25 mg (18,7 %) The same sample as in Example 3 was used. The enzyme according to the invention was added to the sample in an amount of 50 ppm, based on the weight of the wood pulp, and treated at different temperatures for different periods.
The amount of adhesive resin was measured and is shown in Table 4. Table 4 enzyme pH Treatment time temperature 20 ° C 40 ° C 60 ° C Untreated - 115 mg (100%) 102 mg (100%) 117 mg (100%) Li. OF 7 2 hours. - 44 mg (53.9%) - 4 hours 64 mg (55.7%) 29 mg (28.4%) 100 mg (85.5%) 8 hours - 27 mg (26.5%) - Untreated 9 - 128 mg (100%) 121 mg (100%) 134 mg (100%) Li. B 2 hours. - - 43 mg (32.3%) 4 hours 97 mg (75.8%) 27 mg (22.3%) 26 mg (19.4%) 8 hours - - 25 mg (18.7%)

Beispiel 5Example 5

1000 ml eines 1%igen Stoffschlamms, der aus 20 % Altzeitungspapierstoff (105 ml CSF), 25 % Holzschliff (63 ml CSF), 25 % thermomechanischem Holzstoff (107 ml CSF) und 30 % Sulfatzellstoff bestand, wurde als Probe verwendet. Das erfindungsgemäße Enzym wurde dazu in einer Menge von 50 ppm, bezogen auf das Stoffgewicht, zugegeben und 4 Stunden bei 40 °C behandelt und 120 Minuten mit einem Vibromischer mit Polyäthylenbrett gerührt. Die haftende Harzmenge wurde gemessen und wird in Tabelle 5 gezeigt. Tabelle 5 Gehaftete Harzmenge Unbehandelt 65 mg (100 %) Li. OF 18 mg (27,7 %) 1000 ml of a 1% sludge consisting of 20% newsprint (105 ml CSF), 25% wood pulp (63 ml CSF), 25% thermomechanical wood pulp (107 ml CSF) and 30% sulfate pulp was used as a sample. To this end, the enzyme according to the invention was added in an amount of 50 ppm, based on the weight of the substance, and treated for 4 hours at 40 ° C. and stirred for 120 minutes with a vibromixer with a polyethylene board. The amount of adhesive resin was measured and is shown in Table 5. Table 5 Amount of resin stuck Untreated 65 mg (100%) Li. OF 18 mg (27.7%)

Beispiel 6Example 6

3000 ml Rückwasser bei der Filtration des Holzschliffs in der Sortierungsstufe bei japanischem Rotkieferschliff wurden als Probe verwendet. Das erfindungsgemäße Enzym wurde dazu in einer Menge von 0,5 ppm, bezogen auf das Rückwassergewicht, zugegeben, 2 Stunden bei 40 °C behandelt und 120 Minuten mit einem Vibromischer gerührt.3000 ml of backwater in the filtration of the wood pulp in the sorting stage for Japanese red pine polish were used as a sample. To this end, the enzyme according to the invention was added in an amount of 0.5 ppm, based on the weight of the return water, treated at 40 ° C. for 2 hours and stirred with a vibromixer for 120 minutes.

Die an dem Brett haftende Harzmenge wurde gemessen und wird in Tabelle 6 gezeigt. Tabelle 6 Gehaftete Harzmenge Unbehandelt 37 mg (100 %) Li. OF 7 mg (18,9 %) The amount of resin adhered to the board was measured and is shown in Table 6. Table 6 Amount of resin stuck Untreated 37 mg (100%) Li. OF 7 mg (18.9%)

Beispiel 7Example 7

Zeitungspapier mit einem Flächengewicht von etwa 46 g/m² wurde durch die Bel-Baie-Former-Multitrocknermaschine mit 5080 mm Breite und 830 m/min Geschwindigkeit hergestellt, wobei der Papierrohstoff aus 30 % Holzschliff, 45 % Altzeitungspapierstoff (ohne Druckerschwärze), 10 % Nadelholzsulfatzellstoff und 15 % thermomechanischem Holzstoff bestand. Der Holzschliff wurde aus Rotkiefer hergestellt, auf einen Mahlungsgrad von 60-70 ml CSF durch den Nachrefiner eingestellt, als Halbstoff einige Zeit gelagert, gegebenenfalls mit anderen Halbstoffen und Hilfsmitteln gemischt, wieder gelagert und zuletzt einem Papierherstellungsprozeß unterworfen. Es dauert 90 Minuten vom Nachrefiner durch die Bütten und Behälter zur Papiermaschine. Das erfindungsgemäße Enzym wurde zum Holzschliffschlamm von 3,8 % Konzentration vor dem Nachrefiner so zugegeben, daß die Lipase OF eine Konzentration von 3 ppm hatte. Dieses Enzym wurde zwei Wochen lang fortlaufend zum Holzschliff zugegeben. Die an Sieb- und Presseteilen haftende Harzmenge und der Zeitabstand zwischen den zur Entfernung des an der Mittelwalze haftenden Harzes erforderlichen Reinigungsvorgängen wurden bestimmt. Der Ausstoß dieser Maschine war etwa 200 Tonnen pro Tag.Newsprint with a basis weight of approximately 46 g / m² was produced by the Bel-Baie-Former multi-dryer machine with a width of 5080 mm and a speed of 830 m / min, the paper raw material being made from 30% wood pulp, 45% old newspaper paper stock (without printer's ink), 10% Softwood sulfate pulp and 15% thermomechanical pulp existed. The wood pulp was made from red pine, adjusted to a grinding level of 60-70 ml CSF by the post-refiner, stored as a pulp for some time, optionally mixed with other pulps and auxiliaries, stored again and finally subjected to a paper manufacturing process. It takes 90 minutes from the refiner through the laid paper and containers to the paper machine. The enzyme according to the invention was added to the wood pulp sludge of 3.8% concentration before the post-refiner so that the lipase OF had a concentration of 3 ppm. This enzyme was continuously added to the wood pulp for two weeks. The amount of resin adhering to the wire and press parts and the time interval between the cleaning operations required to remove the resin adhering to the center roller were determined. The output of this machine was about 200 tons per day.

