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EP0074983A1 - Procede de saccharification a haut rendement par un solvant organique. - Google Patents

Procede de saccharification a haut rendement par un solvant organique.

Info

Publication number
EP0074983A1
EP0074983A1 EP19820900956 EP82900956A EP0074983A1 EP 0074983 A1 EP0074983 A1 EP 0074983A1 EP 19820900956 EP19820900956 EP 19820900956 EP 82900956 A EP82900956 A EP 82900956A EP 0074983 A1 EP0074983 A1 EP 0074983A1
Authority
EP
European Patent Office
Prior art keywords
acetone
sugars
liquor
cellulosic material
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19820900956
Other languages
German (de)
English (en)
Other versions
EP0074983B1 (fr
Inventor
Laszlo Paszner
Pei-Ching Chang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bau und Forschungsgesellschaft Thermoform AG
Original Assignee
Bau und Forschungsgesellschaft Thermoform AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/248,023 external-priority patent/US4409032A/en
Priority claimed from CA000395820A external-priority patent/CA1201115A/fr
Application filed by Bau und Forschungsgesellschaft Thermoform AG filed Critical Bau und Forschungsgesellschaft Thermoform AG
Priority to AT82900956T priority Critical patent/ATE23364T1/de
Publication of EP0074983A1 publication Critical patent/EP0074983A1/fr
Application granted granted Critical
Publication of EP0074983B1 publication Critical patent/EP0074983B1/fr
Expired legal-status Critical Current

Links

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
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials

Definitions

  • Organosolv hydrolysis processes have been successfully demonstrated on certain types of cellulosic materials particularly lignocellulosics.
  • the easiest wood to delignify by organosolv solutions is aspen while conifers such as hemlock, Douglas-fir and pines showed substantial resistance.
  • Sugarcane rind was found to be relatively easy to hydrolyze.
  • Cotton linters which are essentially cellulose, especially the crystalline fraction; were very difficult to hydrolyze by prior art processes. The reasons for the hydrolysis differences are related to variations and heterogeneity in structure and the chemical composition of cellulosic materials.
  • organosolv processes have been used primarily with cellulosic materials which are easy to delignify.
  • Cotton linters have been avoided especially in saccharification work because of their resistance to hydrolysis and the harsher process conditions required for their hydrolysis in rapid conversion of the polymeric glucan to monomeric sugars.
  • U. S. Patent No. 1,919,623 to Drevfus (1933) describes pretreatment of wood with concentrated acid in acetone-water carrier solvent mixtures and after removal of. the organic solvent heating the acid-containing wood at low temperature for several hours to cause in situ hydrolysis of the carbohydrates without simultaneous dissolution of the lignin.
  • the treated lignocellulose was reportedly practically insoluble in the acetone-ether water mixtures, on treatment of the prehydr ⁇ lysed material with the same solvent, only the excess acid was removed and used in further treatments. Decomposition of the pre-hydrolysed cellulose material to sugars was effected on boiling in an aqueous weak acid solution, U. S. Patent No.
  • the main object of the present invention is to rapidly and quantitatively solubiiize and recover chemical components of cellulosic materials.
  • a further object, of the invention is to reduce the hydrolysis time and substantially increase sugar formation rates in hydrolysing cellulosic materials.
  • a further object of the invention is to reduce sugar degradation to non-sugars during high temperature hydrolysis of cellulosic materials.
  • a further object of the invention is to simultaneously dissolve and then recover separately the chemical constituents of cellulosic materials to yield mainly xylose, hexose sugars and lignin if the material is ligno- cellulosic.
  • a further object of the invention is to, if so desired, convert the isolated centoses and hexoses into respective dehydration products such as furfural and hydrox methyl furfural, levulinic acid by re-exposure to high temperature and recover monomeric furfurals, levulinic acid.
  • a further object of the invention is to quantitatively hydrolyse cellulosic materials at such a rate that when the organic volatiles are evaporated from the hydrolysis liquor and the lignin if any is separated from the aqueous solution, higher than 10 percent by weight sugar solids is obtainable from the solution.
  • a further object of the invention is to substantially reduce the concentration of acid re ⁇ uired to maintain and regulate a given hydrolysis rate and thereby substantially reduce the catalytic effects of acids in degradation of sugars at high temperature.
  • the object of the present invention is to reduce the reaction temperature required to achieve a certain desirable reaction rate during the hydrolysis process and thereby maximize the sugar recovery.
  • a further object of the present invention is to reduce the energy required for hydrolysis by use of a major volume proportion or in excess of 70 percent of acetone which has heat capacity and heat of vaporisation much, lower than that of water and thus can be easily volatilized to cool the hydrolysis liquor.
  • a further object of the invention is to obtain substantially pure low DP cellulose on very short selective delignification and hydrolysis of cellulosic materials, which is useful as animal fodder, food additive and as industrial filler and adsorbent.
  • the present invention relates to an improvement in a. process for the production of carbohydrate hydrolysates as sugars from a comminuted cellulosic material which can contain lignin by treating the material in a pressure vessel with a solvent mixture of acetone and water containing a small amount of an acidic compound at elevated temperatures to form reducing sugars in a liquor, the improvement which comprises:
  • the present invention also relates to an improvement in a process for the production of carbohydrate hydrolysates as sugars and lignin from a comminuted cellulosic material which can contain lignin by treating the material in a pressure vessel with a solvent mixture of acetone and water containing a small amount of an acid compound at elevated temperatures to solubilize any lignin and to form reducing sugars in a liquor, the improvement which comprises:
  • the result of the present invention is that at the selected conditions there is substantially no degradation of sugars during the saccharification process although the acetone complexes are found to hydrolyse roughly 500 times faster than the alkyl giucosides and polyglucan described in the prior art. Further benefit of the acetone sugar complexes is their facile separation into individual sugar species based on such simple processes as volatilization, selective hydrolysis and liquid-liquid extraction. Complex formation of monomer!c sugars in anhydrous acetone in the presence of mineral acids at room temperature is described in Methods in Carbohydrate Chemistry, Vol. IX,pp.318.
  • the term "cellulose material” includes material of vegetable and woody origin, generally in comminuted for
  • the acidic compounds can be of inorganic or organic origin and should be inert with respect to the solvent. Strong inorganic acids as sulphuric, hydrochloric and phosphoric acids are preferred; acidic salts such as aluminum chloride and sulphate, ferric chloride and organic acids such as trifluoroacetic acid can also be used.
  • the elevated temperatures are between 145o0 to and most preferably between 160 oC to 210 oC.
  • the catalytic amount of the acidic compound is preferably between 0.05 to 0.5 percent by weight of the solvent mixture. Smaller amounts are effective especially when high temperatures are selected.
  • a reaction time per treatment of less than required to dissolve 50 percent of the solid residue at the particular acid concentration and reaction temperature should be used and allows generally accept-ably high yield of reducing sugars in dissolved form.
