WO1995021960A1 - Procede et dispositif de lessivage de matiere cellulosique dans un melange contenant de l'acide carboxylique - Google Patents

Procede et dispositif de lessivage de matiere cellulosique dans un melange contenant de l'acide carboxylique Download PDF

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Publication number
WO1995021960A1
WO1995021960A1 PCT/FI1995/000057 FI9500057W WO9521960A1 WO 1995021960 A1 WO1995021960 A1 WO 1995021960A1 FI 9500057 W FI9500057 W FI 9500057W WO 9521960 A1 WO9521960 A1 WO 9521960A1
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WIPO (PCT)
Prior art keywords
lignin
carboxylic acid
acid mixture
cellulose
raw material
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Application number
PCT/FI1995/000057
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English (en)
Inventor
Åke Allan JOHANSSON
Johan Karl Rickard Lindholm
Harri Kai SIPILÄ
Johan Erik Gullichsen
Yakup Yilmaz
Original Assignee
Valtion Teknillinen Tutkimuskeskus
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Application filed by Valtion Teknillinen Tutkimuskeskus filed Critical Valtion Teknillinen Tutkimuskeskus
Publication of WO1995021960A1 publication Critical patent/WO1995021960A1/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
    • D21C3/003—Pulping cellulose-containing materials with organic compounds
    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0014—Combination of various pulping processes with one or several recovery systems (cross-recovery)
    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/12—Combustion of pulp liquors
    • D21C11/125—Decomposition of the pulp liquors in reducing atmosphere or in the absence of oxidants, i.e. gasification or pyrolysis
    • 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

