NO180388B - Process for enzymatic bleaching of cellulose - Google Patents
Process for enzymatic bleaching of cellulose Download PDFInfo
- Publication number
- NO180388B NO180388B NO923601A NO923601A NO180388B NO 180388 B NO180388 B NO 180388B NO 923601 A NO923601 A NO 923601A NO 923601 A NO923601 A NO 923601A NO 180388 B NO180388 B NO 180388B
- Authority
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- Norway
- Prior art keywords
- bleaching
- added
- sulphate
- cellulose
- reaction
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004061 bleaching Methods 0.000 title claims abstract description 24
- 229920002678 cellulose Polymers 0.000 title claims abstract description 22
- 239000001913 cellulose Substances 0.000 title claims abstract description 21
- 230000002255 enzymatic effect Effects 0.000 title claims abstract description 6
- 108090000790 Enzymes Proteins 0.000 claims abstract description 15
- 102000004190 Enzymes Human genes 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000002479 lignolytic effect Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- OEGPRYNGFWGMMV-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC OEGPRYNGFWGMMV-UHFFFAOYSA-N 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000004128 Copper(II) sulphate Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- -1 heme compounds Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229960001922 sodium perborate Drugs 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims description 2
- 102000001554 Hemoglobins Human genes 0.000 claims description 2
- 108010054147 Hemoglobins Proteins 0.000 claims description 2
- 108010029541 Laccase Proteins 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 108700020962 Peroxidase Proteins 0.000 claims description 2
- 102000003992 Peroxidases Human genes 0.000 claims description 2
- 108010059820 Polygalacturonase Proteins 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 108010093305 exopolygalacturonase Proteins 0.000 claims description 2
- 108010002430 hemicellulase Proteins 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 150000002889 oleic acids Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims 2
- 229960003330 pentetic acid Drugs 0.000 claims 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 9
- 229920005610 lignin Polymers 0.000 description 8
- 241000222393 Phanerochaete chrysosporium Species 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 210000004671 cell-free system Anatomy 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JXNCBISRWFPKJU-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O JXNCBISRWFPKJU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- D21C9/00—After-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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
-
- 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
- D21C9/00—After-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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
- D21C9/1089—Bleaching ; Apparatus therefor with reducing compounds with dithionites
-
- 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
- D21C9/00—After-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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
-
- 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
- D21C9/00—After-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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
- D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
-
- 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
- D21C9/00—After-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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Landscapes
- 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)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en fremgangsmåte for en enzymatisk bleking av cellulose. The present invention relates to a method for an enzymatic bleaching of cellulose.
De til nå kjente biologiske fremgangsmåtene for cellulose-fremstilling arbeider med mikroorganisme, særlig sopp. Det er således kjent fra DE-PS 31 10 117 en fremgangsmåte for utvinning av cellulose fra tre eller annet plantefibermate-riale, der lignocellulosen blir nedbrutt ved hjelp av hvitråtesopp. Fremgangsmåten som arbeider med mikroorganismer medfører imidlertid betydelige ulemper. Fremgangsmåten innebærer samtidig vekst av mikroorganismer og tap av cellulose for å oppnå en nedbrytning og løsgjøring av lignin fra sine medfølgende polymerer (cellulose). Gjennom den samtidige veksten opptrer meget lange nedbrytningsperloder, og disse kan vare i flere uker. The hitherto known biological methods for cellulose production work with micro-organisms, in particular fungi. It is thus known from DE-PS 31 10 117 a method for extracting cellulose from wood or other plant fiber material, where the lignocellulose is broken down with the help of white rot fungi. However, the method that works with microorganisms entails significant disadvantages. The method involves simultaneous growth of microorganisms and loss of cellulose to achieve a breakdown and release of lignin from its accompanying polymers (cellulose). Through the simultaneous growth, very long periods of decomposition occur, and these can last for several weeks.
På grunn av de nevnte vanskelighetene er det i de siste årene blitt undersøkt mikroorganismer med anvendelsesmulighet for isolerte enzymsystemer. Særlig er det blitt forsket på enzymene fra hvitråtesoppen Phanerochaete chrysosporium og flere enkeltheter er oppklart. Således er det kjent fra "Biotechnology in the Pulp and Paper Industry, 3. Inter-national Conference, Stockholm 1986", at ved nedbrytning av lignin ligger likevekten i reaksjonen på polymerisasjons-siden, dvs. cellefrie systemer bryter ikke ned lignin hhv. polymeriserer den. Due to the aforementioned difficulties, in recent years, microorganisms with potential applications for isolated enzyme systems have been investigated. In particular, research has been carried out on the enzymes from the white rot fungus Phanerochaete chrysosporium and several details have been clarified. Thus, it is known from "Biotechnology in the Pulp and Paper Industry, 3rd International Conference, Stockholm 1986", that when breaking down lignin, the equilibrium in the reaction lies on the polymerization side, i.e. cell-free systems do not break down lignin or polymerizes it.
