EP0212329B1 - Verfahren zur Delignifizierung von Zellulosematerialien - Google Patents

Verfahren zur Delignifizierung von Zellulosematerialien Download PDF

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Publication number
EP0212329B1
EP0212329B1 EP86110248A EP86110248A EP0212329B1 EP 0212329 B1 EP0212329 B1 EP 0212329B1 EP 86110248 A EP86110248 A EP 86110248A EP 86110248 A EP86110248 A EP 86110248A EP 0212329 B1 EP0212329 B1 EP 0212329B1
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EP
European Patent Office
Prior art keywords
cellulosic materials
process according
delignification
acid
effected
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
EP86110248A
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English (en)
French (fr)
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EP0212329A1 (de
Inventor
Josef S. Dr. Gratzl
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.)
Solvay Chimie SA
Original Assignee
Interox SA
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Publication date
Application filed by Interox SA filed Critical Interox SA
Priority to AT86110248T priority Critical patent/ATE57400T1/de
Publication of EP0212329A1 publication Critical patent/EP0212329A1/de
Application granted granted Critical
Publication of EP0212329B1 publication Critical patent/EP0212329B1/de
Anticipated expiration legal-status Critical
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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
    • D21C3/26—Multistage processes

Definitions

  • the present invention relates to a process for the delignification of lignocellulosic materials for the preparation of pulps intended for the manufacture of paper. It relates more specifically to the field of chemical pulps obtained by cooking cellulosic materials in the presence of chemical reagents with delignifying properties.
  • the invention remedies these drawbacks of known methods, by providing a new method for delignifying cellulosic materials, which makes it possible to achieve high delignification rates while preserving the intrinsic quality of the cellulose, the hemicellulose content and the weight yield. in paste produced.
  • the invention relates to a process for the delignification of cellulosic materials according to which, in a first step, cellulosic materials are treated with an acid, under conditions regulated to carry out a decontamination of the cellulosic materials of the metals which they contain. , in a second step, the cellulosic materials of the first step are treated with hydrogen peroxide in an alkaline medium and, in a third step, the cellulosic materials of the second step are subjected to a baking soda.
  • cellulosic materials is intended to denote woody fragments of plants used as raw materials in the paper industry.
  • examples of such materials are fragments of wood, annual herbaceous plants such as alfa, plants of the monocotyledon class such as cereal straws, bamboo, esparto, rushes and reeds as well as cane sugar, in particular its residue, bagasse, after sugar extraction.
  • the invention applies very particularly to fragments of wood. All types of softwood or hardwood used in the paper industry are suitable for the process according to the invention. Softwood chips and sawmill waste are particularly suitable.
  • the purpose of the treatment with an acid is to decontaminate the cellulosic materials of the metals which they generally contain.
  • All the inorganic or organic acids used in aqueous solution, alone or as a mixture are suitable. Strong inorganic acids such as sulfuric acid or hydrochloric acid are well suited.
  • the first step is carried out in the presence of a metal ion co-complexing agent.
  • mixtures of the strong inorganic acids mentioned above with organic acids from the class of aminopolycarboxylic or aminopolyphosphonic acids or their alkali metal salts are particularly suitable.
  • Examples of suitable aminopolycarboxylic acids are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid and nitrilotriacetic acid.
  • Diethylenetriaminepentaacetic acid DTPA
  • Examples of amino acids Polyphosphonics are diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetra acid (methylenephosphonic) and nitrilotri acid (methylenephosphonic).
  • Diethylenetriaminepentamethylenephosphonic acid (DTMPA) is preferred.
  • the operating conditions of the first step of the process according to the invention are not critical. They must be determined in each particular case according to the type of cellulosic materials and the apparatus in which the treatment is carried out. In general, the choice of acid and the quantity used should be fixed to impose on the medium a pH of less than 7, for example between 0.5 and 6.5; especially advantageous pHs are those between 1.0 and 4.0.