Definitions

  • the invention relates to a process for separating cellulose fibres from lignin, involving the steps of
  • the invention also relates to an equipment for separating cellulose fibres from lignin, comprising
  • a cellulose digester (1) devised for heating a raw material containing cellulosic fibres and lignin along with lignin-dissolving carboxylic acid to provide a digestion mixture containing lignin carboxylic acid solution and solid cellulosic fibre material and
  • a first separating equipment (4) disposed after the cellulose digester (1) for separating the solid lignin carboxylic acid solution from the cellulosic fibre material.
  • cellulose is chemically produced by digesting wood chips in an aqueous solution of chemicals, a sufficient amount of lignin being dissolved to separate fibres nearly without, or completely without, mechanical means.
  • Cellulose may also be produced from other raw materials containing cellulose fibres, such as agricultural plants.
  • a 80 to 100% aqueous solution of organic acid and hydrogen peroxide yielded a Kappa number in the range of 4 to 23/42 to 61 (pine) and 5 to 6/56 to 62% (birch) with digestion at 70 to 90°C according to the publications Sundqvist, Intl. Symp. Wood and Pulping Chem., Vancouver, 1985, Proc, page 13 to 5, and Poppius, K., et al, Paperija Pu , 68 (1986) 87 to 92.
  • the object of the present invention is to achieve a new process for separating cellulosic fibres from lignin, providing more effective solutions to regeneration, environmental and application problems relating to cellulose digestion.
  • the basic idea of the invention is selecting digesting chemicals such that allow cellulose digestion to be associated with raw fuel pyrolysis.
  • This concept is a new one, and thus the scope of protection of the invention, in its broadest form, relates specifically to combining cellulose digestion with pyrolysis such that the chemicals produced by pyrolysis (particularly the water-soluble volatile fraction) is used for separating cellulose fibres from lignin.
  • the range of carboxylic acid supply may vary from complete recycling to the feed of quite fresh carboxylic acid mixture obtained by pyrolysis.
  • the cellulose digester is fed in step (a) with a lignin-dissolving carboxylic acid mixture, which is a mixture of the lignin carboxylic acid solution separated in step (c) and the lignin-dissolving carboxylic acid mixture separated in step (a ⁇ ).
  • a lignin-dissolving carboxylic acid mixture which is a mixture of the lignin carboxylic acid solution separated in step (c) and the lignin-dissolving carboxylic acid mixture separated in step (a ⁇ ).
  • the optimal feed ratio between fresh and spent carboxylic acid i.e. the optimal recycling ratio, can be set with the aid of the know-how of those skilled in the art.
  • the lignin carboxylic acid solution having been separated in the process from solid cellulosic fibre material can be further taken to a drying step (d), in which lignin-dissolving carboxylic acid mixture having remained in step (c) is further separated by evaporation.
  • the carboxylic acid mixture obtained by evaporation can be reconducted to the cellulose digester, either separately or preferably in combination, such that the cellulose digester is supplied with a lignin- dissolving carboxylic acid mixture, which is a mixture of the lignin-dissolving carboxylic acid mixture separated in drying step (d), the lignin carboxylic acid solution separated in step (d) and the fresh carboxylic acid mixture taken from the pyrolyzer in step (a3).
  • a lignin- dissolving carboxylic acid mixture which is a mixture of the lignin-dissolving carboxylic acid mixture separated in drying step (d), the lignin carboxylic acid solution separated in step (d) and the fresh carboxylic acid mixture taken from the pyrolyzer in step (a3).
  • the pulping liquor preferably consists of partly spent and partly regenerated carboxylic acid mixture.
  • part of the spent lignin carboxylic acid solution i.e. the one separated in step (c)
  • a pyrolyzer in which lignin is pyrolized and the carboxylic acid mixture is regenerated by means of cycles (ai) to ) above.
  • the raw material containing cellulose fibres and lignin used in the process claimed may consist of any cellulosic plant material. Nonetheless, it is preferable that such raw material consists of cellulosic fibre material which does not derive from wood. Field plant material is the preferred raw material in this case. Other economic plants, say plants cultivated for agronomic purposes, are also useful, and even plants producing cellulose fibres alone.
  • process step (a) comprises supplying the cellulose digester with lignin-dissolving carboxylic acid mixture consisting of 40 to 80% by volume of acetic acid and 60 to 20% by volume of formic acid. This is partly due to the fact that the acid mixture produced as a pyrolysis by-product has a similar composition.
  • the invention also involves the discovery that this composition is suitable for cellulose digestion, particularly that of field plant cellulose.
  • the carboxylic acid mixture to be separated by pyrolysis may contain other pyrolytic products, which may be present in cellulose digestion and possibly promote it.
  • the carboxylic acid mixture may also be enriched with external substances promoting digestion, such as antrachinone, oxygen, peroxides, organic solvents and inorganic acid catalysts such as HC1 and H2SO4.
  • the process may of course be controlled so as to obtain a different ratio of acetic acid to formic acid.
  • step (a) comprises supplying the cellulose digester with a lignin-dissolving carobxylic acid mixture, which is in the form of an aqueous solution containing 40 to 100% by volume, preferably 60 to 80% by volume of carboxylic acid.
