WO1988003190A1 - Procede de production de cellulose a partir de matieres premieres contenant de la lignine - Google Patents

Procede de production de cellulose a partir de matieres premieres contenant de la lignine Download PDF

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Publication number
WO1988003190A1
WO1988003190A1 PCT/EP1987/000635 EP8700635W WO8803190A1 WO 1988003190 A1 WO1988003190 A1 WO 1988003190A1 EP 8700635 W EP8700635 W EP 8700635W WO 8803190 A1 WO8803190 A1 WO 8803190A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
enzymes
reaction
phenolic compounds
reducing agents
Prior art date
Application number
PCT/EP1987/000635
Other languages
German (de)
English (en)
Inventor
Hans-Peter Call
Original Assignee
Call Hans Peter
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Call Hans Peter filed Critical Call Hans Peter
Priority to HU875790A priority Critical patent/HUT50894A/hu
Priority to DE8787907315T priority patent/DE3784515D1/de
Priority to BR8707844A priority patent/BR8707844A/pt
Priority to AT87907315T priority patent/ATE86318T1/de
Priority to JP62506759A priority patent/JPH0718108B2/ja
Publication of WO1988003190A1 publication Critical patent/WO1988003190A1/fr
Priority to DK344888A priority patent/DK170810B1/da
Priority to NO882808A priority patent/NO175104C/no
Priority to CA000570948A priority patent/CA1336079C/fr
Priority to FI891909A priority patent/FI95289C/fi

Links

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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/228—Automation of the pulping processes
    • 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

