EP0226114B1 - Procédé de blanchiment et délignification de produits cellulosiques - Google Patents

Procédé de blanchiment et délignification de produits cellulosiques Download PDF

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Publication number
EP0226114B1
EP0226114B1 EP86116722A EP86116722A EP0226114B1 EP 0226114 B1 EP0226114 B1 EP 0226114B1 EP 86116722 A EP86116722 A EP 86116722A EP 86116722 A EP86116722 A EP 86116722A EP 0226114 B1 EP0226114 B1 EP 0226114B1
Authority
EP
European Patent Office
Prior art keywords
cyanamide
process according
bleaching
pulp
cellulose
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.)
Expired - Lifetime
Application number
EP86116722A
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German (de)
English (en)
Other versions
EP0226114A1 (fr
Inventor
Benedikt Dr. Hammer
Dr. Michaud Horst
Stefan Dr. Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
SKW Trostberg AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SKW Trostberg AG filed Critical SKW Trostberg AG
Priority to AT86116722T priority Critical patent/ATE54475T1/de
Publication of EP0226114A1 publication Critical patent/EP0226114A1/fr
Application granted granted Critical
Publication of EP0226114B1 publication Critical patent/EP0226114B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes

Definitions

  • the present invention relates to a method for bleaching and delignifying pulp-containing products such as Pulp, wood pulp, wood yield pulp and semi-pulp with peroxides and / or oxygen and / or ozone as bleach.
  • cellulose from wood, reeds, straw, bagasse, etc. these raw materials are subjected to a digestion process (sulfite or sulfate process). After digestion or grinding, the pulp is processed by washing and bleaching.
  • the main purpose of bleaching is to lighten the color of the pulp and to remove a large part of the lignin that is still present.
  • Standard bleaching generally consists of three stages, with the first stage being chlorination of the residual lignin with chlorine water or chlorine gas at pH 1-2. In the second stage the chlorine lignins are then washed out with water or sodium hydroxide solution, while in the third stage the pulp is subjected to an oxidizing and brightening bleaching with hypochlorite at pH> 6.
  • the particularly gentle, but expensive bleach with chlorine dioxide can either be added to the standard bleach or replace the hypochlorite treatment.
  • a disadvantage of these processes is the high environmental impact, which is caused above all by the chlorination, because a large amount of chlorine lignins are produced here, which represent a high pollution of wastewater.
  • a much more environmentally friendly method is bleaching with peroxides (such as sodium peroxide or hydrogen peroxide) or oxygen or oxon.
  • peroxides such as sodium peroxide or hydrogen peroxide
  • oxygen or oxon peroxide bleaching
  • Peroxide bleaching like chlorine dioxide treatment, is used in addition to standard bleaching levels to produce very white pulps.
  • these compounds can also be used as sole bleaching agents, particularly in the case of semi-bleaching.
  • a disadvantage of these processes is the limited bleaching effect of the peroxides or oxygen, so that the quality of a highly bleached pulp cannot be achieved economically. This is one of the main reasons why these bleaching processes have not yet become widespread.
  • FR-A-2 560 898 a method for digesting wood waste from industry and agriculture using peroxide and cyanamide is known.
  • Raw cellulose which is in a crystalline form, is broken down by an alkaline oxidizing treatment under extremely drastic conditions in such a way that it can be digested by microorganisms. In this way, however, no bleached delignified pulp is obtained, but rather a cellulose which is at least partially broken down in such a way that it can be used as feed for ruminants.
  • a method for activating peroxide-based bleaching agents is known, according to which a bleaching composition is obtained which consists of a bleaching agent, a buffer and cyanamide and which is suitable for bleaching fabrics in household washing machines at temperatures of 15 up to 70 ° C.
  • the present invention was therefore based on the object of developing a method for bleaching and delignifying cellulose-containing products with peroxides and / or oxygen and / or ozone, which does not have the disadvantages of the prior art mentioned, but which, despite good environmental compatibility, has an excellent bleaching effect .
  • This object was achieved according to the invention by additionally using 0.01 to 2.5% by weight of cyanamide and / or cyanamide salts, based on the dry weight of the pulp, and adjusting the pH of the bleach to 4 to 13.
  • hydrogen peroxide or sodium peroxide is used in an amount of 1 to 2.5% by weight, based on the dry matter content of the pulp, the H 2 0 2 preferably in a 30 to 35% aqueous solution is used.