Fra litteraturen er det siden oppdagelse av de lignolyttiske enzymene i hvitråtesoppen Phanerochaete chrysosporium kjent en rekke enzymatiske fremgangsmåter for bleking av cellulose med levende soppsystemer og også av cellefrie systemer. Likeledes er det blitt foretatt en rekke forsøk å bleke med hemsystemet ("Håmsystemen"). Alle disse systemene krever reaksjonstid på mer enn 12 timer. Det vil si disse systemene har det felles at det er et stort tidsforbruk og høye kostnader. Det sistnevnte inntrer særlig for de rene hemsystemene. Since the discovery of the lignolytic enzymes in the white rot fungus Phanerochaete chrysosporium, a number of enzymatic methods for bleaching cellulose with living fungal systems and also with cell-free systems have been known from the literature. Likewise, a number of attempts have been made to bleach with the hem system ("Håmsystemen"). All these systems require a reaction time of more than 12 hours. That is to say, these systems have in common that there is a large consumption of time and high costs. The latter occurs particularly for the pure heme systems.
I dag blir en bleking gjennomført rent kjemisk i flere trinn under tilsetning av klor. Klorbleklngen er imidlertid forbundet med store miljøproblemer. Ved blekefremgangsmåter blir kappatallet generelt redusert ved fjerning av de dannede kromofore restlignin-kondensasjonsproduktene som forekommer under kokeprosessen for ligninfjerning, dvs. 1ignininnholdet blir senket slik at cellulosen blir lysere. Today, bleaching is carried out purely chemically in several stages with the addition of chlorine. However, chlorine bleaching is associated with major environmental problems. In bleaching processes, the kappa number is generally reduced by removing the formed chromophoric residual lignin condensation products that occur during the cooking process for lignin removal, i.e. the ignin content is lowered so that the cellulose becomes lighter.
Foreliggende oppfinnelse hår således som oppgave å stille til rådighet en fremgangsmåte for enzymatisk bleking av cellulose, som ikke oppviser de nevnte ulempene ved biologisk og kjemisk bleking. The object of the present invention is therefore to provide a method for enzymatic bleaching of cellulose, which does not exhibit the aforementioned disadvantages of biological and chemical bleaching.
Oppfinnelsen angår således en fremgangsmåte for enzymatisk bleking av cellulose, der det The invention thus concerns a method for enzymatic bleaching of cellulose, where it
a) under samtidig tildosering av oksidasjons- og reduksjonsmidler og tilsats av salter til en vandig oppløsning a) during simultaneous addition of oxidizing and reducing agents and addition of salts to an aqueous solution
blir innstilt et redokspotensiale i området mellom 200 og a redox potential is set in the range between 200 and
5 00 mV og 5 00 mV and
b) ved tilsetning av lignolyttiske enzymer blir det startet en blekereaksjon, b) by adding lignolytic enzymes, a bleaching reaction is started,
kjenntegnet ved at den vandige celluloseholdige oppløsningen blir tilsatt kobber(II)sulfat eller en blanding av kobb-er(II)sulfat med Mn(II)sulfat, Mn(II)acetat, Fe(II)sulfat, Ti(III )klorid, Ce(III)nitrat og/eller Ce(IV)ammoniumnitrat, at det også tilsettes kompleksdannere, og at reaksjonen blir opprettholdt under permanent omrøring i 15 minutter til 2 timer, og det eventuelt også tilsettes polysakkarider, detergenter, tensider, fettsyre, hemforbindelser og/eller blekereagenser. characterized by the addition of copper (II) sulphate or a mixture of copper (II) sulphate with Mn (II) sulphate, Mn (II) acetate, Fe (II) sulphate, Ti (III) chloride to the aqueous cellulose-containing solution, Ce(III) nitrate and/or Ce(IV) ammonium nitrate, that complex formers are also added, and that the reaction is maintained under permanent stirring for 15 minutes to 2 hours, and that polysaccharides, detergents, surfactants, fatty acid, heme compounds and /or bleaching reagents.