Die Beseitigung des haftenden Harzes muß regelmäßig erfolgen, um eine vermehrte Haftung des Harzes an der Zenterwalze zu vermeiden. Der Zeitabstand zwischen den Reinigungsvorgängen wird mit zunehmender, anhaftender Harzmenge kürzer. Die erhaltenen Ergebnisse wurden mit denjenigen eines "unbehandelten" Verfahrens verglichen und werden in Tabelle 7 gezeigt. Tabelle 7 Unbehandelt Li. OF Haftende Harzmenge (g/Tag) Max. 895 89 Min. 73 0 Durchschnitt 207 43 Zeitabstand zwischen den Reinigungsvorgängen (Minuten) Max. 120 240 Min. 30 120 Durchschnitt 80 170 The adhesive resin must be removed regularly in order to avoid increased adhesion of the resin to the centering roller. The time interval between cleaning processes becomes shorter as the amount of resin adheres. The results obtained were compared to those of an "untreated" process and are shown in Table 7. Table 7 Untreated Li. OF Adhesive amount of resin (g / day) Max. 895 89 Min. 73 0 average 207 43 Time interval between cleaning processes (minutes) Max. 120 240 Min. 30th 120 average 80 170

Beispiel 8Example 8

Ein leichtgewichtiges Druckpapier mit einem Flächengewicht von 34 g/m² wurde gemäß Beispiel 7 hergestellt, wobei der Papierrohstoff aus 20 % Holzschliff, 50 % Altzeitungspapierstoff (ohne Druckerschwärze), 15 % Nadelholzsulfatzellstoff und 15 % thermomechanischem Holzstoff bestand. In diesem Fall wurde die Lipase OF zum Holzschliffschlamm in einer Menge von 3 ppm zugegeben. Der Ausstoß dieser Maschine war etwa 200 Tonnen pro Tag. Die haftende Harzmenge in den Sieb- und Presseteilen und die Harzlöcher des Papiers aufgrund der Haftung des Harzes an der Zerfaserwalze wurden bestimmt. Die erhaltenen Ergebnisse wurden mit denjenigen des "unbehandelten" Verfahrens verglichen und werden in Tabelle 8 gezeigt. Tabelle 8 Unbehandelt Li. OF Haftende Harzmenge (g/Tag) Max. 590 98 Min. 132 15 Durchschnitt 221 47 Anzahl der Harzlöcher (pro Tag) Max. 65 14 Min. 13 0 Durchschnitt 38 6 * Diese Zahlen beziehen sich auf den aus der Zerfaserwalze kommenden Papierstreifen A light-weight printing paper with a basis weight of 34 g / m 2 was produced according to Example 7, the paper stock consisting of 20% wood pulp, 50% old newspaper paper stock (without printing ink), 15% softwood sulfate pulp and 15% thermomechanical wood pulp. In this case, the Lipase OF was added to the pulp in an amount of 3 ppm. The output of this machine was about 200 tons per day. The amount of resin adhering in the wire and press parts and the resin holes in the paper due to the resin adhering to the fiberizing roller were determined. The results obtained were compared to those of the "untreated" method and are shown in Table 8. Table 8 Untreated Li. OF Adhesive amount of resin (g / day) Max. 590 98 Min. 132 15 average 221 47 Number of resin holes (per day) Max. 65 14 Min. 13 0 average 38 6 * These numbers refer to the paper strip coming out of the shredding roller

Claims (6)