  • the sugar exposure time to high temperature will regulate the rate of solvent feeding to the reactor and will generally depend on the acid concentration, amount of acetone and level of elevated temperature used. Thus for very rapid hydrolysis acid concentrations ⁇ f 0.04 to 0.06 Normal, acetone concentrations of about 30% and temperatures over 200oC can be used. However, for near theoretical sugar yields, low acid concentration (0.02 Normal and lass) high acetone concentration (above 30 percent) and high temperature (above 200 oC) are most suitable.
  • aqueous weak acid and alcoholic organosoiv processes are relatively slow and have limited hydrolysis power even with aasiiy hydrolysable lignocellul ⁇ sic ⁇ aterials such as. aspen and sugarcane rind (bagasse). These woods usually take between 60 minutes to 6 hours to become hydrolysed where the sugars hydrolysed in a single step.
  • the lignin is resinified to a dark refractory mass insoluble in alkali and most organic solvents. Shorter hydrolysis times between 30 to 90 minutes are specified for continuous percolation processes, however the sugar yields rarely exceed 45 to 50 percent of the theoretical value by such, processing.
  • Reaction vessels with inert linings are used to eliminate the sugar degradation catalyzing effects of transition metal ions such as Ni, Co, Cr, Fe and Cu which may be components of metallic vessel walls, tubing and other control elements wich which the hot liquor comes into contact with.
  • transition metal ions such as Ni, Co, Cr, Fe and Cu which may be components of metallic vessel walls, tubing and other control elements wich which the hot liquor comes into contact with.
  • Purification of the crude lignin is by repeated re-dissolution in acetone, filtration to remove undissolved residues and re-precipitation into large excess of water or by spray drying the highly concentrated acetone solution.
  • the remai ing aqueous solution after filtering off the lignin precipitate is a clear solution of mainly hexose sugars of 10 percent or greater concentration and contains other water soluble compounds.
  • the pentose distillate and he-ose syrup when hydrolyzed by being acidified and boiled for at least 20 minutes yield the major sugar fractions in monosaccharids form and high purity. If so desired, on extended boiling of the separated sugar fractions in the presence of acid, selective conversion of sugars to appropriate dehydration products such as furfurals, levulinic acid and formic acid can be effected, as is known from the prior art.
  • the temperature of the reaction mixture be rapidly lowered to under 100 °C to avoid unwanted degradation of the sugars. This is best accomplished by controlled flashing off of the volatiles since sugar degradation was found to be insignificant below the boiling point of water even in the presence of dilute acids.
  • the cooling of the liquor can be continued to ambient temperatures or less (25oC) before fermentation or further processing.
  • the above described process can be operated in continuous or semi-continuous manner using batch cooking principles for the latter.
  • Semi-continuous saccharification would employ a battery of pressure vessels each at various stage of hydrolysis to simulate a continuous process.
  • ail stages of hydrolysis are accomplished in a single pressure vessel and the product mix is always determined by the particular saccharification program set.
  • Comminuted wood solids and the cooking liquor are fed continuously to the pressure vessel at such a rate that the time elapsed between feeding and exit of the products would not exceed that determined earlier to obtain 50 percent hydrolysis of solid residue at any one stage considered for the process.
  • the residence time would be always fitted to the mcst sensitive stage in ord to provide sugar recoveries exceeding 90 percent for that particular stage.
  • the three major stages of sacchanfication to be considered are:
  • stage (c) proceeding to total saccharification, the residual cellulose of stage (b) is decomposed to moncmeric sugars.
  • This step may take mere than one liquor change to accomplish a better than. 90 percent sugar recovery.
  • liquors collected from the various stages of hydrolysis may contain sugars from all stages (a) to (c) which is the situation with an apparatus having no means of separating the top pre-hydrolysis liquor from the rest of the liquor pumped in with the chips. With the present invention such separation for purificati of the sugars, is unnecessary because the sugars occur as complexes, pentoses having a different volatility than the hexose sugars with which they cay be mixed.
  • the lignin is separated on basis of its insolubility in water and is recovered outside the reactor on flash evaporation of the organic volatiles. Separation of the first and second stage liquors from the rest of the hydrolyzate would have particular significance on continued heating of the liquors to cause dehydration of especially the pentose sugars to produce corresponding furfurals and levulinic acid. In this case only minor amounts of hexose sugars would have to be saccharified. The sensible way to produce furfural from pentose sugars is following the flash evaporation stage and completion of the first reduced pressure separation of the sugars according t o their volatility.
  • steam stripping may also be used with good results and relatively pure pentose solutions be obtained in nearly quantitative yields.
  • Such distillates when acidified can be reheated under highly controlled conditions and high purity furfural be produced in better than 95% yields.
  • the preferred liquor to wood ratio is 7:1 to 10:1. Due to the shrinking mass bed the total amount of liquor required for hydrolysis of 100 kg of aspen wood at a constant liquor to wood ratio of 7:1 is 1356 kg for an overall liquor to wood ratio of 13.56:1. Under these conditions the average sugar concentration in the combined residual aqueous phase (271 kg) is 30 percent (32.3 kg of recovered sugars).
  • the liquor to wood ratio can be kept constant at 10:1 as by necessity successive additions both wood and liquor will carry hydrolyzates of the residuals already within the reactor.
  • This also establishes sugar concentrations to be in the order of 37 to 40 percent following flash evaporation of the volatiles.
  • Such high sugar solids concentrations were hitherto possible only with strong acid hydrolysis systems but not with dilute acid hydrolysis.
