SE502763C2 - Reducing hydrogen peroxide degradation by enzymes in peroxide pulp bleaching process - Google Patents
Reducing hydrogen peroxide degradation by enzymes in peroxide pulp bleaching processInfo
- Publication number
- SE502763C2 SE502763C2 SE9404129A SE9404129A SE502763C2 SE 502763 C2 SE502763 C2 SE 502763C2 SE 9404129 A SE9404129 A SE 9404129A SE 9404129 A SE9404129 A SE 9404129A SE 502763 C2 SE502763 C2 SE 502763C2
- Authority
- SE
- Sweden
- Prior art keywords
- enzymes
- hydrogen peroxide
- bleaching process
- peroxide
- degradation
- Prior art date
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 5
- 150000002978 peroxides Chemical class 0.000 title claims 2
- 230000007515 enzymatic degradation Effects 0.000 title abstract 2
- 238000004076 pulp bleaching Methods 0.000 title 1
- 102000016938 Catalase Human genes 0.000 claims abstract description 12
- 108010053835 Catalase Proteins 0.000 claims abstract description 12
- 102000004190 Enzymes Human genes 0.000 claims abstract description 12
- 108090000790 Enzymes Proteins 0.000 claims abstract description 12
- 238000004061 bleaching Methods 0.000 claims abstract description 8
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 3
- 229920002678 cellulose Polymers 0.000 claims abstract description 3
- 239000001913 cellulose Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 8
- 230000000593 degrading effect Effects 0.000 claims description 3
- 108091005804 Peptidases Proteins 0.000 abstract description 4
- 102000035195 Peptidases Human genes 0.000 abstract description 4
- 239000004365 Protease Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 6
- 229940088598 enzyme Drugs 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000004155 Chlorine dioxide Substances 0.000 description 3
- 108090000787 Subtilisin Proteins 0.000 description 3
- 235000019398 chlorine dioxide Nutrition 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 108700020962 Peroxidase Proteins 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Detergent Compositions (AREA)
Abstract
Description
sw /0 Zf "aO 35 Tillsats av biocider har även föreslagits för att döda rnikroorganismema och förhindra katalasbildning. Biocider är hälsofarliga och olämpliga ur niiljösynpunlct. sw / 0 Zf "aO 35 Addition of biocides has also been proposed to kill the micro-organisms and prevent catalase formation. Biocides are hazardous to health and unsuitable from an environmental point of view.
Närvarande metalljoner, t ex jäm, mangan, koppar och aluminium bryter ned väteperoxid.Metal ions present, such as iron, manganese, copper and aluminum, break down hydrogen peroxide.
För att förhindra detta används idag kelatkomplexbildare och natriumsilikat. Silikater tenderar att sätta igen utrustningen vid massahanteringen och komplexbildarna är dyra och ibland farliga att använda. Deras inverkan på miljön är starkt ifrågasatt och ej utredd.To prevent this, chelating agents and sodium silicate are currently used. Silicates tends to clog the equipment in pulp handling and the complexing agents are expensive and sometimes dangerous to use. Their impact on the environment is strongly questioned and not investigated.
Genom EP O 562 835 är det känt att använda små mängder av klordioxid, brom, klor, jod och ozon som oxiderande, enzyminaktiverande och bakteriedödande medel vid blekning av cellulosamassa med väteperoxid. Enligt utföringsexempel 3 i beskrivningen dödas mikroorganismema i bakvatten med klordioxid. Klordioxid är en giftig, explosiv, korrosiv och svårhanterlig substans, som lätt sönderfaller och måste tillverkas i blekeriet och förvaras där utspädd.From EP 0 562 835 it is known to use small amounts of chlorine dioxide, bromine, chlorine, iodine and ozone as oxidizing, enzyme inactivating and bactericidal agents in bleaching cellulose pulp with hydrogen peroxide. According to Embodiment 3 of the description, killed the microorganisms in the backwater with chlorine dioxide. Chlorine dioxide is a toxic, explosive, corrosive and difficult-to-handle substance, which decomposes easily and must be manufactured in the bleaching plant and stored where diluted.
G. Galland, E. Bemard, Y. Verac föreslår i "Achieving a deinked pulp with high brightness" i Paper Technology, december 1989 olika sätt att öka ljusheten vid bearbetning av returpapper genom att minska förbrukningen av väteperoxid, Det föreslås bland annat att katalas tages bort genom att rnikroorganismerna, som utvecklar enzymet, elimineras eller att katalas förstöres före blekningen. För att förstöra katalas användes t ex en behandling med natriumhypoklorit. Natriumhypoklorit är dock en olämplig substans för miljön.G. Galland, E. Bemard, Y. Verac propose in "Achieving a deinked pulp with high brightness" in Paper Technology, December 1989 different ways to increase the brightness when processing recycled paper by reducing the consumption of hydrogen peroxide, It is proposed, among other things, that catalase be taken by eliminating or catalyzing the micro-organisms that develop the enzyme destroyed before bleaching. To destroy catalase, for example, a treatment was used sodium hypochlorite. However, sodium hypochlorite is an unsuitable substance for the environment.