  • Temperature and pressure are not critical, with room temperature and atmospheric pressure generally suitable.
  • the duration of the treatment can vary within wide limits depending on the type of equipment used, the choice of acid, the temperature and the pressure, for example from 30 minutes to several hours if the treatment is carried out by soaking the cellulosic materials in a vat, from 1 to 120 minutes if it is made by percolation in a column where the cellulosic materials to be treated are stacked.
  • the cellulosic materials can be subjected, before the first step, to a treatment with water vapor.
  • the purpose of this treatment is to facilitate the impregnation operations which will follow.
  • the function of the hydrogen peroxide used in the second stage of the process according to the invention is to accelerate the delignification of the cellulosic materials in the subsequent cooking stage.
  • the optimum amount of hydrogen peroxide to be used depends on the origin of the cellulosic materials. In general, it is necessary to use more than 0.1 g of peroxide, of hydrogen per 100 g of dry cellulosic materials. Amounts of hydrogen peroxide greater than 3 g / 100 g of dry cellulosic materials are rarely necessary to obtain rapid delignification. Usually, doses of hydrogen peroxide of between 0.5 and 2 g / 100 g of dry matter are used. Doses of peroxide between 0.7 and 1.5 g / 100 g of dry matter have given the best results.
  • the hydrogen peroxide used can be anhydrous hydrogen peroxide or, preferably, an aqueous solution, for example a commercial aqueous solution of hydrogen peroxide whose content by weight is between 25 and 90 g of peroxide pure hydrogen per 100 g of solution or a dilute alkaline aqueous solution of hydrogen peroxide produced by electrochemical reduction of oxygen.
  • the treatment of cellulosic materials with alkaline hydrogen peroxide can be carried out in the presence of additives such as, for example, stabilizers and inhibitors of the decomposition of hydrogen peroxide.
  • additives are, for example, sequestrants of inorganic or organic metal ions such as magnesium salts, aminopolycarboxylic acids or sodium silicate of the soluble glass quality.
  • Other additives which can also be used are surfactants, wetting agents, agents capable of protecting the cellulosic chains to prevent their depolymerization, activating agents or anti-corrosion agents.
  • the amount of additive introduced is never greater than 1% of the weight of the cellulosic materials. It is most often between 0 and 0.5% of the weight of these materials.
  • the alkaline medium is obtained by the addition of soluble materials of basic character.
  • Ammonia, carbonates and inorganic hydroxides of alkali or alkaline earth metals such as sodium, potassium or calcium carbonate, sodium, potassium or calcium hydroxide are generally used.
  • Oxides or peroxides of alkali or alkaline earth metals such as Na 2 0, Na 2 0 2 , CaO and Ca0 2 , may also be suitable and in the case of the perplexes supplement the contribution of a portion of the peroxide of hydrogen introduced in the second step of the process.
  • Sodium hydroxide is usually preferred because of its high availability and low cost.
  • the quantities of basic material to be used are chosen so as to adjust the pH of the peroxide solution between 11 and 13.5 and preferably between 12 and 13.
  • the operating conditions of the second step of the process according to the invention can also vary within fairly wide limits depending, in particular, on the type of cellulosic materials and the type of equipment used.
  • the pressure prevailing during the second stage can thus be in the range from 2 kPa to 10 MPa and the temperature in the range from 290 K to 380 K.
  • the treatment with hydrogen peroxide in an alkaline medium of the second stage is generally performed for a time greater than 2 minutes and not exceeding 180 minutes.
  • the cellulosic materials to be treated are subjected to alkaline hydrogen peroxide in a liquor-to-wood weight ratio not exceeding 2.5: 1, and preferably ranging from 1: 1 to 2: 1.
  • the cellulosic materials from the first stage are impregnated in a closed reactor with the alkaline liquor of hydrogen peroxide preheated after which the excess liquor which has not impregnated the cellulosic materials is drained out. of the reactor which is then heated to the reaction temperature.
  • the soaking of the cellulosic materials in the hydrogen peroxide liquor, prior to the reaction generally does not require more than 5 minutes. However, it usually cannot be done in less than 30 seconds.
