EP0091221A2 - Auflösen und Hydrolysieren von Kohlehydraten - Google Patents

Auflösen und Hydrolysieren von Kohlehydraten Download PDF

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Publication number
EP0091221A2
EP0091221A2 EP83301472A EP83301472A EP0091221A2 EP 0091221 A2 EP0091221 A2 EP 0091221A2 EP 83301472 A EP83301472 A EP 83301472A EP 83301472 A EP83301472 A EP 83301472A EP 0091221 A2 EP0091221 A2 EP 0091221A2
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EP
European Patent Office
Prior art keywords
halide
aluminium
process according
carbohydrate
solubilisation
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Granted
Application number
EP83301472A
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English (en)
French (fr)
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EP0091221B1 (de
EP0091221A3 (en
Inventor
Pudens Leonard Ragg
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication of EP0091221A3 publication Critical patent/EP0091221A3/en
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Publication of EP0091221B1 publication Critical patent/EP0091221B1/de
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    • 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
    • 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
    • C13K1/06—Glucose; Glucose-containing syrups obtained by saccharification of starch or raw materials containing starch

Definitions

  • This invention relates to the solubilisation and hydrolysis of glycosidically linked carbohydrates having reducing groups and in particular to the solubilisation and hydrolysis of starch and cellulose to glucose.
  • Cellulose is a polysaccharide which forms the main component of the cell walls of most plants. It is a polymer of B-D-glucose units which are linked together with elimination of water to form chains of 2000-4000 units. In plants it occurs together with other polysaccharides and hemicelluloses derived from other sugars such as xylose, arabinose and mannose. In the woody parts of plants cellulose is intimately mixed and sometimes covalently linked with lignin. Wood, for example, normally contains on a dry weight basis 40-50% cellulose, 20-30)6 lignin and 10-30% hemicelluloses together with mineral salts, waxes, resins and proteins.
  • the solubilisation and hydrolysis of cellulose may be brought about by various treatments, including treatment with acids and with enzymes present in certain bacteria, fungi and protozoa. Such treatments result mainly in cleavage of the glycosidic links in the cellulose chain with a consequent reduction in molecular weight.
  • Partial hydrolysis with acids produces a variety of products, often termed "hydrocelluloses", whose properties are determined by the hydrolysis conditions employed.
  • Complete acid hydrolysis of cellulose yields glucose.
  • Treatment with acid by solution and reprecipitation often increases the accessibility and susceptibility of cellulose to attack by enzymes, microbes and chemical reagents.
  • Solubilisation and hydrolysis of cellulose by enzymes leads to various intermediate products depending upon the enzyme employed.
  • the final product of enzymic treatment of cellulose is usually glucose but rigorous treatment may produce a further breakdown to ethanol, carbon dioxide and water.
  • the products of solubilisation and/or hydrolysis include oligosaccharides, as well as tri-, di- and mono- saccharides.
  • the products from cellulose include cellodextrins, cellotriose, cellobiose and glucose.
  • the susceptible carbohydrate may be treated with an enzyme in which case the exact nature of the final products will depend upon the enzyme employed and upon the reaction conditions. In the case of cellulose treatment with cellulases the product under appropriate conditions will be glucose.
  • glycosidically linked carbohydrate can be present in any suitable state. It can be present as free or combined carbohydrate, in its natural state or in a processed or converted form. The process is particularly useful when applied to the conversion of the following types of carbobydrate-containing feedstocks:-
  • the process is applicable to glycosidically linked carbohydrates whether the glycosidic linkage is a ⁇ -linkage as in cellulose, yeast glucan or laminarin, or an ⁇ -linkage as in starch, glycogen, dextran or nigeran. In particular it is applicable to starch which is converted to lower sugars including maltose and, as the main product, glucose.
  • the process is also applicable to glycosidically linked carbohydrates with other constituent pentoses, hexoses, heptoses, amino sugars and uronic acids, as well as to the previously mentioned naturally occurring polymers of D-glucose.
  • Such polymers with other constituents having industrial significance include wood hemicelluloses, yeast mannan, bacterial and seaweed alginates, industrial gums and mucilages and chitin.
