EP0082116A1 - Verfahren zur Delignifizierung von Holz und anderen Lignozelluloseprodukten - Google Patents

Verfahren zur Delignifizierung von Holz und anderen Lignozelluloseprodukten Download PDF

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Publication number
EP0082116A1
EP0082116A1 EP82810536A EP82810536A EP0082116A1 EP 0082116 A1 EP0082116 A1 EP 0082116A1 EP 82810536 A EP82810536 A EP 82810536A EP 82810536 A EP82810536 A EP 82810536A EP 0082116 A1 EP0082116 A1 EP 0082116A1
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Prior art keywords
phenol
aqueous
lignin
acid
cellulose
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EP82810536A
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French (fr)
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EP0082116B1 (de
Inventor
Hervé Tournier
Allan Johansson
Jean-Pierre Sachetto
Jean-Michel Armanet
Jean-Pierre Michel
Alain Roman
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HYDROCEL Srl
Battelle Memorial Institute Inc
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HYDROCEL Srl
Battelle Memorial Institute Inc
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Priority to AT82810536T priority Critical patent/ATE16206T1/de
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    • 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

Definitions

  • the present invention relates to a process for delignifying wood and other lignocellulosic materials and, simultaneously, hydrolyzing the hemicellulose thereof to monomeric sugars in the presence of aqueous acid, of phenol or mixtures of phenols or other phenolic products.
  • This invention relates to improvements made to a similar process which is the subject of a previously filed application, in particular European application No. 81810246.9.
  • the present invention also relates to improvements in the field of the chemistry of wood constituents in general and, more particularly, the efficient separation and isolation of cellulose pulp, wood pentoses and lignin phenols.
  • SCHWEERS (Chemtech 1974, 491; Applied Polymer Synposium 28, 277 (1975)) describes the use of a mixture of one part of sawdust, four parts of phenol, and 10% water acidified with 0.05 % HCl or 2% oxalic acid, this mixture being heated for 3 h at 160 - 170 ° C in an autoclave.
  • cellulose yields of the order of 40 to 60% are obtained relative to the weight of treated wood, this cellulose having a K index (Kappa) of the order of 40 to 100.
  • K index used in the paper industry to define the quality of delignified cellulose, relates inter alia to the content of cellulose in lignin after delignification; this content is approximately equal to K x 0.15 (TAPPI T - 236 m - 60, 1960).
  • phenolic products such as the various xylenols, catechol, resorcinol, hydroquinone, naphthols and naphthalene-diols were used to delignify the wood at a rate of 2% relative to the latter. and heating (in aqueous medium, wood / water suspension 1/1) '90 min at 175 ° C, all followed by extraction with a dioxane-water mixture (WAYMAN and LORA, TAPPI 61 (6), 55 (1978) )). Under these conditions, cellulose yields of the order of 60% with a residual lignin level of 4.6% (use of ⁇ -naphthol) have been observed.
  • APRIL et al (TAPPI 62 (5), 83 (1979)) mention the heating to 205 ° C of sawdust from pine wood in the presence of 15 parts of a 1: 1 mixture of phenol-water, such treatment leading to a cellulose containing no more than 3% lignin. According to this reference, the yields of purified cellulose are of the order of 40%.
  • an object of the present invention consists of a simple and economical means for separating with excellent yields the constituents of wood and other lignocellulosic materials, in particular, straw, bale, bark, dry leaves and other plant residues.
  • Another object of the invention is a process for delignifying the above-mentioned materials and providing an excellent quality cellulose pulp for the manufacture of cellulose solutions or a starting material for the production of glucose.
  • Another object of the invention is to produce industrially wood phenols with excellent yields and pentoses which can then be transformed into synthetic resins, fuels or other chemicals.
  • Another object of the invention is an effective means of recovering useful products from plant waste or wood which are normally burned or thrown in the sewer, which leads to undesirable pollution.
  • the method of the invention makes it possible to achieve the above aims, remedies the above-mentioned shortcomings and also provides other unexpected and surprising advantages as will be seen below. It is characterized by the fact that one part by weight of the lignocellulosic material is heated with at least 0.5 parts by weight of dilute aqueous acid whose pH does not exceed 1.5 and at least 0.4 part phenol or one or more other phenolic compounds. These phenolic compounds are those mentioned above and others to be defined below.