  • a crucial parameter in cellulose digestion is the liquid/wood ratio L/W.
  • Liquid implies the total liquid weight of the digestion, including the moisture volume of the raw material.
  • Wood again, implies the dry weight of wood.
  • the ratio of the weight of the aqueous solution and the raw material liquid to the dry weight of the raw material is preferably in the range of 30: 1 to 2: 1, most preferably in the range of 10: 1 to 4: 1.
  • Heating, i.e. digestion step (b) of the process according to the invention is carried out by a controlled raise of the temperature in the cellulose digester, after the addition of raw material and carboxylic acid mixture, to the processing temperature mentioned above.
  • the processing time of step (b) of the present invention is preferably 60 to 360 min. and advantageously 120 to 240 min.
  • the temperatures are preferably from 80 to 160°C, advantageously from 90 to 140°C, yet without an absolute correlation between the processing time and the processing temperature.
  • the digestion result may be enhanced by introducing agents promoting delignification into the digestion.
  • the process of the invention may also be combined in an appropriate manner, understood by those skilled in the art, with mechanical cellulose fibre production, which involves mechanical treatment both before and after digestion.
  • step (c) of the process according to the invention the said lignin carboxylic acid solution being preferably separated from the solid cellulosic fibre material by means of a press, a screen and/or by evaporation.
  • separating step (c) is followed by washing the solid cellulosic fibre material with water, and/or diluted alkali, until a neutral wash water is obtained.
  • the cellulosic fibre material may be disintegrated into finished cellulose fibres if necessary, and in this conjunction, the cellulose fibres may be sorted if necessary, with the aid of a screen having an appropriate mesh dimension.
  • the process of the invention optionally comprises an additional step of treating the cellulosic fibre material mechanically so as to separate the useful fibre fraction from it.
  • the reject may be taken to a pyrolyzer.
  • step (a) of the process comprises supplying the pyrolyzer with a pyrolytic raw material, which is biomass.
  • the biomass may consist of say, vegetal or animal waste.
  • the pyrolytic raw material may be pretreated by crashing or drying.
  • the process may utilise any pyrolyzer capable of producing a carboxylic acid mixture out of pyrolytic raw material.
  • pyrolytic apparatus is one that pyrolyzes pyrolytic raw material at a temperature of 400 to 800°C with a delay in the range of 0.1 to 100 s. Pyrolyzers with a high temperature and a short delay, "flash pyrolyzers" are preferable.
  • step f ⁇ i.e. the pyrolysis step, a fluid-bed pyrolyzer may be used, which is of the type of a bubbling reactor or a circulating mass reactor.
  • Step (a3) of the pyrolysis part of the process of the invention preferably starts with separating the liquid fuel and the lignin-dissolving carboxylic acid mixture from the non-volatile pyrolytic product by means of evaporation. Evaporation may take place in the very pyrolyzer by recovering the liquid fuel and the lignin-dissolving carboxylic acid in the top of the pyrolyzer, the condensated heavier fraction being removed from the bottom of the reactor.
  • step (a4) When a mixture containing liquid fuel and carboxylic acid is obtained from the pyrolyzer, these components can be separated in step (a4) by condensating the mixture such that the liquid fuel is condensated, whereas the carboxylic acid remains in a gaseous form, in which it is recovered.
  • the invention also relates to an equipment for separating cellulosic fibres from lignin.
  • the equipment comprises
  • a cellulose digester (1) designed for heating a raw material containing cellulose fibres and lignin along with lignin-dissolving carboxylic acid, in order to obtain a digestion mixture which comprises lignin carboxylic acid solution and solid cellulosic fibre material and
  • a first separating device (4) disposed after the cellulose digester (1) for separating solid lignin carboxylic acid solution from cellulosic fibre material.
  • a raw fuel pyrolyzer (5) disposed in connection with the cellulose digester (1) for pyrolyzing the pyrolytic raw material into liquid fuel, lignin-dissolving carboxylic acid mixture and non-volatile pyrolytic product,
  • a second separating device (6, 7) provided in the pyrolyzer (5) for separating the lignin-dissolving carboxylic acid from the liquid fuel and the non- volatile pyrolytic product and
  • the equipment is an embodiment of the synergistic idea of combining a pyrolyzer producing liquid fuel with a cellulose digester by synergy, the by ⁇ product obtained from the pyrolyzer being suitable as a digesting chemical in the cellulose digester, and the cellulose digester by-products being potential raw materials for the pyrolyzer, and last, the digesting chemicals of the cellulose digester being potentially regenerated in the pyrolyzer.
  • the equipment comprises a pipe or a tube passing from the first separating device, i.e. the one separating cellulosic fibre material and pulping liquor, to the cellulose digester, by means of which the spent liquor, i.e. the lignin carboxylic acid solution, is partly recycled to the cellulose digester.
  • This pipe or tube preferably joins the first feed pipe for carboxylic acid mixture and/or the carboxylic acid mixture feed member.
  • the equipment of the invention may also comprise a dryer connected after the first separating device for cellulosic fibre material and pulping liquor, for removing carboxylic acid mixture remaining in the cellulosic fibre material by means of evaporation.