  • the temperature of the liquor peroxide is most often chosen from 5 to 20 K higher than that prevailing in the reactor and which is maintained for 15 to 120 minutes by means of the heating mantle. A reaction temperature between 310 and 360 K is suitable. The best results have been obtained with a temperature of 323 K and a reaction time of 45 minutes.
  • the third step of the process according to the invention consists in subjecting the cellulosic materials coming from the second step to a baking in the presence of at least one chemical reagent.
  • the chemical reagent is chosen from hydroxides of alkali or alkaline earth metals. Examples of such chemical reagents which are especially suitable are sodium hydroxide and calcium hydroxide.
  • delignifying additives can be added in the third step of the process according to the invention. These additives are generally used to increase delignification during alkaline cooking.
  • Organic compounds are preferred, such as, for example: anthraquinone and its derivatives such as 1-methylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, la.
  • 2-methoxyanthraquinone 2,3-dimethylanthraquinone, 2,7-dimethylanthraquinone, 1,4,4a, 5,8,8a, 9a, 10a-0ctahydroanthraquinone and 1,4,4a, 9a-tetrahydroanthraquinone; hydroquinones such as p-hydroquinone; certain anthracene derivatives such as 9-nitroanthracene, 9,10-dinitro-anthracene and 9-nitro-10-chloro-9,10-dihydroanthracene; certain heterocyclic compounds such as 6,11-dioxo-1H-anthra [1,2-C] pyrazole; polycyclic compounds such as 1,2-benzanthraquinone and phenanthrenequinone; nitrobenzene; amines such as monoethanolamine and ethylenediamine; alcohols such as resorcinol and pyrogallol
  • inorganic compounds examples include hydrazine and the alkali metal borohydride. Anthraquinone and its derivatives are preferred. These additives are advantageously used in amounts not exceeding 2% of the weight of the dry cellulosic substances. Generally, their quantity is less than 1% of this weight.
  • the optimum operating conditions for the third step of the process according to the invention depend on various parameters, in particular on the origin of the cellulosic materials and they can be easily determined in each particular case.
  • a washing with water of the cellulosic materials is carried out between the second and the third stage.
  • This embodiment is advantageous when the last step is carried out in the presence of additives comprising reducing substances.
  • the purpose of this washing is to remove cellulosic materials, at least part of the water-soluble products generated in the second step and to extract the last traces of hydrogen peroxide still present, to avoid unnecessary oxidation of the reducing substances.
  • the method according to the invention makes it possible to significantly speed up the delignification of the cellulosic materials treated, which has the effect of shortening the time required for the third stage of cooking with chemical reagents. This results in the significant advantage of a significant reduction in the size of the cooking equipment, which leads to savings in space and investment cost or, alternatively, increased capacity for a given cooking equipment.
  • the invention also allows, at an equal delignification rate, a substantial reduction in the amount of chemical reagents in the cooking step, leading to substantial savings in chemical reagents.
  • the invention also produces with better weight yields and therefore at lower cost, chemical pastes of higher viscosity than those obtained by the methods of the prior art.
  • Tests 1 to 6R were carried out to demonstrate the improvement brought by the invention on the performance of the technique of cooking lignocellulosic materials.
  • the shavings were then immersed, at ambient temperature, in a solution of 0.003M Na r DTPA and 0.1 N in H 2 SO 4 by suction of the solution into the reactor by means of the reduced pressure produced by the vacuum connection. .
  • the aqueous solution was used in a quantity by weight equal to 8 times the weight of wood in the dry state.
  • the compeaux then underwent 3 washing cycles of 2 hours each with an amount of water equal to 8 times the weight of dry wood.
  • the shavings were centrifuged between cycles.
  • Wood chips as in test 1 subjected directly to the third stage of test 1 under the same conditions, failing to carry out the first and second stages.
  • the total weight yield was determined gravimetrically by weighing the samples before and after the tests.
  • the total carbohydrate content was also calculated by subtracting the lignin content from the total weight yield.
  • the sequential implementation of the first two stages of the process according to the invention has made it possible to reduce the duration of the third cooking stage by at least 30%, and consequently to reduce in parallel the size and cost of the cooking equipment.