I princip innebär förfarandena enligt de två publikationema att man använder de miljöfarliga blekmedlen, som man numer försöker undvika, i mindre mängder för att döda mikroorganismer och inaktivera enzymet.In principle, the procedures according to the two publications involve the use of the environmentally hazardous bleach, which is now being avoided, in small quantities to kill microorganisms and inactivate the enzyme.
Enligt föreliggande uppfinning föreslås användning av substanser som genom sin förmåga att bryta ner proteiner undertrycker eller inhiberar den nedbrytande verkan som vissa enzymer såsom peroxidaser, katalas m fl har på väteperoxid vid blekning av cellulosafibrer med väteperoxid.According to the present invention it is proposed to use substances which by their ability to breaking down proteins suppresses or inhibits the degrading action of certain enzymes such as peroxidases, catalase, etc. have on hydrogen peroxide when bleaching cellulose fibers with hydrogen peroxide.
Dessa substanser är proteolytiska enzym (proteaser) d v s ämnen som utmärker sig genom sin fömiåga att spjälka proteiner. Då peroxidaser och katalas är proteiner kommer de att inaktiveras genom att de bryts ner då de kommer i kontakt med proteaserna. /0 X5' 763 Uppfinningen beskrivs genom följande icke begränsande utföringsexempel.These substances are proteolytic enzymes (proteases), ie substances that are distinguished by its ability to cleave proteins. Since peroxidases and catalase are proteins, they will inactivated by breaking them down when they come in contact with the proteases. / 0 X5 ' 763 The invention is described by the following non-limiting exemplary embodiments.
Exempel l. Katalasinhiberande verkan av det proteolytiska enzymet subtilisin.Example 1. Catalase inhibitory action of the proteolytic enzyme subtilisin.
Fyra lösningar gjordes: l. 83,6 mg/l katalas i vatten. Denna kyldes till O°C. 2. 83,6 mg/l katalas i vatten, 3. 83,6 mg/l katalas och 2,6 mg/l subtilisin. 4. 83,6 mg/1 katalas och 13,2 mg/l subtilisin.Four solutions were made: l. 83.6 mg / l catalase in water. This was cooled to 0 ° C. 2. 83.6 mg / l catalase in water, 3. 83.6 mg / l catalase and 2.6 mg / l subtilisin. 4. 83.6 mg / l catalase and 13.2 mg / l subtilisin.
Lösning 2, 3 och 4 tempererades till 30°C. Eñer lO, 30, 50 och 70 min inkubering togs 100 ul ut av de fyra lösningarna och blandades med 2,9 ml O, l% väteperoxidlösning som var buffrad med fosfat till pH 7.Solutions 2, 3 and 4 were tempered to 30 ° C. One 10, 30, 50 and 70 min incubation was taken 100 μl out of the four solutions and mixed with 2.9 ml of 0.1% hydrogen peroxide solution which was buffered with phosphate to pH 7.
Nedbrytningshastigheten av väteperoxiden mättes sedan med en spektrofotometer vid 256 nm och framgår av diagram där nedbrytningshastigheten mätt som absorbansändring/sekund på y-axeln är angiven mot inkuberingstiden i minuter på x-axeln.The decomposition rate of the hydrogen peroxide was then measured with a spectrophotometer at 256 nm and is shown in diagrams where the degradation rate measured as absorbance change / second on the y-axis is indicated against the incubation time in minutes on the x-axis.
Som framgår av diagrammet är nedbrytningshastigheten ca 1,7 milliabsorbansenheter/sek med lösning l och 2 medan den har sjunkit till ca 1,5 med lösning 3 och till ca 1,2 med lösning 4, alla mätta efter 70 min.As can be seen from the diagram, the degradation rate is about 1.7 milliabsorbent units / sec with solution 1 and 2 while it has dropped to about 1.5 with solution 3 and to about 1.2 with solution 4, all saturated after 70 min.
Exempel 2. Som ovan men vid 40°C.Example 2. As above but at 40 ° C.
Exempel 3. Som ovan med vid 50°C.Example 3. As above with at 50 ° C.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9404129A SE9404129L (en) | 1994-11-28 | 1994-11-28 | Inactivation of peroxide-degrading enzymes in the bleaching of cellulose fibers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9404129A SE9404129L (en) | 1994-11-28 | 1994-11-28 | Inactivation of peroxide-degrading enzymes in the bleaching of cellulose fibers |
Publications (3)
Publication Number | Publication Date |
---|---|
SE9404129D0 SE9404129D0 (en) | 1994-11-28 |
SE502763C2 true SE502763C2 (en) | 1996-01-08 |
SE9404129L SE9404129L (en) | 1996-01-08 |
Family
ID=20396148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SE9404129A SE9404129L (en) | 1994-11-28 | 1994-11-28 | Inactivation of peroxide-degrading enzymes in the bleaching of cellulose fibers |
Country Status (1)
Country | Link |
---|---|
SE (1) | SE9404129L (en) |
-
1994
- 1994-11-28 SE SE9404129A patent/SE9404129L/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
SE9404129D0 (en) | 1994-11-28 |
SE9404129L (en) | 1996-01-08 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
NUG | Patent has lapsed |