EP0418201B1 - Bleichen von Holzstoff mit Enzymen - Google Patents

Bleichen von Holzstoff mit Enzymen Download PDF

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Publication number
EP0418201B1
EP0418201B1 EP90810681A EP90810681A EP0418201B1 EP 0418201 B1 EP0418201 B1 EP 0418201B1 EP 90810681 A EP90810681 A EP 90810681A EP 90810681 A EP90810681 A EP 90810681A EP 0418201 B1 EP0418201 B1 EP 0418201B1
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EP
European Patent Office
Prior art keywords
pulp
lignin
composition according
wood pulp
wood
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90810681A
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English (en)
French (fr)
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EP0418201A3 (en
EP0418201A2 (de
Inventor
Beat Gysin
Theophile Griessmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sandoz AG
Original Assignee
Sandoz AG
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Publication date
Priority claimed from GB898920596A external-priority patent/GB8920596D0/en
Priority claimed from GB898920595A external-priority patent/GB8920595D0/en
Application filed by Sandoz AG filed Critical Sandoz AG
Publication of EP0418201A2 publication Critical patent/EP0418201A2/de
Publication of EP0418201A3 publication Critical patent/EP0418201A3/en
Application granted granted Critical
Publication of EP0418201B1 publication Critical patent/EP0418201B1/de
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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/147Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005Treatment of cellulose-containing material with microorganisms or enzymes

