EP0051237A1 - Procédé de préparation de saccharides à partir de matériaux cellulosiques - Google Patents

Procédé de préparation de saccharides à partir de matériaux cellulosiques Download PDF

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Publication number
EP0051237A1
EP0051237A1 EP81108878A EP81108878A EP0051237A1 EP 0051237 A1 EP0051237 A1 EP 0051237A1 EP 81108878 A EP81108878 A EP 81108878A EP 81108878 A EP81108878 A EP 81108878A EP 0051237 A1 EP0051237 A1 EP 0051237A1
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EP
European Patent Office
Prior art keywords
hydrogen fluoride
wood
cellolignin
cellulose
hydrolysis
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
EP81108878A
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German (de)
English (en)
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EP0051237B1 (fr
Inventor
Rüdiger Dr. Erckel
Raimund Dr. Franz
Merten Dr. Schlingmann
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Hoechst AG
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Hoechst AG
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Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT81108878T priority Critical patent/ATE26129T1/de
Publication of EP0051237A1 publication Critical patent/EP0051237A1/fr
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Classifications

    • 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

  • Cellulose-containing materials are found in nature in large numbers and diversity.
  • a known such natural cellulosic material is e.g. the wood. It consists essentially of cellulose (a material mainly composed of glucose), hemicellulose (a substance mainly composed of pentoses and hexoses) and lignin (a polymeric substance with aromatic rings substituted by methoxy groups). Wood is recycled in a variety of ways, e.g. for heat generation (firing), as a building material in the furniture and building materials sector, etc .; A purely chemical recycling of the wood is also possible.
  • Chemical digestion processes that not only separate wood into its components, hemicellulose, cellulose and lignin, but also break it down and transform it, have long been known.
  • the chemical processes generally provide aqueous solutions of mono-, di- and oligomeric saccharides, which may be subjected to post-hydrolysis to glucose or directly fermented to ethanol, concentrated or evaporated to dryness. Possible areas of application for products obtained in this way are e.g. in the field of animal feed additives or preferably that of fermentation raw materials.
  • DE-PS 560 535 describes the digestion of wood with liquid or vaporous pure HF at low temperatures, the HF being recirculated by evaporation or blowing off and subsequent condensation.
  • a process for the digestion of wood with gaseous hydrogen fluoride is described in DE-PS 585 318, which involves three stages via an absorption of HF on wood at 10 ° to 20 ° C, the digestion at 20 ° to 50 ° C and desorption works at 100 ° - 150 ° C, the HF can be diluted with an inert gas stream.
  • the cooling effort for the condensation of HF has a disadvantage here, as does the fact that when condensation occurs, only a very uneven distribution of the hydrogen fluoride on the reaction material occurs, a circumstance which can only be counteracted by very long dwell times or a sharp increase in the use of hydrogen fluoride otherwise the yields can be severely impaired.
  • the distribution form of the hydrogen fluoride which is present as a fine mist in the air, is very uneven, all the more so since the air present complicates the uniformity of the reaction that when saccharifying wood with concentrated hydrogen fluoride, both in the liquid and in the gaseous state, the wood particles react quickly on the surface with the concentrated hydrogen fluoride, form a hard, rather impenetrable skin and shrink, which inhibits the further penetration of the gas into the interior Furthermore, d It is difficult for the wood particles to penetrate the air in the cells. It An outer crust forms very quickly, which includes unsugared material and prevents further saccharification.
  • wood consists only of the smallest part of wood mass itself and for the most part of air, which is located between and in the wooden cells.
  • practically water-free wood consists of approximately 15% wood mass and approximately 85% air. Since the wooden cells are extremely small in relation to the size of the wood, no matter how small it is, the air content plays a major role even with sawdust.
  • Another problem is the separation of the acetic acid formed in the hydrolysis of hemicellulose, which makes the loss of HF in the circle as difficult as possible, as well as the easy decomposition of the pentoses to furfural.
  • “Cellolignin” here means vegetable materials such as wood, straw, bagasse and similar raw materials which have been subjected to a pre-hydrolysis which is known per se.