  • the heating temperatures are in the range of reflux temperatures of the phenolic aqueous mixture at ordinary pressure or slightly below or beyond it, for example between about 90 and 110 ° C.
  • the weight of the lignocellulosic material is counted on the basis of the dry matter, that is to say by subtracting the weight of natural moisture.
  • the liquid is stirred or moved so as to ensure good contact between it and the solid to be treated.
  • it is advantageous to continuously percolate the liquid in the solid which allows effective dissolution of the lignin and hydrolysis of the hemicellulose. In this case, the reflux effect of the liquid will provide the desired degree of contact.
  • aqueous acid used is not critical, as long as it is a strong acid.
  • mineral acids such as H 2 SO 4 , HCl, H 3 PO 4 are suitable, but sulfuric and hydrochloric acids are preferred.
  • Strong organic acids can also be used if desired, such as, for example, oxalic, benzene sulfonic acids and other aromatic sulfonic acids, trichloroacetic acid, etc., i.e. general, highly water-soluble acids whose pH is less than 2.
  • HCl is used with a concentration of between 0.5 and 5%, preferably between 1 and 3%.
  • phenol and other phenolic compounds it is possible to use, in addition to hydroxybenzene and most of the commercially available phenols, in particular the following compounds: p-cresol, o-cresol, guaiacol, 4-ethylphenol, 2,4-xylenol, 4-methylguaiacol , 4-ethylguaiacol, 2-ethylguaiacol, 4-vinylguaiacol, 4-prcpylguaiacol, eugenol, 1,3-dimethoxy-pyrogallol, vanillin, 1,3-dimethoxy-5-methylpyrogallol, trans-isoeugenol, catechol, phloroglucinol , homocatechol, etc.
  • any mixtures of these phenols where, also, mixtures of phenolic products resulting from the pyrolysis of phenolignin, the latter being, as already indicated above, the product of reaction between phenol (or other phenolic compounds) with degraded and dissolved lignin during the delignification of wood in the presence of phenol (or other phenols).
  • the phenol-lignin itself (provided that it is not too resinified by reaction with the thermal decomposition products of the pentoses from the hydrolysis of hemicellulose, for example, furfural).
  • this ligno-phenolic phase can then provide, by distillation and pyrolysis, an exceptional yield of wood phenols (a mixture which is perfectly suitable for the use of the present process) which makes the invention autonomous, and even excess, in phenol and other phenolic compounds.
  • the invention therefore makes it possible to produce, under exceptional economic conditions and with excellent yields: cellulose of high degree of purity (even from lignocellulosic products with a high percentage of lignin), easily separable pentoses and usable for other purposes, and phenols, part of which is naturally recycled in the process and the rest can be treated by the usual means (distillation, extraction, etc.) to separate the various components for later use.
  • the amount of acidulated water that is used relative to the lignocellulosic materials ground or in powder is not particularly critical provided that a good liquid / solid contact is ensured and that the quantity of water present is stoichiometrically sufficient to hydrolyze the pentosanes.
  • the stirring or percolation effect provided by the boiling of the water-phenol mixture is sufficient to ensure good contact, continuously renewed , between solid and liquid.
  • the proportion of water relative to the solid must be sufficient to provide a fluid medium, that is to say a suspension of said solid in water and acid.
  • a fluid medium that is to say a suspension of said solid in water and acid.
  • 4 parts of aqueous liquid for one part of solid in suspension is sufficient, but one can operate with more liquid if desired, for example from 5 to 50 parts of liquid; however, using very large volumes of liquid is impractical due to space issues.
  • liquid / solid ratio is rather low, i.e. less than 2: 1 or 3: 1, it is generally sufficient to mix the aqueous acid and the phenols with the plant material divided by kneading, for example in a paddle kneader or, more simply, by simultaneously penetrating the solid and the liquid into a tubular reactor by means of a screw and by slowly moving the intimate mixture of the solid and the liquid in the heating zone of the reactor.
  • the solid / liquid mixture gradually reacts, contracts and acquires sufficient fluidity so that it can be extracted at the opposite end of the reactor by other means of displacement.
  • phenol or phenols for delignification again this is not critical provided that enough is used to ensure good delignification of the wood.