  • the amount of cyanamide or cyanamide salt used according to the invention depends essentially on the peroxide or oxygen or ozone content and is 0.01 to 2.5% by weight, preferably 0.1 to 1.0% by weight. , based on the dry matter content of the pulp.
  • Cyanamide itself can be used both as a solid and as an aqueous solution (for example in the form of a 10 to 60% strength aqueous solution).
  • the alkaline salts such as sodium hydrogen cyanamide, calcium cyanamide or magnesium cyanamide are preferably used as cyanamide salts, because a certain alkaline pH value adjustment can be carried out at the same time.
  • the alkaline earth ions calcium and magnesium simultaneously have a stabilizing effect on the H 2 0 2 solution, as will be explained in more detail below.
  • Decomposition of the peroxide during the bleaching process is highly undesirable, since not only is the bleaching effect reduced, but at the same time there is also noticeable damage to the cellulose fiber.
  • stabilizers such as e.g. Water glass or complexing agents such as Na-EDTA in an amount of 0.1 to 5 wt .-%, based on the dry content of the pulp.
  • such an addition can generally be dispensed with if the heavy metal salts are removed by washing the pulp before bleaching.
  • the cellulose suspension can also be mixed with metal salts, which in addition to the stabilizing effect also have an activating effect on the peroxide.
  • metal salts which in addition to the stabilizing effect also have an activating effect on the peroxide.
  • amounts of 0.1 to 5% by weight, based on the dry weight of the pulp are recommended.
  • the aluminum salts or alkaline earth metal salts such as magnesium, calcium and barium salts are preferred as the metal salts, while the oxides, hydroxides, sulfates, chlorides and nitrates are particularly suitable as anions due to their low cost.
  • the optimum pH is 4.0 to 13.0, preferably 5.0 to 10.0, and that temperatures of 20 ° C. to 150 ° C. are to be regarded as preferred. In these conditions, the best results are generally high degree of whiteness possible with a relatively short treatment time and under gentle conditions, whereby the exact process parameters depend on the type and pretreatment of the pulp used.
  • the pulp suspension which generally has a solids content of 3 to 20% by weight, is adjusted to the desired pH with the customary acidic or basic reacting substances, and the stabilizers or activators such as water glass or metal salts are then added . The peroxide or oxygen or ozone and cyanamide are then added. After bleaching at a certain temperature, which takes between 15 minutes and 4 hours, depending on the type of whiteness desired, the pulp is worked up. For this purpose, the pulp suspension is adjusted to a pH of 5 to 7 and then the pulp is dewatered or dried.
  • the degree of delignification which is defined by the kappa value (see examples), is about 50% cheaper for peroxide or oxygen bleaching with cyanamide than for bleaching without cyanamide.
  • the viscosity which is a measure of the degree of polymerization of the cellulose and thus a direct indication of the damage (decomposition) of the cellulose fiber, is significantly better in the process according to the invention than in the processes according to the prior art.
  • the method according to the invention can in principle apply to all cellulose-containing products such as Sulfite or sulfate pulp, CTMP pulp, needle pulp or wood pulp and can be used in all bleaching stages such as pre-bleaching or post-bleaching. It is also possible to combine different bleaching levels, e.g. Peroxide and chlorine dioxide bleach if this appears beneficial for any reason.
  • cyanamide in the examples are given in% by weight and, unless stated otherwise, relate to the dry content of the pulp.
  • Example 2 The procedure was as in Example 1 but was carried out after the hydrogen peroxide addition another addition of 20 mg of cyanamide in the form of 0.2 g of a 10% cyanamide solution ( ⁇ -_ 0.2 wt .-% based on the dry content of the Pulp).
  • Example 1 The procedure is as in Example 4, but 0.5 g of a 10% strength aqueous cyanamide solution (0.5% by weight) were added after the H 2 O 2 addition. Refurbishment see Example 1.
  • Example 6 The procedure is as in Example 6, but with the addition of 4.0 g of a 10% strength aqueous cyanamide solution (1% by weight).
  • Example 10 The procedure is as in Example 10, but with the addition of 0.5 g of a 10% aqueous cyanamide solution.
  • Example 12 The procedure was as in Example 12, but with the addition of 0.5 g of a 10% cyanamide solution (0.5% by weight).
  • Example 14 The procedure is as in Example 14, but with the addition of 0.5 g of a 10% cyanamide solution.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
  • Prostheses (AREA)
  • Optical Transform (AREA)
  • Cereal-Derived Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Detergent Compositions (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)

