WO2004104293A1 - Procede de delignification de materiaux bruts lignocellulosiques - Google Patents

Procede de delignification de materiaux bruts lignocellulosiques Download PDF

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Publication number
WO2004104293A1
WO2004104293A1 PCT/EP2004/005411 EP2004005411W WO2004104293A1 WO 2004104293 A1 WO2004104293 A1 WO 2004104293A1 EP 2004005411 W EP2004005411 W EP 2004005411W WO 2004104293 A1 WO2004104293 A1 WO 2004104293A1
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WO
WIPO (PCT)
Prior art keywords
weight
digestion
alkaline component
minutes
component
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Application number
PCT/EP2004/005411
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German (de)
English (en)
Inventor
Rudolf Patt
Björn ROSE
Othar Kordsachia
Volker Gehr
Hans-Ludwig Schubert
Original Assignee
Voith Paper Fiber Systems Gmbh & Co. Kg
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 Voith Paper Fiber Systems Gmbh & Co. Kg filed Critical Voith Paper Fiber Systems Gmbh & Co. Kg
Publication of WO2004104293A1 publication Critical patent/WO2004104293A1/fr

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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
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D21C3/06—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides sulfur dioxide; sulfurous acid; bisulfites sulfites

Definitions

  • the invention relates to a method for delignifying lignocellulosic raw materials. Such a process is technically known as digestion.
  • Lignocellulose-containing raw materials such as wood or grass are used to produce pulp.
  • the aim is to remove as much lignin as possible in the first process step, the digestion, without degrading the cellulose too much. Only if the delignification can be continued down to a low residual lignin content is bleaching to high degrees of whiteness possible with an acceptable use of chemicals.
  • pretreatment processes include the use of chemicals, solvents and temperature, possibly in combination. What the pretreatment processes have in common is that chemicals and solvents are used in amounts that are typically lower than the chemical inputs of the actual digestion. The temperatures are also lower than the usual digestion temperatures. Above all, the aim of the pre-treatments is not to completely delignify the respective raw material. Sometimes even the requirement is set that the substance losses z. B. to keep minimal by lignin degradation. This is particularly the case if the raw material is only to be prepared for further disassembly in a mechanical process.
  • fibers according to the AS-AQ process (alkaline sulphite process with anthraquinone) and the NS-AQ process (neutral sulphite process with anthraquinone) are therefore mainly used for unbleached or semi-bleached pulp products.
  • the pulps which are characterized by a high residual lignin content, but excellent yield and good strength properties, are e.g. B. suitable for the production of corrugated cardboard products.
  • alkaline sulfite processes A new development in alkaline sulfite processes is the split addition of the alkaline component.
  • at least 15% by weight of the alkali component are added at the beginning of the actual digestion, that is to say together with the addition of the sulfite component and at the start of heating to the reaction temperature.
  • the second alkaline component will be added later. This so-called alkali splitting leads to pulps with a high degree of whiteness and high viscosity.
  • This object is achieved in that sulfites in aqueous solution act on the lignocellulosic raw material using elevated temperature and pressure, an alkaline component, in particular sodium hydroxide or sodium carbonate or a mixture thereof, being added at the earliest at the start of delignification. Contrary to the expectations of the experts, this procedure leads to a selective increase in tear length and yield.
  • sodium hydroxide (NaOH) or sodium carbonate (Na 2 C0 3 ) is predominantly used as the alkaline component, but potassium or ammonium compounds are also suitable.
  • Ingruber teaches to control the pH from the beginning of the digestion and by continuously adding NaOH, during the heating and also in the subsequent sections of the Digestion to ensure that the high alkaline pH set at the beginning of the digestion is kept unchanged.
  • the digestion results published in the cited document show that, with an extraordinarily high, economically unacceptable use of chemicals of over 50% based on dry (absolutely dry) wood mass, it is possible to digest low residual lignin contents, but at the price of low yield and extraordinary loss of strength ,
  • the alkaline component is added about 15 minutes after the beginning of the digestion.