  • This pre-hydrolysis of the wood which is known per se, consists of a relatively short-term treatment with highly dilute mineral acid at higher temperatures and pressures, with essentially the pentosans and hexosans contained in the hemicelluloses down to the monomer units, e.g. Xylose or mannose, split. Depending on the reaction conditions, these can then be isolated as such or undergo further changes, e.g. Dehydration to furfural or hydroxymethylfurfural (see Ullmann, loc. Cit., Vol. 7 (1957), p.711). Apart from fermentation, the reduction of xylose to xylitol is another example of a technical use of hemicellulose degradation products. It is therefore possible to obtain valuable products from wood by pre-hydrolysis before the digestion process according to the invention is used.
  • cellolignin is also understood to mean paper material (e.g. waste paper) which is low in hemicelluloses. During the pre-hydrolysis of wood, its structure is largely preserved, but the cellolignin that can be obtained in this way has a much more wear-resistant and porous quality than the native state, so that HF, even when mixed with air or another inert carrier gas, can easily penetrate without one Encrustation of the surface occurs. Working in a vacuum is not necessary.
  • reaction material is significantly easier to handle in terms of process technology.
  • this is due to the fact that cellolignin has a bulk volume of only about half that of wood of the same grain size and therefore has a significantly lower degree of shrinkage when digested with hydrogen fluoride gas, which e.g. a great relief for the dimensioning of reactors.
  • reaction material made of cellolignin remains pourable and free-flowing even when it is loaded with hydrogen fluoride, whereas that made from native wood tends to stick together due to resinous accompanying substances and fission products of the hemicelluloses and is difficult to promote.
  • Another advantage is the possibility the absorption of HF on cellolignin above the boiling point of HF, so that external cooling is no longer necessary. It was also surprising that in the process according to the invention yields of> 90% glucose or oligomeric glucose based on the cellulose used in cellolignin can be achieved in a simple manner, the resulting sugars being of high quality, ie almost colorless.
  • the subject of the invention is therefore a process for obtaining water-soluble saccharides (glucose or oligomeric glucose) from cellulose-containing material by treating the same with gaseous hydrogen fluoride, optionally diluted with an inert gas, at temperatures between about 20 and 120 ° C. between about 40 and 80 ° C; the process is characterized in that cellolignin is subjected to a treatment with hydrogen fluoride.
  • gaseous hydrogen fluoride optionally diluted with an inert gas
  • cellolignin is understood to mean a material largely consisting of cellulose and lignin.
  • the cellolignin which is particularly suitable according to the invention for degradation to water-soluble sugars is obtained by pre-hydrolysis of natural cellulose-containing material (wood, straw, bagasse, etc.) with dilute aqueous mineral acid, preferably dilute hydrochloric or sulfuric acid.
  • Prehydrolysis is - as already indicated in the description of the prior art - known in wood saccharification and can also be found in the more recent literature such as Ullmann's Encyclopedia of Industrial Chemistry, 3rd Edition, Volume 8 (-1957), pp. 591-595 as well as in the book by W. Sandermann, "Chemische Holzvertechnisch", Bayrischerêtverlag, Kunststoff 1963, p. 253.
  • They are preferably used as fermentation raw materials or for the extraction of xylitol.
  • Waste paper low in hemicellulose is also well suited for use.
  • the digestion according to the invention can be accomplished, for example, in such a way that the pre-digested material (cellolignin or, for example, paper shredder material) dried to a moisture content of 0 - about 20%, advantageously about 2 - 5% and crushed if necessary, either discontinuously in one suitable mixing vessel made of hydrogen fluoride - resistant material in contact with HF gas, possibly in a mixture with air or another inert carrier gas, or that an HF-containing gas mixture is advantageously countered in a conveyor system to a continuous flow of the substrate to be digested.
  • the pre-digested material cellolignin or, for example, paper shredder material
  • the contact of the substrate with hydrogen fluoride gas is maintained until one part by weight of the material has absorbed about 0.2 to 3.0, preferably about 0.4 to 0.8, part by weight of hydrogen fluoride.
  • the reaction is now advantageously carried out in such a way that, depending on the type of substrate and the conditions of HFw absorption, a residence time is selected which Achieving the high yield is sufficient.
