EP0442425A1 - Procédé pour le blanchiment et la délignification exempt de chlore de pâtes cellulosiques - Google Patents
Procédé pour le blanchiment et la délignification exempt de chlore de pâtes cellulosiques Download PDFInfo
- Publication number
- EP0442425A1 EP0442425A1 EP91101890A EP91101890A EP0442425A1 EP 0442425 A1 EP0442425 A1 EP 0442425A1 EP 91101890 A EP91101890 A EP 91101890A EP 91101890 A EP91101890 A EP 91101890A EP 0442425 A1 EP0442425 A1 EP 0442425A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pulp
- cyanamide
- weight
- treatment
- peroxide
- 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 34
- 238000000034 method Methods 0.000 title claims description 19
- 150000002978 peroxides Chemical class 0.000 claims abstract description 25
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001912 cyanamides Chemical class 0.000 claims abstract description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000460 chlorine Substances 0.000 abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 235000019641 whiteness Nutrition 0.000 description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 24
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000000605 extraction Methods 0.000 description 8
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- LPHFLPKXBKBHRW-UHFFFAOYSA-L magnesium;hydrogen sulfite Chemical compound [Mg+2].OS([O-])=O.OS([O-])=O LPHFLPKXBKBHRW-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004155 Chlorine dioxide Substances 0.000 description 3
- 241001070947 Fagus Species 0.000 description 3
- 235000010099 Fagus sylvatica Nutrition 0.000 description 3
- 241000218657 Picea Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000019398 chlorine dioxide Nutrition 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000004182 chemical digestion Methods 0.000 description 1
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- GOKQBRXJUKTYSC-UHFFFAOYSA-N magnesium;azanidylidenemethylideneazanide Chemical compound [Mg+2].[N-]=C=[N-] GOKQBRXJUKTYSC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- MBEGFNBBAVRKLK-UHFFFAOYSA-N sodium;iminomethylideneazanide Chemical compound [Na+].[NH-]C#N MBEGFNBBAVRKLK-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood 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
- D21C9/147—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
- D21C9/1026—Other features in bleaching processes
- D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- 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
Definitions
- the present invention relates to a process for chlorine-free bleaching and delignification of cellulose which has already been pre-bleached with oxygen and peroxide or oxygen and ozone.
- Lignin-free pulp is largely required to produce white-stable and / or high-strength paper products.
- the pulp made from vegetable raw materials such as wood, reeds, straw, bagasse or the like. is obtained by chemical digestion (sulfate or sulfite digestion), subjected to a delignifying bleach.
- the present invention is therefore based on the object of developing a process for chlorine-free bleaching and delignification of pulp pre-bleached with oxygen and peroxide or oxygen and ozone, which does not have the disadvantages of the prior art mentioned, but rather with little technical effort and without assistance of chlorine-containing treatment agents enables the production of pulps with high whiteness.
- This object has been achieved according to the invention by subjecting the pre-bleached pulp to a double treatment with peroxide which has been activated with cyanamide and / or cyanamide salts.
- pre-bleached pulp is used as the starting material, which has been pretreated with oxygen and peroxide or oxygen and ozone by a conventional extraction step and which has quite different degrees of whiteness depending on the type of pulp.
- pre-bleached spruce pulps have whiteness levels of 65% to 75%, the corresponding whiteness levels of beech pulp are already over 80% in some cases.
- the kappa values for the degree of delignification are normally between 2 and 10, in particular between 3 and 8.
- the two treatment stages according to the invention include the bleaching and delignification of peroxide with cyanamide or cyanamide salts, which are preferably in the form of the alkaline salts such as e.g. Sodium hydrogen cyanamide, calcium cyanamide or magnesium cyanamide can be used.
- cyanamide or cyanamide salts which are preferably in the form of the alkaline salts such as e.g. Sodium hydrogen cyanamide, calcium cyanamide or magnesium cyanamide can be used.
- the amounts of peroxide and cyanamide derivatives differ only slightly in the two treatment stages. All water-soluble bleach-active peroxy compounds can be used as the peroxide. Hydrogen peroxide or sodium peroxide are preferred.
- the second stage is preferably carried out at a cyanamide content of 0.01 to 0.7% by weight, in particular 0.03 to 0.23% by weight, in each case based on the dry weight of the pulp.
- the peroxide content can preferably be varied between 0.1 and 3.0% by weight during the first treatment stage and between 0.1 and 2.0% by weight based on the dry weight of the pulp during the second treatment stage.
- the pH is made alkaline and can generally be from 9 to 12.
- the pH is adjusted with the known alkaline substances, sodium hydroxide being preferred for reasons of better solubility. Normally, 0.3 to 1.5% by weight of sodium hydroxide, based on the dry weight of the pulp, is sufficient to set the desired pH.
- the solid densities can be varied within wide limits in both treatment stages, solid densities of 5 to 30% by weight, in particular those of 7 to 20% by weight, being particularly preferred.
- the treatment stages according to the invention are preferably carried out at temperatures from 30 ° to 95 ° C., particularly preferably from 55 ° to 80 ° C., wherein treatment times of 1 to 8 hours are usually required in order to achieve the desired degree of whiteness to reach.
- the addition of cyanamide and / or cyanamide salts generally makes it possible to shorten the reaction time and / or to lower the temperature compared to peroxide treatment without this activator, if this is desired for any reason.