  1. Process for preparing mechanical pulp and/or paper which contains the mechanical pulp characterised in that one treats the paper raw material and/or the return water with an acyl glycerine lipase.
  2. Process according to Claim 1 characterised in that one uses an acyl glycerine lipase which is produced by at least one micro-organism which is selected from Aspergillus niger, Pseudomonas fluorescens, Pseudomonas fragi, Geotrichum candidum and Candida cylindracea.
  3. Process according to Claim 1 or 2 characterised in that the acyl glycerin lipase is added in a quantity of 0.1-1000 ppm taken on the weight of the mechanical pulp.
  4. Process according to one of Claims 1 to 3 characterised in that the treatment of the paper raw material and/or the return water takes place at 10-70°C.
  5. Process according to Claim 4 characterised in that the treatment of the paper raw material and/or the return water takes place at 35-55°C.
  6. Process according to one of Claims 1 to 5 characterised in that the pH value of the paper raw material and/or of the return water is adjusted to 3-11.
EP89122946A 1988-12-13 1989-12-12 Process for preparing mechanical pulp and for paper containing said pulp Expired - Lifetime EP0374700B1 (en)

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DE (1) DE58907179D1 (en)
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ZA904441B (en) * 1989-06-22 1991-03-27 Int Paper Co Enzymatic delignification of lignocellulosic material
NZ235983A (en) * 1989-11-08 1993-01-27 Novo Nordisk As Process for hydrolysis of resins in lignocellulosic pulp using enzymes simultaneously with peroxy bleaching; ctmp fluff-pulp and absorbent articles produced therefrom
FI88315C (en) * 1990-04-04 1993-04-26 Enso Gutzeit Oy FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA
GB9018426D0 (en) * 1990-08-22 1990-10-03 Sandoz Ltd Improvements in or relating to novel compounds
DK249990D0 (en) * 1990-10-17 1990-10-17 Novo Nordisk As PROCEDURE FOR ENZYMATIC PULP TREATMENT
JPH04240286A (en) * 1991-01-25 1992-08-27 Novo Nordisk As Method for preventing pitch trouble caused by heat resisting lipase
FI93230C (en) * 1991-03-22 1995-03-10 Genencor Int Europ Method for reducing resin difficulties in mechanical pulp
EP0579708B1 (en) * 1991-04-10 1998-11-04 Novo Nordisk A/S Lipase-catalyzed ester hydrolysis
US5616215A (en) * 1991-04-19 1997-04-01 Novo Nordisk A/S Method of making paper from pulp treated with lipase and an aluminum salt
US5667634A (en) * 1991-05-01 1997-09-16 Novo Nordisk A/S Method for controlling pitch deposits in papermaking process using lipase and polyelectrolyte
EP0583319B1 (en) * 1991-05-01 1995-07-12 Novo Nordisk A/S Lipase-catalyzed ester hydrolysis
US5256252A (en) * 1992-07-15 1993-10-26 Nalco Chemical Company Method for controlling pitch deposits using lipase and cationic polymer
FR2727130B1 (en) * 1994-11-21 1996-12-20 Elf Aquitaine PROCESS FOR THE ENZYMATIC PRETREATMENT OF WELLBORE
EP1038898A4 (en) 1998-10-13 2002-01-09 Mitsui Chemicals Inc Binder composition and process for manufacturing board by using the binder composition
US7226770B2 (en) 2000-04-28 2007-06-05 Novozymes A/S Lipolytic enzyme variant
DE60231700D1 (en) 2001-01-10 2009-05-07 Novozymes As VARIANT OF A LIPOLYTIC ENZYME
EP1924744A2 (en) * 2005-09-13 2008-05-28 JohnsonDiversey Inc. Processes used in the manufacture of paper products
PT2864541T (en) * 2012-06-22 2017-07-24 Buckman Laboratories Int Inc Methods of using combinations of a lipase and an oxidant for pitch control in paper making processes and products thereof
ES2956266T3 (en) 2013-07-19 2023-12-18 Danisco Us Inc Compositions and methods comprising a lipolytic enzyme variant

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CA758488A (en) * 1967-05-09 C. Jenness Lyle Process for treating paper pulp
GB1189604A (en) * 1965-07-20 1970-04-29 Mo Och Domsjoe Ab A process for Removing Resin Constituents from Wood Chips
JP2691735B2 (en) * 1988-07-29 1997-12-17 サンノプコ株式会社 Pitch adhesion prevention agent for papermaking

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AU4582289A (en) 1990-06-21
ES2052874T3 (en) 1994-07-16
FI96520C (en) 1996-07-10
CA2005087C (en) 1998-12-01
EP0374700A2 (en) 1990-06-27
DE58907179D1 (en) 1994-04-14
ATE102667T1 (en) 1994-03-15
NZ231637A (en) 1991-06-25
NO174433C (en) 1994-05-04
CA2005087A1 (en) 1990-06-13
NO894988D0 (en) 1989-12-12
NO174433B (en) 1994-01-24
EP0374700A3 (en) 1991-11-21
JPH0429794B2 (en) 1992-05-19
AU622738B2 (en) 1992-04-16
NO894988L (en) 1990-06-14
JPH02160997A (en) 1990-06-20
FI96520B (en) 1996-03-29

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