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EP0008783A1 - Procédé et moyen pour la décomposition de matières végétales - Google Patents

Procédé et moyen pour la décomposition de matières végétales Download PDF

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Publication number
EP0008783A1
EP0008783A1 EP79103230A EP79103230A EP0008783A1 EP 0008783 A1 EP0008783 A1 EP 0008783A1 EP 79103230 A EP79103230 A EP 79103230A EP 79103230 A EP79103230 A EP 79103230A EP 0008783 A1 EP0008783 A1 EP 0008783A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
lignin
water
acids
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.)
Withdrawn
Application number
EP79103230A
Other languages
German (de)
English (en)
Inventor
Klaus Dr. Sommer
Wilhelm Spatz
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.)
BK Giulini Chemie GmbH
Original Assignee
Benckiser Knapsack GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Benckiser Knapsack GmbH filed Critical Benckiser Knapsack GmbH
Publication of EP0008783A1 publication Critical patent/EP0008783A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13KSACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00Sugars not otherwise provided for in this class
    • C13K13/002Xylose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00Pulping cellulose-containing materials
    • D21C3/20Pulping cellulose-containing materials with organic solvents or in solvent environment

Definitions

  • the present invention relates to a method and a means for digesting vegetable raw materials at higher temperatures and elevated pressure for the simultaneous production of pentoses, lignin and cellulose.
  • the method by which vegetable raw materials are broken down depends on whether one prefers to obtain cellulose or pentoses from the raw material. To Ge When cellulose is obtained, the materials are broken down using alkali and alkaline earth sulfites or the sulfate process. The lignin is obtained in the form of sulfo compounds as an annoying by-product.
  • the vegetable raw materials are preferably subjected to acidic hydrolysis, as can be seen, for example, from German patent 12 04 149.
  • Cello lignin is obtained as a solid residue.
  • German patent specification 19 29 268 describes the processing of sulfite lye to obtain pentoses by extraction with organic solvents.
  • a method for the production of xylose and cellulose is described in French patent specification 1 477 305; treating plant material with dilute acids and hydrolyzing and dissolving the hemicelluloses contained therein.
  • the residue, which contains lignin and cellulose is freed of lignin by sulfite or sulfate digestion.
  • the cellulose obtained can be processed into spinnable viscose. With this digestion, large amounts of wastewater are naturally produced, which are associated with the degradation pro products of the lignin are heavily contaminated.
  • the aim of the present invention is a method and an agent with which both cellulose, pentoses and lignin are obtained in a directly usable form during digestion. Contrary to the finding in Ullmann's Encyclopedia, Volume 11, page 780, that acid lignin, ie lignin from vegetable material treated with strong acids, is insoluble in acids and organic solvents, it was surprisingly found that extraction of Lig nin together with a high proportion of hemicellulose hydrolyzates is readily possible if the hydrolysis of the vegetable raw material is carried out with the addition of strong acids, water and alcohol. A cellulose containing only a little lignin and hemicelluloses is thus obtained.
  • Mineral or organic acids which have a dissociation constant of at least 1.76 are advantageously used for the digestion process. 10 -4 have, or mixtures thereof.
  • Preferred acids are sulfuric acid, sulfurous acid, hydrochloric acid, methane and toluenesulfonic acid.
  • Oxalic acid, tartaric acid and citric acid as well as phosphoric acid and phosphonic acids are also suitable for the digestion process.
  • anhydrides can also be used.
  • the sulfurous acid is particularly suitable, as it is very easy to remove after the digestion has ended, since it is volatile and can be distilled off with the alcohol and part of the water, with the lignin precipitating. The extensive treatment with anion exchangers can thus largely be avoided.
  • sulphurous acid used in similar concentrations to sulfuric acid, leads to equally good results with short digestion times.
  • sulphurous acid can be added to the digestion mixture as a solution or can be introduced into the hydrolysis mixture in gaseous form as an anhydride.
  • the lignin is precipitated in a known manner by evaporating the added alcohol, although separation problems can occur due to the resinous separation of the lignin.
  • This disadvantage can be overcome when using plant material containing tannins, e.g. Oak wood, chestnut wood, sawn timber or grape combs as such or in a mixture with other types of wood, e.g. Avoid beech and birch, or straw as much as possible.
  • the mixture used for the digestion should contain 10 to 40% by weight of alcohol, 0.2 to 2% by weight of the acids mentioned and the remainder water. Preference is given to a digestion mixture containing 0.4 to 1.5, in particular 0.8 to 1.2,% by weight of sulfurous acid, 0.4 to 0.6% by weight, hydrochloric acid or 0.5 to 0.8% by weight. % Sulfuric acid, 20 to 40 wt.% Alkanol and water contains.
  • Lower alcohols are suitable as alkanols; methanol, ethanol, propanols and butanols are preferably used.
  • the process is carried out in such a way that the material to be digested is heated in a pressure vessel to temperatures of 140 to 190.degree. C., in particular 160 to 180.degree. C. after the alcohol-acid / water mixture has been added for 1 to 5 hours.
  • a liquor ratio of solid: hydrolysis liquid of 1: 3 to 1:10, preferably 1: 4 to 1: 6, is set.
  • the hydrolysis solution is decanted off and the residue, which mainly consists of cellulose, is washed several times with 50% alcohol and then dried.
  • the hydrolysis and washing solution are concentrated to 1/5 to 1/6 of their volume, the lignin precipitating.
  • the P are entosen contained in the remaining solution, is carried out its work-up for the recovery of the pentoses, particularly xylose in a conventional manner, namely, treatment with Entfärberharz, deionization and evaporation to crystallization.
  • 200g beech chips (calculated as dry matter) are mixed in a stainless steel autoclave with 180g ethanol and 220g dilute sulfuric acid, which contains 1.8g H 2 S0 4 .
  • the pressure vessel is then heated to 175 to 180 ° C and left in this temperature range for 1 hour. After cooling, the dark brown solution is decanted off and the residue is washed twice with 200 ml of warm 50% ethanol. After drying, 77.9 g of residue with a methoxyl content of less than 2% are obtained.
  • the combined solutions are concentrated in a water jet vacuum to 1/5 to 1/6 of their original volume, a resinous mass separating out, which mainly consists of lignin.
  • the brownish-colored solution decanted from this contains 39.2 g of reducing sugar.
  • the pentose content is 34.6 g.
  • 21 g of xylose could be crystallized by adding methanol.
  • the solution contains 47.2 g of reducing sugar, the dry cellulose residue is 65.3 g and 50.2 g are separated off as the lignin tanning powder. After decolorization and deionization of the sugar solution, 26.4 g of xylose could be obtained after repeated crystallization.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
EP79103230A 1978-09-02 1979-08-31 Procédé et moyen pour la décomposition de matières végétales Withdrawn EP0008783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2838380 1978-09-02
DE19782838380 DE2838380A1 (de) 1978-09-02 1978-09-02 Verfahren und mittel zum aufschliessen pflanzlicher rohstoffe