Gjennom denne fremgangsmåtegjennomføringen forhindrer man en repolymerisering av lignin og gjør en depolymerisering først mulig. By carrying out this process, repolymerisation of lignin is prevented and depolymerisation is first possible.
Redokspotensialet ligger fortrinnsvis mellom 250 og 450 mV. Det kan ifølge fremgangsmåten i oppfinnelsen bli målt med en redokselektrode og blir holdt konstant ved hjelp av en regulator og et reguleringsledd under den samlede reak-sjonstiden ved tilsetning av oksidasjons- og reduksjonsmidler, salter og fenoliske forbindelser. The redox potential is preferably between 250 and 450 mV. According to the method in the invention, it can be measured with a redox electrode and is kept constant with the help of a regulator and a control link during the overall reaction time by adding oxidizing and reducing agents, salts and phenolic compounds.
Som oksidasjonsmiddel blir det fortrinnsvis anvendt hydrogen-peroksid, oksygen og ozon. Som reduksjonsmidler er det aktuelt med askorbinsyre, ditionitt og natrium-bisulfitt. Hydrogen peroxide, oxygen and ozone are preferably used as oxidising agents. Suitable reducing agents are ascorbic acid, dithionite and sodium bisulphite.
Som salter blir celluloseinnholdige vandige kobber(II)sulfat tilsatt. Videre kan det som salter bli anvendt Mn(II)sulfat, Mn(III)acetat, Fe(II)sulfat, Ti(III )klorid, Ce(IIIJnitrat og Ce(IV)ammoniumnitrat. Likeledes kommer salter med elementene zink, antimon og bly i betraktning. Aqueous copper (II) sulphate containing cellulose is added as salts. Furthermore, Mn(II) sulphate, Mn(III) acetate, Fe(II) sulphate, Ti(III) chloride, Ce(III) nitrate and Ce(IV) ammonium nitrate can also be used as salts. Likewise, salts with the elements zinc, antimony and lead into consideration.
Eventuelt kan de vandige celluloseholdige oppløsningene bli tilsatt fenoliske forbindelser. Når det gjelder slike er særlig feratrylalkoholer aktuelle. Optionally, phenolic compounds can be added to the aqueous cellulose-containing solutions. When it comes to such, ferratryl alcohols are particularly relevant.
Videre kan de vandige celluloseholdige oppløsningene bli tilsatt fettsyrer, f.eks. oljesyrer, hemforbindelse f.eks. hemoglobin og blekereagenser f.eks. natriumperborat. Videre kan det bli gjennomført en etterbleking med vanlige blekemid-ler, som natriumhypokloritt, O2, klordioksid, ozon, H2O2 og natriumtionitt. Furthermore, fatty acids can be added to the aqueous cellulose-containing solutions, e.g. oleic acids, heme compound e.g. hemoglobin and bleaching reagents e.g. sodium perborate. Further bleaching can be carried out with common bleaching agents, such as sodium hypochlorite, O2, chlorine dioxide, ozone, H2O2 and sodium thionite.
Dessuten skal det bemerkes til at tilsetning av kompleksdannere for gjennomføring av fremgangsmåten ifølge oppfinnelsen er meget viktig. Slike som fortrinnsvis blir anvendt er etylendiamintetraeddiksyre (EDTA) eller dietyltri-aminpentaeddiksyre (DTPA). Straks det nødvendige redokspotensiale er innstilt, begynner blekeprosessen relativt raskt, og den kan bli avsluttet i løpet av noen få minutter, med nesten ikke noe lavere kappatall, som i avhengighet av celluloseinn-holdet etter noen timer kan bli forminsket til 90$. Furthermore, it should be noted that the addition of complexing agents for carrying out the method according to the invention is very important. Those that are preferably used are ethylenediaminetetraacetic acid (EDTA) or diethyltriaminepentaacetic acid (DTPA). As soon as the necessary redox potential is set, the bleaching process begins relatively quickly, and it can be finished within a few minutes, with almost no lower kappa number, which, depending on the cellulose content, can be reduced to 90$ after a few hours.