  • more phenol can be used, if desired, i.e., 10, 20 or even 50 parts of phenol.
  • the cellulosic materials in the divided state it is preferred to use, for one part of the cellulosic materials in the divided state, from 1 to 6 parts of phenol and from 1 to 10 parts of dilute acid, for example HCl at 1.5 - 2% or aqueous H 2 S0 4 at 3 - 6% by weight. It is also preferred that the water / phenol weight ratio is greater than 1 and, advantageously, of the order of 3: 2 or 2: 1.
  • the mixture is mixed in a container (laboratory flask, glass or stainless steel reactor in industry) lignocellulosic material in divided form (for example, chips, shavings or sawdust) with dilute acid and phenol or mixture of phenols and the mixture is brought to the boil from 1 to 8 h. If desired, more sophisticated equipment can also be used as will be seen below.
  • 2 to 4 h of reflux are sufficient, which again constitutes an advantage of the invention compared to the prior art where the heating times (under pressure) are much longer. Once the reflux period has ended.
  • the residual solid which is constituted by very pure cellulose (K being of the order of 30 to 100) is drained with a yield of the order of 80 to 90% relative to the theoretical yield of the sample of corrected cellulose like 100% and we have it wash with a little hot water, possibly alkalized with NaOH or KOH and / or a water-soluble solvent (for example, acetone or methanol) in order to remove practically all the phenol. Then we resume the liquid phase (dilute acid plus phenol plus phenol-lignin produced by delignification) and we recycle it with a new portion of sawdust. This recycling can then be repeated at least four times, the efficiency of delignification and the purity of the cellulose produced decreasing only slowly.
  • K being of the order of 30 to 100
  • the aqueous phase rich in pentoses is separated from the lignophenolic phase by simple decantation.
  • the pentoses are then extracted from the aqueous solution by the usual means or, if desired, this solution can be directly treated with heat, so as to transform the pentoses into furan carposés.
  • This aqueous solution can also be subjected to fermentation (preparation of protein substances, alcohol, etc.), the phenol dissolved in this aqueous phase also being able to be recovered therefrom (for example by extraction and by distillation).
  • the liquid organic phase As for the liquid organic phase, it is first distilled, which makes it possible to recover a large quantity of pure phenol and a mixture of lignin phenols; then the indistinguishable residue is pyrolysed, which again provides phenols and a porous carbonaceous residue usable as fuel or as adsorbent carbon as well as volatile materials (gases) also combustible.
  • the liquid / solid ratio exceeds a certain value (of the order of 2: 1 to approximately 4: 1) at which the solid disperses easily in the liquid and at which, when the reaction is finished, the liquid easily separates from the solid by the usual means, for example vacuum filtration or use of filter presses.
  • liquid / solid ratio is less than such a value (in fact this value is not strictly fixed since it can naturally depend on factors such as the nature of the lignocellulosic material, the chopping techniques and the size and the surface condition of the particles), that is to say when the liquid / solid ratio is lower than that at which the solid disperses freely in the liquid and in the case where the liquid is rather in the " adsorbed "on the solid in particular, other handling techniques are preferably used.
  • the solid in particular is kneaded or kneaded together, the aqueous acid and the phenol (or phenols) by any usual means, for example a slow-running agitator, a kneader or the like and the pasty mass kneaded in a device suitable for the heating operation.
  • a device suitable for the heating operation can be a closed tube or a reactor.
  • a screw device advantageously connected to a vertical tubular reactor is advantageously used. The material is introduced in divided form into the hopper of the screw device and the liquids are injected laterally into the conduit of the screw device, which allows an effective liquid / solid mixture during the movement of the materials towards the reactor.
  • the pasty mass is subjected to treatments for separating the components of the lignocellulosic material (that is to say, cellulose, the monomeric sugars and the phenolic compounds) which are still mixed together but potential Lately split from each other (in the chemical sense) by the process described above.
  • treatments include washes similar to the rinsing steps already described with regard to the portions of delignified cellulose.
  • the pasty mass can be taken up with a suitable aqueous solvent to entrain soluble contaminants and separate them from the delignified cellulose. Cane such solvent, hot water saturated with phenol is suitable.