  • Longer dwell times are not disadvantageous, but they are also of no advantage. They can be between about 15 minutes and several hours. Reaction conditions are preferred in which the residence time does not exceed about one hour.
  • the subsequent HF desorption can, according to the prior art, be carried out by heating the reaction material and / or by evacuation or by treatment with an inert gas stream (for example nitrogen, air, CO 2 or noble gas) of suitable strength, in turn with or without simultaneous heating and / or evacuation , respectively.
  • an inert gas stream for example nitrogen, air, CO 2 or noble gas
  • the hydrogen fluoride thus recovered can be isolated by condensation or reacted directly with fresh substrate, so that a cycle of gaseous hydrogen fluoride is formed.
  • the further processing of the now digested (“saccharified”) material can also be carried out in a manner known per se, as described, for example, by K. Fredenhagen and G. Cadenbach, Angewandte Chemie 46 (1933), pp. 113 to 117 Hot water, filtered from the insoluble lignin, neutralized the small amount of hydrogen fluoride carried in the filtrate by means of calcium carbonate or hydroxide and concentrated.
  • the amount of "wood sugar” (or “straw sugar” etc.) obtained after drying the evaporation residue in the procedure according to the invention is consistently over about 90% of the cellulose contained in the substrate (calculated on dry substance).
  • the invention represents a not inconsiderable advance in this area.
  • the oligomeric glucose building blocks can be subjected to further utilization in the form obtained (fermentation to ethanol, concentration or evaporation and use as animal feed additives or as fermentation raw materials etc.) or also in a manner known per se for post-hydrolysis to monomeric glucose.
  • spruce wood cellolignin 59% cellulose + 41% lignin
  • a grain size of approx. 2 mm 500 g were placed in a round 2 1 container made of transparent polyethylene with a stirrer, thermometer and gas inlet and with a mixture of air and fluorine gas which was obtained prepared by passing air over liquid hydrogen fluoride at 20 ° C (water bath) treated. The material was slowly stirred and turned dark brown. The air flow and HF evaporation were regulated so that the internal temperature did not exceed 70 ° C.
  • the contents of the reactor were then digested with about 2 liters of hot water for 15 minutes, filtered off with suction and washed with a little water.
  • the dark brown filter residue weighed about 250 g after drying and thus consisted of 82% lignin and 18% undigested cellulose.
  • the filtrate was made alkaline while still hot with technical calcium hydroxide, the excess hydroxyl ion was neutralized with carbon dioxide, and the calcium fluoride and carbonate were filtered off, possibly with the aid of a filtration aid.
  • the clear, pale yellow, neutral solution was brought to dryness in a vacuum. This gave about 250 g of slightly yellowish wood sugar, corresponding to a yield of 85% of theory
  • the product was clearly water-soluble and contained between 2 and 10% monomeric glucose, the rest consisted of oligomeric glucose.
  • a jacketed, hydrogen fluoride-resistant tube 30 cm long and 4 cm wide was filled in the horizontal position with 30 g cellolignin with a grain size of 1-2 mm approximately half-way and closed at both ends with pierced rubber stoppers.
  • cellolignin layer as well as in the free space above was a thin steel tube perforated over the entire length.
  • These pipes led on both sides through bores of the sealing plugs to the outside and were used for supplying and discharging the HF-air mixture. In this way it was possible to gas the cellolignin perpendicular to the surface of the bed.
  • the material was allowed to absorb hydrogen fluoride and, during the subsequent dwell time, an internal temperature of 50 ° C. was ensured by appropriate heating. Subsequently, instead of the HF Air mixture was blown hot air through the bed for 15 minutes and the reaction product thus obtained and freed from the majority of the hydrogen fluoride was worked up as described in Example 1.
  • the following table shows the yields as a function of the amount of HF absorbed and the residence time.
  • a cellulose lignin filling was entrained with a hydrogen fluoride / carrier gas mixture demonstrated that the material at the HF inlet end of the tube had a content of approx. 60% HF, based on cellolignin, but only pure carrier gas flowed out at the cellolignin inlet end.
  • the reaction material was continuously discharged at the HF inlet end, while fresh cellolignin was supplied on the opposite side.
  • the material discharged was freed of hydrogen fluoride by blowing off after passing through a half-hour residence time and the HF-rich gas mixture thus obtained was returned to the reaction tube.
  • the digested cellolignin is worked up in the manner already described in Example 1. The yield of wood sugar was approx. 85% of theory

