EP0021264B1 - Procédé de délignification de matières lignocellulosiques - Google Patents

Procédé de délignification de matières lignocellulosiques Download PDF

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Publication number
EP0021264B1
EP0021264B1 EP80103278A EP80103278A EP0021264B1 EP 0021264 B1 EP0021264 B1 EP 0021264B1 EP 80103278 A EP80103278 A EP 80103278A EP 80103278 A EP80103278 A EP 80103278A EP 0021264 B1 EP0021264 B1 EP 0021264B1
Authority
EP
European Patent Office
Prior art keywords
nitro
dinitroanthraquinone
anthraquinone
weight
nitroanthraquinone
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
Application number
EP80103278A
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German (de)
English (en)
Other versions
EP0021264A1 (fr
Inventor
Heinz Ulrich Dr. Blank
Günther Dr. Klag
Peter Dr. Schnegg
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.)
Bayer AG
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Priority to AT80103278T priority Critical patent/ATE2279T1/de
Publication of EP0021264A1 publication Critical patent/EP0021264A1/fr
Application granted granted Critical
Publication of EP0021264B1 publication Critical patent/EP0021264B1/fr
Expired 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes

Definitions

  • the invention relates to a method for delignifying lignocellulose materials with the addition of nitroanthraquinone compounds.
  • nitroanthraquinone compounds have now been found as auxiliaries for the digestion of lignocellulose materials which do not have the disadvantages of aromatic nitro compounds, such as nitrobenzene, which have been investigated as wood digesters, but which are more potent than the previous ones by one or two powers of ten Aromatic nitro compounds used as digestion aids.
  • the invention therefore relates to a process for delignifying lignocellulose materials by disintegrating lignocellulose materials with conventional cooking liquids under conventional cooking conditions in the presence of aromatic nitro compounds, which is characterized in that one or more nitroanthraquinone compounds are used as aromatic nitro compounds.
  • lignocellulose materials can be delignified using the method according to the invention.
  • conifers such as spruce, pine and fir, hardwoods such as beech, birch, eucalyptus, aspen, poplar, willow, hornbeam, alder, oak and maple, and straw and bagasse from annual plants are suitable.
  • Spruce, pine, fir, birch and beech are preferably delignified by the method according to the invention.
  • one or more nitroanthraquinone compounds are added to the cooking liquid.
  • One of the usual cooking liquids for alkaline cooking processes or sulfite processes or similar processes can be used as the cooking liquid.
  • the term "alkaline cooking method” encompasses various methods, for example the soda method, the sulfate method, the polysulfide method and the like, and the term “sulfite method” used here includes various methods, for example the alkaline, neutral and acidic sulfite method , the bisulfite process and the like (see P. Lengyel, S. Morvay, Chemistry and Technology of Pulp Production, Güntter-Staib Verlag, Biberach / Riss, 1973, pages 62 ff).
  • the additives according to the invention are preferably added to alkaline cooking liquids, as are used, for example, in the processes known as the soda process, sulfate process and polysulfide process.
  • the additives according to the invention are very particularly preferably added to alkaline cooking liquids, such as are used in the process known as the soda process.
  • the process according to the invention can be carried out in a closed reaction vessel in which the lignocellulose material with the cooking liquid at maximum temperatures in the range from 150 to 200 ° C., preferably from 160 to 180 ° C., over a period of 0.5 to 480 minutes , preferably from 15 to 200 minutes.
  • the delignified material can be worked up in a conventional manner, for example by displacing the cooking liquid from the lignocellulose material (pulp) by adding water or an aqueous liquid which is inert to the lignocellulose material (pulp).
  • the lignocellulosic material (pulp) processed in this way and optionally mechanically shredded can be used without further treatment or subjected to conventional bleaching processes.
  • the delignified lignocellulosic material (pulp) can be further treated in the following way:
  • the material is in an aqueous suspension, the content of lignocellulosic material (pulp) is 2 to 40% by weight, for 0.5 to 60 minutes at 20 to 90 ° C with 2 to 20 wt .-% of an alkali metal base and optionally subsequently with oxygen or an oxygen-containing gas for 0.5 to 120 minutes at a temperature of 80 to 150 ° C and treated with an oxygen partial pressure of 1.4 to 14 kg / cm 2 .
  • the lignocellulose material used is made of wood, it is advantageous to convert it into chips first.
  • nitroanthraquinone compounds can also be added to the lignocellulose material during the impregnation.