- Beech magnesium bisulfite pulp was further treated after an EOP pretreatment with 82.6% whiteness analogously to Example 1 under the following conditions:
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cereal-Derived Products (AREA)
- Eye Examination Apparatus (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Gyroscopes (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT91101890T ATE103649T1 (de) | 1990-02-13 | 1991-02-11 | Verfahren zur chlorfreien bleiche und delignifizierung von zellstoff. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4004364 | 1990-02-13 | ||
| DE4004364A DE4004364A1 (de) | 1990-02-13 | 1990-02-13 | Verfahren zur chlorfreien bleiche und delignifizierung von zellstoff |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0442425A1 true EP0442425A1 (fr) | 1991-08-21 |
| EP0442425B1 EP0442425B1 (fr) | 1994-03-30 |
Family
ID=6400030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91101890A Expired - Lifetime EP0442425B1 (fr) | 1990-02-13 | 1991-02-11 | Procédé pour le blanchiment et la délignification exempt de chlore de pâtes cellulosiques |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0442425B1 (fr) |
| AT (1) | ATE103649T1 (fr) |
| CA (1) | CA2036173C (fr) |
| DE (2) | DE4004364A1 (fr) |
| ES (1) | ES2051531T3 (fr) |
| FI (1) | FI910703L (fr) |
| NO (1) | NO176329C (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0479319A1 (fr) * | 1990-10-05 | 1992-04-08 | SKW Trostberg Aktiengesellschaft | Procédé pour le blanchiment et la délignification pauvre en chlore de pâtes cellulosiques |
| WO1992012289A1 (fr) * | 1991-01-03 | 1992-07-23 | Union Camp Patent Holding, Inc. | Procede de decoloration de pulpe lignocellulosique sans utilisation de chlore |
| EP0543175A1 (fr) * | 1991-11-19 | 1993-05-26 | Degussa Aktiengesellschaft | Procédé pour améliorer la blancheur dans le blanchiment au peroxyde de pâtes à papier par l'addition de cyanates |
| WO1996013634A1 (fr) * | 1994-10-31 | 1996-05-09 | Pulp And Paper Research Institute Of Canada | Procede de delignification et de blanchiment de cellulose chimique |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0226114A1 (fr) * | 1985-12-16 | 1987-06-24 | SKW Trostberg Aktiengesellschaft | Procédé de blanchiment et délignification de produits cellulosiques |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196043A (en) * | 1970-12-21 | 1980-04-01 | Scott Paper Company | Kraft pulp bleaching and recovery process |
| DE3714107A1 (de) * | 1987-04-28 | 1988-11-10 | Sueddeutsche Kalkstickstoff | Verfahren zur entfernung von rest-wasserstoffperoxid aus waessrigen loesungen |
| DE3802401A1 (de) * | 1988-01-28 | 1989-08-03 | Degussa | Verfahren zur herstellung von halbgebleichtem kraftzellstoff |
-
1990
- 1990-02-13 DE DE4004364A patent/DE4004364A1/de active Granted
-
1991
- 1991-02-06 NO NO910458A patent/NO176329C/no unknown
- 1991-02-11 AT AT91101890T patent/ATE103649T1/de not_active IP Right Cessation
- 1991-02-11 ES ES91101890T patent/ES2051531T3/es not_active Expired - Lifetime
- 1991-02-11 DE DE91101890T patent/DE59101249D1/de not_active Expired - Fee Related
- 1991-02-11 EP EP91101890A patent/EP0442425B1/fr not_active Expired - Lifetime
- 1991-02-12 CA CA002036173A patent/CA2036173C/fr not_active Expired - Fee Related
- 1991-02-13 FI FI910703A patent/FI910703L/fi not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0226114A1 (fr) * | 1985-12-16 | 1987-06-24 | SKW Trostberg Aktiengesellschaft | Procédé de blanchiment et délignification de produits cellulosiques |
Non-Patent Citations (1)
| Title |
|---|
| Wochenblatt für Papierfabrikation, Band 118, Nr. 10, Oktober 1990, Seite 423-424; Sturm,W.: "Hochweisse Sulfitzellstoffe durch absolut chlorfreie Bleiche-Aktivierung von Peroxid durch Nitrilamin." * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0479319A1 (fr) * | 1990-10-05 | 1992-04-08 | SKW Trostberg Aktiengesellschaft | Procédé pour le blanchiment et la délignification pauvre en chlore de pâtes cellulosiques |
| WO1992012289A1 (fr) * | 1991-01-03 | 1992-07-23 | Union Camp Patent Holding, Inc. | Procede de decoloration de pulpe lignocellulosique sans utilisation de chlore |
| EP0543175A1 (fr) * | 1991-11-19 | 1993-05-26 | Degussa Aktiengesellschaft | Procédé pour améliorer la blancheur dans le blanchiment au peroxyde de pâtes à papier par l'addition de cyanates |
| WO1996013634A1 (fr) * | 1994-10-31 | 1996-05-09 | Pulp And Paper Research Institute Of Canada | Procede de delignification et de blanchiment de cellulose chimique |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2036173C (fr) | 1996-01-23 |
| DE4004364A1 (de) | 1991-08-14 |
| ES2051531T3 (es) | 1994-06-16 |
| NO176329B (no) | 1994-12-05 |
| NO910458D0 (no) | 1991-02-06 |
| FI910703A0 (fi) | 1991-02-13 |
| NO176329C (no) | 1995-03-15 |
| DE59101249D1 (de) | 1994-05-05 |
| ATE103649T1 (de) | 1994-04-15 |
| CA2036173A1 (fr) | 1991-08-14 |
| NO910458L (no) | 1991-08-14 |
| FI910703A7 (fi) | 1991-08-14 |
| DE4004364C2 (fr) | 1992-11-19 |
| FI910703L (fi) | 1991-08-14 |
| EP0442425B1 (fr) | 1994-03-30 |
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