HUT64119A - Method for enzyme-bleaching cellulose - Google Patents
Method for enzyme-bleaching cellulose Download PDFInfo
- Publication number
- HUT64119A HUT64119A HU922982A HUP9202982A HUT64119A HU T64119 A HUT64119 A HU T64119A HU 922982 A HU922982 A HU 922982A HU P9202982 A HUP9202982 A HU P9202982A HU T64119 A HUT64119 A HU T64119A
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- HU
- Hungary
- Prior art keywords
- process according
- cellulose
- added
- bleaching
- aqueous solution
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 229920002678 cellulose Polymers 0.000 title claims abstract description 29
- 239000001913 cellulose Substances 0.000 title claims abstract description 28
- 238000004061 bleaching Methods 0.000 title claims abstract description 20
- 108090000790 Enzymes Proteins 0.000 claims abstract description 15
- 102000004190 Enzymes Human genes 0.000 claims abstract description 15
- 230000002479 lignolytic effect Effects 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000002255 enzymatic effect Effects 0.000 claims abstract description 4
- 229940088598 enzyme Drugs 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- OEGPRYNGFWGMMV-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC OEGPRYNGFWGMMV-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- -1 heme compound Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229960001922 sodium perborate Drugs 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical group [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 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
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims description 2
- 108010029541 Laccase Proteins 0.000 claims description 2
- 108010059820 Polygalacturonase Proteins 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 2
- 108010093305 exopolygalacturonase Proteins 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229940059442 hemicellulase Drugs 0.000 claims description 2
- 108010002430 hemicellulase Proteins 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- AHSBSUVHXDIAEY-UHFFFAOYSA-K manganese(iii) acetate Chemical compound [Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AHSBSUVHXDIAEY-UHFFFAOYSA-K 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 108010054320 Lignin peroxidase Proteins 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- 235000007079 manganese sulphate Nutrition 0.000 claims 1
- 239000011702 manganese sulphate Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 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
- 229920005610 lignin Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 241000233866 Fungi Species 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 241000222393 Phanerochaete chrysosporium Species 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GMPWPTYBCCEVKH-UHFFFAOYSA-N 1,2-bis(3,4-dimethoxyphenyl)ethane-1,2-dione Chemical compound C1=C(OC)C(OC)=CC=C1C(=O)C(=O)C1=CC=C(OC)C(OC)=C1 GMPWPTYBCCEVKH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 102000011727 Caspases Human genes 0.000 description 1
- 108010076667 Caspases Proteins 0.000 description 1
- 241001579660 Chrysosporum Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 241000222385 Phanerochaete Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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 class [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000004671 cell-free system Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
Abstract
Description
A találmány tárgya eljárás cellulóz enzimes fehérítésére .The present invention relates to a process for the enzymatic bleaching of cellulose.
A cellulóz előállítására eddig ismert biológiai eljárások során mikroorganizmusokat, főleg gombákat alkalmaznak. A 3 110 117 sz. német szabadalmi leírás például olyan eljárást ismertet, amely során cellulózt nyernek fából vagy egyébb növényi rostanyagból oly módon, hogy a lignocellulózt fehérrothadásgombákkal lebontják. A mikroorganizmusok alkalmazásának azonban lényeges hátrányai vannak, például mindezideig a lignin és kisérőpolimerjének (a cellulóz) szétválasztását nem sikerült megoldani úgy, hogy a mikroorganizmus ne nőjön, ne okozzon veszteséget a cellulóz-hozamban. A lebontási időigen hosszú, több hetet is tarthat a lebontás.Microorganisms, especially fungi, are known in the biological processes known to date for the production of cellulose. No. 3,110,117. For example, German Patent No. 4,600,125 discloses a process for obtaining cellulose from wood or other vegetable fibers by degrading lignocellulose with white rot fungi. However, the use of microorganisms has significant disadvantages, for example the separation of lignin and its accompanying polymer (cellulose) has not been solved so far that the microorganism does not grow or cause loss in the cellulose yield. The breakdown time is very long and may take several weeks.
A fenti problémák miatt az utóbbi években inkább az elkülönített enzimrendszerek felhasználási lehetőségeit vizsgálták. Főleg a fehérrothadásgomba (Phanerochaete chrysosporium) enzimjeit kutatták és sok részletet tisztáztak. Ismertté vált (Biotechnology in the Pulp and Paper Industry 3. International Conference, Stockholm 1986), hogy a lignin lebontásakor a reakció egyensúlya a polimerizáció oldalán van, azaz a sejtmentes rendszerek nem bontják a lignint, hanem inkább polimerizálják.Due to the above problems, the potential applications of isolated enzyme systems have been explored in recent years. In particular, the enzymes of the white rot fungus (Phanerochaete chrysosporium) have been researched and many details have been clarified. It has become known (Biotechnology in the Pulp and Paper Industry 3rd International Conference, Stockholm 1986) that the reaction equilibrium upon lignin degradation is on the side of polymerisation, that is, cellular systems do not decompose lignin but rather polymerize it.