  • nitroanthraquinone compounds can also be advantageous to allow nitroanthraquinone compounds to act on the lignocellulose material in a pretreatment phase together with the digestion chemicals in the temperature range from about 90 ° -1500 ° C. in such a way that the lignin content is not significant, i. H. is brought to less than 20% in solution and that, if necessary, the proportion of nitroanthraquinone compounds which has not penetrated into the lignocellulose material can be recovered.
  • one or more nitroanthraquinone compounds are added to the digestion process.
  • mono- and / or dinitroanthraquinones are suitable, which may optionally have one or more further substituents in addition to the nitro groups.
  • further substituents are alkyl, alkoxy, halogen, amino, hydroxyl, carboxy and / or sulfo groups and / or fused iso- or heterocyclic rings.
  • Preferred further substituents are alkyl and alkoxy groups each having 1 to 4 carbon atoms and chloro and / or sulfo groups.
  • the number of further substituents can be, for example, 1 to 6, preferably 1 to 4.
  • nitroanthraquinone compounds to be added are: 1- and 2-nitroanthraquinone; 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and 2,7-dinitroanthraquinone; 1-nitro-5-, 1-nitro-7-, 1-nitro-8-sulfo-anthraquinone; 1-nitro-4-chloro-5-sulfo-anthraquinone; 1-nitro-5-, 1-nitro-6-, 1-nitro-8-, 2-nitro-1-chloro-anthraquinone; 2-nitro-4,5-dichloro-anthraquinone; 2-nitro-1,4-, 1-nitro-5,8-diamino-anthraquinone; 1-nitro-4-amino-anthraquinone; 1,3-dinitro-4-amino-anthraquinone; 1-nitro-4-hydroxyanthraquinone; 1-nitro-3,4-, 1-nitro-5,8-, 1,5-dinitro
  • 1- and 2-nitroanthraquinone 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and 2,7-dinitroanthraquinone, 1-nitro-5-chloro-anthraquinone are preferred, 1-nitro-8-sulfo-anthraquinone, 1-nitro-4-amino-anthraquinone, 1-nitro-4-hydroxy-anthraquinone, 1-nitro-2-carboxy-anthraquinone, 1-nitro-5-ethoxy-anthraquinone and / or 2-methyl-1-nitro-anthraquinone, in particular the aforementioned dinitro compounds.
  • the aforementioned compounds can be added individually or in any mixtures with one another.
  • mixtures which contain unsubstituted mono- and / or dinitroanthraquinones is particularly preferred. Such mixtures can be obtained, for example, in the industrial nitration of anthraquinone and / or mononitroanthraquinone.
  • mixtures of mono- and / or dinitroanthraquinones can be used in the process according to the invention, which are obtained when anthraquinone is mono- or dinitrated on an industrial scale and / or nitronated with mononitroanthraquinone mixtures and, for example, the isomers important as dye intermediates from the resulting products, e.g. B.
  • Particularly preferred mixtures contain, for example, 0 to 3% by weight of 1-nitroanthraquinone, 5 to 12% by weight of 1,5-dinitroanthraquinone, 15 to 35% by weight of 1,6-dinitroanthraquinone, 15 to 35% by weight of 1 , 7-dinitroanthraquinone, 15 to 50% by weight 1,8-dinitroanthraquinone, 0.5 to 3% by weight 2,6-dinitroanthraquinone and 0.5 to 3% by weight 2,7-dinitroanthraquinone.
  • nitroanthraquinone compounds according to the invention can take place, for example, in amounts of 0.001 to 10% by weight, based on the lignocellulose material used. 0.01 to 1.0% by weight of the additives, based on lignocellulose material, are preferably used.
  • the method according to the invention has the advantage that it leads to a substantial acceleration of delignification in the soda process. A significant acceleration is also observed in the sulfate process and polysulfide process.
  • the process according to the invention has the further advantage that substances and mixtures of substances which have hitherto been undesirable by-products in the nitration of anthraquinone can be recycled in a technically advantageous manner.
  • the increase in the delignification speed can be used in different ways depending on the circumstances.
  • a given Kappa number can e.g. B. achieved in a shorter time, ie, the capacity of an already installed pulp cooker can be expanded. However, it can also be digested at a lower maximum cooking temperature. Energy is saved in both cases.
  • Instead of shortening the cooking time and / or lowering the maximum cooking temperature can also be used with a reduced use of chemicals, which has a known effect (see TAPPI, 50 (8), p. 400 [1967]) which has a favorable effect on the reduced formation of strongly smelling by-products.
  • TAPPI, 50 (8), p. 400 [1967] which has a favorable effect on the reduced formation of strongly smelling by-products.
  • the way in which these advantages can be optimally used in individual cases depends on the circumstances of the pulp production process used.
  • the process according to the invention also has a stabilizing effect on the cellulose, so that the cellulose can be obtained in a higher yield for a given kappa number.
  • Spruce wood chips were digested in a laboratory cooker with a soda liquor containing 22% active alkali (based on the weight of the wood).
  • the ratio of liquid to wood was 4: 1, the heating time was 60 minutes, the cooking time at 175 ° C was 80 minutes (digestion A).
  • a further digestion was carried out in the same way (digestion B), in which, however, 0.1% by weight (based on oven-dry wood) of a mixture of dinitroanthraquinone of the following composition was added to the mixture of wood and cooking liquor:

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  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Bakery Products And Manufacturing Methods Therefor (AREA)
  • External Artificial Organs (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (6)

1. Procédé pour éliminer la lignine contenue dans les matières lignocellulosiques par attaque de ces matières à l'aide de liquides de cuisson usuels dans des conditions de cuisson usuelles, en présence de composés aromatiques nitrés, caractérisé en ce que l'on ajoute en tant que composé aromatique nitré une ou plusieurs nitroanthraquinones.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise en tant que composé aromatique nitré la 1-nitroanthraquinone, la 2-nitroanthraquinone, la 1,5-dinitroanthraquinone, la 1,6-dinitroanthraquinone, la 1,7-dinitroanthraquinone, la 1,8-dinitroanthraquinone, la 2,6-dinitroanthraquinone, ia 2,7-dinitroanthraquinone, la 1-nitro-5-chloro-anthraquinone, la 1-nitro-8-sulfo-anthraquinone, la 1-nitro-4-amino-anthraquinone, la 1-nitro-4-hydroxy-anthraquinone, la 1-nitro-2-carboxy-anthraquinone, la 1-nitro-5-éthoxy-anthraquinone, et/ou la 2-méthyl-1 -nitroantraquinone.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on ajoute une ou plusieurs nitroanthraquinones en quantité de 0,01 à 1% en poids par rapport à la matière lignocellulosique mise en oeuvre.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on ajoute une ou plusieurs nitroanthraquinones à un liquide de cuisson alcalin.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que l'attaque est effectuée dans un récipient de réaction fermé à des températures maximales dans l'intervalle de 150 à 200°C et dans une durée de 0,5 à 480 min.
6. Procédé selon les revendications 1 à 5, caractérisé en ce que l'on ajoute en tant que nitroanthraquinones un mélange contenant de 0 à 3% en poids de 1-nitroanthraquinone, de 5 à 12% en poids de 1,5-dinitroanthraquinone, de 15 à 35% en poids de 1,6-dinitroanthraquinone, de 15 à 35% en poids de 1,7-dinitroanthraquinone, de 15 à 50% en poids de 1,8-dinitroanthraquinone, de 0,5 à 3% en poids de 2,6-dinitroanthraquinone et de 0,5 à 3% en poids de 2,7-dinitroanthraquinone.
EP80103278A 1979-06-25 1980-06-12 Procédé de délignification de matières lignocellulosiques Expired EP0021264B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80103278T ATE2279T1 (de) 1979-06-25 1980-06-12 Verfahren zur delignifizierung von lignocellulose-materialien.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792925544 DE2925544A1 (de) 1979-06-25 1979-06-25 Verfahren zur delignifizierung von lignocellulose-materialien
DE2925544 1979-06-25