  • liquor to wood ratio is extremely important in organosolv and acid hydrolysis processes since it directly relates to energy inputs during the hydrolysis and solvent recovery as well as during alcohol recovery from the resulting aqueous solution following fermentation of the sugars to ethanol or other organic solvents.
  • liquor to wood ratio will have a profound effect on the economics of biomass conversion to liquid chemicals as well as the energy efficiency (energy gained over energy expanded in conversion) of the process.
  • the combined filtrates were diluted to 100 ml with water and a half milli ⁇ ter aliquot was placed in a test tube with 3 ml of 2.0 Normal sulfuric acid added and subjected to a secondary hydrolysis at 100oC by heating in a boiling water bath for 40 minutes.
  • the solution was neutralized on cooling and the sugars present in the solution were determined by their reducing power.
  • the results were thus uniform based essentially on the resultant monosaccharides liberated during the hydrolysis process.
  • Theoretical percentage of reducing sugars available after the hydrolysis of the substrate was determined by difference between the known chemical composition of the starting material and the weight loss incurred due to the hydrolysis.
  • the weight loss is normally multiplied by 1.1111, the weight percentage (11.11%) of the added water to the cellulose in hydrolysis to monomeric sugars.
  • the complexes are very readily and safely hydrolyzable to free sugars on heating with dilute acid, at 100°C for a limited amount of time.
  • ethanol concentration was higher than 80 percent neither deiignification nor hydrolysis was obtained due to the fact that the acid catalyst was quickly consumed by reaction with the alcohol by formation of ethyl hydrogen sulfate (C 2 H 5 -O-SO 2 -OH) and formation of diethyl ether via condensation of two ethanol molecules. Ether formation was quite substantial under these conditions.
  • alkyl glucosides formed in high concentration alcohol solution are substantially more difficult to hydrolyse to free sugars than the corresponding acetone complexes, and alcoholysis results in oligomeric sugars rather than monomers as is the case in acetone-water solutions.
  • alcohols prove to be largely unsuited for hydrolysis media due to the unwanted solvent loss and general danger from the explosive ether.
  • With lignified materials the low deiignification power of acidified alcohol solutions is clearly a drawback. With 80: 20 ethanol:water cooks in the presence of 0.190 percent (0.04 Normal ⁇ sulfuric acid at 180oC the hydrolysis rate was 5.47 ⁇ 10 3 min -1 and the half life of cotton linters decomposition was 126.8 minutes.
  • EXAMPLE III Temperature effects on hydrolysis of cotton linters were studied with acidified aqueous acetone solutions containing 0.04 Normal sulfuric acid in 80:20 acetone water at different hydrolysis times so that weight losses of 25, 50, 75 and 99 percent could be determined as in Example I. All cooks were preconditioned to 3.5 °C before being placed in the oil bath to minimize the effect of heating-up time at the various temperature levels studied. Work-up of the products and analysis followed the same procedure as described in EXAMPLE I and the results are summarized in TABLE 3.
  • EXAMPLE V One gram samples of several wood species were hydr ⁇ - lyzed in 30:20 acetonerwater containing 0.04 Normal sulfuric acid at 180 °C. Hydrolysis rates were calculated only for the crystalline cellulose fractions to avoid the confounding effect of easily hydroiyzable lignin and hemiceiluloses . Times to mass losses of 25, 50, 75 and 99 percent of the original oven dry mass along with the calculated reaction rates are recorded in TABLE 4. Work-up of the products followed the same procedure as indicated in EXAMPLE I except that after removal of the volatiles by distillation it was necessary to remove the precipitated lignins by filtration ⁇ r centrifuging.
  • the rate of Douglas-fir hydrolysis was somewhat slower than that of aspen and sugarcane rind.
  • a hydrolysis rate of 0.5 ⁇ 10 3 min was obtained and only 6 percent weight loss was recorded for a 280 min long cook at 180 oC the usual dilute acid hydrolysis temperature.
  • the high acetone content hydrolysis liquor allowed at least 100 times faster hydrolysis of Douglas fir by simultaneous dissolution of the lignxn than possible in purely aqueous systems.
  • solid residues of about 30 to 35 % yield are pure white, devoid of residual lignin.
  • This cellulosic fraction has a crystallinity index of 80% from aspen wood and a degree of polymerization (DP) of between 80 to 280. Similar results are obtained with the other wood species.
  • the invention allows facile segregation and nearly quantitative isolation of the five major wood sugars , if so desired.
  • the mixed nature of the sugar derivatives in aqueous hydrolyzates if such thorough and detai led separa- tion is desired , it is always necessary to neutrali ze the recovered aqueous sugar wort after removal of the volatiles and concentrate the wort to a syrup .
  • the syrup is then redissolved in anhydrous acetone containing 3 percent acid , allowed to stand at least 6 hr unti l all sugars formed their respective di-acetone comp lexes before attempting the detaile separation as described below .
  • the separated sugar comp lexes are readily hydrolyzed in dilute acid on boiling at least 20 to 40 minutes .
  • the undissolved residue was 0.12 g following 2 h drying in an oven at 105oC.
  • the combined liquor of H-1 and H-2 yielded 2.39 g lignin on low temperature evaporation of the volatiles and 135 mi of aqueous liquor was collected on filtration of the powdered lignin.
  • the dried lignin had a weight average molecular weight of 3200.
  • the filtrate was neutralized to pH 8 and subjected to steam distillation in an all glass apparatus.
  • the 28 ml distillate which was collected contained 0.62 g pentoses which after passing the filtrate through a cation exchange resin in the acid form and repeated steam distillation of the filtrate yielded 0.58 g xylose as determined by GC analysis.
  • the ethanol-petroieum ether solution was extracted with 5 ml portions of water and the collected aqueous layer combined with the syrup removed from the crystalline product above..
  • the solution was briefly heated to expel the alcohol, made up to 3 percent acid with hydrochloric acid, boiled for 40 min, neutralized with silver carbonate and alditol acetates were prepared for GC analysis.
  • the combined syrup and filtrate contained a total of 58 g sugars of which 0.29 g was galactose, 0.25 g was glucose and 0.04 g was mannose. Hydrolysate No. 3 gave 1.89 g pure glucose with

