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EP2844796B1 - Procédé de fabrication de pâte à papier à faible teneur en lignine à partir de matière lignocellulosique - Google Patents

Procédé de fabrication de pâte à papier à faible teneur en lignine à partir de matière lignocellulosique Download PDF

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Publication number
EP2844796B1
EP2844796B1 EP13723025.6A EP13723025A EP2844796B1 EP 2844796 B1 EP2844796 B1 EP 2844796B1 EP 13723025 A EP13723025 A EP 13723025A EP 2844796 B1 EP2844796 B1 EP 2844796B1
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Prior art keywords
hemicellulose
lignin
cellulose
pulp
temperature
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German (de)
English (en)
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EP2844796A1 (fr
Inventor
Alexander DYBOV
Florian Boeck
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Annikki GmbH
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Annikki GmbH
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • 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
    • 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
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • 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
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D21C3/026—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of O2, e.g. air
    • 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
    • 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
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • 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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes

Definitions

  • the present invention relates to a process for the production of low lignin pulp from lignocellulosic material.
  • the present invention follows the second route:
  • the polymeric components cellulose and lignin
  • lignocellulose are to be separated from lignocellulose, with as few changes as possible in the said components after the separation process.
  • unselective pulping processes are generally used in which lignin and xylan are simultaneously removed from the lignocellulosic material at high temperatures in the presence of sulfur-containing reagents.
  • the removed lignin is greatly altered in its structure by ring condensation and attack of the sulfur-containing reagents and can usually be used only as a fuel.
  • high temperature processes can cause the formation of heterocyclic substances (e.g., furfural) from sugars, necessitating expensive recycling processes.
  • a technological improvement in this area would be the development of low-temperature processes (ie at a temperature of less than 100 ° C and below), all of which are as pure as possible and maximize material yield. This would mean a significant advance, since lignocellulosic material in successive digestions at low temperatures ( ⁇ 100 ° C) can be separated into the individual pure substance classes lignin, xylan and pulp and then converted to higher-value products. In addition, such processes can be an energetically economical process due to the low temperatures.
  • the soda process was developed in 1851 by Burgess and Watts and dispenses with the use of environmentally hazardous sulfur compounds. Only sodium hydroxide is used as the digestive chemical, which is why the process must be carried out for sufficient delignification at high temperatures. In comparison with other processes, a high degradation of carbohydrates takes place, so that a lower degree of polymerization and a lower tear strength in the cellulose is obtained. In addition, the method is only suitable for slightly bleachable materials. In some cases, anthraquinone is added to stabilize the carbohydrates and for better delignification (soda-anthraquinone method).
  • the soda process offers a way to obtain lignin without or with very low sulfur content compared to the kraft process.
  • the lignin removal must be performed at even higher temperatures than the Kraft process, thereby obtaining more condensed lignin.
  • carbohydrates are heated at soda process temperatures, heterocyclic substances such as furfural are formed, which must be separated in a complicated manner.
  • the sulfite process was first patented by Benjamin Tilghman in 1867.
  • the first industrial process using this process started in 1874 in Sweden.
  • mixtures of various salts of sulfurous acid are usually added as active reagents.
  • the most common are the calcium and magnesium salts.
  • the process can be operated from the strongly acidic to the basic environment.
  • a two-step combination of both has also proven useful in some cases.
  • the sulfite chemically modifies the lignin and makes it more soluble in water. Due to the environmental harmfulness of the process, it has today a minor importance, but is often used for the production of chemical pulp, since this easily bleachable cellulose is produced.
  • EP 1 375 734 For example, there is known a process for making cellulose wherein lignocellulosic material is treated with magnesium bisulfite, optionally with excess SO 2 , at a temperature between 130 ° C and 165 ° C to remove lignin.
  • the method also includes a combination with a bleaching sequence after removal of the lignin, which is performed exclusively with chlorine-free reagents.