  • Carbohydrates containing 0- sulphate, N- sulphate, N- acetyl, 0- acetyl and pyruvate groups can also be treated by the process of the invention as can carbohydrates derived by carboxymethylation, acylation, hydrox y etbylation and other substitution processes provided that such carbohydrates contain glycosidic linkages. Acid labile substituents on carbohydrates may be lost during the process of the invention.
  • Preferred inorganic acids are hydrochloric, hydrobromic and hydriodic acids, hydrochloric acid being most economical and especially prefferred.
  • the preferred hydrated aluminium halide is the hexahydrate A1 Cl 3 .6H 2 O.
  • the hydrated aluminium halide can be present as the sole metal halide or in combination with other metal halides or precursors thereof.
  • the halide present together with the hydrated aluminium halide is preferably a halide (especially a chloride) of lithium, calcium and/or magnesium or a precursor of such a halide.
  • the halide ions can be present as complex halide ions, these complex ions being generated within the mixture.
  • an aqueous solution of the hydrated aluminium halide is prepared and is thereafter acidified.
  • the acid is added to the aqueous solution of the halide.
  • acidification can be achieved in the reverse manner, i.e. by adding the aqueous solution of the metallic salt to the acid.
  • the acid employed has a concentration in the range 0.5 to 5 molar and is added to the aqueous solution of the metallic salt.
  • the acidified aqueous solution of the metallic salt is used to treat the carbohydrate - preferably being added thereto. It should be noted that the extent to which aluminium chloride is soluble in aqueous hydrochloric acid varies inversely with the concentration of the acid.
  • the treatment of the carbohydrate is preferably carried out at a temperature in the range 50° to 90°, especially in the range 65° to 75° where the aim is to achieve solubilisation and hydrolysis.
  • the conditions employed in the process of the present invention are similar to those employed in that of published European Patent Specification No. 44622.
  • the process of the invention may be used as stated above to produce carbohydrate of enhanced susceptibility to enzymic hydrolysis.
  • the susceptible carbohydrates can then be treated with an enzyme in a second step, which is preferably carried out at a pH in the range 4 to 9, to produce the final product which can be for example glucose.
  • the relative proportions in which the two halides are present is preferably in the range 10:1 and 1:10 w/w.
  • the process of the present invention has the following advantages:-1. Ability to dissolve and hydrolyse to soluble oligosaccharides as well as. to tri-, di and mono- saccharides such as glucose without prior delignification.
  • Any suitable technique may be used to separate aluminium ions from the mixture produced by solubilisation and hydrolysis. Two suitable techniques are illustrated in Examples 2 and 3.
  • a series of starch hydrolysis reactions was performed using either technique 1 or technique 2, the technique used in any particular reaction depending upon convenience and upon the concentration of AlCl 3 .6H 2 O employed.
  • Technique 1 To an aqueous solution of aluminium chloride AlCl 3 .6H 2 O (saturated at 20°C) was added concentrated (10 M) hydrochloric acid to give a final hydrochloric acid concentration of 2 M. Dottles were prepared containing hydrochloric acid saturated with aluminium chloride and starch and were allowed to stand at room temperature for 15 minutes. At the end of this time the bottles were placed in a water bath at 70°C. After one hour at 70°C the contents of the bottles were analysed for D-glucose by the glucose oxidase method.
  • Figares 1 and 2 of the drawings are graphs of percentage yield of glucose against time in hours for starch solutions hydrolysed in the presence of hydrochloric acid and aluminium chloride Al Cl 3 .6H 2 O.
  • a solution of a mixture of 1 molar hydrochloric acid, 2 molar aluminium chloride (Al Cl 3 .6H 2 O) containing 20% w /v glucose was reduced in volume from 200 ml to 100 ml by heating to 60°C under reduced pressure. At this volume the crystals which formed were removed from the glucose solution by filtration. These crystals (37 g wet) contained 9.1% w /w aluminium (81% w/w Al Cl 3 . 6H20) and 8.4% w/w glucose. This represents 35% of the original aluminium content of the hydrochloric acid/aluminium chloride/ glucose mixture. The remaining syrup contained 28.9% w /w glucose and 4.6% w /w aluminium (i.e. the remainder or 65% of the original aluminium). This recovery procedure is set out in Table 2.
  • a solution of a mixture of 2 molar hydrochloric acid, 2 molar aluminium chloride Al Cl 3 .6H 2 O containing 20% w/v glucose was reduced in volume from approximately 400 ml to approximately 250 mls by heating to 60°C under reduced pressure. 92 g of crystals formed and were removed by filtration. These crystals contained 9.7% w /w aluminium (86.8% Al Cl 3 .6H 2 O) and 7.1% w /w glucose.
  • the first stage of this separation process gave a yield of aluminium of 41% while the second stage gave a maximum yield of a further 20% of aluminium leaving 1.6% w /w aluminium in the glucose syrup.

