EP0395792A2 - Procédé de blanchiment de pâte - Google Patents
Procédé de blanchiment de pâte Download PDFInfo
- Publication number
- EP0395792A2 EP0395792A2 EP89117233A EP89117233A EP0395792A2 EP 0395792 A2 EP0395792 A2 EP 0395792A2 EP 89117233 A EP89117233 A EP 89117233A EP 89117233 A EP89117233 A EP 89117233A EP 0395792 A2 EP0395792 A2 EP 0395792A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching
- pulp
- chlorine
- oxygen
- enzyme treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004061 bleaching Methods 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000011282 treatment Methods 0.000 claims abstract description 59
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 108090000790 Enzymes Proteins 0.000 claims abstract description 46
- 102000004190 Enzymes Human genes 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000001301 oxygen Substances 0.000 claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 35
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 25
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 25
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 25
- 239000007844 bleaching agent Substances 0.000 claims abstract description 18
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940088598 enzyme Drugs 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229940059442 hemicellulase Drugs 0.000 claims description 5
- 108010002430 hemicellulase Proteins 0.000 claims description 5
- 108010059892 Cellulase Proteins 0.000 claims description 3
- 108090000371 Esterases Proteins 0.000 claims description 3
- 108010059820 Polygalacturonase Proteins 0.000 claims description 3
- 229940106157 cellulase Drugs 0.000 claims description 3
- 108010093305 exopolygalacturonase Proteins 0.000 claims description 3
- 239000011122 softwood Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 11
- 231100000167 toxic agent Toxicity 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 26
- 235000017168 chlorine Nutrition 0.000 description 22
- 229940060038 chlorine Drugs 0.000 description 22
- 229940099041 chlorine dioxide Drugs 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000004045 organic chlorine compounds Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 239000007857 degradation product Substances 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 244000155172 Podocarpus elatus Species 0.000 description 1
- 235000003209 Podocarpus elatus Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000223259 Trichoderma Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000009896 oxidative bleaching Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
- D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
- D21C9/144—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites with ClO2/Cl2 and other bleaching agents in a multistage process
-
- 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
- D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16
-
- 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
Definitions
- the present invention relates to a procedure for the bleaching of pulp, in which procedure the oxidating bleaching chemical is oxygen.
- Especially pulp obtained from a sulphate pulping process is of brown colour, which is mainly due to the lignin remaining in the pulp.
- Lignin is removed from the pulp by bleaching, which is a process consisting of several stages. During this process, the pulp is treated alternately with oxidizing, lignin-degrading chemicals and chemicals dissolving the degradation products. Oxidizing agents commonly used are oxygen and chlorine-containing chemicals, whereas alkali solutions are used for eliminating the degradation products.
- the spent bleach liquors causing the worst environmental pollution load are produced during the washing following the first chlorination and the first alkali treatment in the bleaching process.
- Various methods have been employed to reduce the pollution load, e.g. by replacing chlorine gas with chlorine dioxide or using oxygen as the oxidizing agent in the first bleaching stage, or by biological purification of the spent bleach liquor.
- the results achieved by these methods have not been completely satisfactory.
- Al though the amounts of chlorophenols and other toxic chlorine compounds in the spent bleach liquor have been significantly reduced by employing chlorine dioxide and oxygen bleaching, it has not been possible to achieve a sufficient reduction in the chemical oxygen demand values of the liquors. Therefore, the methods referred to have required the employment of efficient biological purification.
- the object of the present invention is to achieve a solution that enables the toxic content and the value of chemical oxygen demand of the spent bleach liquor to be reduced so as to reduce the need for purification of the liquor.
- the invention is based on oxygen bleaching and it is characterized in that oxygen is used in the first oxidation stage of the bleaching process, that the pulp is subjected to enzyme treatment, and that after the oxygen bleaching and enzyme treatment, the pulp is washed.
- enzyme treatment involves an essential reduction in the amount of toxic compounds in the spent bleach liquor while at the same time reducing its chemical oxygen demand, especially when the oxidizing chemical used in the first bleaching stage is oxygen.
- oxidizing chemical i.e. pure chlorine gas
- the pulp can be subjected to enzyme treatment and washing before the first oxidation stage.