Landscapes

  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dental Preparations (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Materials For Medical Uses (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • External Artificial Organs (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (10)

1. Verfahren zur Delignifizierung von Zellulosematerialien, dadurch gekennzeichnet, daß man in einer ersten Stufe die Zellulosematerialien mit einer Säure unter bestimmten Bedingungen behandelt, um eine Dekontaminierung der Zellulosematerialien von Metallen, die sie enthalten, durchzuführen, in einer zweiten Stufe die Zellulosematerialien der ersten Stufe mit Wasserstoffperoxyd in alkalischem Milieu behandelt und, in einer dritten Stufe die Zellulosematerialien der zweiten Stufe einem Kochen mit Soda unterzieht.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die erste Stufe bei einem pH im Bereich von 1 bis 4 durchführt.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die erste Stufe in Anwesenheit einer anorganischen Säure durchgeführt wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die erste Stufe in Anwesenheit eines Komplexbildners der Metallionen durchgeführt wird.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Kochen mit Soda in Anwesenheit eines Delignifizierungszusatzstoffes, ausgewählt unter Anthrachinon und den Derivaten des Anthrachinons, durchgeführt wird.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die zweite Stufe bei einem Anfangs-pH im Bereich von 12 bis 13 durchgeführt wird.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die zweite Stufe bei einer Temperatur im Bereich von 313 bis 353K während 10 bis 60 Minuten durchgeführt wird.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die zweite Stufe mit einer Menge an Wasserstoffperoxyd im Bereich von 0,5 bis 2 g/100 g trockene Zellulosematerialien und einem Gewichtsverhältnis von Flüssigkeit zu Holz im Bereich von 1:1 bis 2:1 durchgeführt wird.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Wasserstoffperoxyd der zweiten Stufe in wäßriger Lösung eingesetzt wird.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Zellulosematerialien Holzspäne sind, ausgewählt aus der Klasse der harzhaltigen Holzspäne.
EP86110248A 1985-08-05 1986-07-25 Verfahren zur Delignifizierung von Zellulosematerialien Expired - Lifetime EP0212329B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86110248T ATE57400T1 (de) 1985-08-05 1986-07-25 Verfahren zur delignifizierung von zellulosematerialien.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76272685A 1985-08-05 1985-08-05
US762726 1985-08-05

Publications (2)

Publication Number Publication Date
EP0212329A1 EP0212329A1 (de) 1987-03-04
EP0212329B1 true EP0212329B1 (de) 1990-10-10

Family

ID=25065883

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86110248A Expired - Lifetime EP0212329B1 (de) 1985-08-05 1986-07-25 Verfahren zur Delignifizierung von Zellulosematerialien

Country Status (13)

Country Link
EP (1) EP0212329B1 (de)
JP (1) JPH0742670B2 (de)
AT (1) ATE57400T1 (de)
AU (1) AU591509B2 (de)
BR (1) BR8603672A (de)
CA (1) CA1311093C (de)
DE (1) DE3674859D1 (de)
ES (1) ES2000385A6 (de)
FI (1) FI85726C (de)
NO (1) NO168490C (de)
NZ (1) NZ217002A (de)
PT (1) PT83118B (de)
YU (1) YU45351B (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN167959B (de) * 1985-08-05 1991-01-12 Interox

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1474276A (fr) * 1965-03-19 1967-03-24 Electro Chimie Soc D Perfectionnements à la fabrication de pâte à papier
SE373896B (de) * 1972-07-05 1975-02-17 Mo Och Domsjoe Ab
SE380298B (sv) * 1974-03-14 1975-11-03 Mo Forfarande for delignifiering genom syrgas-alkalibehandling av lignocelluosahaltigt material
SE7612248L (sv) * 1976-11-03 1978-05-04 Mo Och Domsjoe Ab Kokning av lignocellulosahaltiga material
SU821614A1 (ru) * 1979-06-19 1981-04-15 Белорусский Технологический Институт Им.C.M.Кирова Способ получени целлюлозного полу-фАбРиКАТА
IN167959B (de) * 1985-08-05 1991-01-12 Interox

Also Published As

Publication number Publication date
NO863133D0 (no) 1986-08-04
FI863194L (fi) 1987-02-06
NO863133L (no) 1987-02-06
NZ217002A (en) 1988-11-29
EP0212329A1 (de) 1987-03-04
BR8603672A (pt) 1987-03-10
AU6054486A (en) 1987-02-12
FI863194A0 (fi) 1986-08-05
DE3674859D1 (de) 1990-11-15
FI85726C (fi) 1992-05-25
YU136986A (en) 1987-10-31
PT83118B (pt) 1988-10-14
JPH0742670B2 (ja) 1995-05-10
ATE57400T1 (de) 1990-10-15
NO168490C (no) 1992-02-26
CA1311093C (fr) 1992-12-08
JPS6297992A (ja) 1987-05-07
NO168490B (no) 1991-11-18
YU45351B (en) 1992-05-28
ES2000385A6 (es) 1988-02-16
PT83118A (fr) 1986-09-01
AU591509B2 (en) 1989-12-07
FI85726B (fi) 1992-02-14

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