Definitions

  • This invention relates to a novel enzymatic composition for treating wood pulp, comprising at least one lignin-peroxidase derived from a fungus culture which is chemically modified so that it cannot be adsorbed onto the pulp.
  • the invention further provides a process for bleaching wood pulp which comprises treating the pulp with such an enzymatic composition and it also provides a process for treating waste water with such a composition.
  • Wood is a complex material which is composed of cellulose, hemicellulose and lignin along with other minor components.
  • the lignin is associated with and even covalently bound to a matrix of cellulose and hemicellulose.
  • lignin should be removed from the wood pulp since it reduces the strength, confers a brownish colour and imparts other undesirable characteristics to the finished product.
  • wood chips are first treated with sodium sulphide (Na2S) and sodium hydroxide (NaOH) to degrade the lignin substantially. This is called the sulphate or Kraft process.
  • other treatments may be of use e.g. the sulphite process.
  • the pulps obtained therefrom are called "chemical pulps".
  • Chemical pulp e.g. Kraft pulp usually contains about 4-12% by weight of residual lignin which gives the pulp a characteristic brown colour.
  • the kappa number which reflects the lignin content of the pulp is usually from 10 to 45, more frequently from 12 to 30.
  • the lignin content should be further reduced in one or more treatments or stages commonly referred to as bleaching.
  • bleaching Many industrial bleaching processes already exist but almost all of them are divided into two main parts: A complementary delignification followed by a "true bleaching" for improving the brightness level.
  • the complementary delignification typically starts with an oxygen stage or a chlorination-extraction step (C-E) stage or both.
  • Chlorination and extraction are usually carried out in sequence, first forming chlorinated lignin compounds which are then solubilized in the subsequent extraction step.
  • the objective is exclusively to delignify the pulp as very little brightening occurs at the C-E stage.
  • a complementary process for brightening the lignin may further include the use of components other than chlorine such as chlorine containing chemicals e.g. hypochlorite and chlorine dioxide; or oxygen and hydrogen peroxide.
  • E-1 effluents contain a very large number of chlorinated organic compounds which are hazardous for the environment e.g. dioxines. Also, due to their highly corrosive nature, it is quite difficult to recycle the effluents. Thus, from the environmental point of view, it is clear that new techniques for bleaching which may reduce pollution are highly desirable.
  • an enzymatic treatment may be usefully substituted for at least one of the chemical treatments involving chlorine compounds in pulp bleaching.
  • Lignin peroxidases also called ligninases
  • MnII-dependent peroxidase are enzymes of particular interest which are secreted by many microbial strains, especially filamentous fungi.
  • Phanerochaete chrysosporium is a fungus which produces essentially both types of peroxidases. These enzymes are able to modify the lignin content of wood so that lignin is released from the hemicellulose matrix or made releasable upon washing or extraction.
  • Lignin peroxidases have been described up to now as enzymes which require the presence of H2O2 to be effective in degrading lignin with the optional presence of oxygen.
  • EP 345715 A1 it is claimed that this system works without the use of oxygen but in the presence of ⁇ -hydroxy acids and detergents.
  • the peroxide needs to be produced in situ enzymatically.
  • DE 3636208 A1 it is claimed that certain oxidation and reducing agents have to be present and the redox potential has to be maintained at a certain level throughout the course of the reaction.
  • the processes described in these two patents are commercially not feasible because of the high costs of the co-substrates needed.
  • the invention provides an enzymatic composition for treating wood pulp comprising at least one lignin peroxidase derived from a fungal culture, which lignin peroxidase is chemically modified so that it cannot be adsorbed onto pulp.
  • bleaching process as used herein is meant a process for delignifying wood pulp or improving the whiteness or brightness of wood pulp or both.
  • lignin as used herein is meant not only natural, unmodified forms but also the forms as found in chemically treated pulps which are, in whole or in part, chemically modified by various agents such as those used in the Kraft, organosolv or sulphite pulping process and in the effluent of these processes.
  • lignin-degrading enzyme as used herein is meant to encompass peroxidases.
  • Preferred peroxidases are MnII-dependent peroxidases, and lignin peroxidases (also called ligninases).
  • Lignin-degrading peroxidases are secreted by many microbial strains particularly filamentous fungi.
  • lignin peroxidases as used herein is meant to encompass the crude enzyme preparation produced by the fungus under ligninolytic conditions as well as the individual lignin peroxidase isoenzymes from natural or recombinant producers.
  • lignin peroxidase of a white-rot fungus e.g. P. chrysosporium either from its native origin or in recombinant form.
  • the recombinant form of a lignin peroxidase of P. chrysosporium may be obtained as described in PCT patent application No. WO-A-88/02023.
  • a suitable culture medium is the nitrogen-limited BIII/glucose medium which contains 1.08 x 10 ⁇ 3 M ammonium tartrate, 1.47 x 10 ⁇ 2M KH2PO4, 2.03 x 10 ⁇ 3M MgSO 4. 7H2O, 6.8 x 10 ⁇ 4M CaCl2 ⁇ 2H2O, 2.96 x 10 ⁇ 6M thiamine ⁇ HCl and 10 ml ⁇ L ⁇ 1 of a trace element solution.
  • the trace element solution contains 7.8 x 10 ⁇ 3M nitrilo-acetic acid, 1.2 x 10 ⁇ 2M MgSO4 ⁇ 7HO2, 1.7 x 10 ⁇ 2M NaCl, 3.59 x 10 ⁇ 4M FeSO4 ⁇ 7H2O, 7.75 x 10 ⁇ 4M CoCl2, 9.0 x 10 ⁇ 4M CaCl2, 3.48 x 10 ⁇ 4M ZnSO4, 4 x 10 ⁇ 5M CuSO4 ⁇ 5H2O, 2.1 x 10 ⁇ 5M AlK(SO4)2 ⁇ 12H2O, 1.6 x 10 ⁇ 4M H3BO3, 4.1 x 10 ⁇ 5M NaMoO4 ⁇ 2H2O and 2.9 x 10 ⁇ 3M MnSO4 ⁇ H2O.
  • the lignin-degrading enzyme is chemically modified by covalent or non-covalent linkage to water-soluble or insoluble polymeric compounds which prevent the enzyme from being adsorbed onto pulp during the treatment.
  • Suitable polymeric compounds are for example, polyethylene glycol (PEG), polypropylene glycol (PPG), polyacrylamides and polymeric sugars of various degrees of polymerization and composition like CM-cellulose, cellulose, agarose, alginate and chitosan.