  • the tear length and yield are further increased if the addition of the alkaline component takes place after about 30 minutes, preferably after about 60 minutes, particularly preferably after about 90 minutes.
  • the digestion is controlled as a function of the temperature, there are positive effects in the development of the tearing length and yield if the addition of the alkaline component is carried out at at least approx. 70 ° C., preferably above 100, particularly preferably above approx. 125 ° C takes place.
  • the best results so far in terms of increasing the yield and the tearing length were obtained when the alkaline component was added when the maximum digestion temperature was reached.
  • the breaking length and yield can be increased significantly by adding the alkaline component.
  • the aqueous solution used for the digestion of the lignocellulosic raw material contains at least one sulfide component.
  • the acceptance of sulfide components reduces the requirements for the purity of the chemicals used for the digestion, which leads to an overall more economical process.
  • An extraordinary advantage of the method according to the invention is that the technology installed in practice can continue to be used essentially unchanged. Apart from the installation for the supply of the alkaline component, the plants for the digestion of the raw material and also for the reprocessing of the aqueous solution with the digestion chemicals remain unchanged. The complex balance of digestion and - above all - the recovery of the digestion chemicals is not disturbed. The total volume of the aqueous solution with the digestion chemicals contained therein does not have to be changed either, so that no adjustments to the evaporation system or the like are necessary.
  • Pulp with good strength properties and a low residual lignin content is obtained if the digestion is carried out with a duration of at least 90 minutes, preferably at least 120 minutes, particularly preferably at least 150 minutes or advantageously at least 360 minutes.
  • the total duration of the digestion is relatively short with a time between at least 90 and at least 360 minutes, which is attributed to the fact that, in the method according to the invention, the pH value is already significantly delignified during the heating phase by the drop in the pH value further delignification after addition of the alkaline component is well prepared.
  • a preferred embodiment of the method according to the invention provides that the digestion of the lignocellulosic raw material in the aqueous solution with the sulfite and the alkaline component contained therein and optionally the quinone component with a digestion time of at least 30 minutes, preferably between 60 minutes and 360 minutes , particularly preferably between 120 minutes and 180 minutes at the maximum digestion temperature.
  • the duration of the digestion can be kept short at maximum temperature.
  • the duration of the digest at maximum temperature is preferably between 60 and 180 minutes, generally between 120 and 150 minutes. If a relatively low digestion temperature, for example between 160 ° C and 170 ° C, is chosen for procedural reasons, it may be necessary to extend the digestion time at maximum temperature up to 300 minutes.
  • the digestion according to the invention with the addition of the alkaline component after the beginning of the digestion can be carried out under relatively mild conditions. Already at a digestion temperature of e.g. Bleachable cellulose is obtained after approx. 60 minutes at 150 ° C. It is preferred if the maximum digestion temperature is between 160 ° C and 180 ° C. If the lignocellulosic raw material is difficult to digest, the temperature can be increased further, with an economic limit of around 190 ° C.
  • the total use of chemicals that is to say sulfite with an alkaline component and, if appropriate, quinone or sulfide components and, if appropriate, addition of alcohol, can be kept low.
  • a total use of chemicals of at least 18% by weight based on dry wood is sufficient to achieve extensive delignification. If wood that is difficult to impregnate and contains a high proportion of lignin is to be digested, up to approx. 45% by weight of total chemicals based on dry wood must be used.
  • the total use of chemicals can be selected in a wide range. A good delignification is possible with a total use of chemicals between approx. 22% by weight and approx.
  • a total use of chemicals between approx. 25% by weight and approx. 35% by weight is preferred, advantageously between approx. 28% by weight -% and approx. 32% by weight.