  • a dryer connected after the first separating device for cellulosic fibre material and pulping liquor, for removing carboxylic acid mixture remaining in the cellulosic fibre material by means of evaporation.
  • the second feed pipe for evaporated carboxylic acid mixture passes from the dryer to the cellulose digester, advantageously joining the first feed pipe and/or feed member for carboxylic acid mixture.
  • one embodiment of the equipment is provided with a branch pipe passing from the lignin carboxylic acid solution recycling pipe to the pyrolyzer, in order to feed a part flow of the solution to be regenerated in the pyrolyzer.
  • the cellulose digester of the invention may as well be a batch reactor as a continuous reactor. Various reactors are known in the field, and most of them can be converted so as to allow cellulose digestion in carboxylic acid liquor.
  • the digester may be provided with devices for pretreating the raw material containing cellulose fibres and lignin, such as mechanical treatment devices and screens, and also evaporators.
  • the digester may be a low-pressure or a high-pressure digester, and it may have static, back-current or forward-current operation. It may comprise one or more zones with varying conditions.
  • the separator following the cellulose digester, serving for separating cellulosic fibre material and lignin carboxylic acid solution is preferably a press and/or a screen.
  • the press may for instance be a roller press.
  • a washer may be provided at any point after the first separator for washing solid cellulosic fibre material.
  • a disintegrating unit and a screen may be disposed for mechanically disintegrating the separated, and perhaps washed and dryed, cellulosic fibre material in view of separating a high-value fibre fraction.
  • the equipment may be provided with a pipe passing from the screen to the pyrolyzer for feeding reject to the pyrolyzer, the pipe preferably joining a branch pipe conveying the pulping liquor to be regenerated.
  • the pyrolyzer of the equipment of the invention may be any reactor usable for processing raw fuel into liquid fuel.
  • the pyrolyzer operates at a temperature of 400 to 800°C and with a delay of 0.1 - 100 s.
  • the pyrolyzer be a fluid-bed reactor, such as a device of bubbling or circulating mass type.
  • the separators following the pyrolyzer may be of the type that are commonly known in the field, such as cyclons and condensers, provided that they separate the lighter liquid fuel carboxylic acid fraction from the heavier fraction, and similarly, the lightest carboxylic acid fraction from the slightly heavier liquid fuel fraction.
  • the pyrolyzer may be preceded by a raw fuel crasher, a defibrator and/or a dryer.
  • the figure shows a block diagram of the process and the equipment of one embodiment of the invention for separating cellulose fibres from lignin.
  • the equipment comprises a cellulose digester 1, supplied by a feed member 2 for raw material containing cellulose fibres and lignin, and a feed member 3 for carboxylic acid mixture.
  • the cellulose digester 1 is followed by a first separator 4 for separating solid cellulosic fibre material from lignin carboxylic acid solution.
  • the upper half of the figure illustrates the pyrolysis installation including the pyrolyzer 5, disposed in connection with the cellulose digester 1, and consisting of a reactor vessel, acting simultaneously as a separator 6 of the lighter and the heavier fraction.
  • the pyrolyzer 5 produces liquid fuel and carboxylic acid out of raw fuel, these two components being jointly separated from the non- volatile or poorly volatile pyrolytic product, such as solid residue and/or tar.
  • the pyrolyzer 5 is followed by a separate separator 7 for separating the lighter carboxylic acid fraction from the heavier liquid fuel.
  • a first feed pipe 8 passes from this separator to the cellulose digester 1 or its feed member 3.
  • the cellulose digester 1 is equipped with a pulping liquor circulating system such that a pipe 9 returns from the first separator 4 after the digester to the cellulose digester 1.
  • the lignin carboxylic acid solution separated from the cellulosic fibre material is recycled by means of the pipe at least partly back to the cellulose digester 1.
  • the cellulose digester 1 and the successive first separator 4 are followed by a dryer 10, where the cellulosic fibre material is heated such that even the remaining carboxylic acid evaporates.
  • a feed pipe 11 for the evaporated carboxylic acid amount returns from the dryer 10 to the cellulose digester 1 such that the pipe 11 joins the first feed pipe 8 and the feed member 3 for carboxylic acid mixture.
  • the equipment is provided with a branch pipe 12 passing from the recycling pipe 9 for lignin carboxylic acid solution to the pyrolyzer 5 for feeding spent pulping liquor, i.e. a part flow of the lignin carboxylic acid solution to be regenerated in the pyrolyzer 5.
  • This branch pipe 12 joins the feed pipe for raw fuel leading to the pyrolyzer 5.
  • the cellulosic fibre fraction may be further treated with a mechanical treating device 13 and a screen 14 to separate the fibre fraction. Enrichment of the fibre fraction may also be performed before digestion, and in that case the waste thus produced may be conducted to the pyrolyzer.
  • the device is not shown in the figure.
  • the reject feed pipe 15 passes from the screen 14 to the pyrolyzer such that the pipe 15 joins the pipe for pulping liquor to be regenerated, i.e. the branch pipe 12.
  • a raw fuel crusher 16 and a dryer 17 are disposed in connection with the raw material feed to the pyrolyzer 5.
  • the operation of the device is such that a raw material containing cellulosic fibres and lignin is fed through a feed member 2 to the cellulose digester 1.
  • the cellulose digester 1 is also supplied with lignin-dissolving carboxylic acid through the feed member 3.