Mióta a Phanerochaete chrysosporium fehérrothadásgomba lignolitikus enzimjeit ismerik, cellulóz fehérítésére irányuló enzimes eljárásokat is dolgoztak ki, amelyek vagy élő gombával, vagy sejtmentes rendszerrel dolgoznak. Hemrendszerekkel is próbálkoztak fehéríteni, de a reakcióidő meghaladja a 12 órát. Az összes ismert rendszerre jellemző a nagy időigényesség és a magas költség. Ez különösen a tiszta hem-rendszerekre jellemző.Since the lignolytic enzymes of the white rot fungus Phanerochaete chrysosporium have been known, enzymatic methods for bleaching cellulose have been developed that work with either a live fungus or a cell-free system. Hem systems have also been tried to bleach, but the reaction time exceeds 12 hours. All known systems are time consuming and expensive. This is especially true for pure heme systems.
Jelenleg a cellulóz fehérítését több lépcsőben, tisztán kémiailag, klór adagolásával végzik. A klórós fehérítés azonban erősen terheli a környezetet. Általában a fehérítés abban áll, hogy a lignin eltávolítása céljából végzett forralás során a maradék ligninből keletkező kromofor kondenzációs termékeket eltávolítják, azaz a kappa-számot (a lignintartalmat) csökkentik.Currently, cellulose bleaching is carried out in several steps, purely chemically, by the addition of chlorine. However, chlorine bleaching is a heavy burden on the environment. Generally, bleaching consists in removing the chromophore condensation products formed from residual lignin by boiling to remove lignin, i.e., reducing the kappa number (lignin content).
A találmány feladata cellulóz fehérítésére alkalmas enzimes eljárás kidolgozása volt, amely a fent részletezett hátrányoktól mentes.SUMMARY OF THE INVENTION It is an object of the present invention to provide an enzymatic process for bleaching cellulose which is free of the drawbacks detailed above.
A fenti feladatot olyan eljárással oldottuk meg, amelynek soránThe above problem was solved by a process in which
a) a vizes, cellulóz-tartalmú oldathoz oxidáló és redukálószert, sókat és komplexképzőket adagolva az oldat redox-potenciálját 200 és 500 mV közötti értékre állítjuk,a) adding an oxidizing and reducing agent, salts and complexing agents to the aqueous cellulose solution, adjusting the solution to a redox potential of 200 to 500 mV,
b) lignolitikus enzim adagolásával a fehérítést beindítjuk ésb) initiating bleaching by adding the lignolytic enzyme and
c) és a reakciót keverés közben 15 perctől 12 óráig terjedő időn keresztül fenntartjuk. E körülmények között a lignin visszapolimerizálódását kizárjuk, lebontását elősegítjük.c) and maintaining the reaction with stirring for 15 minutes to 12 hours. Under these conditions, the re-polymerization of lignin is excluded, and degradation is promoted.
A redox-potenciál előnyösen 250 és 450 mV közötti.The redox potential is preferably between 250 and 450 mV.
A találmány szerinti eljárás során a redox-potenciált redoxelektródával folyamatosan mérhetjük, szabályozó és szabályo• · · ·In the process of the present invention, the redox potential can be continuously measured by a redox electrode, a regulator and a regulator.
- 4 zó tag segítségével a teljes reakcióidő alatt oxidálószer, redukálószer, sók és fenol jellegű vegyületek adagolásával állandó értéken tarthatjuk.It can be kept constant by the addition of an oxidizing agent, a reducing agent, salts and phenolic compounds with the aid of 4 zones.
Oxidálószerként előnyösen hidrogénperoxidot, oxigént vagy ózont alkalmazunk. Redukálószerként aszkorbinsav, ditionit és nátriumhidrogén-szulfit jöhet számításba.The oxidizing agent is preferably hydrogen peroxide, oxygen or ozone. As reducing agents, ascorbic acid, dithionite and sodium bisulfite may be used.