  • the liquid phase entails the phenolic constituents, the acid and the hydrolysis pentoses, this liquid phase then separating out an organic layer (phenol) and an aqueous layer (sugar solution) which can be decanted and which can then be processed. ted separately as described above.
  • phenol phenol
  • aqueous layer sucgar solution
  • the saturation of the phenolic solvent with phenol-lignin will occur rapidly (already after a normal operating cycle ⁇ and there is no need to provide for the restoration. direct play of the phenol-phenol-lignin mixture. Therefore, such cases relate rather to a continuous process according to which the material to be delignified as well as the other reagents are continuously introduced into the apparatus to be delignified, and harvested directly. the products formed with a view to their further purification.
  • Patent USP 3,776,897 relates to the addition of an organic solvent to a sulphite liquor for the delignification of wood after acidification thereof; it results first from the separation of
  • the liquid phase originating from the filtration of the cellulose separated into two phases which were isolated by decantation by means of a tap funnel.
  • the upper aqueous phase analyzed by the method of LISOV & YAROTSKII (IZVEST. AKAD NAUK SSSR, Ser, Khim. (4), 877-88 (1974) contained 1.47 g (85%) of pentoses and 0.43 g (8%) of hexoses accompanied by a small amount of dissolved phenol.
  • the heavier organic phase (42 g) contained the bulk of the phenol, and in solution therein, the phenol-lignin produced by the wood delignification. A significant amount of phenol was also recovered in the cellulose washing waters.
  • Example 1 In a 2 liter flask equipped as described in Example 1, 100 g of beech sawdust (see composition in Example 1), 400 g of phenol and 600 ml of 1.85% aqueous HCl were placed. After 4 h of boiling, it was drained on a büchner and washed with hot 1.85% HCl until a filtrate weighing a total of 1000 g was obtained. A sample of this filtrate was taken for analysis, then the above procedure was repeated using again 100 g of sawdust and the 1000 g of filtrate mentioned above. The above operation was then repeated twice more, still with fresh portions of 100 g of sawdust and, as in the liquid phase, the filtrate from the previous operation. Samples were taken for analysis each time. The results are recorded in Table I below with, including, the results of analysis of the portions of delignified cellulose obtained.
  • Example 1 After the last operation, the liquid was separated as in Example 1 into its aqueous phase and its organic phase.
  • the aqueous phase was extracted with toluene against the current and the extracts, after evaporation of the solvent, added to the organic layer.
  • the aqueous phase contained about 60 g of pentoses. By steam distillation of this aqueous phase, these pentoses were transformed into furfural.
  • the combined organic phases (approximately 490 g) were distilled (73 ° C / 13 Torr) which provided 323 g of phenol (approximately 67%), the remainder consisting of a mixture of wood phenols and partially degraded lignin which was shown by NMR analysis.
  • the residue from the pyrolysis (51.3 g, 30.7%) consisted of porous carbon residue and the difference to make 100% was due to the departure of non-condensable gases.
  • a comparative test was carried out by subjecting 10 g of sawdust to 4 h of hydrolysis in 100 ml of HCl at 1.85% but without phenol.
  • the yield of pentoses was only about 70%, which shows, and this is a surprising and unexpected effect, that the phenols promote the hydrolysis of hemicellulose in lignocellulosic materials at the same time. time they carry out the delignification of these.
  • the delignified paste was separated by wringing and extracted with 5% aqueous caustic soda so as to remove all of the phenol adsorbed in the form of alkaline phenolate (then the phenolate was acidified so that the phenol separated and this second crop of phenol was added to the first crop obtained in the wringing liquid).
  • the content of the aqueous phase in Ce and C 6 sugars was measured.
  • the apparatus shown comprises a reactor 1 filled with particulate plant material up to the level of a screen 2 for retaining the solid but which lets the delignification liquid pass. Via a valve 3, the bottom of the reactor communicates with a tank 4 of the delignification solution. By means of a pump 7, this solution is circulated from the bottom of the tank 4 to the upper part of the reactor 1 by means of the valves 5 and 6. From there, the liquid comes into contact with the particles of the plant material thus effecting continuous leaching of these.
  • the reactor 1 comprises a reflux condenser 8 and the reservoir 4 comprises a condenser 9.