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Emergency Medicine (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Saccharide Compounds (AREA)
  • Processing Of Solid Wastes (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
EP81108878A 1980-10-30 1981-10-24 Procédé de préparation de saccharides à partir de matériaux cellulosiques Expired EP0051237B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81108878T ATE26129T1 (de) 1980-10-30 1981-10-24 Verfahren zur gewinnung wasserloeslicher saccharide aus cellulosehaltigem material.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3040850A DE3040850C2 (de) 1980-10-30 1980-10-30 Verfahren zur Gewinnung wasserlöslicher Saccharide aus cellulosehaltigem Material
DE3040850 1980-10-30

Publications (2)

Publication Number Publication Date
EP0051237A1 true EP0051237A1 (fr) 1982-05-12
EP0051237B1 EP0051237B1 (fr) 1987-03-25

Family

ID=6115523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81108878A Expired EP0051237B1 (fr) 1980-10-30 1981-10-24 Procédé de préparation de saccharides à partir de matériaux cellulosiques

Country Status (14)

Country Link
EP (1) EP0051237B1 (fr)
JP (1) JPS57105200A (fr)
AT (1) ATE26129T1 (fr)
AU (1) AU7694281A (fr)
BR (1) BR8107016A (fr)
CA (1) CA1181397A (fr)
DD (1) DD208173A5 (fr)
DE (2) DE3040850C2 (fr)
DK (1) DK478381A (fr)
FI (1) FI813370L (fr)
NZ (1) NZ198780A (fr)
PH (1) PH17341A (fr)
PL (1) PL233621A1 (fr)
ZA (1) ZA817493B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2515209A1 (fr) * 1981-10-24 1983-04-29 Hoechst Ag Procede de desagregation d'une matiere cellulosique par de l'acide fluorhydrique gazeux
FR2515210A1 (fr) * 1981-10-24 1983-04-29 Hoechst Ag Procede de desagregation des matieres cellulosiques avec de l'acide fluorhydrique gazeux
EP0078023A1 (fr) * 1981-10-24 1983-05-04 Hoechst Aktiengesellschaft Procédé pour traiter des matières cellulosiques avec de l'acide fluorhydrique gazeux
FR2597872A1 (fr) * 1986-04-25 1987-10-30 Beghin Say Sa Procede de preparation d'oligo- et polyosides ramifies notamment a partir de l'amidon
US6265037B1 (en) 1999-04-16 2001-07-24 Andersen Corporation Polyolefin wood fiber composite
WO2012097781A1 (fr) * 2010-11-25 2012-07-26 Studiengesellschaft Kohle Mbh Procédé de dépolymérisation de cellulose, catalysée par de l'acide

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3312450C2 (de) * 1983-04-07 1985-02-07 Knauth, Hans, Dipl.-Ing., 7758 Meersburg Zweistufiges Verfahren zur Herstellung von Furfurol und Glucose aus cellulosehaltigen Stoffen durch saure Hydrolyse
RU2135510C1 (ru) * 1998-12-21 1999-08-27 Общество с ограниченной ответственностью "ПлУГ" Способ переработки древесины лиственницы и установка для его осуществления
EP2427534A4 (fr) * 2009-04-30 2014-11-12 Eve Res Inc Préparation de biocombustibles et d'autres produits utiles tels que le 5-(hydroxyméthyl)furfural
JP2012525507A (ja) * 2009-04-30 2012-10-22 イヴ リサーチ インコーポレイテッド コート紙製品をリサイクルするためのプロセスおよび装置
DE102016013620A1 (de) 2016-11-15 2018-05-17 Christine Apelt Verfahren zur stofflichen und energetischen Verwertung von Reststoffen der Zuckerrohrverarbeitung und Anordnung zur Durchführung des Verfahrens