  • DE 103 23 376 describes a process for delignifying lignocellulosic raw materials, wherein the lignin is removed by using sulfites in the presence of an alkaline component, especially sodium hydroxide or sodium carbonate, or a mixture thereof, in aqueous solution using elevated temperature and pressure. At the beginning of a digestion aqueous sulfite solution is used and the temperature is increased up to the maximum reaction temperature. The alkaline component is added only after the beginning of the digestion.
  • an alkaline component especially sodium hydroxide or sodium carbonate, or a mixture thereof
  • the force process was developed in 1884 by Carlerson Dahl in Gdansk (see eg US 296,935 ) and includes a method in which lignin is dissolved out of the pulp by means of a mixture of sodium sulfate, sodium carbonate, sodium hydroxide and sodium sulfide under an overpressure of 5 to 14 atmospheres.
  • the lignin is obtained as a soluble alkali metal in the black liquor and has a high sulfur content.
  • Lignin by force process contains between 1.5 and 3.0% sulfur ( Marton J. "Lignins; Occurrence, Formation, Structure and Reactions", 1971, Wiley-Interscience, Eds. Sarcans KV and Ludwig CH, USA, p 666 ). It is burned in most cases as an energy source to generate the heat demand for the process.
  • the Kraft process is currently the most common process for the production of paper pulp.
  • US 2011/0073264 A1 is a method for increasing kraft pulp yield and increasing the viscosity of the resulting pulp is known. This is achieved by pre-treating lignocellulosic material with hot water or steam at a temperature of 160 ° C. Remaining lignin is then removed by treatment with Na 2 S and NaOH under force conditions.
  • EP 0 468 016 For example, a pulp-making process is known in which lignocellulosic material is loaded with loaded cooking liquor at a temperature between 20 ° C and 100 ° C. The pretreated lignocellulosic material is heated at a temperature between 135 ° C and 155 ° C and delignified.
  • An advantage of the Kraft process described above is the relatively easy way to produce delignified, readily further bleachable cellulose.
  • a major disadvantage of this is that the potentially high-quality lignin is only suitable for further use because it is strongly changed in its structure after separation from the other raw material components by high-temperature condensation reactions.
  • the lignin is strongly modified with sulfur by the reaction with sulfide.
  • organosolv processes have recently been taken up again. These were first described in the 1970s. At that time, extended cooking strategies were developed, mainly based on increasing the degree of delignification and reducing bleaching costs.
  • the solvents used were predominantly alcohols, such as ethanol or methanol, which were mainly intended to increase the solubility of lignin, while acids, alkalis, sulphite or sulphide or oxidative reagents continued to act as actual digestion chemicals ( H. Hergert, 1998, Developments in organosolv pulping; In: RA Young and M. Akhtar, Environmentally friendly technologies for the pulp and paper industry; John Wiley & Sons Inc., New York, 5-68 ).
  • organosolv processes can be subdivided into acidic and basic variants.
  • An acidic process is, for example, the Allcell process, which was taken over and further developed by LIGNOL ( C. Arato, EK Pye, G. Gjennestad, 2005, The Lignol approach to biorefining woody biomass to produce ethanol and chemicals; Appl. Biochem. Biotechnol., Vol. 121-124, p. 871-882 ). Wood, straw or bagasse are used as substrates.
  • the underlying chemical reaction is the autohydrolytic cleavage of hemicelluose at a pH of 2.0 to 3.8, which results from the cleaved by xylan acetic acid (conditions: 180 ° C to 195 ° C, ethanol concentration: 35 wt. % to 70% by weight, liquid to solid ratio: from 4: 1 to 10: 1, reaction time 30 to 90 minutes).
  • xylan acetic acid conditions: 180 ° C to 195 ° C, ethanol concentration: 35 wt. % to 70% by weight, liquid to solid ratio: from 4: 1 to 10: 1, reaction time 30 to 90 minutes.