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des materiaux cellulosiques finement broyes contenant ou ne contenant pas de la lignine sont partiellement ou totalement hydrolyses ou saccharifies par un procede ameliore par solvants organiques en utilisant un melange aqueux de solvants a l'acetone contenant une petite quantite d'un compose acide et contenant au moins environ de 70% en volume d'acetone jusqu'a de l'acetone pratiquement anhydre. Le procede s'effectue a des temperatures elevees de reaction, de preference entre 145 C et 230 C, pendant une periode de temps limitee puis on procede a un refroidissement pour que les sucres dissous obtenus par hydrolyse ne se degradent pas en non-sucres. En particulier, la reaction s'effectue de sorte que le materiau cellulosique soit dissout et qu'au moins 90% ou plus de sucres disponibles dans le materiau cellulosique soient recuperes. D'une maniere surprenante, il s'est revele que l'acetone a forte concentration forme des complexes stables avec les sucres, ce qui empeche leur degradation et facilite aussi la separation des sucres. La lignine et les sucres derives sont des composes chimiques d'utilisation commerciale.
EP19820900956 1981-03-26 1982-03-26 Procede de saccharification a haut rendement par un solvant organique Expired EP0074983B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82900956T ATE23364T1 (de) 1981-03-26 1982-03-26 Sehr effektives verzuckerungsverfahren unter verwendung organischer loesungsmittel.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US248023 1981-03-26
US06/248,023 US4409032A (en) 1977-08-31 1981-03-26 Organosolv delignification and saccharification process for lignocellulosic plant materials
CA395820 1982-02-09
CA000395820A CA1201115A (fr) 1981-03-26 1982-02-09 Procede de saccharification a haut rendement avec solvant organique

