EP0213376A1 - Verfahren zur Delignifizierung von Zellulosematerialien - Google Patents

Verfahren zur Delignifizierung von Zellulosematerialien Download PDF

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Publication number
EP0213376A1
EP0213376A1 EP86110249A EP86110249A EP0213376A1 EP 0213376 A1 EP0213376 A1 EP 0213376A1 EP 86110249 A EP86110249 A EP 86110249A EP 86110249 A EP86110249 A EP 86110249A EP 0213376 A1 EP0213376 A1 EP 0213376A1
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EP
European Patent Office
Prior art keywords
cellulosic materials
cooking
carried out
hydrogen peroxide
minutes
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
Application number
EP86110249A
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English (en)
French (fr)
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EP0213376B1 (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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Application filed by Interox SA filed Critical Interox SA
Priority to AT86110249T priority Critical patent/ATE57401T1/de
Publication of EP0213376A1 publication Critical patent/EP0213376A1/de
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Publication of EP0213376B1 publication Critical patent/EP0213376B1/de
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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 and the weight yield of pulp 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, in a second step, the cellulosic materials of the first step are treated with peroxide of hydrogen in an alkaline medium and, in a third step, the cellulosic materials of the second step are subjected to cooking in the presence of at least one chemical reagent selected from sulfur products and oxygen.
  • 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 class of monocots 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 treatment with an acid aims 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. Mixtures of such acids with organic acids from the class of aminopolycarboxylic or aminopolyphosphonic acids or their alkali metal salts which have sequestering properties against metal ions are particularly suitable.
  • suitable aminopolycarboxylic acids are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid and nitrilotriacetic acid.
  • Diethylenetriaminepentaacetic acid is preferred.
  • aminopolyphosphonic acids are diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetra- (methylenephosphonic acid) and nitrilotri (methylenephosphonic acid).
  • Diethylenetriaminepentamethylenephosphonic acid 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 hydrogen peroxide 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 of pure hydrogen per 100 g of solution or alternatively 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 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 , Ca0 and Ca0 2 , may also be suitable and in the case of peroxides supplement the supply of part 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 step 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. during 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 peroxide liquor is most often chosen from 5 to 20 K higher than that which prevails 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 were obtained with a temperature of 323 K and for 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.
  • chemical reagents we mean acid or alkaline sulfur products such as those used in baking well known in the pulp industry under the names of sodium sulfite or magnesium baking, sodium bisulfite, magnesium or calcium, with acid sulfite of sodium, magnesium or calcium as well as with sodium sulfate, or kraft cooking. Oxygen cooking is also included in the category of cooking with chemical reagents.
  • 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 third step is carried out using sulfur-containing reagents.
  • 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 sulfur reactants used in the third cooking step.
  • the process 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 significant reduction in the amount of chemical reagents in the cooking step. This results in a substantial saving in chemical reagents and less pollution of the environment, in particular by gaseous and liquid sulfur discharges in the case where sulfur-containing chemical reagents are used.
  • the invention also produces with better weight yields and therefore at lower cost, chemical pulps of higher mechanical strength than those obtained by the methods of the prior art.
  • tests 1 to 6R were First series of tests (tests 1 to 6R)
  • Tests 1 to 6R aim to show the advantage provided by the invention over the performance of the chemical cooking technique for cellulosic materials.
  • Test 1 (according to the invention)