  • some cellulose in the form of insoluble oligosaccharides and a large part of the hemicellulose is cleaved to soluble oligo- and monosaccharides.
  • Part of the pentoses is oxidized to furfural under the reaction conditions.
  • Lignin is also partially hydrolyzed and falls together with the other degradation products in the cooking liquor, from which the degradation products are then recovered.
  • the other, unhydrolyzed part remains in the solid and can, for example, be hydrolyzed enzymatically to sugars and fermented to ethanol.
  • the lignin remaining in the solid (20% to 25% of the original) falls as fermentation residue and can only be burned.
  • the organocell process for pulp cooking was developed in industrial applications until the 1990s (N. Zier, 1996, Structural Characteristics of Organosolv Lignin with Variation of Parameters, Dissertation, Dresden University of Technology).
  • the process is carried out in two stages, starting with an alcohol-water impregnation (ratio: 3 parts of alcohol: 7 parts of water) at 110 ° C to 140 ° C and subsequent boiling at 165 ° C to 170 ° C with the addition of 30% sodium hydroxide solution and 0.1% anthraquinone, based on the dry weight of the substrate.
  • the process is suitable for the decomposition of deciduous and coniferous wood, as well as for annual plants.
  • the pulp quality is comparable to kraft pulp and bleached with chlorine-free oxygen. According to various sources, the plant was closed soon after commissioning due to technical problems, some of which related to the recovery of the high volume of caustic soda ( El-Sakhawy et al., 1996: Organosolv pulping, (3), ethanol pulping of wheat straw; Cellul. Chem. Technol. 30, 281-296 ).
  • WO 2011/014894 and WO 2012/027767 are known low temperature method for the separation of said lignin from lignocellulosic material such as straw, bagasse, energy grasses and or husks.
  • the digestion process provides for a low temperature delignification process at below 100 ° C, after which the resulting cellulose and hemicellulose enriched material can be treated with at least one carbohydrate-splitting enzyme.
  • One variant is the use of xylanases, which selectively degrades xylan and produces highly cellulose-enriched material.
  • a disadvantage of such a low-temperature process is, compared to pulp from kraft or soda processes, high lignin content in the cellulose.
  • WO 2010/124312 is a method for separating hemicellulose from a hemicellulose and cellulose enriched material, which after WO 2011/014894 is prepared described.
  • the solid mixture obtained after digestion is suspended in an acetate buffer and treated with xylanases to selectively depolymerize and dissolve hemicellose.
  • the highly cellulose-enriched solid obtained after separation can then be used to obtain glucose, for example by reaction with cellulases.
  • a chemical method for xylan separation from Kraft pulp for the production of chemical pulp is in WO 2005/118923 A1 described.
  • the resulting pulp is treated with at least 5%, preferably 9% sodium hydroxide solution at a temperature of less than 25 ° C.
  • the obtained xylanh Vietnamese solution can, as in US 2010/0021975 A1 concentrated by nanofiltration and precipitated by the addition of mineral acid.
  • the addition of a mono- or polyhydric alcohol may promote this precipitation.
  • a method provided in accordance with the present invention is also referred to herein as the "method of (in accordance with) the present invention.”
  • lignin-containing organic material is used as the lignocellulosic material, e.g. Annual plants, such as (dry) grasses, or parts of grasses, preferably grasses, straw, energy grasses, such. Switchgrass, elephant grass or abaca, sisal, bagasse or atypical lignocellulosic substrates such as husks, e.g. Lemmas such as rice husks, more preferably straw, energy grasses bagasse or husks, even more preferably straw or bagasse, e.g. Straw, such as wheat straw.
  • husks e.g. Lemmas such as rice husks, more preferably straw, energy grasses bagasse or husks, even more preferably straw or bagasse, e.g. Straw, such as wheat straw.