  • PEG is a preferred polymeric compound.
  • the enzyme may be deglycosylated so that the carbohydrate residues which are usually involved in the mechanism of adsorption are at least partially removed.
  • Deglycosylation may be performed by known methods, for example, by treating a sample of lignin-degrading enzyme with an enzyme such as an endoglycosidase capable of degrading carbohydrate residues on a glycoprotein.
  • composition of the invention may be produced by chemical modification of a crude extract, filtrate, or supernatant obtained from a fungal culture, preferably after concentration.
  • the enzymes may be purified from a fungal material before any chemical treatment. It is particularly advantageous to use lignin peroxidases from a species or strain which does not produce cellulases especially when the enzyme is not purified. Of preferred use is the lignin peroxidase of a white-rot fungus, e.g. P. chrysosporium as indicated above.
  • the process of the invention may be applied to a wide variety of wood pulps the residual lignin content of which is to be reduced.
  • Unbleached wood pulps which may be treated with the process of the invention are advantageously mechanical pulps, e.g. groundwood pulp, including the thermomechanical pulps such as thermomechanical pulps (TMP), chemimechanical pulps (CMP), chemithermomechanical pulps (CTMP) and chemical pulps (CP) such as sulphite and Kraft pulps, these latter being preferred.
  • the process of this invention is preferably carried out in the absence of added peroxide and in the presence of added oxygen.
  • Optimal enzyme concentration depends upon the commercial origin and type of pulp.
  • Wood pulp is advantageously submitted to alkaline extraction before being enzymatically treated.
  • the enzymatic treatment is advantageously carried out at a pulp consistency of from 0.1 % to 15 %, preferably of from 1 % to 5 %.
  • the pulp consistency is determined by a standard procedure as the dry weight of pulp after drying for 2 to 10 hours at about 105°C.
  • the unbleached wood pulp may be diluted with deionized water, fresh water or tap water during the bleaching process.
  • fresh water or tap water is preferred since it has been found that the characteristics of the water do not influence the final results.
  • fresh water is meant water pumped directly e.g. from lakes, ponds or rivers.
  • the period of time necessary for treating the pulp may greatly vary with respect to the quality of the substrate and the nature of the enzyme modification from a few minutes to several hours.
  • Optimal temperature and pH conditions should be adapted to the particular enzyme of use.
  • temperature is generally in the range from 20 to 50°C, preferably from 40 to 50 °C.
  • the pH of the system is usually in the range of from 2 to 5, preferably from 3 to 4.
  • the reaction time is usually 30 to 60 minutes.
  • extractants include, for example, bases such as alkali metal hydroxides, dimethylformamide, dioxane, acetone and alcohol.
  • bases such as alkali metal hydroxides, dimethylformamide, dioxane, acetone and alcohol.
  • a dilute aqueous sodium hydroxide extraction is generally preferred.
  • a typical extraction step may be carried out at a pulp consistency from 1 to 20%, preferably from 1 to 5% at a temperature between 40 and 60°C.
  • the final pH is preferably from 10 to 11.
  • Reaction time may be from 30 minutes to 3 hrs, preferably from 45 minutes to 2 hrs.
  • the extent of delignification of the pulp may be indicated by the Kappa number as measured in a standard method described in TAPPI Test Methods (Tappi, Atlanta, Ga.) Vol. 1, 1988 "Kappa number of pulp - T 236 cm 85".
  • the Kappa number is the volume (in millilitres) of 0.1N potassium permanganate solution consumed by one gram of moisture-free pulp under the conditions specified in the above method.
  • a lower Kappa number is desirable as it indicates that a smaller amount of lignin is present in the pulp.
  • Another similar process of particular interest involves also the treatment of aqueous waste water released from the pulping process of wood or from the bleaching process of wood pulp in order to further degrade the lignin component.
  • a typical waste water which may be treated with a lignin peroxidase in the exclusive presence of oxygen as a co-substrate is the E1 effluent of the Kraft process.
  • Crude lignin peroxidase from Phanerochaete chrysosporium was either produced according to published procedures (e.g. H. Janshekar, A. Fiechter; J. of Biotechnology 1988, 8 , 97-112) or purchased from Cultor Ltd., Helsinki; Finland.
  • the enzyme preparation prepared as described in Example 1 is then added to the pulp suspension and the reaction is then performed for one hour at 40°C. The reaction is terminated by filtration and a subsequent sodium hydroxide extraction as described above.
  • the degree of delignification is measured by determination of the Kappa number.
  • the lignin is also analytically detectable in the combined filtrate/alkaline extract e.g. by gel filtration high performance liquid chromatography using UV/Vis spectroscopy for detection.
  • a PEG modified bovine serum albumine prepared in the same way as the modified enzyme preparation, bovine Heme (Sigma Nr. H-2250), 10 ⁇ g/ml.
  • b 5 VAO-units/g pulp.
  • c 50 VAO-units/g pulp.
  • Example 2 is repeated using 50 VAO units/g pulp of the enzymatic mixture as prepared in Example 1 c). When added at the same concentration, the enzymatic mixture treated with endoglycosidase F is more effective in delignifying the pulp than a non-modified mixture.
  • reaction products were analysed by gel permeation high performance liquid chromatography (HPLC) on two serially connected TSK (GMP W&L, 7.8 x 300 mm) columns (Toya Soda, Japan).
  • HPLC gel permeation high performance liquid chromatography
  • the flow rate was 1 ml/min. and sodium carbonate (10 mM, pH 10.5) with 0.05% polyethylene glycol (PEG 6000) was used as eluent.
  • Absorption at 250, 310 and 360 nm was recorded using a diode array UV-detector.
  • the enzyme treated lignin was extensively modified. Substantial brightening of the lignin suspension was observed after the enzyme treatment. The UV absorption spectra at 250, 310 and 360 nm of the individual lignin components after separation by gel permeation chromatography was extensively altered.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Claims (7)