Definitions

  • the invention relates to a method and a plant for the removal and / or conversion of lignin from lignooellulose-containing material.
  • the lingocellulose-containing material such as wood or annual plants, must be freed from the lignin, since this considerably improves the mechanical and physicochemical properties of the paper made from the cellulose.
  • Conventional processes work with high pressures and temperatures using environmentally harmful chemicals.
  • German Patent 3110117 discloses a process for the production of cellulose from wood or other plant fiber materials, in which the lignocellulose is produced using
  • the object of the present invention is to provide a method and a plant for removing and / or converting lignin from lignocellulose-containing material, in which the disadvantages of the use of microorganisms, enzymes and chemicals shown above are avoided.
  • This object is achieved in that a redox potential in the range of 200-500 mV is set by adding one or more oxidizing and / or reducing agents and / or salts and / or phenolic compounds to an acidic aqueous solution of the lignin-containing raw materials, then by adding enzymes, microorganisms, animal or plant cells started a lignin-degrading reaction with simultaneous bleaching, the reaction in a value oscillating around a constant redox potential value, constant temperature, constant pH value and with constant stirring for several hours.
  • the redox potential is preferably 250 to 350 mV.
  • it can be determined by means of a redox electrode and kept constant by means of a regulator and an actuator during the entire reaction time by adding oxidizing and / or reducing agents and / or salts and / or phenolic compounds and / or organic acids.
  • Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent.
  • Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents.
  • MnSO 4 and / or FeCl 2 is preferably suitable as the salt.
  • Veratryl alcohol can be used as the phenolic compound. Lactic acid, for example, is suitable as the organic acid.
  • Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These preferably include phenol oxidases, lallases and peroxidases.
  • the effectiveness of the method according to the invention can be increased by adding pectinases and / or hemicellulases.
  • those enzymes can be used which are obtained from the white rot fungus Phanerochaete chrysosporium. If necessary, Phanerochaete chrysosporium itself can also be added for the degradation process.
  • the pH in the process according to the invention is between 2 and 5. A pH of 3 is particularly preferred.
  • the temperature is 20 to 60 ° C.
  • the reaction is preferably carried out at 40 ° C. If the stated conditions of the process according to the invention are observed, a redox potential of 250-350 mV can be set! As a result, the lignin content of wheat straw (approx. 18% lignin content) can be reduced to almost 0%. Spruce wood (about 28-30% lignin content) can be broken down to similar end values. Surprisingly, these results can be achieved in 2 to 6 hours, in many cases even within 2 hours. This does not include the physical and / or chemical pretreatment that is particularly necessary when using wood or annual plants.
  • the redox potential is set by the ratio of the various substances added in the reaction vessel.
  • Addition of the oxidizing and reducing agents, the salts and the phenolic compounds can maintain a certain redox potential throughout the course of the reaction.
  • the aim of operating the redox system set in this way is to prevent repolymerization of the lignin.
  • the process also has a significant bleaching effect during the degradation and / or conversion reaction, which allows it to be done with significantly less pollution Bleach to work.
  • the method according to the invention is therefore also suitable as a bleaching or post-bending method for various processes.
  • the process can therefore also be used for the biological bleaching and biological wastewater treatment of pulp industry wastewater and other wastewater.
  • the method can be used wherever decolorization and detoxification of waste water is to be achieved.
  • Another advantage of the process according to the invention is the possibility of continuous process control.
  • the process can be carried out particularly economically if the used enzymes are reprocessed and returned to the reaction process. This goal can be achieved with the help of affinity chromatography.
  • the enzyme is passed over a separation column, purified there and returned to the reaction process.
  • the enzyme purification is carried out in the separation column by means of affinity chromatography.
  • new specific types of ligands have been developed, which are used together with the corresponding enzyme technology know-how.
  • ligands are described in patent application PCT / EP 87/00214.
  • phenolic compounds can be used here.