- a preferable alternative solution is to carry out the enzyme treatment and washing after the first oxidation stage.
- the enzyme breaks down hemicellulose and/or lignin contained in the pulp and renders the pulp more spongy, thus enhancing the effect of the chemicals in subsequent oxidation and alkali treatment stages.
- the degradation products are removed and can be directed to incineration so that they will not contribute to the pollution load at all but are instead utilized in the energy handling system of the plant.
- the subsequent oxidation stages after oxygen bleaching can be implemented using a bleaching chemical containing chlorine, e.g. chlorine gas and/or chlorine dioxide.
- a bleaching chemical containing chlorine e.g. chlorine gas and/or chlorine dioxide.
- the production of detrimental chlorine compounds will thus be limited to these process stages, and to minimize the amounts of these compounds it is preferable to use chlorine dioxide to as large an extent as possible. This makes it possible to reduce the content of organic chlorine compounds in the spent bleach liquor by more than 70% even in the bleaching of softwood pulp. This is a result unattainable with previously known bleaching methods.
- the bleaching of pulp by the procedure of the invention can be performed by employing alternate oxidation and alkali phases and washing the pulp after each of these phases to remove the bleaching chemicals and degradation products.
- the enzyme treatment in the procedure of the invention is preferably carried out in a temperature range of 10-90 °C, the most suitable range being 40-80 °C, with pH values in the range 3.0-10.0, most suitably 4.0-8.0.
- the enzyme used can be a hemicellulase, cellulase, pectinase, esterase or a mixture of these.
- the invention also concerns the use of an enzyme in the bleaching of pulp, with oxygen used as the bleaching chemical used in the first oxidation stage, and especially its use as a means of reducing the chlorine content of the spent bleach liquor when the bleaching chemical used in the first oxidation stage is oxygen and in subsequent oxidation stages a chemical containing chlorine, e.g. chlorine gas or chlorine dioxide.
- the enzyme is preferably a hemicellulase, cellulase, pectinase, esterase or a mixture of these, and it is used essentially in the manner explained in the above description of the bleaching procedure.
- a diluted enzyme mixture KD 50 (hemicellulase) was added to 220 g of dry matter obtained from pine sulphate pulp (with a dry matter content of 30%) so that a mixture with a consistency of 10% and a xylanase activity of 5 U/g of pulp dry matter was obtained.
- the temperature in the enzyme treatment was 55 °C and the duration of treatment 2 h.
- the pulp was subjected to preliminary oxygen bleaching.
- the acidity of the pulp was adjusted to pH 12.
- the temperature was 100 °C, overpressure 2 bar and duration of treatment 45 min.
- the pulp was washed in a Buchner funnel with a 20-fold amount of water.
- the pulp was subjected to an oxidizing bleaching treatment using a mixture containing 50 % chlorine dioxide and 50 % chlorine gas. Of this mixture, a dose equal to 2.0 x kappa number after oxygen bleaching was used. Treatment temperature was 40 °C and duration 45 min. After oxidation the pulp was washed in a Buchner funnel with a 20-fold amount of water.
- the mass was subjected to an alkali treatment using a 5 % sodium hydroxide solution in a dose of 0.9 x kappa. Consistency of solution was 10 %, treatment temperature 60 °C and duration of treatment 90 min. After the alkali treatment the pulp was washed in the same way as after oxidation.
- the bleaching was continued by repeating the oxidation and alkali phases and then once more the oxidation phase and washing the pulp between these phases as described above.
- the amount of chlorine dioxide in the second oxidation phase was 26 % and in the third phase 13 % of the amount of chlorine dioxide in the first oxidation phase.
- the dosage of sodium hydroxide was 1 % of the amount of chemical pulp.
- the liquids obtained from the washing stages phases after oxidation and enzyme treatment can be burned in a soda recovery boiler, in which case the amount of organic matter left in the spent bleach liquor is substantially smaller than in conventional chlorine bleaching and also smaller than in oxygen bleaching carried out without using an enzyme.