  • the apparatus also comprises two heating mantles 10 and 11 with circulation of liquid for the reactor and the reservoir, respectively; the heating liquid (oil or any liquid) is circulated by a pump and heated by a heating element 13 thermostatically controlled.
  • a bypass valve 14 is placed between the pump 7 and the valve 6 to allow the flow rate of the delignification liquid to be controlled so as to maintain the liquid at gentle boiling in the reactor 1.
  • the total of the phenol in these various fractions is 393 g, which corresponds to almost all of the phenol involved.
  • the washed and dried fiber weighed 15.5 g. Its K index was 87.45, which corresponds to a residual lignin level of 13.11% (2.03 g).
  • the weight of lignin initially present was 4 g; as a result, 50% of this starting lignin has been dissolved.
  • Example 10 Tests similar to those of Example 10 were carried out using 42.5 g of birch chips (38.25 g dry), 53.55 g of phenol and 80.32 g of 1.85 aqueous HCl %. Four samples were heated for different times. The results are reported in Table VII.
  • Example 11 Four tests identical to those of Example 11 were carried out using 110 g portions of birch chips with the addition of 80 g of phenol and 120 g of 1.85% aqueous HCl (sample A) or addition of 160 g of phenol and 240 g of 1.85% HCl (sample B).
  • the heating periods were: 20 min of preheating until reflux, then 2 and 4 h at reflux. After cooling, the fiber was washed with boiling water, hot dilute NaOH and water again.
  • the 80 ml of the organic phase were boiled for 1 hour with 80 ml of the combined washing water fraction and, after cooling and separation of the phases, it was found by analysis that 80% of sugars originally retained in the organic phase had passed in aqueous solution. Thus, the yield of pentoses (dissolved in the aqueous phase) was 76%. The other analytical results showed that 88% of the lignin in the sample had been dissolved, the level of residual lignin in the fiber being 6.3%.
  • Example 15 The same type of tests was carried out as those of Example 15 using 150 g of birch chips (135.6 g dry, having the following composition in% by weight: pentosans 23.4 (potential pentoses 26, 6); cellulose 40.0 (potential hexoses 44.44); lignin 20.33; uronic acids 8.98; acetyl groups 3.6; extractable in water and in organic medium 3.6); 217 g of phenol and 325 g of 1.85% HCl. We carried 4 hours at reflux instead of one hour as in Example 15, all the other working conditions being the same as in this Example. Details and results are shown in Table X.
  • the process of the present invention was also carried out using pheydrolysed lignocellulosic materials instead of raw lignocellulosic materials.
  • This prehydrolysis is carried out by bringing to the boil a mixture of wood chips or other materials in the divided state and aqueous HCl or H 2 SO 4 diluted according to the usual technique. During the prehydrolysis in this dilute acid (for example 1 to 5% by weight in the solution), part of the pentosans is converted into pentoses which dissolve in the prehydrolysis solution.
  • the process according to the invention was carried out, either by removing all or part of the prehydrolysis solution and replacing it with the appropriate quantity of dilute acid and phenol according to the conditions described above, or by leaving in the presence of the prehydrolysis solution and adding the required amount of phenol and adjusting the pH (by adding more water or acid depending on the concentration of the prehydrolysis solution) so as to obtain the desired acid ratios and phenol suitable for the present delignification solution.
  • the main advantage of this variant comprising a prehydrolysis preceding the implementation of the invention consists in a better subsequent recovery of the phenol involved; it is also not known exactly why such conditions improve this recovery of phenol.
  • Another advantage is the shortening in certain cases of the time necessary for the delignification of the specimens of pre-hydrolysed lignocellulosic materials.
  • the prehydrolysis solution can either be treated separately to remove the dissolved pentoses, or it can be combined with the aqueous phase resulting from the delignification in order to a global sugar recovery treatment.
  • red oak shavings having the following composition in% by weight were used: pentosans 18 (potential pentoses 20.5); cellulose 39.9 (potential glucose 44.33); lignin 22.2; uronic acids 3.2; acetyl groups 5; ashes, indeterminate substances and substances extractable from water and solvents, organic 11.68.
  • pentosans 18 potential pentoses 20.5
  • cellulose 39.9 potential glucose 44.33
  • lignin 22.2 uronic acids 3.2
  • acetyl groups 5 ashes, indeterminate substances and substances extractable from water and solvents, organic 11.68.