Publications (1)

Publication Number Publication Date
EP0008783A1 true EP0008783A1 (fr) 1980-03-19

Family

ID=6048563

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79103230A Withdrawn EP0008783A1 (fr) 1978-09-02 1979-08-31 Procédé et moyen pour la décomposition de matières végétales

Country Status (2)

Country Link
EP (1) EP0008783A1 (fr)
DE (1) DE2838380A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0224470A1 (fr) * 1985-11-29 1987-06-03 Neusiedler Aktiengesellschaft für Papierfabrikation Procédé de production de pâte cellulosique à partir de matière fibreuse végétale
WO1991005102A1 (fr) * 1989-09-28 1991-04-18 Feldmühle Aktiengesellschaft Procede pour fabriquer des pates chimio-mecaniques et/ou chimio-thermo-mecaniques
EP2027159A4 (fr) * 2006-06-12 2012-02-01 American Process Inc Procédé de traitement étape par étape d'un matériau lignocellulosique pour produire des composés chimiques de base réactifs

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4965825A (en) 1981-11-03 1990-10-23 The Personalized Mass Media Corporation Signal processing apparatus and methods

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1856567A (en) * 1929-11-02 1932-05-03 Kleinert Theodor Process of decomposing vegetable fibrous matter for the purpose of the simultaneous recovery both of the cellulose and of the incrusting ingredients
US2380448A (en) * 1941-01-25 1945-07-31 Northwood Chemical Company Lignin and method of production
US2959500A (en) * 1956-02-14 1960-11-08 Schweizerische Eidgenossenschaft Process for the saccharification of cellulose and cellulosic materials
CH358391A (de) * 1956-12-12 1961-11-15 Udic Societe Anonyme Verfahren zur Herstellung von Zuckerlösungen aus Pflanzenmaterialien
WO1979000119A1 (fr) * 1977-08-31 1979-03-22 Thermoform Ag Procede permettant la delignification et la transformation en sucre de materiaux vegetaux lignocellulosiques par utilisation de solvants organiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1856567A (en) * 1929-11-02 1932-05-03 Kleinert Theodor Process of decomposing vegetable fibrous matter for the purpose of the simultaneous recovery both of the cellulose and of the incrusting ingredients
US2380448A (en) * 1941-01-25 1945-07-31 Northwood Chemical Company Lignin and method of production
US2959500A (en) * 1956-02-14 1960-11-08 Schweizerische Eidgenossenschaft Process for the saccharification of cellulose and cellulosic materials
CH358391A (de) * 1956-12-12 1961-11-15 Udic Societe Anonyme Verfahren zur Herstellung von Zuckerlösungen aus Pflanzenmaterialien
WO1979000119A1 (fr) * 1977-08-31 1979-03-22 Thermoform Ag Procede permettant la delignification et la transformation en sucre de materiaux vegetaux lignocellulosiques par utilisation de solvants organiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
THE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. LXIII, Juli-Dezember 1941, Seiten 3041-3048 W.B. HEWSON et al.: "Studies on Lignin and Related Compounds. LVII. Mechanism of the Ethanolysis Reaction" * Seite 3046; Tabel I * *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0224470A1 (fr) * 1985-11-29 1987-06-03 Neusiedler Aktiengesellschaft für Papierfabrikation Procédé de production de pâte cellulosique à partir de matière fibreuse végétale
WO1991005102A1 (fr) * 1989-09-28 1991-04-18 Feldmühle Aktiengesellschaft Procede pour fabriquer des pates chimio-mecaniques et/ou chimio-thermo-mecaniques
EP2027159A4 (fr) * 2006-06-12 2012-02-01 American Process Inc Procédé de traitement étape par étape d'un matériau lignocellulosique pour produire des composés chimiques de base réactifs

Also Published As

Publication number Publication date
DE2838380A1 (de) 1980-03-20

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19810223

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Inventor name: SPATZ, WILHELM

Inventor name: SOMMER, KLAUS, DR.