  1. Enzymatische Zusammensetzung zur Behandlung von Zellstoff, welche zumindest eine Lignin-Peroxidase, die von einer Pilzkultur stammt, umfasst und welche chemisch modifiziert ist, so dass sie nicht an den Zellstoff adsorbiert werden kann.
  2. Zusammensetzung nach Anspruch 1, worin die Lignin-Peroxidase mit einer wasserlöslichen oder unlöslichen polymeren Verbindung durch kovalente oder nichtkovalente Bindung assoziiert ist.
  3. Zusammensetzung nach Anspruch 1, umfassend eine Lignin-Peroxidase, die zumindest teilweise deglycosiliert ist.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3 ausgewählt aus einem Rohextrakt, einem Filtrat oder einem Überstand von Phanerochaete chrysosporium.
  5. Verfahren zum Bleichen von Zellstoff, welches die Behandlung von Zellstoff mit einer Zusammensetzung nach einem der Ansprüche 1 bis 4 umfasst.
  6. Verfahren nach Anspruch 5, welches in Abwesenheit von hinzugefügtem Peroxid und in Gegenwart von Sauerstoff durchgeführt wird.
  7. Verfahren zur Behandlung von Abwasser, das vom Zellaufschlussverfahren von Holz oder von der Bleichbehandlung von Zellstoff freigesetzt wird, welches die Behandlung des Abwassers mit einer Zusammensetzung gemäss einem der Ansprüche 1 bis 4 in Abwesenheit von einem Peroxid und in Gegenwart von Sauerstoff umfasst.
EP90810681A 1989-09-12 1990-09-10 Bleichen von Holzstoff mit Enzymen Expired - Lifetime EP0418201B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8920595 1989-09-12
GB898920596A GB8920596D0 (en) 1989-09-12 1989-09-12 Improvements in or relating to organic compounds
GB8920596 1989-09-12
GB898920595A GB8920595D0 (en) 1989-09-12 1989-09-12 Improvements in or relating to organic compounds