- Preliminary oxygen bleaching of 670 g of brown pine sulphate pulp was performed as follows: The pH value of the pulp was adjusted to 12 using NaOH, whereupon the pulp was subjected to a 45-min. oxygen treatment in an autoclave at a temperature of 100 °C and an oxygen overpressure of 2 bar.
- the pulp was acidated with sulphuric acid to pH 6.
- An amount of diluted enzyme mixture (Trichoderma [r] hemicellulase MK 901, Cultor Oy) was then added to the pulp so that a mixture consistency of 10 % and xylanase activity of 5 U/g of pulp dry matter was obtained.
- the pulp was subjected to a 2-hour enzyme treatment at 55 °C.
- the pulp was subjected to an oxidating bleaching treatment using chlorine dioxide in a dosage of 6.6 % of pulp dry matter. Consistency of the mixture was 10 %, temperature during treatment 70 °C, and duration of treatment 180 min. After the treatment the pulp was washed in a Buchner funnel with a 20-fold amount of water.
- the pulp was treated with NaOH (amount of NaOH 1 % of the dry matter of the pulp) for 90 min. Viscosity of the pulp was 10 %. After treatment, the pulp was washed with a 20-fold amount of water.
- the pulp was subjected to a chlorine dioxide treatment.
- the dosage of chlorine dioxide was 3.3 % of pulp dry matter, mixture viscosity 10 %, treatment temperature 75 °C and duration 240 min. After treatment, the pulp was again washed with a 20-fold amount of water.
- Such a procedure allows the amount of organing chlorine compounds in the spent bleach liquor to be substantially reduced, even by more than 70 %. If the spent bleach liquors from all those stages which precede bleaching stages involving chlorine chemicals are subjected to burning, then the chemical oxygen demand of the spent bleach liquor will also be reduced by more than 50 %.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Paper (AREA)
- Cereal-Derived Products (AREA)
- Noodles (AREA)
- Bakery Products And Manufacturing Methods Therefor (AREA)
- Table Devices Or Equipment (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Hard Magnetic Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89117233T ATE91518T1 (de) | 1989-05-04 | 1989-09-18 | Verfahren zum bleichen von zellstoff. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI892151 | 1989-05-04 | ||
FI892151A FI86896B (fi) | 1989-05-04 | 1989-05-04 | Foerfarande foer blekning av cellulosamassa. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0395792A2 true EP0395792A2 (fr) | 1990-11-07 |
EP0395792A3 EP0395792A3 (fr) | 1991-01-16 |
EP0395792B1 EP0395792B1 (fr) | 1993-07-14 |
Family
ID=8528357
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89117233A Revoked EP0395792B1 (fr) | 1989-05-04 | 1989-09-18 | Procédé de blanchiment de pâte |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0395792B1 (fr) |
JP (1) | JPH02293486A (fr) |
AT (1) | ATE91518T1 (fr) |
CA (1) | CA1339593C (fr) |
DE (1) | DE68907593D1 (fr) |
ES (1) | ES2045320T3 (fr) |
FI (1) | FI86896B (fr) |
NO (1) | NO172355C (fr) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2248075A (en) * | 1990-09-11 | 1992-03-25 | Sandoz Ltd | Bleaching chemical pulp |
US5231022A (en) * | 1990-07-24 | 1993-07-27 | Showa Denko K.K. | Cellulase isolated from bacillus ferm bp-3431 or a mutant strain thereof |
AU647891B2 (en) * | 1991-01-21 | 1994-03-31 | Kabushiki Kaisha Kobe Seiko Sho | Process for bleaching pulp |
US5434071A (en) * | 1990-01-10 | 1995-07-18 | Korsnas Aktiebolag | α-L-arabinofuranosidase and xylanase from Bacillus stearothermophilus NCIMB 40221, NCIMB 40222 or mutant thereof for delignification |
US5487812A (en) * | 1991-05-02 | 1996-01-30 | Mesta-Serla Oy | Treatment of alkaline bleached mechanical wood pulp with pectinase |