I tillegg til de nevnte stoffene kan den vandige celluloseholdige oppløsningen bli tilsatt ytterligere substanser. Følgende kan da komme i betraktning natriumhypokloritt, natriumperborat, detergenter , tensider og polysakkarider, som glukan og xantan. In addition to the substances mentioned, further substances can be added to the aqueous cellulose-containing solution. The following can then come into consideration: sodium hypochlorite, sodium perborate, detergents, surfactants and polysaccharides, such as glucan and xanthan.
Som enzymer blir det i fremgangsmåten ifølge oppfinnelsen fortrinnsvis anvendt 1ignolyttiske enzymer. Her kan blant annet nevnes fenoloksidaser, lakkaser og peroksidaser. Virkningen av fremgangsmåten kan ytterligere bli forhøyet ved anvendelse av pektinase og/eller hemicellulaser. Spesielt egnede 1ignolyttiske enzymer er slike som er utvunnet fra hvitråtesoppen Phanerochaete chrysosporium. Anvendelse av slike enzymer er allerede kjent fra US-PS 4.692.413, 4.690.895 og 4.687.741. Ifølge disse patentdokumentene blir det utvunnet enzymer fra spesielle mutanter av phanerochaete chrysosporium til bleking. Ifølge foreliggende oppfinnelse er dette derimot ikke nødvendig. Under overholdelse av de nevnte betingelsene kan alle dagens kjente 1ignolyttiske enzymer bli anvendt. Hovedforskjellen er å se i funksjon av de tildoserte eller oksiderende stoffene og mediatorene, som fungerer som radikalfangere. Disse stoffene forhindrer nemlig en repolymerisering av lignin og muliggjør først en lignin-utvinning på beskreven måte og mengde innenfor det nevnte korte tidsrommet. As enzymes, ignolytic enzymes are preferably used in the method according to the invention. Among other things, phenol oxidases, laccases and peroxidases can be mentioned here. The effect of the method can be further increased by using pectinase and/or hemicellulases. Particularly suitable ignolytic enzymes are those extracted from the white rot fungus Phanerochaete chrysosporium. Use of such enzymes is already known from US-PS 4,692,413, 4,690,895 and 4,687,741. According to these patent documents, enzymes are extracted from special mutants of phanerochaete chrysosporium for bleaching. According to the present invention, however, this is not necessary. Subject to compliance with the aforementioned conditions, all of today's known ignolytic enzymes can be used. The main difference is to be seen in the function of the dosed or oxidizing substances and mediators, which function as radical scavengers. These substances prevent a repolymerization of lignin and first enable lignin extraction in the described manner and quantity within the aforementioned short period of time.
Ved fremgangsmåten ifølge oppfinnelsen ligger pH-verdien vanligvis mellom 2 og 5. Spesielt foretrukket er en pH-verdi på 3. Temperaturen utgjør 20 til 60°C, fortrinnsvis 40°C. Ved overholdelse av betingelsene blir det under tilsats av de nevnte stoffene innstilt et redokspotensial fra 200 til 500 mV. Dette blir bestemt med forholdet av de forskjellige tilsatte stoffene i reaksjonsbeholderen. Gjennom tilsvarende måling og regulering av tilsetning av oksidasjons- og reduksjonsmidler, salter og eventuelle fenoliske forbindelser, kan dette bli opprettholdt i hele den samlede reak-sj onstiden. In the method according to the invention, the pH value is usually between 2 and 5. A pH value of 3 is particularly preferred. The temperature is 20 to 60°C, preferably 40°C. If the conditions are met, a redox potential of 200 to 500 mV is set during the addition of the mentioned substances. This is determined by the ratio of the various added substances in the reaction vessel. Through corresponding measurement and regulation of the addition of oxidizing and reducing agents, salts and any phenolic compounds, this can be maintained throughout the entire reaction time.
Med den beskrevne blekefremgangsmåten har det for første gang lykkes, i løpet av kort tid (15 minutter - 2 timer) ved fysiologiske temperaturer (40°C) uten trykk og med liten tilsetning av kjemiske stoffer, å bleke cellulose på en kostnadsgunstig og fremfor alt miljøvennlig måte. En ytterligere fordel ved fremgangsmåten i oppfinnelsen er muligheten ved kontinuerlig gjennomføring av fremgangsmåten. With the described bleaching method, it has been possible for the first time, within a short time (15 minutes - 2 hours) at physiological temperatures (40°C) without pressure and with little addition of chemical substances, to bleach cellulose in a cost-effective and above all environmentally friendly way. A further advantage of the method in the invention is the possibility of continuous execution of the method.