  • the raw material and the lignin-dissolving carboxylic acid mixture are heated, the raw material containing cellulose fibres and lignin being disintegrated into cellulosic fibre material and lignin, and in this connection, lignin is dissolved at least partly in the carboxylic acid mixture.
  • a digestion mixture containing lignin carobxylic acid solution and solid cellulosic fibre material is produced.
  • the mixture obtained from the cellulose digester .1 is then fed to a first separator 4, where the lignin carboxylic acid solution is separated from the solid cellulosic fibre material.
  • the lignin-dissolving carboxylic acid mixture is produced by feeding pyrolytic raw material through the crusher 16 and the dryer 17 to the pyrolyzer 5, where is its thermally disintegrated into a light fraction, containing liquid fuel and carboxylic acid mixture, and a hevy fraction, containing solid residue and/or tar.
  • the fraction containing liquid fuel and lignin-dissolving carboxylic acid mixture is separated from the non-volatile pyrolytic product and is recovered fom the top of the pyrolyzer-separator 5,6.
  • the upper fraction of the pyrolyzer mentioned above is further processed in a second separator 7 so that the volatile, lignin-dissolving carboxylic acid mixture is separated from the liquid fuel.
  • the liquid fuel is utilised, and the lignin-dissolving carboxylic acid mixture is conducted through the first feed pipe 8 for carboxylic acid mixture back to the cellulose digester 1.
  • the pipe 8 joins the feed member 3 leading to the cellulose digester 1.
  • the lignin carboxylic acid solution obtained after the cellulose digester 1 and the first separator 4 is partly refed to the cellulose digester 1 through the pipe 9, which joins the feed pipe 8 for fresh carobxylic acid mixture and the feed member 3 leading to the cellulose digester 1.
  • Part of the lignin carboxylic acid solution is led through a branch pipe 12 to the pyrolyzer, where the lignin fraction is pyrolyzed into liquid fuel and the carboxylic acid fraction is recovered in a regenerated form.
  • the separated cellulosic fibre material is fed to a dryer 10, where the remainder of carboxylic acid is separated by evaporation from the cellulosic fibre material.
  • the evaporated carboxylic acid residue is led through the feed pipe 11 to a carboxylic acid recycling system, comprising a fresh pipe 8, a recycling pipe 9 and a feed member 3.
  • a carboxylic acid recycling system comprising a fresh pipe 8, a recycling pipe 9 and a feed member 3.
  • the cellulosic fibre material is mechanically treated 13, and by means of the screen 14 a usable fibre fraction is separated and recovered, and an unusable fine fraction is separated, which is introduced in the lignin carboxylic acid solution to be regenerated via the pipe 15, which in turn is fed to the pyrolyzer 5 through the branch pipe 12.
  • the objective of the invention was to delignify annual or perennial plants with various mixtures of formic acid, acetic acid and water. What makes the method particularly interesting is that the delignification chemicals required are obtained from a pyrolytic process connected with the digestion process. After the digestion processes, the spent liquors can be recycled to the pyrolyzer.
  • Flax was treated in a manner different from the other plants before digestion. Flax straw was introduced in a "garden" chopper, where the fibre fraction (approx. 20% of the dry substance) of the flax straw was separated with a fair yield. The separated fibres were cut into about 2 cm long fragments before digestion.
  • the remaining material was cut into approx. 2 - 3 cm long fragments before digestion.
  • the pulping liquor consisted of 75% by volume of acid mixture in an aqeuous solution.
  • the acid fraction consisted of 65% by volume of acetic acid and 35% by volume of formic acid.
  • the acid ratio roughly equals the composition of the acid fraction to be separated from the pyrolytic oil.
  • Digestion processes were conducted on a laboratory scale by means of a Buchi Rotavapor EL 130 device. The device was equipped with a reflux condenser.
  • the reactor used was a 1 1 round-bottomed flask and heat was provided by an oil bath, which was maintained at a temperature of about 125°C. This equipment did not allow pressurized digestion tests to be carried out.
  • Constant parameters 75% by volume of acid (consisting of 65% of acetic acid and
  • Reed canary grass digestion was used as an example (digestion No 2).
  • Reed canary grass was cut into about 2 - 3 cm fragments, and the material was stored in sealed plastic bags for about 24 hours. Two material samples (about 3 g each) were taken, and the moisture percentage was determined according to SCAN standard.
  • the amount of raw material used in digestion was 20 g, and thus, with a 92.04% dry matter content, 21.73 g of material was weighed into the round-bottomed flask.
  • the defibrated pulp was removed from the reactor and washed both with hot and cold water in a washer equipped with a metal wire net. Washing was carried on until the wash water reacted neutrally (pH about 6 - 7).
  • the pulp was wet disintegrated and water was removed by centrifugation, after which the pulp quantity was weighed. After 24 hours of storage in plastic bags two samples were taken, and the moisture percentage was determined. The dry pulp amount thus obtained is referred to as total yield in this conjunction.
  • the Kappa number was determined according to SCAN standard.
  • the ratio acetic acid:formic acid in the pulping liquor may vary from zero to one hundred per cent, involving any mixtures of these acids, but also pure formic or acetic acid.
  • the total acid (% by volume) may vary in the range of 40 to 100%, depending on digestion time and raw material.