  • the solids content at the beginning of the delignification process according to measure a) is preferably from 3 to 30% by weight of the lignocellulosic material in the aqueous solution. and is preferably present in a consistency of from 3 to 30 wt .-%, in particular 5 to 20 wt .-% before.
  • the alcohol used is preferably an aliphatic alcohol, such as a C 1-6 -alcohol, more preferably a C 1-4 -alcohol, such as ethanol or isopropanol, to separate lignin from lignocellulosic material according to measure a) ,
  • the pH of the solution according to measure a) can be adjusted with a base, preferably an inorganic base, for example a hydroxide, such as sodium hydroxide solution, potassium hydroxide solution.
  • a base preferably an inorganic base, for example a hydroxide, such as sodium hydroxide solution, potassium hydroxide solution.
  • the lignin digestion according to measure a) in a process according to the present invention is carried out at a temperature of below 100.degree. C., preferably from 40.degree. C. to 90.degree. C., more preferably from 50.degree. C. to 70.degree. It has been found that when using temperatures of more than 100 ° C increased condensation products of lignin occur, for example, condensed, phenolic fragments of the formulas which arise through ring condensation reactions.
  • the present invention is based on the finding that lignocellulosic material less strongly condensed from a lignocellulosic material treated with an aqueous basic solution which comprises an alcohol, in particular a C 1-6 -alcohol and a pH of 10 to 14 can be won.
  • the treated cellulosic and hemicellulose enriched material proves to be a more useful material for enzymatic degradation to carbohydrate cleavage products.
  • An advantage of the method according to the present invention is that, because hemicellulose has a low solubility at higher alcohol concentrations, selective isolation of pure lignin is possible. Hemicellulose may be isolated as a pure product in a follow-up step of measure b) from cellulosic and hemicellulose-enriched lignocellulosic material.
  • hemicellulose preferably xylan
  • hemicellulose can be separated by a combination of chemical and enzymatic treatment to obtain as pure as possible dexylanated cellulose.
  • the depletion and optionally isolation of the hemicellulose in a process according to the present invention according to measure b) can be carried out chemically or enzymatically.
  • the present invention provides a method according to the present invention in which according to measure b) either Hemicellulose from the cellulosic and hemicellulose-enriched material of a) is brought into solution by treatment with at least one carbohydrate-splitting enzyme, or Hemicellulose from the cellulosic and hemicellulose-enriched material from a) is brought into solution by treatment with aqueous alkaline solution at a temperature of 20 ° C to 50 ° C, preferably from 25 ° C to 35 ° C, or Hemicellulose from the cellulosic and hemicellulose-enriched material from a) both by treatment with aqueous alkaline solution at a temperature of 20 ° C to 50 ° C, preferably from 25 ° C to 35 ° C, as well as by treatment with at least one carbohydrate-splitting enzyme is brought into solution.
  • the dissolved hemicellulose can be isolated by separating the solution from the solid from the solution.
  • the combined measures a) and b) in a process according to the present invention have proven to be particularly suitable for the depletion of cellulose from a lignocellulosic material.
  • the process of the present invention for producing delignified pulp from lignocellulosic material is a process in which the separate isolation of all streams is made possible to obtain high-grade sulfur-free lignin.
  • An essential advantage of the process according to the present invention is the high delignification with high selectivity.
  • the delignification carried out in the digestion according to measure a) increases the porosity of the cell walls of the lignocellulosic material, so that carbohydrate-splitting enzymes can penetrate into the straw and hydrolyze the xylan contained.
  • activity losses of the enzymes can be reduced by non-specific binding to the lignin.
  • pure endo-1,4- ⁇ -xylanases e.g. Enzyme preparations with pure endoxylanase activity.
  • xylan can also be extracted chemically according to one aspect of the measure b). This exploits the high functionalization with acidic residues compared to cellulose.
  • xylan can be selectively extracted from a cellulose and hemicellulose enriched material.