Sóként a cellulóz-tartalmú vizes oldathoz réz(II)szulfátot adunk. Járulékosan még az alábbi sókat alkalmazhatjuk: mangán(II)szulfát, mangán(III)acetét, vas(II)szulfát, titán(III)klorid, cérium(III)nitrát és cérium(IV)ammóniumnitrát. A cink, antimon és ólom sói szintén számításba jönnek. A vizes, cellulóz-tartalmú oldathoz adott esetben fenol jellegű vegyületeket is adagolhatunk, ilyenként főleg a veratrilalkoholok váltak be.As a salt, copper (II) sulfate is added to the cellulose-containing aqueous solution. Additionally, the following salts may be used: manganese (II) sulfate, manganese (III) acetate, iron (II) sulfate, titanium (III) chloride, cerium (III) nitrate and cerium (IV) ammonium nitrate. Zinc, antimony and lead salts are also contemplated. Phenolic compounds may also be added to the aqueous cellulose-containing solution, in particular veratryl alcohols.
A vizes, celluÍz-tartalmú oldathoz továbbá zsírsavat, például olajsavat, vagy hem-vegyületet, például hemoglobint, fehérítő reagenst, például nátrium-perborátot adhatunk. Ezen túlmenően utófehérítést végezhetünk a szokásos fehérítőszerekkel, például nátrium-hipokloriddal, oxigénnel, klór-dioxiddal, ózonnal, hidrogén-peroxiddal vagy nátrium-tionittal.Further, a fatty acid such as oleic acid or a heme compound such as hemoglobin, a bleaching reagent such as sodium perborate can be added to the aqueous cellulose-containing solution. In addition, post-bleaching can be carried out with standard bleaching agents such as sodium hypochlorite, oxygen, chlorine dioxide, ozone, hydrogen peroxide or sodium thionite.
A találmány szerinti eljárás során a komplexképző adagolása nagyon fontos. Komplexképzőként előnyösen etiléndiamin-tetraecetsavat (EDTA) vagy dietilén-triamin-pentaecetsavat (DTPA) alkalmazunk. Ha a megfelelő redoxpotenciált beállítottuk, a fehérítés folyamata viszonylag gyorsan elkezdődik, és néhány perc elteltével már be is feje • ♦ · ·Dosing of the complexing agent is very important in the process of the invention. Preferably, the complexing agent is ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). Once the correct redox potential has been set, the bleaching process begins relatively quickly and is complete after a few minutes • ♦ · ·
- 5 ződhet, bár akkor a kappaszám alig csökken, mig több órás kezelés után - a cellulóz-tartalomtól függően - a kasppaszám akár 90 %-os csökkenése érhető el.- 5 may occur, although then the number of cabbage barely decreases, whereas after several hours of treatment, depending on the cellulose content, a reduction of up to 90% in the number of caspases can be achieved.
A felsorolt anyagokon túlmenően a vizes, cellulóztartalmú oldathoz még az alábbiakat adagolhatjuk: nátriumhipoklorid, nátriumperborát, detergensek, tenzidek és poliszacharidek, így glukán vagy xantán.In addition to the substances listed above, the following can be added to the aqueous cellulosic solution: sodium hypochlorite, sodium perborate, detergents, surfactants and polysaccharides such as glucan or xanthan.
Enzimként a találmány szerinti eljárásban előnyösen lignolitikus enzimet alkalmazunk. Ide tartoznak például a fenoloxidáz-, lakkáz- és peroxidáz-enzimek. Az eljárás hatékonyságát pektináz és/vagy hemicelluláz adagolásával még fokozhatjuk. Különösen alkalmasak a Phanerochaete chrysosporium fehérrothadásgomba lignolitikus enzimjei. Ezeknek az enzimeknek az alkalmazása ismert a 4 692 413, 4 690 895 és 4 687 741 sz. amerikai egyesült államokbeli szabadalmi leírásokból, amelyek szerint azonban a Phanerochaete chrysosporum meghatározott mutánsaiból nyert enzimet alkalmaznak fehérítésre. A találmány értelmében erre nincs szükség, ellenkezőleg: a fent részletezett feltételek betartása esetén tetszőleges lignolitikus enzim alkalmazható. Az ismert és a találmány szerinti eljárás fő különbségét az adagolt redukáló és oxidáló anyagok funkciójában kell látni. Ezek az anyagok ugyanis fogják a gyököket, így megakadályozzák a lignin visszapolimerizálódását, ill. elősegítik a lignin lebontását az említett rövid reakcióidő alattPreferably, the enzyme used in the process of the invention is a lignolytic enzyme. These include, for example, the enzymes phenol oxidase, laccase and peroxidase. The effectiveness of the process can be further enhanced by the addition of pectinase and / or hemicellulase. Lignolytic