EP0487557B1 (fr) * | 1989-08-14 | 1996-02-14 | Genencor International Europe Oy | Amelioration du blanchiment d'une pate |
US5591304A (en) * | 1991-05-07 | 1997-01-07 | Von Kreisler Selting Werner | Method for the use of enzymes in bleaching paper pulp |
US5785811A (en) * | 1992-11-09 | 1998-07-28 | The Mead Corporation | Process for treating lignocellulosic material with soybean peroxidase in the presence of peroxide |
US5837515A (en) * | 1990-05-16 | 1998-11-17 | Alko-Yhtiot Oy | Enzyme preparations and methods for their production |
US5871730A (en) * | 1994-07-29 | 1999-02-16 | Universite De Sherbrooke | Thermostable xylanase DNA, protein and methods of use |
US5935836A (en) * | 1994-07-29 | 1999-08-10 | Rohm Enzyme Finland Oy | Actinomadura xylanase sequences and methods of use |
EP1039020A1 (fr) * | 1999-03-23 | 2000-09-27 | Oji Paper Co., Ltd. | Procede de blanchiment de pate lignocellulosique |
US6300114B1 (en) | 1994-07-29 | 2001-10-09 | Rohm Enzyme Finland Oy | Sequences of xylanase and xylanase expression vectors |
US6824646B2 (en) | 1999-03-23 | 2004-11-30 | Oji Paper Co., Ltd. | Process for oxygen bleaching and enzyme treating lignocellulosic pulp with liquid treatment and recovery |
US6942754B2 (en) | 1999-03-23 | 2005-09-13 | Oji Paper Co., Ltd. | Process for producing xylooligosaccharide from lignocellulose pulp |
US7541175B1 (en) | 2000-12-22 | 2009-06-02 | Iogen Energy Corporation | Alkaline extraction stages comprising xylanase |
US7816129B2 (en) | 1994-07-29 | 2010-10-19 | Ab Enzymes Gmbh | Production and secretion of proteins of bacterial origin in filamentous fungi |
US9096519B2 (en) | 2013-01-10 | 2015-08-04 | California Institute Of Technology | Process for the synthesis of ketones from internal alkenes |
US9586883B2 (en) | 2013-04-19 | 2017-03-07 | California Institute Of Technology | Aldehyde-selective wacker-type oxidation of unbiased alkenes |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111979823A (zh) * | 2020-08-07 | 2020-11-24 | 齐鲁工业大学 | 一种硫酸盐木浆短程序ecf漂白工艺x/d-z-p(x/z-d-p) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5468402A (en) * | 1977-11-09 | 1979-06-01 | Kogyo Gijutsuin | Property modification of biochemical pulp |
FI81395B (fi) * | 1988-03-14 | 1990-06-29 | Cultor Oy | Foerfarande foer blekning av cellulosamassa. |
FI90888B (fi) * | 1989-02-14 | 1993-12-31 | Enso Gutzeit Oy | Menetelmä selluloosamassan valkaisemiseksi |
-
1989
- 1989-05-04 FI FI892151A patent/FI86896B/fi not_active Application Discontinuation
- 1989-09-18 ES ES89117233T patent/ES2045320T3/es not_active Expired - Lifetime
- 1989-09-18 NO NO893716A patent/NO172355C/no not_active IP Right Cessation
- 1989-09-18 JP JP1241666A patent/JPH02293486A/ja active Pending
- 1989-09-18 CA CA000611771A patent/CA1339593C/fr not_active Expired - Fee Related
- 1989-09-18 EP EP89117233A patent/EP0395792B1/fr not_active Revoked
- 1989-09-18 AT AT89117233T patent/ATE91518T1/de not_active IP Right Cessation
- 1989-09-18 DE DE8989117233T patent/DE68907593D1/de not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
None |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0487557B1 (fr) * | 1989-08-14 | 1996-02-14 | Genencor International Europe Oy | Amelioration du blanchiment d'une pate |
US5434071A (en) * | 1990-01-10 | 1995-07-18 | Korsnas Aktiebolag | α-L-arabinofuranosidase and xylanase from Bacillus stearothermophilus NCIMB 40221, NCIMB 40222 or mutant thereof for delignification |
US5837515A (en) * | 1990-05-16 | 1998-11-17 | Alko-Yhtiot Oy | Enzyme preparations and methods for their production |
US5231022A (en) * | 1990-07-24 | 1993-07-27 | Showa Denko K.K. | Cellulase isolated from bacillus ferm bp-3431 or a mutant strain thereof |