Claims (14)

1. Procédé de blanchiment et de délignification de produits cellulosiques avec des peroxydes et/ou l'oxygène et/ou l'ozone, caractérisé en ce que l'on utilise en outre de 0,01 à 2,5% en poids de cyanamide et/ ou de sels de cyanamide, par rapport au poids sec de la cellulose, et l'on règle le pH du blanchiment entre 4 et 13.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise de 0,1 à 1,0% en poids de cyanamide et/ou de sels de cyanamide.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que le rapport molaire cyanamide:peroxyde est de 0,1 à 0,7.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on utilise le cyanamide sous forme d'une solution aqueuse de 10 à 60%.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que l'on utilise comme sel de cyanamide l'hydrogénocyanamide de sodium.
6. Procédé selon les revendications 1 à 5, caractérisé en ce que l'on utilise comme sel de cyanamide le cyanamide de calcium.
7. Procédé selon les revendications 1 à 6, caractérisé en ce que l'on ajoute encore à la suspension de cellulose des stabilisants de peroxyde en des quantités de 0,1 à 5% en poids par rapport au poids sec de la cellulose.
8. Procédé selon la revendication 7, caractérisé en ce que l'on utilise comme stabilisant de peroxyde du verre soluble.
9. Procédé selon la revendication 7, caractérisé en ce que l'on utilise comme stabilisant de peroxyde un complexant comme par exemple l'éthylènediaminetétraacétate de sodium.
10. Procédé selon les revendications 1 à 9, caractérisé en ce que l'on fait réagir la suspension de cellulose avec des sels métalliques en des quantités de 0,1 à 5% en poids par rapport à la teneur sèche de la cellulose.
11. Procédé selon la revendication 10, caractérisé en ce que l'on utilise comme sel métallique un sel d'aluminium.
12. Procédé selon la revendication 10, caractérisé en ce que l'on utilise comme sel métallique un sel de métal alcalino-terreux.
13. Procédé selon les revendications 1 à 12, caractérisé en ce que l'on règle le pH avant le blanchiment à une valeur comprise entre 5,0 et 10,0.
14. Procédé selon les revendications 1 à 13, caractérisé en ce que la température de la réaction est comprise entre 20 et 150°C.
EP86116722A 1985-12-16 1986-12-02 Procédé de blanchiment et délignification de produits cellulosiques Expired - Lifetime EP0226114B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86116722T ATE54475T1 (de) 1985-12-16 1986-12-02 Verfahren zur bleiche und delignifizierung von zellstoffhaltigen produkten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853544398 DE3544398A1 (de) 1985-12-16 1985-12-16 Verfahren zur bleiche und delignifizierung von zellstoffhaltigen produkten
DE3544398 1985-12-16

Publications (2)

Publication Number Publication Date
EP0226114A1 EP0226114A1 (fr) 1987-06-24
EP0226114B1 true EP0226114B1 (fr) 1990-07-11

Family

ID=6288532

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86116722A Expired - Lifetime EP0226114B1 (fr) 1985-12-16 1986-12-02 Procédé de blanchiment et délignification de produits cellulosiques

Country Status (9)

Country Link
US (1) US5034096A (fr)
EP (1) EP0226114B1 (fr)
JP (1) JPH0723593B2 (fr)
AT (1) ATE54475T1 (fr)
CA (1) CA1277457C (fr)
DE (2) DE3544398A1 (fr)
ES (1) ES2016084B3 (fr)
FI (1) FI85390C (fr)
NO (1) NO169023C (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4114135A1 (de) * 1991-04-30 1992-11-05 Sueddeutsche Kalkstickstoff Verfahren zur chlorfreien bleiche und delignifizierung von alkalizellstoff