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Abstract

L'invention concerne un procédé amélioré destiné à intégrer la production de fibres agricoles dans la production d'énergie à partir de plantes de culture. Le procédé consiste à séparer les fibres de cellulose de la lignine, et comprend les étapes consistant (a) à chauffer une matière brute contenant des fibres de cellulose ainsi qu'un mélange à base d'acide carboxylique dissolvant la lignine dans un lessiveur de cellulose afin de produire un mélange de lessivage contenant une solution d'acide carboxylique et de lignine, ainsi qu'une matière fibreuse cellulosique solide, et (c) à séparer la solution d'acide carboxylique et de lignine de la matière fibreuse cellulosique solide, le mélange d'acide carboxylique dissolvant la lignine étant obtenu par (a1) alimentation en matière brute pyrolytique d'un pyrolyseur relié au lessiveur de cellulose, (a2) chauffage de la matière brute pyrolytique dans le pyrolyseur afin de la pyrolyser dans un combustible liquide, un mélange d'acide carboxylique dissolvant la lignine ainsi qu'un produit pyrolytique non volatil et (a3) séparation du mélange d'acide carboxylique dissolvant la lignine du combustible liquide et du produit pyrolytique non volatil.
PCT/FI1995/000057 1994-02-11 1995-02-10 Procede et dispositif de lessivage de matiere cellulosique dans un melange contenant de l'acide carboxylique WO1995021960A1 (fr)

Applications Claiming Priority (2)

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FI940639A FI95159C (fi) 1994-02-11 1994-02-11 Menetelmä ja laite selluloosakuitujen erottamiseksi ligniinistä
FI940639 1994-02-11

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WO1995021960A1 true WO1995021960A1 (fr) 1995-08-17

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO1999057364A1 (fr) * 1998-05-05 1999-11-11 Chempolis Oy Procede de production de pate avec un melange d'acide formique et d'acide acetique utilise comme produit chimique de cuisson
WO2000068494A1 (fr) * 1999-05-06 2000-11-16 Compagnie Industrielle Des Matieres Vegetales Procede de production de pate a papier, lignines, sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique en milieu acide formique/acide acetique
WO2006117295A1 (fr) * 2005-05-03 2006-11-09 Compagnie Industrielle De La Matiere Vegetale Installation permettant de mettre en oeuvre un procede de production de pulpe de papier, de lignines et de sucres et procede de production utilisant cette installation
WO2009092749A1 (fr) 2008-01-25 2009-07-30 Compagnie Industrielle De La Matiere Vegetale Cimv Procédé pour prétraiter un matériau lignocellulosique en vue de produire du bioéthanol, et procédé de production de bioéthanol