  • the pH according to measure b) is determined by an inorganic base, e.g. a hydroxide, preferably sodium hydroxide, adjusted at a molar amount of 1 to 20 wt .-% based on the amount of liquid.
  • the extraction is preferably carried out at a temperature of 20 ° C to 50 ° C, more preferably from 25 ° C to 35 ° C.
  • pulp is a highly cellulose-fortified material such as, for example, material produced by delignification and dexylanation according to the process described above.
  • the material obtained in accordance with measure b), which has been depleted with hemicellulose removes lignin, namely residual lignin, from the pulp.
  • lignin namely residual lignin
  • the solution obtained after removal of the (residual) lignin also provides opportunities to isolate and utilize the removed lignin.
  • the kappa value is a measure of the residual lignin content of the pulp.
  • Sulphite such as sodium sulphite
  • Sulphite is preferably used in an amount of from 10 to 100% by weight, particularly preferably 20% by weight, based on the dry mass.
  • an inorganic base preferably a hydroxide, e.g. Sodium hydroxide, in a concentration of 0.1 to 3.0 wt .-%, based on the dry mass used.
  • a hydroxide e.g. Sodium hydroxide
  • an anthraquinone derivative preferably sodium anthraquinone-2-sulfonate, in an amount preferably from 0.05 to 5 wt .-%, particularly preferably in an amount of 0.1 to 1 wt .-%, most preferably in an amount of 0.5% by weight, based on the dry matter, as a mediator to increase delignification efficiency.
  • the (residual) lignin can be removed by means of oxygen treatment at a temperature of 60 to 130 ° C, preferably from 80 ° C to 100 ° C, particularly preferably at 90 ° C. become.
  • an inorganic base for example a hydroxide, such as sodium hydroxide, in an amount of 1.0 to 10.0 wt .-%, preferably in an amount of 6 wt .-%, based on the dry mass used.
  • an oxygen pressure preferably from 1 to 20 bar, particularly preferably 10 bar, is used.
  • an anthraquinone derivative preferably sodium anthraquinone-2-sulfonate, in an amount of 0.05 to 5 wt .-%, preferably in an amount of 0.1 and 1 wt .-%, particularly preferably in one Amount of 0.5 wt .-% based on the dry mass added as a mediator. It has surprisingly been found that an embodiment in which an aqueous solution with 0.1 to 60% by volume of alcohol, preferably 1 to 5% by volume, particularly preferably 3% by volume is used, gives improved delignification efficiency.
  • the respective percentage compositions of all delignification components and the reaction parameters temperature, reaction time and solids concentration can be adjusted.
  • Pulp made in accordance with the present invention is e.g. with the kappa number and viscosity achievable by the process of the present invention.
  • pulp producible, in particular manufactured is disclosed by a process of the present invention.
  • Wheat straw (21.0% by weight lignin content, 20.9% by weight xylan content, 36.8% by weight cellulose content based on the dry mass) is comminuted to a particle size of 2 mm with an ultracentrifugal mill.
  • the crushed straw is suspended in a mixture of water, ethanol (alcohol content 60% by volume) and sodium hydroxide solution (8% by weight, based on dry matter).
  • the mixture is stirred mechanically at a constant temperature of 70 ° C for 18 hours.
  • the resulting solid is squeezed and washed with sufficient water to give a cellulosic and hemicellulose-enriched material. Yield and important parameters of the resulting material are shown in Table 2 below.
  • Cellulose and hemicellulose-enriched material from a) (about 58.2% by weight)
  • Cellulose content about 36.9% by weight xylan content, about 8.2% by weight lignin content
  • the material is first suspended in a tempered at 30 ° C 10% sodium hydroxide solution to a dry weight fraction of 10 wt .-% and stirred at this temperature for 30 minutes. After this time, the homogeneous mixture is filtered off and washed neutral with dilute hydrochloric acid and water. The resulting filter cake is suspended in a 50 mm acetate buffer solution to a solids content of 10% based on the dry mass, after which the pH is corrected to 5.