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB271410A (en) * 1926-05-20 1928-01-05 Brevets Etrangers Lefranc Et C Process for the hydrolysis of cellulosic substances
DE560535C (de) * 1927-03-15 1932-10-05 I G Farbenindustrie Akt Ges Verfahren zur Umwandlung von Polysacchariden
DE577764C (de) * 1930-03-18 1933-06-03 I G Farbenindustrie Akt Ges Verfahren zur Umwandlung von Polysacchariden
CH246473A (de) * 1944-01-12 1947-01-15 Scholler Heinrich Ing Dr Verfahren zur Herstellung von nicht hauptsächlich zur Ernährung bestimmtem Zucker.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB271410A (en) * 1926-05-20 1928-01-05 Brevets Etrangers Lefranc Et C Process for the hydrolysis of cellulosic substances
DE560535C (de) * 1927-03-15 1932-10-05 I G Farbenindustrie Akt Ges Verfahren zur Umwandlung von Polysacchariden
DE577764C (de) * 1930-03-18 1933-06-03 I G Farbenindustrie Akt Ges Verfahren zur Umwandlung von Polysacchariden
CH246473A (de) * 1944-01-12 1947-01-15 Scholler Heinrich Ing Dr Verfahren zur Herstellung von nicht hauptsächlich zur Ernährung bestimmtem Zucker.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 80, Nr. 16, 22. April 1974, seite 101, Nr. 84884d Columbus, Ohio, U.S.A. L.V. KOZLOVA et al.: "Effect of the Concentration of Acid on the Compositions of Compounds of Sulfuric Acid with Products of the Hydrolysis of Cellolignin Polysaccharides" & Gidroliz. Lesohkim. Prom. 1973, (8), 3-5 * Zusammenfassung * *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2515209A1 (fr) * 1981-10-24 1983-04-29 Hoechst Ag Procede de desagregation d'une matiere cellulosique par de l'acide fluorhydrique gazeux
FR2515210A1 (fr) * 1981-10-24 1983-04-29 Hoechst Ag Procede de desagregation des matieres cellulosiques avec de l'acide fluorhydrique gazeux
EP0078023A1 (fr) * 1981-10-24 1983-05-04 Hoechst Aktiengesellschaft Procédé pour traiter des matières cellulosiques avec de l'acide fluorhydrique gazeux
US4556431A (en) * 1981-10-24 1985-12-03 Hoechst Aktiengesellschaft Process for hydrolyzing cellulose-containing material with gaseous hydrogen fluoride
US4556432A (en) * 1981-10-24 1985-12-03 Hoechst Aktiengesellschaft Process for hydrolyzing cellulose-containing material with gaseous hydrogen fluoride
US4589924A (en) * 1981-10-24 1986-05-20 Hoechst Aktiengesellschaft Process for hydrolyzing cellulose-containing material with gaseous hydrogen fluoride
FR2597872A1 (fr) * 1986-04-25 1987-10-30 Beghin Say Sa Procede de preparation d'oligo- et polyosides ramifies notamment a partir de l'amidon
WO1987006592A1 (fr) * 1986-04-25 1987-11-05 Beghin-Say Sa Procede de preparation, a haute concentration dans le fluorure d'hydrogene, d'oligo et polyosides ramifies notamment a partir de l'amidon
US6265037B1 (en) 1999-04-16 2001-07-24 Andersen Corporation Polyolefin wood fiber composite
WO2012097781A1 (fr) * 2010-11-25 2012-07-26 Studiengesellschaft Kohle Mbh Procédé de dépolymérisation de cellulose, catalysée par de l'acide
EA023989B1 (ru) * 2010-11-25 2016-08-31 Штудиенгезельшафт Коле Мбх Способ кислотно-катализируемой деполимеризации целлюлозы

Also Published As

Publication number Publication date
DD208173A5 (de) 1984-03-28
FI813370L (fi) 1982-05-01
PH17341A (en) 1984-08-01
BR8107016A (pt) 1982-07-13
DK478381A (da) 1982-05-01
DE3040850C2 (de) 1982-11-18
DE3040850A1 (de) 1982-05-13
ATE26129T1 (de) 1987-04-15
PL233621A1 (fr) 1982-06-07
ZA817493B (en) 1982-11-24
NZ198780A (en) 1984-12-14
DE3176031D1 (en) 1987-04-30
JPS57105200A (en) 1982-06-30
CA1181397A (fr) 1985-01-22
AU7694281A (en) 1982-05-06
EP0051237B1 (fr) 1987-03-25

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