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DE3445132A1 (de) * 1984-12-11 1986-06-12 Nimz, Horst H., Prof.Dr., 2050 Hamburg Holzaufschluss mit essigsaeure
WO1991018864A1 (fr) * 1990-05-29 1991-12-12 Kemira Oy Procede de recuperation d'un acide aliphatique inferieur
WO1993022490A1 (fr) * 1992-05-05 1993-11-11 Granit S.A. Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver

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Publication number Priority date Publication date Assignee Title
US3553076A (en) * 1968-01-22 1971-01-05 Weyerhaeuser Co Non-catalytic process for the production of cellulose from lignocellulosic materials using acetic acid
DE3445132A1 (de) * 1984-12-11 1986-06-12 Nimz, Horst H., Prof.Dr., 2050 Hamburg Holzaufschluss mit essigsaeure
WO1991018864A1 (fr) * 1990-05-29 1991-12-12 Kemira Oy Procede de recuperation d'un acide aliphatique inferieur
WO1993022490A1 (fr) * 1992-05-05 1993-11-11 Granit S.A. Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6562191B1 (en) 1998-05-05 2003-05-13 Chempolis Oy Process for producing pulp with a mixture of formic acid and acetic acid as cooking chemical
WO1999057364A1 (fr) * 1998-05-05 1999-11-11 Chempolis Oy Procede de production de pate avec un melange d'acide formique et d'acide acetique utilise comme produit chimique de cuisson
AU755788B2 (en) * 1998-05-05 2002-12-19 Chempolis Oy Process for producing pulp with a mixture of formic acid and acetic acid as cooking chemical
US7402224B1 (en) 1999-05-06 2008-07-22 Compagnie Industrielle De La Matiere Vegetale Method for producing paper pulp, lignins, sugars and acetic acid by frantionation of lignocellulosic vegetable material in formic/acetic acid medium
WO2000068494A1 (fr) * 1999-05-06 2000-11-16 Compagnie Industrielle Des Matieres Vegetales Procede de production de pate a papier, lignines, sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique en milieu acide formique/acide acetique
WO2006117295A1 (fr) * 2005-05-03 2006-11-09 Compagnie Industrielle De La Matiere Vegetale Installation permettant de mettre en oeuvre un procede de production de pulpe de papier, de lignines et de sucres et procede de production utilisant cette installation
FR2885371A1 (fr) * 2005-05-03 2006-11-10 Cie Ind De La Matiere Vegetale Installation pour la mise en oeuvre d'un procede de production de pate a papier, de lignines et de sucres et procede de production au moyen d'une telle installation
EA012118B1 (ru) * 2005-05-03 2009-08-28 Компани Эндюстриель Де Ля Матьер Вежеталь Установка для осуществления способа получения целлюлозы для производства бумаги, лигнинов и сахаров и способ получения, в котором используется такая установка
AU2006243234B2 (en) * 2005-05-03 2010-10-28 Compagnie Industrielle De La Matiere Vegetale Installation for implementing a method for producing paper pulp, lignins and sugars and production method using such an installation
US8157964B2 (en) 2005-05-03 2012-04-17 Compagnie Industrielle De La Matiere Vegetale Installation for implementing a method for producing paper pulp, lignins and sugars and production method using such an installation
WO2009092749A1 (fr) 2008-01-25 2009-07-30 Compagnie Industrielle De La Matiere Vegetale Cimv Procédé pour prétraiter un matériau lignocellulosique en vue de produire du bioéthanol, et procédé de production de bioéthanol
FR2926824A1 (fr) * 2008-01-25 2009-07-31 Cie Ind De La Matiere Vegetale Procede de pretraitement d'une matiere vegetale lignocellulosique en vue de la production de bioethanol.
AU2009207678B2 (en) * 2008-01-25 2013-09-12 Compagnie Industrielle De La Matiere Vegetale Cimv Process for pretreating a lignocellulosic material with a view to producing bioethanol, and bioethanol production process
US8551747B2 (en) 2008-01-25 2013-10-08 Campagnie Industrielle de la Matiere Vegetale CIMV Process for producing bioethanol from lignocellulosic plant raw material
EA019155B1 (ru) * 2008-01-25 2014-01-30 Компани Эндюстриель Де Ля Матьер Вежеталь Кэмв Способ получения биоэтанола из лигноцеллюлозного растительного исходного материала

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FI95159B (fi) 1995-09-15
FI940639A0 (fi) 1994-02-11

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