US5314637A (en) * | 1990-07-24 | 1994-05-24 | Showa Denko K.K. | Detergent comprising isolated cellulase from bacillus ferm bp-3431 or a mutant strain thereof, surfactant and builder |
US5318905A (en) * | 1990-07-24 | 1994-06-07 | Showa Denko K.K. | Composition containing celluase from Bacillus Ferm BP-3431 or a mutant strain thereof, and paper pulp and method of using celluase to treat paper pulp slurry |
GB2248075A (en) * | 1990-09-11 | 1992-03-25 | Sandoz Ltd | Bleaching chemical pulp |
GB2248075B (en) * | 1990-09-11 | 1994-06-29 | Sandoz Ltd | Chlorine-free process for bleaching pulp |
AU647891B2 (en) * | 1991-01-21 | 1994-03-31 | Kabushiki Kaisha Kobe Seiko Sho | Process for bleaching pulp |
US5487812A (en) * | 1991-05-02 | 1996-01-30 | Mesta-Serla Oy | Treatment of alkaline bleached mechanical wood pulp with pectinase |
US5591304A (en) * | 1991-05-07 | 1997-01-07 | Von Kreisler Selting Werner | Method for the use of enzymes in bleaching paper pulp |
US5785811A (en) * | 1992-11-09 | 1998-07-28 | The Mead Corporation | Process for treating lignocellulosic material with soybean peroxidase in the presence of peroxide |
US5871730A (en) * | 1994-07-29 | 1999-02-16 | Universite De Sherbrooke | Thermostable xylanase DNA, protein and methods of use |
US5935836A (en) * | 1994-07-29 | 1999-08-10 | Rohm Enzyme Finland Oy | Actinomadura xylanase sequences and methods of use |
US6300114B1 (en) | 1994-07-29 | 2001-10-09 | Rohm Enzyme Finland Oy | Sequences of xylanase and xylanase expression vectors |
US6506593B2 (en) | 1994-07-29 | 2003-01-14 | Rohm Enzyme Finland Oy | Production and secretion of proteins of bacterial origin in filamentous fungi |
US6667170B1 (en) | 1994-07-29 | 2003-12-23 | Röhm Enzyme Finland OY | Sequences of Xylanase and Xylanase expression vectors |
US7816129B2 (en) | 1994-07-29 | 2010-10-19 | Ab Enzymes Gmbh | Production and secretion of proteins of bacterial origin in filamentous fungi |
EP1039020A1 (fr) * | 1999-03-23 | 2000-09-27 | Oji Paper Co., Ltd. | Procede de blanchiment de pate lignocellulosique |
US6824646B2 (en) | 1999-03-23 | 2004-11-30 | Oji Paper Co., Ltd. | Process for oxygen bleaching and enzyme treating lignocellulosic pulp with liquid treatment and recovery |
US6942754B2 (en) | 1999-03-23 | 2005-09-13 | Oji Paper Co., Ltd. | Process for producing xylooligosaccharide from lignocellulose pulp |
US7541175B1 (en) | 2000-12-22 | 2009-06-02 | Iogen Energy Corporation | Alkaline extraction stages comprising xylanase |
US9096519B2 (en) | 2013-01-10 | 2015-08-04 | California Institute Of Technology | Process for the synthesis of ketones from internal alkenes |
US9586883B2 (en) | 2013-04-19 | 2017-03-07 | California Institute Of Technology | Aldehyde-selective wacker-type oxidation of unbiased alkenes |
Also Published As
Publication number | Publication date |
---|---|
EP0395792B1 (fr) | 1993-07-14 |
NO172355C (no) | 1993-07-07 |
ES2045320T3 (es) | 1994-01-16 |
NO172355B (no) | 1993-03-29 |
CA1339593C (fr) | 1997-12-23 |
NO893716L (no) | 1990-11-05 |
ATE91518T1 (de) | 1993-07-15 |
EP0395792A3 (fr) | 1991-01-16 |
FI86896B (fi) | 1992-07-15 |
JPH02293486A (ja) | 1990-12-04 |
FI892151A0 (fi) | 1989-05-04 |
FI892151A (fi) | 1990-11-05 |
DE68907593D1 (de) | 1993-08-19 |
NO893716D0 (no) | 1989-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0395792B1 (fr) | Procédé de blanchiment de pâte | |
EP0512590B1 (fr) | Procédé de blanchiment de matériaux contenant de la lignocellulose | |
EP0511695B1 (fr) | Procédé pour le blanchiment de pâte à papier contenant de la lignocellulose | |
EP0383999B1 (fr) | Procédé de blanchiment de pâte | |
JP2825346B2 (ja) | リグノセルロース物質の環境上改良された漂白方法 | |