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  • Compounds Of Unknown Constitution (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
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EP82810536A 1981-12-10 1982-12-09 Verfahren zur Delignifizierung von Holz und anderen Lignozelluloseprodukten Expired EP0082116B1 (de)

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AT82810536T ATE16206T1 (de) 1981-12-10 1982-12-09 Verfahren zur delignifizierung von holz und anderen lignozelluloseprodukten.

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US32936081A 1981-12-10 1981-12-10
US329360 1981-12-10

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EP82810536A Expired EP0082116B1 (de) 1981-12-10 1982-12-09 Verfahren zur Delignifizierung von Holz und anderen Lignozelluloseprodukten

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AT (1) ATE16206T1 (de)
BE (1) BE895299A (de)
BR (1) BR8208011A (de)
CA (1) CA1210209A (de)
CH (1) CH653054A5 (de)
DE (1) DE3267062D1 (de)
ES (1) ES8404725A1 (de)
FI (1) FI70938C (de)
FR (1) FR2518141B1 (de)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273759A2 (de) * 1986-12-31 1988-07-06 Neste Oy Verfahren zum Wiederumlauf von Phenol in einem Verfahren zum Aufschluss von Lignozellulosematerialien
EP0273758A2 (de) * 1986-12-31 1988-07-06 Neste Oy Verfahren zur Trennung von Lignin und Phenol aus phenolischen Lösungen

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DE19856582C1 (de) * 1998-12-08 2001-03-15 Rhodia Acetow Ag Verfahren zur Gewinnung von Chemiezellstoff aus Hackschnitzeln
BRPI0920639A2 (pt) * 2008-10-23 2015-08-04 Japan Science & Tech Agency Unidade de tratamento de ácido concentrado, planta de sistema de separação de fase, e, métodos de tratamento de ácido concentrado, e para conversão do sistema de separação de fase para recurso botânico
CA3110389A1 (en) * 2021-02-25 2022-08-25 Sixring Inc. Modified sulfuric acid and uses thereof
CN113307983B (zh) * 2021-05-21 2022-08-05 北京林业大学 一种绿色溶剂快速、高得率分离木质素的方法
CN116770613A (zh) * 2023-08-01 2023-09-19 贵州大学 热致液液相分离溶剂和纤维素预处理及组分分离的方法