Publications (2)

Publication Number Publication Date
EP0021264A1 EP0021264A1 (fr) 1981-01-07
EP0021264B1 true EP0021264B1 (fr) 1983-01-19

Family

ID=6074073

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80103278A Expired EP0021264B1 (fr) 1979-06-25 1980-06-12 Procédé de délignification de matières lignocellulosiques

Country Status (13)

Country Link
US (1) US4350566A (fr)
EP (1) EP0021264B1 (fr)
JP (1) JPS568403A (fr)
AT (1) ATE2279T1 (fr)
AU (1) AU5932980A (fr)
BR (1) BR8003938A (fr)
CA (1) CA1154208A (fr)
DE (2) DE2925544A1 (fr)
ES (1) ES8103227A1 (fr)
FI (1) FI72541C (fr)
NO (1) NO155585C (fr)
NZ (1) NZ194113A (fr)
ZA (1) ZA803766B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728265A (en) * 1995-06-12 1998-03-17 Henkel Corporation Process for enhancing white liquor penetration into wood chips by contacting the chips with a mixture of the white liquor and a polymethylalkyl siloxane

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036080A (en) * 1974-11-29 1977-07-19 The Garrett Corporation Multi-rim flywheel

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1449828A (en) * 1973-04-26 1976-09-15 Canadian Ind Oxygen pulping process
JPS5143403A (en) * 1974-10-09 1976-04-14 Honshu Paper Co Ltd Arukariparupuno seizohoho
CA1073161A (fr) * 1975-09-05 1980-03-11 Canadian Industries Limited Procede de delignification
JPS5845562B2 (ja) * 1976-07-21 1983-10-11 株式会社日立製作所 タ−ビン等の振動状態表示制御方法
NZ185937A (en) * 1976-12-13 1979-10-25 Australian Paper Manufacturers Delignification of lignocellulosic material with amine based liquor containing quinones or hydroqinones
US4036680A (en) * 1976-12-14 1977-07-19 Canadian Industries, Ltd. Delignification of lignocellulosic material with a soda pulping liquor containing a Diels Alder adduct of benzoquinone or naphthoquinone in admixture with a nitro aromatic compound
CA1094264A (fr) * 1976-12-14 1981-01-27 Canadian Industries Limited Delignification de materiel lignocellulosique par une liqueur a la soude contenant un compose cyclique du type ceto- et un compose nitroaromatique
JPS54100332A (en) * 1978-01-20 1979-08-08 Nippon Steel Chem Co Ltd Quinone compound composition and its preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036080A (en) * 1974-11-29 1977-07-19 The Garrett Corporation Multi-rim flywheel

Also Published As

Publication number Publication date
NO801742L (no) 1980-12-29
BR8003938A (pt) 1981-01-27
ES492781A0 (es) 1981-02-16
AU5932980A (en) 1981-01-08
EP0021264A1 (fr) 1981-01-07
NO155585C (no) 1987-04-22
ATE2279T1 (de) 1983-02-15
FI72541C (fi) 1987-06-08
DE3061673D1 (en) 1983-02-24
ES8103227A1 (es) 1981-02-16
US4350566A (en) 1982-09-21
DE2925544A1 (de) 1981-01-22
NO155585B (no) 1987-01-12
JPS568403A (en) 1981-01-28
NZ194113A (en) 1982-06-29
CA1154208A (fr) 1983-09-27
ZA803766B (en) 1981-07-29
JPS6258362B2 (fr) 1987-12-05
FI802001A (fi) 1980-12-26
FI72541B (fi) 1987-02-27

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