Publications (2)

Publication Number Publication Date
EP0074983A1 true EP0074983A1 (fr) 1983-03-30
EP0074983B1 EP0074983B1 (fr) 1986-11-05

Family

ID=25669563

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820900956 Expired EP0074983B1 (fr) 1981-03-26 1982-03-26 Procede de saccharification a haut rendement par un solvant organique

Country Status (6)

Country Link
EP (1) EP0074983B1 (fr)
JP (1) JPH0785720B2 (fr)
AR (1) AR227462A1 (fr)
BR (1) BR8207243A (fr)
DE (1) DE3274120D1 (fr)
WO (1) WO1982003409A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU197774B (en) * 1983-02-16 1989-05-29 Laszlo Paszner Organic solvent process for the hydrolytic saccharification of vegetable materials of starch type
BR9600672A (pt) * 1996-03-08 1997-12-30 Dedini S A Administracao E Par Processo de hidrólise ácido de material lignocelulósico e reator de hidrólise
BRPI0505212A (pt) * 2005-11-01 2007-08-07 Dedini Sa Ind De Base aperfeiçoamentos em processo de hidrólise ácida rápida de material lignocelulósico e em reator de hidrólise
WO2008050740A1 (fr) 2006-10-26 2008-05-02 Kawasaki Plant Systems Kabushiki Kaisha Procédé de saccharification/décomposition d'une biomasse à base de cellulose et dispositif de saccharification/décomposition
JP2010527619A (ja) * 2007-05-31 2010-08-19 リグノル イノヴェイションズ リミテッド リグノセルロース系原料の連続向流オルガノソルブ処理
JP2010081917A (ja) * 2008-10-02 2010-04-15 Toyota Motor Corp バイオマスの処理方法、及び有機酸又はアルコールの製造方法
BR112013012614A2 (pt) * 2010-11-25 2016-09-20 Studiengesellschaft Kohle Mbh método para despolimerização catalisada por ácido de celulose

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB416549A (en) * 1933-03-07 1934-09-07 Henry Dreyfus Improvements in the manufacture of cellulose and lignocellulosic materials
CH202534A (de) * 1937-05-27 1939-01-31 F Reemtsma Philipp Verfahren zur Herstellung eines nicht zur Ernährung von Meschen oder Tieren bestimmten zuckerhaltigen Produktes durch Aufschliessen cellulosehaltiger Massen mittels Halogenwasserstoff in Gegenwart eines flüssigen organischen Lösungsmittels für letzteren.
DE2737118A1 (de) * 1977-08-17 1979-03-01 Projektierung Chem Verfahrenst Verfahren zur gewinnung von zuckern, gegebenenfalls cellulose und gegebenenfalls lignin aus lignocellulosischen pflanzlichen rohstoffen
JPS5526279A (en) * 1978-08-11 1980-02-25 Paszner Laszlo Treatment of lignocellulose containing substance
CA1150012A (fr) * 1980-07-25 1983-07-19 Pei-Ching Chang Preparation de la pate de lignocellulose en milieu aqueux par catalyse aux solvants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8203409A1 *

Also Published As

Publication number Publication date
BR8207243A (pt) 1983-03-01
JPH0785720B2 (ja) 1995-09-20
EP0074983B1 (fr) 1986-11-05
AR227462A1 (es) 1982-10-29
DE3274120D1 (en) 1986-12-11
WO1982003409A1 (fr) 1982-10-14
JPS58500431A (ja) 1983-03-24

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