  • Pinus taeda wood flour (particle size fraction passing through a 40 mesh sieve and refused to a 60 mesh sieve of the TYLER standard) was subjected to a treatment with hydrochloric acid carried out by soaking the flour in a solution 0.1 M HC1 for 4 hours at room temperature.
  • the aqueous solution was used in an amount by weight equal to 40 times the weight of the treated wood flour (First step).
  • Wood flour from the first stage in an amount equivalent to 10 g of dry matter was introduced into a 200 ml reactor lined internally with a coating of polytetrafluoroethylene. After preheating the reactor to 323 K in a polyethylene glycol bath, 150 g of an aqueous solution of 0.04 M of hydrogen peroxide and 0.5 M of sodium hydroxide were introduced into the reactor. The reactor was then heated to 353 K in 30 minutes, then kept 15 minutes at this latter temperature. The reactor was then cooled and the wood flour was washed (Second step).
  • a comparison of the results of trial 1 with those of trials 2R, 3R and 4R shows the unexpected synergistic effect of the combined implementation of the first and second steps of the invention on the delignification rate at the end of l 'subsequent cooking step.
  • the sequential application of the first two stages of the process according to the invention has also made it possible, quite surprisingly, to annihilate the drop in viscosity of the dough due to the action of the oxidant: comparison of test 1 with test 4R even shows an improvement in the viscosity of the dough obtained according to the method of the invention.
  • Tests 5R and 6R were carried out as a reference in order to evaluate the weight yield and the viscosity of the delignified pasta by means of the only cooking step (in accordance with the process of the prior art), for a delignification rate ( measured by the index kappa) equivalent to that obtained in test 1.
  • a delignification rate measured by the index kappa
  • Tests 7 to 11R also aim to show the impact of the invention on the performance of the chemical cooking technique for cellulosic materials.
  • Pinus taeda wood chips were introduced at the rate of 300 g of dry matter into a glass-lined reactor fitted with a tight cover.
  • the cover was provided with two orifices: the first was connected to a vacuum pump and the second allowed the introduction to the bottom of the reactor of a tubular probe. This probe was connected to the reagent tank which communicated itself with the atmosphere or with a vacuum pump via a 3-way valve.
  • the shavings were impregnated, at room temperature, with an 0.003 M aqueous solution of pentasodium salt of diethylenetriaminepentaacetic acid (Na 5 DTPA) and 0.1 N in H 2 SO 4 by suction of the solution in the reactor by means of the reduced pressure produced by the vacuum distribution; the aqueous solution was used in a quantity equal to 8 times the weight of wood in the dry state. After 4 hours of impregnation, the shavings were then subjected to 3 washing cycles of 2 hours each with an amount of water equal to 8 times the weight of dry wood (First step).
  • Na 5 DTPA diethylenetriaminepentaacetic acid
  • the dough obtained at the end of the cooking step was analyzed under the same aspects and according to the same methods as in tests 1 to 6R except, however, as regards viscosity.
  • test 7 carried out according to the process of the invention with test 11R shows that at an equivalent delignification rate, the process according to the invention provides, after cooking, a kraft paste of higher weight yield.
  • Tests 7, 8R, 9R and 10R also show, as in the first series of tests, that, in the method according to the invention, the combination of the first two stages achieves an unexpected synergistic effect.
  • Tests 12 and 13 both in accordance with the invention, have the objective of showing the advantage obtained by the particular embodiment of the invention which consists in interposing, between the second and the third stage of the process, a washing with cellulosic materials.
  • test 12 we then go directly to the third step of the process while in test 13, we first carry out 3 washing cycles with hot water, each lasting 2 hours, the weight quantity of water used being 8 times the weight of dry wood.
  • the object of tests 14 to 16 in accordance with the invention was to illustrate the effect of pH during treatment with peroxide of hydrogen in the second step of the process according to the invention. These tests were carried out on pinus taeda wood flour under the same operating conditions as in the third series of tests except the quantities of NaOH in the second stage which were adjusted to vary the pH of this stage in the range from 10.1 to 12.9 at the start of the reaction.
  • the most advantageous kappa index was that of test 16 where the pH is between 12 and 13 in the second step.
  • the increase in pH has no marked effect on the drop in yield.