  • Protein-specific ligands are also suitable. Tannin is an example.
  • the method also relates to a plant for removing and / or converting lignin or its
  • Degradation products made from lignocellulose-containing material This consists of a reactor, a device for adding microorganisms or enzymes, a device for adding oxidizing agents, reducing agents, salts or phenolic compounds, a drain for the converted raw material, used oxidizing agents, reducing agents, Salts, phenolic compounds, enzymes and microorganisms, a device for the separation of dissolved and undissolved substances, a column for affinity chromatography, in which enzymes are reprocessed for the lignin degradation reaction and a reflux for the return of the reprocessed enzymes to the reactor. Filters or thickeners, for example, can be used as the device for separating dissolved and undissolved substances.
  • Microorganisms or enzymes are added to the reactor via the inflow 7.
  • the microorganisms or enzymes can optionally also be immobilized in the reactor.
  • Conventional fillers and carriers can be used for the immobilization.
  • Oxidizing agents, reducing agents, salts or phenolic compounds can be metered in via the inflow 4.
  • the dosage can be controlled depending on the respective redox potential.
  • a redox electrode must be attached to the reactor (not shown in the picture), by means of which the redox potential is continuously determined. By connecting to an appropriate control system, the redox potential can then be kept constant during the entire course of the reaction.
  • the raw materials are also added via the feed line 7.
  • Lignin and waste water containing lignin can also be treated in the plant according to the invention.
  • the lignin is broken down in the reactor with the aid of lignolytic enzymes or microorganisms. Enzymes which come from the fungus Phanerochaete chrysosporium are particularly suitable. Microorganisms are particularly suitable as cell-free and hemicellulase-free mutants. In particular, mutants of Phenerochaeta Chrysosporium can be used.
  • the converted raw material flows out of the reactor via the drain 8 together with the used chemicals, microorganisms or enzymes.
  • the mixture of substances is passed, for example, through a filter 3, where .solved and undissolved substances are separated from one another.
  • the enzyme-containing solution is passed through a chromatography column 2. This column works on the principle of affinity chromatography. Here the enzymes are reprocessed and then fed back to the reaction process via line 5.
  • the substances separated from the enzymes are discharged via line 6.
  • Special enzyme-specific ligands are used for affinity chromatography, especially phenolic compounds! Protein-specific ligands, in particular tannin, can also be used.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Audible-Bandwidth Dynamoelectric Transducers Other Than Pickups (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Un procédé et un appareil servent à transformer et/ou à extraire de la lignine ou ses produits de décomposition à partir de matériaux contenant de la lignine-cellulose. A cet effet, on maintient un potentiel redox compris ente 200 et 500 mV en ajoutant des agents oxydants et/ou réducteurs et/ou des sels et/ou des composés phénoliques à une solution acide aqueuse des matières premières contenant de la lignine. On fait démarrer la réaction de décomposition de la lignine en même temps que le blanchiment en ajoutant des enzymes, des micro-organismes, des cellules animales ou végétales. On maintient la reßction pendant plusieurs heures à un potentiel redox oscillant autour d'une valeur constante, à une température constante et sous agitation constante.
PCT/EP1987/000635 1986-10-24 1987-10-24 Procede de production de cellulose a partir de matieres premieres contenant de la lignine WO1988003190A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
HU875790A HUT50894A (en) 1986-10-24 1987-10-24 Method and apparatus for gaining cellulose from lignine-bearing matters
DE8787907315T DE3784515D1 (de) 1986-10-24 1987-10-24 Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen.
BR8707844A BR8707844A (pt) 1986-10-24 1987-10-24 Processo para a preparacao de celulose a partir de materias-primas contendo lignina
AT87907315T ATE86318T1 (de) 1986-10-24 1987-10-24 Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen.
JP62506759A JPH0718108B2 (ja) 1986-10-24 1987-10-24 リグニン含有原料からセルロースを製造する方法
DK344888A DK170810B1 (da) 1986-10-24 1988-06-23 Fremgangsmåde til fremstilling af cellulose fra l igninholdige råmaterialer
NO882808A NO175104C (no) 1986-10-24 1988-06-24 Fremgangsmåte for fjerning og/eller omdanning av lignin fra lignocelluloseholdig materiale
CA000570948A CA1336079C (fr) 1987-10-24 1988-06-30 Procede pour eliminer ou transformer la lignine
FI891909A FI95289C (fi) 1986-10-24 1989-04-21 Menetelmä selluloosan valmistamiseksi ligniinipitoisista materiaaleista