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Publication number Priority date Publication date Assignee Title
CH237790A (de) * 1943-02-27 1945-05-31 Phrix Arbeitsgemeinschaft Verfahren zur Herstellung von Zellstoffen von hohem Alpha- und niedrigen Pentosangehalt.
US2539093A (en) * 1944-09-07 1951-01-23 Mainguet Henri Nitric acid digestion of straw
US3215588A (en) * 1963-08-15 1965-11-02 Lummus Co Continuous impregnation, cooking, and washing of fibrous material
AT336992B (de) * 1975-02-18 1977-06-10 Visch Khim T I Nis Verfahren und vorrichtung zum herstellen von fasermaterial aus pflanzenrohstoffen
EP0043342A1 (de) * 1980-06-20 1982-01-06 Battelle Memorial Institute Verfahren zur Delignifizierung von Holz und anderen Lignocellulosematerialien
EP0054015A1 (de) * 1980-11-20 1982-06-16 Simmering-Graz-Pauker Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung von Zellstoff

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH237790A (de) * 1943-02-27 1945-05-31 Phrix Arbeitsgemeinschaft Verfahren zur Herstellung von Zellstoffen von hohem Alpha- und niedrigen Pentosangehalt.
US2539093A (en) * 1944-09-07 1951-01-23 Mainguet Henri Nitric acid digestion of straw
US3215588A (en) * 1963-08-15 1965-11-02 Lummus Co Continuous impregnation, cooking, and washing of fibrous material
AT336992B (de) * 1975-02-18 1977-06-10 Visch Khim T I Nis Verfahren und vorrichtung zum herstellen von fasermaterial aus pflanzenrohstoffen
EP0043342A1 (de) * 1980-06-20 1982-01-06 Battelle Memorial Institute Verfahren zur Delignifizierung von Holz und anderen Lignocellulosematerialien
EP0054015A1 (de) * 1980-11-20 1982-06-16 Simmering-Graz-Pauker Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung von Zellstoff

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Title
CHEMICAL ABSTRACTS, vol. 94, no. 12, 23 mars 1981, page 107, colonne de gauche, no. 85954c, Columbus Ohio (USA); *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273759A2 (de) * 1986-12-31 1988-07-06 Neste Oy Verfahren zum Wiederumlauf von Phenol in einem Verfahren zum Aufschluss von Lignozellulosematerialien
EP0273758A2 (de) * 1986-12-31 1988-07-06 Neste Oy Verfahren zur Trennung von Lignin und Phenol aus phenolischen Lösungen
EP0273759A3 (en) * 1986-12-31 1989-08-16 Neste Oy Procedure for recirculating phenol in a lignocellulosic materials digestion process
EP0273758A3 (en) * 1986-12-31 1989-08-23 Neste Oy Procedure for separating lignin and phenol from phenol solutions

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Publication number Publication date
EP0082116B1 (de) 1985-10-23
DE3267062D1 (en) 1985-11-28
FI824244A0 (fi) 1982-12-10
BR8208011A (pt) 1983-11-08
CA1210209A (fr) 1986-08-26
EP0097188A1 (de) 1984-01-04
CH653054A5 (fr) 1985-12-13
FI70938B (fi) 1986-07-18
NO832783L (no) 1983-08-01
WO1983002125A1 (en) 1983-06-23
ES518003A0 (es) 1984-05-01
FR2518141A1 (fr) 1983-06-17
FI824244L (fi) 1983-06-11
ES8404725A1 (es) 1984-05-01
FI70938C (fi) 1986-10-27
FR2518141B1 (fr) 1986-08-14
ATE16206T1 (de) 1985-11-15
BE895299A (fr) 1983-06-09

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