Fremgangsmåten ifølge oppfinnelsen blir nærmere forklart ved hjelp av følgende eksempel: 50 g atrocellulose (sulfatcellulose) blir omrørt i en rørebeholder ved 1% stofftetthet ved ca. 500 rpm og 40°C. pH-verdien blir innstilt ved 1 n HCL til pH 3. Det blir tilsatt 0,1-1, 5Sé E202 med hensyn på atrostoff, 2 x 10~<5># - 2 x 10~ 3% veratrylalkohol (VA) og 0, 1% EDTA eller DTPA, 0,001-0,01^ kobber(II)sulfat med hensyn på atrostoff. Etter tilsetning av 500-5000 IU lignolyttisk enzym (1 IU = omsetning av 1 nmol VA/min. i veratrylaldehyd) blir blekeprosessen satt i gang ved samtidig dosering av H2O2 og natriumbisulfitt-oppløsning. Med dette blir redokspotensialet opprettholdt på ca. 400 mV. Etter at prosessen er innledet, blir den fortsatt i 2 timer. Styring og regulering av prosessen blir gjennomført ved hjelp av en redokselektrode og en pumpestyring. The method according to the invention is explained in more detail with the help of the following example: 50 g of atrocellulose (sulphate cellulose) is stirred in a mixing container at 1% material density at approx. 500 rpm and 40°C. The pH value is adjusted with 1 n HCL to pH 3. 0.1-1.5Sé E202 is added with regard to atro substance, 2 x 10~<5># - 2 x 10~ 3% veratryl alcohol (VA) and 0 , 1% EDTA or DTPA, 0.001-0.01^ copper (II) sulfate with respect to atrogen. After adding 500-5000 IU of lignolytic enzyme (1 IU = turnover of 1 nmol VA/min. in veratrylaldehyde), the bleaching process is started by simultaneous dosing of H2O2 and sodium bisulphite solution. With this, the redox potential is maintained at approx. 400 mV. After the process is initiated, it continues for 2 hours. Control and regulation of the process is carried out using a redox electrode and a pump controller.
Claims (17)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4008893A DE4008893A1 (en) | 1990-03-20 | 1990-03-20 | METHOD FOR ENZYMATIC BLEACHING OF CELLULAS |
| PCT/EP1991/000540 WO1991014823A1 (en) | 1990-03-20 | 1991-03-19 | Process for the enzymatic bleaching of celluloses |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO923601L NO923601L (en) | 1992-09-16 |
| NO923601D0 NO923601D0 (en) | 1992-09-16 |
| NO180388B true NO180388B (en) | 1996-12-30 |
| NO180388C NO180388C (en) | 1997-04-09 |
Family
ID=6402620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO923601A NO180388C (en) | 1990-03-20 | 1992-09-16 | Process for enzymatic bleaching of cellulose |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0447673B1 (en) |
| JP (1) | JPH05505857A (en) |
| AT (1) | ATE119593T1 (en) |
| AU (1) | AU641494B2 (en) |
| BR (1) | BR9106411A (en) |
| CA (1) | CA2078345A1 (en) |
| DE (2) | DE4008893A1 (en) |
| DK (1) | DK0447673T3 (en) |
| ES (1) | ES2072965T3 (en) |
| FI (1) | FI924169A (en) |
| HU (1) | HUT64119A (en) |
| NO (1) | NO180388C (en) |
| WO (1) | WO1991014823A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4137761A1 (en) * | 1991-05-17 | 1992-11-19 | Call Hans Peter | METHOD FOR DELIGNIFYING LIGNOCELLULOSE-CONTAINING MATERIAL, BLEACHING AND TREATING WASTEWATER BY LACCASE WITH EXTENDED EFFECTIVENESS |
| FI914780A0 (en) * | 1991-10-10 | 1991-10-10 | Valtion Teknillinen | FOERFARANDE FOER ENTSYMATISK BEHANDLING AV LIGNOCELLULOSAHALTIGA MATERIAL, I SYNNERHET CELLULOSAMASSOR. |
| CA2115881C (en) * | 1993-02-25 | 2000-05-23 | Michael G. Paice | Non-chlorine bleaching of kraft pulp |
| ES2122299T3 (en) * | 1993-06-16 | 1998-12-16 | Lignozym Gmbh | PROCESS FOR MODIFICATION, DEGRADATION OR BLEACHING OF LIGNINE, MATERIALS CONTAINING LIGNIN OR COAL. |