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3636208.5 1986-10-24
DE19863636208 DE3636208A1 (de) 1986-10-24 1986-10-24 Verfahren zur delignifizierung und bleichung von lignicellulosehaltigem bzw. ligninhaltigem material bzw. lignin durch enzymatische behandlung

Publications (1)

Publication Number Publication Date
WO1988003190A1 true WO1988003190A1 (fr) 1988-05-05

Family

ID=6312392

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1987/000635 WO1988003190A1 (fr) 1986-10-24 1987-10-24 Procede de production de cellulose a partir de matieres premieres contenant de la lignine

Country Status (11)

Country Link
EP (1) EP0327576B1 (fr)
JP (1) JPH0718108B2 (fr)
AT (1) ATE86318T1 (fr)
AU (1) AU605215B2 (fr)
BR (1) BR8707844A (fr)
DE (2) DE3636208A1 (fr)
DK (1) DK170810B1 (fr)
FI (1) FI95289C (fr)
HU (2) HU202938B (fr)
NO (1) NO175104C (fr)
WO (1) WO1988003190A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0429422A1 (fr) * 1989-11-17 1991-05-29 Enso-Gutzeit Oy Procédé de fabrication de pâte
EP0430915A1 (fr) * 1989-11-27 1991-06-05 Enso-Gutzeit Oy Procédé de fabrication de pâte de bois
EP0433258A1 (fr) * 1989-12-12 1991-06-19 Enso-Gutzeit Oy Procédé de fabrication de pâte
WO1991011552A1 (fr) * 1990-02-02 1991-08-08 Enso-Gutzeit Oy Procede de production de pulpes
EP0447672A1 (fr) * 1990-03-20 1991-09-25 LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERTRIEB VON ENZYMEN mbH Procédé pour le traitement de vieux papier par désencrage enzymatique
EP0447673A1 (fr) * 1990-03-20 1991-09-25 LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERTRIEB VON ENZYMEN mbH Procédé pour le blanchiment enzymatique de pâtes
WO1992009741A1 (fr) * 1990-12-03 1992-06-11 Enso-Gutzeit Oy Procede de blanchiment de pate
WO1992020857A1 (fr) * 1991-05-17 1992-11-26 Call Hans Peter Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases
WO1993007332A1 (fr) * 1991-10-10 1993-04-15 Valtion Teknillinen Tutkimuskeskus Procede de traitement enzymatique de matieres lignocellulosiques, notamment des pates de cellulose
US5338403A (en) * 1990-10-17 1994-08-16 Novo Nordisk A/S Hydrolysis of resin in pulp with an enzyme and a hydrosulfite
US5356517A (en) * 1989-11-08 1994-10-18 Novo Nordisk A/S Hydrolysis of resin in pulp with an enzyme and a peroxide
WO1997029237A1 (fr) * 1996-02-08 1997-08-14 Novo Nordisk A/S Procede d'accroissement de la charge d'un materiau ligno-cellulosique, produit obtenu selon ce procede et utilisation de ce produit pour l'elaboration d'un produit a base de ligno-cellulose
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
US5885412A (en) * 1993-12-23 1999-03-23 Bim Kemi Ab Inhibition of hydrogen peroxide decomposing enzymes during bleaching of cellulose fibers
US6824646B2 (en) 1999-03-23 2004-11-30 Oji Paper Co., Ltd. Process for oxygen bleaching and enzyme treating lignocellulosic pulp with liquid treatment and recovery
US6942754B2 (en) 1999-03-23 2005-09-13 Oji Paper Co., Ltd. Process for producing xylooligosaccharide from lignocellulose pulp
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA894239B (en) * 1988-06-08 1990-03-28 Int Paper Co Enzymatic delignification of lignocellulosic material
FI88316C (fi) * 1989-07-10 1993-04-26 Enso Gutzeit Oy Foerfarande foer blekning av cellulosamassa
FI904456A0 (fi) * 1989-09-12 1990-09-10 Sandoz Ag Foerfarande foer blekning av cellulosa.
EP0486125A1 (fr) * 1990-11-13 1992-05-20 JAPAN PULP & PAPER RESEARCH INSTITUTE, INC. Composition lignocellulolytique, procédé pour sa fabrication et son application
JPH04240287A (ja) * 1991-01-21 1992-08-27 Kobe Steel Ltd パルプの漂白方法
FI93230C (fi) * 1991-03-22 1995-03-10 Genencor Int Europ Menetelmä mekaanisen massan pihkavaikeuksien vähentämiseksi
AT400153B (de) * 1991-05-02 1995-10-25 Voest Alpine Ind Anlagen Verfahren zum bleichen von xylan- und lignocellulosehältigen materialien
JP3262646B2 (ja) * 1993-07-09 2002-03-04 日本製紙株式会社 パルプの漂白方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1262117B (de) * 1964-05-05 1968-02-29 Aschaffenburger Zellstoffwerke Verfahren zur Kontrolle der Bleiche mit Chlordioxyd
FR1524581A (fr) * 1966-05-25 1968-05-10 Solvay Procédé de réglage de la blancheur d'une pâte cellulosique traitée par le peroxyde d'hydrogène ou un produit similaire
EP0188053A2 (fr) * 1985-01-17 1986-07-23 Albert D. Friesen Purification de superoxyde dismutase

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1262117B (de) * 1964-05-05 1968-02-29 Aschaffenburger Zellstoffwerke Verfahren zur Kontrolle der Bleiche mit Chlordioxyd
FR1524581A (fr) * 1966-05-25 1968-05-10 Solvay Procédé de réglage de la blancheur d'une pâte cellulosique traitée par le peroxyde d'hydrogène ou un produit similaire
EP0188053A2 (fr) * 1985-01-17 1986-07-23 Albert D. Friesen Purification de superoxyde dismutase