CA1150011A (fr) | Methode de blanchiment en matieres a teneur de lignocellulose | |
EP0407421B1 (fr) | Procede de reduction de chlorure residuelle dans des pates feuillus | |
EP0402335A2 (fr) | Procédé de blanchiment de pâtes contenant de la lignocellulose | |
JPS61138793A (ja) | 強化酸化抽出法 | |
EP0456626B1 (fr) | Procédé de blanchiment de matériaux contenant de la lignocellulose | |
US5409570A (en) | Process for ozone bleaching of oxygen delignified pulp while conveying the pulp through a reaction zone | |
FI105213B (fi) | Menetelmä valkaistun massan valmistamiseksi lignoselluloosamateriaalista | |
EP0513140B2 (fr) | Procede de blanchiment de pulpe chimique | |
EP0408803A1 (fr) | Procédé de blanchiment de pâte au sulfate | |
US4560437A (en) | Process for delignification of chemical wood pulp using sodium sulphite or bisulphite prior to oxygen-alkali treatment | |
FI96973B (fi) | Menetelmä halogeeniorgaanisten yhdisteiden vähentämiseksi valkaisujätevesissä | |
EP0494519A1 (fr) | Procédé de lessivage à haut rendement | |
WO1992007998A1 (fr) | Procede de blanchiment de pate | |
EP0717800A1 (fr) | Blanchiment d'une p te a papier a concentration moyenne avec de l'ozone, apres decoloration de cette p te a haute concentration avec de l'ozone | |
JPH08218290A (ja) | 非塩素漂白パルプの製造方法 | |
CN108560301A (zh) | 一种固体缓释型生物酶制浆补充漂白剂及其制备方法 | |
JPH06294087A (ja) | 漂白クラフトパルプ | |
WO1989003451A1 (fr) | Procede de blanchiment de pulpe de cellulose | |
CA2130906A1 (fr) | Methode pour le traitement enzymatique de la pate chimique avant le blanchiment | |
WO1991015627A1 (fr) | Procede relatif au blanchiment d'une pate chimique |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19910415 |
|
17Q | First examination report despatched |
Effective date: 19911210 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 19930714 Ref country code: DE Effective date: 19930714 Ref country code: CH Effective date: 19930714 Ref country code: NL Effective date: 19930714 Ref country code: LI Effective date: 19930714 |
|
REF | Corresponds to: |
Ref document number: 91518 Country of ref document: AT Date of ref document: 19930715 Kind code of ref document: T |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 68907593 Country of ref document: DE Date of ref document: 19930819 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19931014 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19931015 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2045320 Country of ref document: ES Kind code of ref document: T3 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
26 | Opposition filed |
Opponent name: SANDOZ LTD. Effective date: 19940412 |
|
26 | Opposition filed |
Opponent name: CALL, HANS-PETER, DR. Effective date: 19940413 Opponent name: SANDOZ LTD. Effective date: 19940412 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19931014 |
|
26 | Opposition filed |
Opponent name: SANDOZ LTD. Effective date: 19940412 Opponent name: GIST-BROCADES NV Effective date: 19940414 Opponent name: CALL, HANS-PETER, DR. Effective date: 19940413 |
|
R26 | Opposition filed (corrected) |
Opponent name: SANDOZ LTD. * 940413 CALL, HANS-PETER, DR. * 94041 Effective date: 19940412 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 89117233.0 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19950807 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19950905 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19950919 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19950928 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19950929 Year of fee payment: 7 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
27W | Patent revoked |
Effective date: 19960513 |