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4004364A1 (de) * 1990-02-13 1991-08-14 Sueddeutsche Kalkstickstoff Verfahren zur chlorfreien bleiche und delignifizierung von zellstoff
DE4031597A1 (de) * 1990-10-05 1992-04-09 Sueddeutsche Kalkstickstoff Verfahren zur chlorarmen bleiche und delignifizierung von zellstoff
US5242464A (en) * 1991-04-22 1993-09-07 Pyxis Corporation Method of bleaching wood
US6398908B1 (en) 1991-04-30 2002-06-04 Eka Nobel Ab Process for acid bleaching of lignocellulose-containing pulp with a magnesium compound
DE4114134A1 (de) * 1991-04-30 1992-11-05 Sueddeutsche Kalkstickstoff Verfahren zur chlorfreien bleiche und delignifizierung von alkalizellstoff
DE4128968A1 (de) * 1991-08-31 1993-03-04 Genkinger Hebe Foerdertech Verfahren und vorrichtung zum wechseln eines warenbaums in einer webmaschine
US5411635A (en) * 1993-03-22 1995-05-02 The Research Foundation Of State University Of New York Ozone/peroxymonosulfate process for delignifying a lignocellulosic material
DK0644965T3 (da) * 1993-04-06 1998-04-14 Air Liquide Blegning af genbrugspulp med ozon og hydrogenperoxid
US5620563A (en) * 1994-10-31 1997-04-15 Pulp Paper Res Inst Process for delignification and bleaching of chemical wood pulps with hydrogen peroxide and a dicyandiamide activator
US6302997B1 (en) * 1999-08-30 2001-10-16 North Carolina State University Process for producing a pulp suitable for papermaking from nonwood fibrous materials
US8268122B2 (en) * 2005-12-02 2012-09-18 Akzo Nobel N.V. Process of producing high-yield pulp
CA2631545C (fr) * 2005-12-02 2014-08-19 Akzo Nobel N.V. Procede de production de pate a haut rendement
US20100224336A1 (en) * 2005-12-14 2010-09-09 University Of Maine System Board Of Trustees Process of bleaching a wood pulp
US20070131364A1 (en) * 2005-12-14 2007-06-14 University Of Maine Process for treating a cellulose-lignin pulp
CA2876082C (fr) 2012-06-13 2021-06-01 University Of Maine System Board Of Trustees Procede ecoenergetique pour la preparation de fibres de nanocellulose

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE532222C (de) * 1929-08-30 1931-08-29 Noviston Akt Ges Verfahren zur Herstellung von Zellstoff durch alkalischen Aufschluss
US4025453A (en) * 1976-02-09 1977-05-24 Shell Oil Company Activated bleaching process and compositions therefor
US4158595A (en) * 1977-07-27 1979-06-19 Hercules Incorporated Preparation of hydrophilic styrene maleic anhydride copolymer fibers for use in papermaking
US4426466A (en) * 1982-06-09 1984-01-17 Minnesota Mining And Manufacturing Company Paper treatment compositions containing fluorochemical carboxylic acid and epoxidic cationic resin
FR2557605B1 (fr) * 1983-12-29 1987-12-11 Atochem Procede de blanchiment de pates papetieres par le peroxyde d'hydrogene
FR2560898B1 (fr) * 1984-03-06 1988-01-08 Air Liquide Procede de destructuration de matieres lignocellulosiques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4114135A1 (de) * 1991-04-30 1992-11-05 Sueddeutsche Kalkstickstoff Verfahren zur chlorfreien bleiche und delignifizierung von alkalizellstoff

Also Published As

Publication number Publication date
EP0226114A1 (fr) 1987-06-24
DE3544398A1 (de) 1987-06-19
NO169023C (no) 1992-04-29
NO864983D0 (no) 1986-12-10
FI85390C (fi) 1992-04-10
NO864983L (no) 1987-06-17
US5034096A (en) 1991-07-23
DE3672577D1 (de) 1990-08-16
FI865100A (fi) 1987-06-17
ATE54475T1 (de) 1990-07-15
FI865100A0 (fi) 1986-12-15
JPS62191588A (ja) 1987-08-21
FI85390B (fi) 1991-12-31
CA1277457C (fr) 1990-12-11
JPH0723593B2 (ja) 1995-03-15
NO169023B (no) 1992-01-20
ES2016084B3 (es) 1990-10-16

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