Publications (3)

Publication Number Publication Date
EP0418201A2 EP0418201A2 (de) 1991-03-20
EP0418201A3 EP0418201A3 (en) 1992-09-23
EP0418201B1 true EP0418201B1 (de) 1994-12-21

Family

ID=26295910

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90810681A Expired - Lifetime EP0418201B1 (de) 1989-09-12 1990-09-10 Bleichen von Holzstoff mit Enzymen

Country Status (10)

Country Link
EP (1) EP0418201B1 (de)
JP (1) JPH03104993A (de)
AU (1) AU646403B2 (de)
BR (1) BR9004525A (de)
CA (1) CA2025079A1 (de)
DE (1) DE69015294T2 (de)
ES (1) ES2067719T3 (de)
FI (1) FI904456A0 (de)
NO (1) NO178201C (de)
PT (1) PT95273A (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0691290A (ja) * 1991-10-11 1994-04-05 Kobe Steel Ltd パルプ漂白廃水の処理方法
JP2525704B2 (ja) * 1992-03-16 1996-08-21 日本製紙株式会社 積層板用原紙の製造法
US5369024A (en) * 1992-03-25 1994-11-29 The United States Of America As Represented By The Secretary Of Agriculture Xylanase from streptomyces roseiscleroticus NRRL-11019 for removing color from kraft wood pulps
US5498534A (en) * 1992-03-25 1996-03-12 The United States Of America As Represented By The Secretary Of Agriculture Method of removing color from wood pulp using xylanase from streptomyces roseiscleroticus NRRL B-11019
FI970158A (fi) * 1997-01-14 1998-07-15 Neste Oy Uusi kuitulevyliima
US6372464B1 (en) * 2000-06-19 2002-04-16 Novozymes Biotech, Inc. Polypeptides having peroxidase activity and nucleic acids encoding same
CN105082302A (zh) * 2015-03-31 2015-11-25 西南林业大学 一种高强度刨花板的制备方法
CN113957737A (zh) * 2021-11-10 2022-01-21 安徽鑫光新材料科技股份有限公司 一种秸秆生物法无污染制浆工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345715A1 (de) * 1988-06-08 1989-12-13 International Paper Company Enzymatische Delignifizierung von lignocellulosehaltigem Material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4690895A (en) * 1985-07-15 1987-09-01 Repligen Corporation Use of rLDM™ 1-6 and other ligninolytic enzymes in the bleaching of kraft pulp
JPH0671424B2 (ja) * 1986-03-18 1994-09-14 新王子製紙株式会社 リグニン分解酵素およびその製造方法
AU606081B2 (en) * 1986-09-12 1991-01-31 Sandoz Ag Recombinant ligninase
DE3636208A1 (de) * 1986-10-24 1988-05-05 Call Hans Peter Verfahren zur delignifizierung und bleichung von lignicellulosehaltigem bzw. ligninhaltigem material bzw. lignin durch enzymatische behandlung
US4830708A (en) * 1987-11-30 1989-05-16 Pulp And Paper Research Institute Of Canada Direct biological bleaching of hardwood kraft pulp with the fungus Coriolus versicolor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345715A1 (de) * 1988-06-08 1989-12-13 International Paper Company Enzymatische Delignifizierung von lignocellulosehaltigem Material

Also Published As

Publication number Publication date
ES2067719T3 (es) 1995-04-01
NO903924D0 (no) 1990-09-10
AU646403B2 (en) 1994-02-24
AU6232390A (en) 1991-03-21
DE69015294T2 (de) 1995-05-18
EP0418201A3 (en) 1992-09-23
EP0418201A2 (de) 1991-03-20
NO178201C (no) 1996-02-07
NO178201B (no) 1995-10-30
PT95273A (pt) 1991-05-22
CA2025079A1 (en) 1991-03-13
DE69015294D1 (de) 1995-02-02
JPH03104993A (ja) 1991-05-01
NO903924L (no) 1991-03-13
FI904456A0 (fi) 1990-09-10
BR9004525A (pt) 1991-09-10

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