| BE1007272A3 (en) * | 1993-07-15 | 1995-05-09 | Solvay | Method of a pulp bleach. |
| EP0652321B1 (en) * | 1993-11-04 | 1998-01-21 | Morton International, Inc. | Chemical pulp bleaching |
| DE19820947B4 (en) * | 1997-05-12 | 2005-12-01 | Call, Krimhild | Enzymatic bleaching system with novel enzyme action enhancing compounds for altering, degrading or bleaching lignin, lignin containing materials, or altering or degrading coal, and methods using the bleaching system |
| AU3859597A (en) | 1997-08-14 | 1999-03-08 | Kurt Messner | Chemical method for lignin depolymerization |
| ATE224476T1 (en) * | 1998-04-16 | 2002-10-15 | Pulp Paper Res Inst | METHOD FOR PULP AND DYE OXIDATION USING OXIDASE |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3110117C2 (en) * | 1981-03-16 | 1983-09-29 | Adolf 5340 St. Gilgen Basler | Production of cellulose from wood or other lignocellulose-containing plants through microbial degradation of the lignocellulose |
| 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 |
| US4687741A (en) * | 1985-07-15 | 1987-08-18 | Repligen Corporation | Novel enzymes which catalyze the degradation and modification of lignin |
| US4692413A (en) * | 1985-07-15 | 1987-09-08 | Repligen Corporation | Use of rLDM™ 1-6 and other ligninolytic enzymes for the decolorization of E1 effluent |
| DE3636208A1 (en) * | 1986-10-24 | 1988-05-05 | Call Hans Peter | METHOD FOR DELIGNIFYING AND WHICH BLEACHING LIGNICELLULOSE-CONTAINING OR LIGNINAL MATERIAL OR LIGNIN BY ENZYMATIC TREATMENT |
| ZA894239B (en) * | 1988-06-08 | 1990-03-28 | Int Paper Co | Enzymatic delignification of lignocellulosic material |
-
1990
- 1990-03-20 DE DE4008893A patent/DE4008893A1/en active Granted
- 1990-12-22 ES ES90125380T patent/ES2072965T3/en not_active Expired - Lifetime
- 1990-12-22 DE DE59008655T patent/DE59008655D1/en not_active Expired - Fee Related
- 1990-12-22 AT AT90125380T patent/ATE119593T1/en active
- 1990-12-22 EP EP90125380A patent/EP0447673B1/en not_active Expired - Lifetime
- 1990-12-22 DK DK90125380.7T patent/DK0447673T3/en active
-
1991
- 1991-03-19 WO PCT/EP1991/000540 patent/WO1991014823A1/en active Application Filing
- 1991-03-19 HU HU922982A patent/HUT64119A/en unknown
- 1991-03-19 CA CA002078345A patent/CA2078345A1/en not_active Abandoned
- 1991-03-19 AU AU75432/91A patent/AU641494B2/en not_active Ceased
- 1991-03-19 BR BR919106411A patent/BR9106411A/en not_active Application Discontinuation
- 1991-03-19 JP JP91506306A patent/JPH05505857A/en active Pending
-
1992
- 1992-09-16 NO NO923601A patent/NO180388C/en unknown
- 1992-09-17 FI FI924169A patent/FI924169A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DK0447673T3 (en) | 1995-07-24 |
| CA2078345A1 (en) | 1991-09-21 |
| HU9202982D0 (en) | 1993-01-28 |
| BR9106411A (en) | 1993-05-04 |
| DE4008893C2 (en) | 1992-09-03 |
| DE4008893A1 (en) | 1991-09-26 |
| AU641494B2 (en) | 1993-09-23 |
| NO923601L (en) | 1992-09-16 |
| HUT64119A (en) | 1993-11-29 |
| ES2072965T3 (en) | 1995-08-01 |
| NO923601D0 (en) | 1992-09-16 |
| AU7543291A (en) | 1991-10-21 |
| ATE119593T1 (en) | 1995-03-15 |
| FI924169A0 (en) | 1992-09-17 |
| JPH05505857A (en) | 1993-08-26 |
| FI924169A (en) | 1992-09-17 |
| EP0447673B1 (en) | 1995-03-08 |
| EP0447673A1 (en) | 1991-09-25 |
| DE59008655D1 (en) | 1995-04-13 |
| NO180388C (en) | 1997-04-09 |
| WO1991014823A1 (en) | 1991-10-03 |
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