  • the pulp of b) was suspended in water to a dry weight content of 4% by weight. 7.6% by weight of NaOH and 0.5% by weight of Mg 2+ based on the dry weight of the pulp were added to the reaction mixture. The delignification was carried out under O 2 pressure of 10 bar and at a temperature of 90 ° C for 4 hours. Thereafter, the pulp was washed with a sufficient amount of water and dried. Subsequently, the kappa number and viscosity were determined.
  • Example 1 Digestion and dexylanation were carried out as in Example 1. Procedure and approach of delignification correspond to Example 1a), except that instead of water, a 3% aqueous ethanol solution was used as the reaction medium.
  • Example 2 Digestion and dexylanation were carried out as in Example 1. Carrying out and approach of the delignification correspond to Example 1, but added during the delignification in addition 6.3 wt .-% anthraquinone-2-sulfonic acid sodium salt monohydrate based on the total dried mass as a mediator.
  • Example 1 Digestion and dexylanation were carried out as in Example 1. The procedure and approach of delignification are the same as Example 3, except that instead of water, a 3% ethanol aqueous solution was used as the reaction medium.
  • Example 2 Digestion and dexylanation were carried out as in Example 1. The procedure and approach of (residual) delignification correspond to Example 5, except that instead of water, a 3% ethanol-water mixture was used as the reaction medium.
  • Example 1 Digestion and dexylanation were carried out as in Example 1.
  • the pulp was suspended in the water to delignify to a dry weight level of 4% by weight and containing 64% by weight of sodium sulfite and 1.5% by weight of sodium hydroxide in the presence of 2.0% by weight of anthraquinone-2-sulfonic acid Sodium salt monohydrate based on the dry mass of the pulp reacted.
  • the reaction time was 1 hour at a temperature of 130 ° C. After delignification, the pulp became a sufficient amount Washed water and dried. Subsequently, the kappa number and viscosity were determined.
  • the pulp prepared according to Example 7 was bleached with oxygen and alkali.
  • the reaction procedure and the reaction mixture were as described in Example 4 for the delignification.
  • Example 1 Digestion and dexylanation were carried out as in Example 1.
  • the procedure and approach of delignification are the same as Example 7, except that the reaction was carried out at a temperature of 140 ° C for 3 hours.
  • the pulp prepared according to Example 9 was bleached with oxygen and alkali.
  • the reaction procedure and the reaction batch corresponded to the information described in Example 4 with respect to the delignification.
  • the kappa numbers and viscosity results of the individual delignification methods are shown in Table 4 below.
  • the kappa value is determined according to DIN 54357 and is a measure of the (residual) lignin content of the pulp.
  • the viscosity determination was carried out in 0.5 m aqueous copper ethylenediamine solution (CuEn) with an Ubbelohde capillary viscometer after a simplified test procedure, using the same capillary for sample and blank value (SCAN-C 15:62, SCAN-C 16:62 and SCAN-CM 15:88).
  • pulp was additionally delignified with Na 2 SO 3 before oxygen bleaching, it was surprisingly possible to achieve a significantly lower kappa number of 7.7 ml after two bleaching steps, which corresponds to a total delignification of 86.6%.
  • kappa number difference of about 6.9 ml. This difference is significant in terms of industrial application, considering that, generally with low kappa, lignin removal becomes more difficult and expensive selective delignification reagents are needed.
  • the viscosity of the pulp delignified in a two-stage process is higher than that of pulp which has been bleached only with oxygen.
  • the pulp prepared according to Example 10 was further bleached with peroxyacetic acid.
  • Peroxyacetic acid was used in an amount of 10% by weight, based on dry matter. The consistency was 4%, the temperature 70 ° C. After a reaction time of 3 hours, the pulp was washed with a sufficient amount of water and dried. Subsequently, a kappa number of 1.2 ml was measured.