enzymes of the white rot fungus Phanerochaete chrysosporium are particularly suitable. The use of these enzymes is known in U.S. Patent Nos. 4,692,413, 4,690,895 and 4,687,741. however, the enzyme obtained from certain mutants of Phanerochaete chrysosporum is used for bleaching. According to the invention, this is not necessary; on the contrary, any lignolytic enzyme may be used provided the conditions detailed above are met. The main difference between the known process and the invention is the function of the reducing and oxidizing agents added. These substances hold the radicals, thus preventing the lignin from being re-polymerized or being blocked. they promote the degradation of lignin during the short reaction time mentioned
A találmány szerinti eljárás során a pH-értéket általában 2 és 5 között tartjuk, különösen előnyös a 3 körüli pH. A hőmérséklet 20 °C és 60 °C közötti, előnyösen 40 ’C. Ha ezeket a feltételeket betartjuk, az említett anyagok adagolása révén 200 mV és 500 mV közötti redoxpotenciál alakítható ki. A redoxpotenciált az adagolt anyagok mennyiségi aránya határozza meg. Az oxidáló és redukálószerek, sók és adott esetben fenol jellegű anyagok adagolásának megfelelő mérése és szabályozása révén a redoxpotenciált az egész reakcióidő alatt állandó értéken tartjuk.In the process of the invention, the pH is generally maintained between 2 and 5, with a pH of about 3 being particularly preferred. The temperature is between 20 ° C and 60 ° C, preferably 40 ° C. If these conditions are met, a redox potential of 200 mV to 500 mV can be achieved by the addition of said substances. Redox potential is determined by the volume ratio of the substances added. By appropriately measuring and controlling the addition of oxidizing and reducing agents, salts and optionally phenolic substances, the redox potential is maintained constant throughout the reaction.
A fenti eljárással első ízben sikerült a cellulóz fehérítése igen rövid idő alatt (15 perc - 2 óra), fiziológiás hőmérsékleten (40 ’C), nyomás nélkül és minimális vegyszer adagolásával, alacsony költséggel és környezetbarát módon. A találmány szerinti eljárás további előnye, hogy folyamatosan is kivitelezhető.The above process succeeded for the first time in bleaching cellulose in a very short time (15 minutes to 2 hours), at physiological temperature (40 ° C), without pressure and with minimal chemical addition, at low cost and in an environmentally friendly manner. A further advantage of the process according to the invention is that it can be carried out continuously.
A találmány szerinti eljárást az alábbi példával közelebbről ismertetjük.The following example illustrates the process according to the invention.
Példa g atro-cellulóz (szulfát-cellulóz) 1 t%-os vizes szuszpenzióját 40 ’C-on 50 perc-3 fordulatszám mellett keverjük. A pH-értéket In sósav-oldattal 3-ra állítjuk. Cellulózra vonatkoztatva 0,1-1,5 t% hídrogén-peroxidot, mintegy 2xl0-5...2xl0“3 t% veratrilalkoholt, 0,1 t% EDTA-t vagy DTPA-t és 0,001...0,01 t% réz(II)szulfátot adagolunk. 500 5000 NE lignolitikus enzim (1 NE - percenként 1 nmol veratrilalkoholt veratrilaldehiddá oxidálja) adagolása után beindítjuk a fehérítést hidrogén-peroxid és nátriumhidrogénszulfit egyidejű adagolásával. Közben a kb. 400 mV-os • «4 «* * ·· ·· * Λ ·4 4 • 4 4 * ·· • · ·4*4· »44 «·· 4 »444444EXAMPLE 1 A 1% aqueous suspension of g cellular cellulose (sulfate cellulose) was stirred at 40 ° C for 50 minutes at -3 rpm. The pH was adjusted to 3 with IN hydrochloric acid. 0.1-1.5% hydrogen peroxide per cellulose, approximately 2x10 -5 to 2x10 3 % v / v veratril alcohol, 0.1% EDTA or DTPA and 0.001 to 0.01% % copper (II) sulfate is added. After addition of 500 to 5,000 IU of lignolytic enzyme (1 IU to 1 nmol of veratryl alcohol oxidized to veratrilaldehyde per minute), bleaching is initiated by the simultaneous addition of hydrogen peroxide and sodium hydrogen sulfite. Meanwhile, the app. 400 mV • «4« * * ·· ·· * Λ · 4 4 • 4 4 * ·· • · · 4 * 4 · »44« ·· 4 »444444
- 7 redoxpotenciált végig fenntartjuk, és a fehérítést 2 órán át folytatjuk. A folyamat vezetése és szabályozása redoxelektródával és szivattyúval történik.- 7 redox potentials are maintained and bleaching is continued for 2 hours. The process is controlled and controlled by a redox electrode and a pump.