Landscapes

  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dental Preparations (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Organic Insulating Materials (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)
  • External Artificial Organs (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP86110249A 1985-08-05 1986-07-25 Verfahren zur Delignifizierung von Zellulosematerialien Expired - Lifetime EP0213376B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86110249T ATE57401T1 (de) 1985-08-05 1986-07-25 Verfahren zur delignifizierung von zellulosematerialien.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76272485A 1985-08-05 1985-08-05
US762724 1985-08-05

Publications (2)

Publication Number Publication Date
EP0213376A1 true EP0213376A1 (de) 1987-03-11
EP0213376B1 EP0213376B1 (de) 1990-10-10

Family

ID=25065878

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86110249A Expired - Lifetime EP0213376B1 (de) 1985-08-05 1986-07-25 Verfahren zur Delignifizierung von Zellulosematerialien

Country Status (14)

Country Link
EP (1) EP0213376B1 (de)
JP (1) JPH0742669B2 (de)
AT (1) ATE57401T1 (de)
AU (1) AU591508B2 (de)
BR (1) BR8603671A (de)
CA (1) CA1282911C (de)
DE (1) DE3674866D1 (de)
ES (1) ES2000831A6 (de)
FI (1) FI85725C (de)
IN (1) IN167959B (de)
NO (1) NO168375C (de)
NZ (1) NZ217001A (de)
PT (1) PT83117B (de)
YU (1) YU45352B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0921228A3 (de) * 1997-12-08 2000-02-23 Sunds Defibrator Pori Oy Verfahren zur Herstellung von vorgereignigtem Zellstoff

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU591509B2 (en) * 1985-08-05 1989-12-07 Interox Societe Anonyme Process for the delignification of cellulosic substances
AU2008253520B2 (en) * 2007-05-23 2013-05-09 Innotech Alberta Inc. Method to remove hemicellulose from cellulosic fibres using a solution of ammonia and hydrogen peroxide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE873649C (de) * 1944-08-25 1953-04-16 Degussa Verfahren zur Herstellung von ungebleichten Zellstoffen mit hohem Weissgehalt
FR2190974A1 (de) * 1972-07-05 1974-02-01 Mo Och Domsjoe Ab
FR2264125A1 (de) * 1974-03-14 1975-10-10 Mo Och Domsjoe Ab
US4486267A (en) * 1983-11-14 1984-12-04 Mead Corporation Chemithermomechanical pulping process employing separate alkali and sulfite treatments

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU591509B2 (en) * 1985-08-05 1989-12-07 Interox Societe Anonyme Process for the delignification of cellulosic substances

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE873649C (de) * 1944-08-25 1953-04-16 Degussa Verfahren zur Herstellung von ungebleichten Zellstoffen mit hohem Weissgehalt
FR2190974A1 (de) * 1972-07-05 1974-02-01 Mo Och Domsjoe Ab
FR2264125A1 (de) * 1974-03-14 1975-10-10 Mo Och Domsjoe Ab
US4486267A (en) * 1983-11-14 1984-12-04 Mead Corporation Chemithermomechanical pulping process employing separate alkali and sulfite treatments

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 52, no. 4, octobre 1981, page 483, résumé no. 4428, Appleton, Wisconsin, US; & SU-A-821 614 (M.A. ZIL'BERGREIT et al.) 15-04-1981 *
ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 52, no. 7, janvier 1982, page 859, résumé no. 8072, Appleton, Wisconsin, US; & JP-A-56 085489 (JAPAN NATIONAL RESEARCH INSTITUTE OF INDUSTRY & TECHNOLOGY) 11-07-1981 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0921228A3 (de) * 1997-12-08 2000-02-23 Sunds Defibrator Pori Oy Verfahren zur Herstellung von vorgereignigtem Zellstoff

Also Published As

Publication number Publication date
ATE57401T1 (de) 1990-10-15
EP0213376B1 (de) 1990-10-10
FI863193L (fi) 1987-02-06
PT83117B (pt) 1988-10-14
NO168375C (no) 1992-02-12
YU137086A (en) 1987-10-31
IN167959B (de) 1991-01-12
FI863193A0 (fi) 1986-08-05
JPS6297991A (ja) 1987-05-07
NZ217001A (en) 1989-01-27
BR8603671A (pt) 1987-03-10
CA1282911C (fr) 1991-04-16
JPH0742669B2 (ja) 1995-05-10
PT83117A (fr) 1986-09-01
FI85725B (fi) 1992-02-14
DE3674866D1 (de) 1990-11-15
AU591508B2 (en) 1989-12-07
NO863132L (no) 1987-02-06
FI85725C (fi) 1992-05-25
ES2000831A6 (es) 1988-03-16
AU6054386A (en) 1987-02-12
NO863132D0 (no) 1986-08-04
NO168375B (no) 1991-11-04
YU45352B (en) 1992-05-28

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