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Claims (9)

  1. Procédé d'obtention de matière cellulosique à faible teneur en lignine, caractérisé par une combinaison d'opérations consistant à :
    a) traiter de la matière lignocellulosique avec une solution aqueuse qui contient un alcool en C1-6 et présente un pH de 10 à 14, à une température inférieure à 100°C, à la suite de quoi la solution aqueuse dans laquelle se trouve de la lignine sous forme dissoute, qui a été clivée à partir de la lignocellulose, est séparée de la matière solide qui constitue une matière enrichie en cellulose et en hémicellulose,
    b) éliminer l'hémicellulose de la matière enrichie en cellulose et en hémicellulose provenant de l'étape a),
    c) traiter la matière obtenue à l'étape b) qui est appauvrie en hémicellulose, dans une solution aqueuse alcaline avec un sulfite d'alcalin, d'alcalino-terreux ou d'ammonium, en particulier du Na2SO3, et le cas échéant en plus avec de l'oxygène, dans lequel la lignine est solubilisée et de la matière cellulosique à faible teneur en lignine est obtenue.
  2. Procédé selon la revendication 1, caractérisé en ce que, à l'étape b), l'hémicellulose est solubilisée à partir de la matière enrichie en cellulose et en hémicellulose provenant de l'étape a) par traitement avec au moins une enzyme de clivage des hydrates de carbone.
  3. Procédé selon la revendication 1, caractérisé en ce que, à l'étape b), l'hémicellulose est solubilisée à partir de la matière enrichie en cellulose et en hémicellulose provenant de l'étape a) par traitement avec une solution aqueuse alcaline à une température de 20°C à 50°C, de préférence de 25°C à 35°C.
  4. Procédé selon la revendication 1, caractérisé en ce que, à l'étape b), l'hémicellulose est solubilisée à partir de la matière enrichie en cellulose et en hémicellulose provenant de l'étape a) aussi bien par traitement avec une solution aqueuse alcaline à une température de 20°C à 50°C, de préférence de 25°C à 35°C, que par traitement avec au moins une enzyme de clivage des hydrates de carbone.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que, à l'étape c), une température de 90°C à 150°C, de préférence de 120°C à 140°C, est utilisée lors du traitement avec le sulfite d'alcalin, d'alcalino-terreux ou d'ammonium.
  6. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que, à l'étape c), une température de 60°C à 130°C, de préférence de 80°C à 100°C, est utilisée quand de l'oxygène est mis en oeuvre.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que de la paille, de la bagasse, des herbes énergétiques, en particulier les herbes à éléphants, le panic érigé, et/ou les balles, en particulier les glumelles, sont mis en oeuvre comme matière lignocellulosique.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la matière lignocellulosique se présente en solution aqueuse en une densité de 3 à 30 % en poids par rapport à la matière sèche.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que, à l'étape c), un dérivé d'anthraquinone, de préférence du 2-sulfonate d'anthraquinone sodique, est ajouté comme médiateur en une quantité de 0,05 à 5 % en poids, de préférence en une quantité de 0,1 à 1 % en poids, particulièrement préférentiellement en une quantité de 0,5 % en poids, par rapport à la matière sèche.
EP13723025.6A 2012-05-03 2013-04-24 Procédé de fabrication de pâte à papier à faible teneur en lignine à partir de matière lignocellulosique Active EP2844796B1 (fr)

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EP13723025.6A EP2844796B1 (fr) 2012-05-03 2013-04-24 Procédé de fabrication de pâte à papier à faible teneur en lignine à partir de matière lignocellulosique
PCT/EP2013/058535 WO2013164234A1 (fr) 2012-05-03 2013-04-24 Procédé de production de cellulose à faible teneur en lignine à partir d'un matériau lignocellulosique

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US20150122429A1 (en) 2015-05-07
WO2013164234A1 (fr) 2013-11-07
AR091998A1 (es) 2015-03-18

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