  • the ratio between sulfite and the alkaline component can be set within a wide range. Since the quinone component which may be added is used only in minimal additions, it is insignificant for the adjustment of the sulfite: alkali ratio. A ratio of sulfite: alkaline component in a range between 80:20 and 20:80 is suitable for obtaining good quality pulps. A ratio of sulfite is particularly preferred; alkaline component between 60: 40 and 50: 50, in particular 40: 60.
  • the distribution of the total amount of chemicals for the digestion, i.e. sulfite and alkaline component can depend on the lignocellulosic raw material and, if applicable, the parameters of the selected digestion (temperature, duration ) can be set.
  • the invention also relates to a cellulose obtained by a method for delignification according to at least one of the preceding claims, in particular cellulose with a residual lignin content after digestion of less than kappa number 35, preferably less than kappa number 30, particularly preferably less than capa number 25 , particularly advantageous of less than Kappa number 20.
  • the low residual lignin content ensures good bleachability.
  • Good bleachability is characterized by the use of small amounts of bleaching chemicals and / or low energy consumption to achieve whiteness levels above 88% ISO.
  • the viscosity was determined according to leaflet IV / 36/61 of the Association of Pulp and Paper Chemists and Engineers (Zellcheming).
  • the degree of whiteness was determined by producing the test sheets according to Zellcheming leaflet V / 19/63, measured according to SCAN C 11:75 with an elrepho 2000 photometer; the whiteness is given in percent according to ISO standard 2470.
  • the residual lignin content was determined according to Zellcheming leaflet IV / 37/63.
  • the paper technology properties were determined on test sheets which were produced according to Zellcheming data sheet V / 8/76. Bulk density and tearing length were determined according to Zellcheming regulations N / 11/57 and V / 12/57.
  • the tear resistance was determined according to DI ⁇ 53 128 Elmendorf.
  • the degree of grinding was determined according to Zellcheming data sheet V / 3/62.
  • the yield was calculated by weighing the raw material used and the pulp obtained after the digestion, each dried at 105 ° C. to constant weight (atro).
  • the tensile, tear and burst index was determined in accordance with TAPPI 220 sp-96.
  • wood chips from a mixture of 2/3 spruce and 1/3 pine are mixed with an alkaline sodium sulfite digestion solution at a liquor ratio of 4: 1.
  • the total use of chemicals based on atro wood is 27.5% by weight based on atro wood.
  • the alkali ratio of sodium sulfite to ⁇ aOH was set at 60:40.
  • Half of the amount of sodium hydroxide is used as the first portion (50%) together with the sodium sulfite and 0.1% by weight of anthraquinone, based on dry wood, are added to the digestion solution.
  • the raw material and digestion solution are then heated to 175 ° C in 90 minutes.
  • the second portion of NaOH (50%) in aqueous solution is metered in. This increases the liquor ratio to: i-
  • the wood chips mixture is then digested for 150 minutes at 175 ° C.
  • the cooker is then degassed, cooled to below 100 ° C and the digestion material removed. It is washed, the chips are opened in a pulper and broken down into fibers. The fibers are sorted in a slot sorter. Then the yield, residual lignin content (expressed as kappa number), whiteness, tear length and burst strength are analyzed.
  • the total yield is 49.0% based on the starting raw material, of which 46.4% is good and 2.6% is split.
  • the degree of wisdom is measured at 27.5% ISO, the Kappa number is 22.1.
  • the same raw material is broken down into fibers under the same digestion conditions, but with a sulfite-alkali ratio of 55:45.
  • the alkaline component, NaOH is added 100% only when the maximum cooking temperature is reached.
  • the fibers would hardly have been delignified, since NaOH or other alkaline components are regarded as an essential factor for lignin degradation, especially in the initial phase of the digestion.
  • the yield is extraordinarily high at 51% with a kappa number of 22, as can be seen in a direct comparison with example 1. This applies not only to the overall yield but also to the share of accepted material, which remains intact at 49.5%, with a splinter share of 1.5%.
  • the whiteness is measured at 32% ISO.
  • Figure 1 shows the breaking length, given in 1 cm, depending on the beating degree, measured in ° SR (Schopper-Riegler).
  • the results of the tear length for example 1 are shown on the left in the group of three, the results of Example 2 are shown on the right in the group of three.
  • the middle bar is not important for the description of the method according to the invention. It is shown that the delayed addition of the alkaline component brings about clear advantages in the development of the tearing length.