Claims (27)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4008893A DE4008893A1 (en) | 1990-03-20 | 1990-03-20 | METHOD FOR ENZYMATIC BLEACHING OF CELLULAS |
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| Publication Number | Publication Date |
|---|---|
| HU9202982D0 HU9202982D0 (en) | 1993-01-28 |
| HUT64119A true HUT64119A (en) | 1993-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HU922982A HUT64119A (en) | 1990-03-20 | 1991-03-19 | Method for enzyme-bleaching 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) | FI924169L (en) |
| HU (1) | HUT64119A (en) |
| NO (1) | NO180388C (en) |
| WO (1) | WO1991014823A1 (en) |
Families Citing this family (12)
| 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 |
| NZ268359A (en) * | 1993-06-16 | 1998-01-26 | Lignozym Gmbh | Process for breaking down lignin, using oxidation catalysts, oxidising agents and compounds containing an n-o group |
| 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 |
| DE19632623A1 (en) * | 1996-08-13 | 1998-02-19 | Consortium Elektrochem Ind | Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as methods for their use |
| PT925401E (en) * | 1996-09-11 | 2002-07-31 | Solvay Interox Sa | Process for bleaching paper pulp |
| DE19651099A1 (en) * | 1996-12-09 | 1998-06-10 | Consortium Elektrochem Ind | Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as methods for their use |
| 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 |
| ATE254688T1 (en) * | 1997-08-14 | 2003-12-15 | Takashi Watanabe | CHEMICAL PROCESS FOR DEPOLYMERIZING LIGNIN |
| ID26087A (en) * | 1998-04-16 | 2000-11-23 | Pulp And Paper Res Institusi O | OXIDATION PROCESS FOR OXIDATION OF WOOD AND DYE MATERIALS |
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| 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 |
| 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 |
| US4687741A (en) * | 1985-07-15 | 1987-08-18 | Repligen Corporation | Novel enzymes which catalyze the degradation and modification of lignin |
| 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 DE DE59008655T patent/DE59008655D1/en not_active Expired - Fee Related
- 1990-12-22 DK DK90125380.7T patent/DK0447673T3/en active
- 1990-12-22 AT AT90125380T patent/ATE119593T1/en active
- 1990-12-22 ES ES90125380T patent/ES2072965T3/en not_active Expired - Lifetime
- 1990-12-22 EP EP90125380A patent/EP0447673B1/en not_active Expired - Lifetime
-
1991
- 1991-03-19 JP JP91506306A patent/JPH05505857A/en active Pending
- 1991-03-19 FI FI924169A patent/FI924169L/en not_active Application Discontinuation
- 1991-03-19 WO PCT/EP1991/000540 patent/WO1991014823A1/en not_active Ceased
- 1991-03-19 CA CA002078345A patent/CA2078345A1/en not_active Abandoned
- 1991-03-19 HU HU922982A patent/HUT64119A/en unknown
- 1991-03-19 BR BR919106411A patent/BR9106411A/en not_active Application Discontinuation
- 1991-03-19 AU AU75432/91A patent/AU641494B2/en not_active Ceased
-
1992
- 1992-09-16 NO NO923601A patent/NO180388C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FI924169A7 (en) | 1992-09-17 |
| HU9202982D0 (en) | 1993-01-28 |
| CA2078345A1 (en) | 1991-09-21 |
| DE4008893C2 (en) | 1992-09-03 |
| ES2072965T3 (en) | 1995-08-01 |
| WO1991014823A1 (en) | 1991-10-03 |
| FI924169A0 (en) | 1992-09-17 |
| NO180388C (en) | 1997-04-09 |
| JPH05505857A (en) | 1993-08-26 |
| NO923601D0 (en) | 1992-09-16 |
| DK0447673T3 (en) | 1995-07-24 |
| AU7543291A (en) | 1991-10-21 |
| DE4008893A1 (en) | 1991-09-26 |
| NO180388B (en) | 1996-12-30 |
| ATE119593T1 (en) | 1995-03-15 |
| NO923601L (en) | 1992-09-16 |
| DE59008655D1 (en) | 1995-04-13 |
| AU641494B2 (en) | 1993-09-23 |
| EP0447673B1 (en) | 1995-03-08 |
| FI924169L (en) | 1992-09-17 |
| EP0447673A1 (en) | 1991-09-25 |
| BR9106411A (en) | 1993-05-04 |
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