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5356517A (en) * 1989-11-08 1994-10-18 Novo Nordisk A/S Hydrolysis of resin in pulp with an enzyme and a peroxide
EP0429422A1 (fr) * 1989-11-17 1991-05-29 Enso-Gutzeit Oy Procédé de fabrication de pâte
EP0430915A1 (fr) * 1989-11-27 1991-06-05 Enso-Gutzeit Oy Procédé de fabrication de pâte de bois
EP0433258A1 (fr) * 1989-12-12 1991-06-19 Enso-Gutzeit Oy Procédé de fabrication de pâte
WO1991011552A1 (fr) * 1990-02-02 1991-08-08 Enso-Gutzeit Oy Procede de production de pulpes
EP0447672A1 (fr) * 1990-03-20 1991-09-25 LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERTRIEB VON ENZYMEN mbH Procédé pour le traitement de vieux papier par désencrage enzymatique
DE4008894A1 (de) * 1990-03-20 1991-09-26 Call Hans Peter Verfahren zur altpapieraufbereitung mit enzymatischer druckfarbenentfernung
DE4008893A1 (de) * 1990-03-20 1991-09-26 Call Hans Peter Verfahren zum enzymatischen bleichen von zellstoffen
WO1991014820A1 (fr) * 1990-03-20 1991-10-03 Call Hans Peter Procede de traitement de vieux papiers avec elimination enzymatique de l'encre d'impression
WO1991014823A1 (fr) * 1990-03-20 1991-10-03 Call Hans Peter Procede de blanchiment enzymatique de celluloses
EP0447673A1 (fr) * 1990-03-20 1991-09-25 LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERTRIEB VON ENZYMEN mbH Procédé pour le blanchiment enzymatique de pâtes
AU641494B2 (en) * 1990-03-20 1993-09-23 Hans-Peter Call Process for the enzymatic bleaching of celluloses
AU652358B2 (en) * 1990-03-20 1994-08-25 Hans-Peter Call Process for processing waste paper with enzymatic removal of printing ink
US5338403A (en) * 1990-10-17 1994-08-16 Novo Nordisk A/S Hydrolysis of resin in pulp with an enzyme and a hydrosulfite
WO1992009741A1 (fr) * 1990-12-03 1992-06-11 Enso-Gutzeit Oy Procede de blanchiment de pate
WO1992020857A1 (fr) * 1991-05-17 1992-11-26 Call Hans Peter Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases
WO1993007332A1 (fr) * 1991-10-10 1993-04-15 Valtion Teknillinen Tutkimuskeskus Procede de traitement enzymatique de matieres lignocellulosiques, notamment des pates de cellulose
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
US5885412A (en) * 1993-12-23 1999-03-23 Bim Kemi Ab Inhibition of hydrogen peroxide decomposing enzymes during bleaching of cellulose fibers
WO1997029237A1 (fr) * 1996-02-08 1997-08-14 Novo Nordisk A/S Procede d'accroissement de la charge d'un materiau ligno-cellulosique, produit obtenu selon ce procede et utilisation de ce produit pour l'elaboration d'un produit a base de ligno-cellulose
US6187136B1 (en) 1996-02-08 2001-02-13 Novo Nordisk A/S Process for increasing the charge on a lignocellulosic material
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
US6824646B2 (en) 1999-03-23 2004-11-30 Oji Paper Co., Ltd. Process for oxygen bleaching and enzyme treating lignocellulosic pulp with liquid treatment and recovery
US6942754B2 (en) 1999-03-23 2005-09-13 Oji Paper Co., Ltd. Process for producing xylooligosaccharide from lignocellulose pulp

Also Published As

Publication number Publication date
BR8707844A (pt) 1989-10-03
HU202938B (en) 1991-04-29
FI95289B (fi) 1995-09-29
DK170810B1 (da) 1996-01-22
DK344888D0 (da) 1988-06-23
DE3784515D1 (de) 1993-04-08
DE3636208A1 (de) 1988-05-05
ATE86318T1 (de) 1993-03-15
FI95289C (fi) 1996-01-10
JPH02500990A (ja) 1990-04-05
HUT50894A (en) 1990-03-28
FI891909A (fi) 1989-04-21
AU605215B2 (en) 1991-01-10
DK344888A (da) 1988-06-23
NO175104C (no) 1994-08-31
JPH0718108B2 (ja) 1995-03-01
AU8230387A (en) 1988-05-25
EP0327576A1 (fr) 1989-08-16
EP0327576B1 (fr) 1993-03-03
NO175104B (no) 1994-05-24
FI891909A0 (fi) 1989-04-21
NO882808L (no) 1988-06-24
NO882808D0 (no) 1988-06-24

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