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Abstract

L'invention concerne un procédé de délignification de matériaux bruts lignocellulosiques au moyen de sulfites, en présence d'un composant alcalin, notamment d'hydroxyde de sodium ou de carbonate de sodium ou d'un mélange de ceux-ci, dans une solution aqueuse, sous pression et température augmentées. Le procédé selon l'invention est caractérisé en ce que la solution de sulfites aqueuse est employée et la température est portée à la température de réaction maximale au début de la dissolution, le composant alcalin n'étant additionné qu'après le début de la dissolution.
PCT/EP2004/005411 2003-05-21 2004-05-19 Procede de delignification de materiaux bruts lignocellulosiques WO2004104293A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003123376 DE10323376A1 (de) 2003-05-21 2003-05-21 Verfahren zum Delignifizieren
DE10323376.8 2003-05-21

Publications (1)

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WO2004104293A1 true WO2004104293A1 (fr) 2004-12-02

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR091998A1 (es) 2012-05-03 2015-03-18 Annikki Gmbh Procedimiento de preparacion de celulosa con baja concentracion de lignina

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1815383A1 (de) * 1968-02-16 1969-10-16 Canadian Internat Paper Compan Verfahren zur Herstellung von Holzstoffmassen
US4211605A (en) * 1978-08-03 1980-07-08 Canadian International Paper Company High yield chemimechanical pulping processes
US4213821A (en) * 1976-06-02 1980-07-22 Australian Paper Manufacturers Limited Pulping with quinones and hydroquinones
EP0205778A1 (fr) * 1985-05-18 1986-12-30 Kraftanlagen AG. Procédé de cuisson au sulfite pour la préparation de pâte cellulosique à partir des matériaux lignocellulosiques avec récupération des agents chimiques de cuisson
US5409570A (en) * 1989-02-15 1995-04-25 Union Camp Patent Holding, Inc. Process for ozone bleaching of oxygen delignified pulp while conveying the pulp through a reaction zone
WO1995032331A1 (fr) * 1994-05-24 1995-11-30 Nils Mannbro Impregnation sulfuree de copeaux pour procede alcalin de trituration
EP0892107A1 (fr) * 1997-07-17 1999-01-20 Donohue Inc. Préparation de pâtes méchaniques à partir de bois avec réduction d' energie
WO2000047813A1 (fr) * 1999-02-09 2000-08-17 Stfi Delignification a l'oxygene de la pate a papier en presence de carbonates comme alcali
DE10229546A1 (de) * 2001-06-29 2003-01-16 Voith Paper Fiber Systems Gmbh Verfahren zum Delignifizieren lignocellulosischer Rohstoffe

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2318027C (fr) * 1999-09-13 2008-07-08 Andritz-Ahlstrom Inc. Traitement de la pate a papier avec un additif ameliorant le rendement ou la resistance

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1815383A1 (de) * 1968-02-16 1969-10-16 Canadian Internat Paper Compan Verfahren zur Herstellung von Holzstoffmassen
US4213821A (en) * 1976-06-02 1980-07-22 Australian Paper Manufacturers Limited Pulping with quinones and hydroquinones
US4211605A (en) * 1978-08-03 1980-07-08 Canadian International Paper Company High yield chemimechanical pulping processes
EP0205778A1 (fr) * 1985-05-18 1986-12-30 Kraftanlagen AG. Procédé de cuisson au sulfite pour la préparation de pâte cellulosique à partir des matériaux lignocellulosiques avec récupération des agents chimiques de cuisson
US5409570A (en) * 1989-02-15 1995-04-25 Union Camp Patent Holding, Inc. Process for ozone bleaching of oxygen delignified pulp while conveying the pulp through a reaction zone
WO1995032331A1 (fr) * 1994-05-24 1995-11-30 Nils Mannbro Impregnation sulfuree de copeaux pour procede alcalin de trituration
EP0892107A1 (fr) * 1997-07-17 1999-01-20 Donohue Inc. Préparation de pâtes méchaniques à partir de bois avec réduction d' energie
WO2000047813A1 (fr) * 1999-02-09 2000-08-17 Stfi Delignification a l'oxygene de la pate a papier en presence de carbonates comme alcali
DE10229546A1 (de) * 2001-06-29 2003-01-16 Voith Paper Fiber Systems Gmbh Verfahren zum Delignifizieren lignocellulosischer Rohstoffe

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