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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)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
EP19830301472 1982-04-05 1983-03-16 Auflösen und Hydrolysieren von Kohlehydraten Expired EP0091221B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8210005 1982-04-05
GB8210005 1982-04-05

Publications (3)

Publication Number Publication Date
EP0091221A2 true EP0091221A2 (de) 1983-10-12
EP0091221A3 EP0091221A3 (en) 1985-03-13
EP0091221B1 EP0091221B1 (de) 1987-09-09

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ID=10529523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830301472 Expired EP0091221B1 (de) 1982-04-05 1983-03-16 Auflösen und Hydrolysieren von Kohlehydraten

Country Status (3)

Country Link
EP (1) EP0091221B1 (de)
JP (1) JPS58190400A (de)
DE (1) DE3373493D1 (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0187422A2 (de) * 1985-01-08 1986-07-16 Shell Internationale Researchmaatschappij B.V. Verfahren zur Dampfbehandlung von Biomasse, das dabei erhaltene Produkt und seine Verwendung sowie der Reaktor
US4637835A (en) * 1985-06-28 1987-01-20 Power Alcohol, Inc. Methods of hydrolyzing cellulose to glucose and other (poly)saccharides
WO2002012529A1 (en) * 2000-08-09 2002-02-14 Midwest Research Institute Dilute acid/metal salt hydrolysis of lignocellulosics
WO2006084343A2 (en) * 2005-02-11 2006-08-17 Acquaquímica Ltda. Carbonylated compounds preparation process from a vegetable product and resulting carbonylated compounds
EP2100972A1 (de) 2008-03-13 2009-09-16 BIOeCON International Holding N.V. Verfahren zum Umwandeln von Polysacchariden in einem geschmolzenen Salzhydrat
WO2010106053A2 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106057A1 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106052A1 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106055A1 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2011035978A1 (de) 2009-09-23 2011-03-31 Basf Se Oligosaccharide und deren herstellung durch saure hydrolyse von stärke
FR2963008A1 (fr) * 2010-07-23 2012-01-27 IFP Energies Nouvelles Procede de production de sucres a partir de biomasse lignocellulosique pretraitee avec un melange de sels inorganiques hydrates et de sels metalliques
WO2013034818A1 (fr) * 2011-09-08 2013-03-14 IFP Energies Nouvelles Procédé de pretraitement de la biomasse lignocellulosique avec un sel de fer hydraté
FR2985736A1 (fr) * 2012-01-18 2013-07-19 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate permettant d'obtenir une fraction cellulosique et une fraction hemicellulosique
FR2985737A1 (fr) * 2012-01-18 2013-07-19 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate comprenant une etape d'hydrolyse acide preliminaire

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011206044A (ja) * 2009-09-30 2011-10-20 Sekisui Chem Co Ltd セルロース糖化方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB718174A (en) * 1950-03-01 1954-11-10 Corn Prod Refining Co Improvements in or relating to processes for modifying and converting starch
FR1239523A (fr) * 1958-10-15 1960-08-26 Res And Mechanical Applic S P Fabrication du furfurol, de la cellulose et de provendes à partir de déchets végétaux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB718174A (en) * 1950-03-01 1954-11-10 Corn Prod Refining Co Improvements in or relating to processes for modifying and converting starch
FR1239523A (fr) * 1958-10-15 1960-08-26 Res And Mechanical Applic S P Fabrication du furfurol, de la cellulose et de provendes à partir de déchets végétaux

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0187422A2 (de) * 1985-01-08 1986-07-16 Shell Internationale Researchmaatschappij B.V. Verfahren zur Dampfbehandlung von Biomasse, das dabei erhaltene Produkt und seine Verwendung sowie der Reaktor
EP0187422A3 (de) * 1985-01-08 1988-07-13 Shell Internationale Researchmaatschappij B.V. Verfahren zur Dampfbehandlung von Biomasse, das dabei erhaltene Produkt und seine Verwendung sowie der Reaktor
US4637835A (en) * 1985-06-28 1987-01-20 Power Alcohol, Inc. Methods of hydrolyzing cellulose to glucose and other (poly)saccharides
WO2002012529A1 (en) * 2000-08-09 2002-02-14 Midwest Research Institute Dilute acid/metal salt hydrolysis of lignocellulosics
WO2002018610A1 (en) * 2000-08-09 2002-03-07 Midwest Research Institute Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics
US6660506B2 (en) 2000-08-09 2003-12-09 Midwest Research Institute Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics
WO2006084343A2 (en) * 2005-02-11 2006-08-17 Acquaquímica Ltda. Carbonylated compounds preparation process from a vegetable product and resulting carbonylated compounds
WO2006084343A3 (en) * 2005-02-11 2007-10-25 Acquaquimica Ltda Carbonylated compounds preparation process from a vegetable product and resulting carbonylated compounds
EP2100972A1 (de) 2008-03-13 2009-09-16 BIOeCON International Holding N.V. Verfahren zum Umwandeln von Polysacchariden in einem geschmolzenen Salzhydrat
US8445704B2 (en) 2008-03-13 2013-05-21 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106055A1 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
US8440845B2 (en) 2009-03-17 2013-05-14 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106057A1 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106053A2 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2010106052A1 (en) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2011035978A1 (de) 2009-09-23 2011-03-31 Basf Se Oligosaccharide und deren herstellung durch saure hydrolyse von stärke
FR2963008A1 (fr) * 2010-07-23 2012-01-27 IFP Energies Nouvelles Procede de production de sucres a partir de biomasse lignocellulosique pretraitee avec un melange de sels inorganiques hydrates et de sels metalliques
WO2012010750A3 (fr) * 2010-07-23 2012-04-12 IFP Energies Nouvelles Procédé de production de sucres a partir de biomasse lignocellulosique prétraitée avec un mélange de sels inorganiques hydratés et de sels métalliques
FR2979913A1 (fr) * 2011-09-08 2013-03-15 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avrc un sel de fer hydrate
WO2013034818A1 (fr) * 2011-09-08 2013-03-14 IFP Energies Nouvelles Procédé de pretraitement de la biomasse lignocellulosique avec un sel de fer hydraté
FR2985736A1 (fr) * 2012-01-18 2013-07-19 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate permettant d'obtenir une fraction cellulosique et une fraction hemicellulosique
FR2985737A1 (fr) * 2012-01-18 2013-07-19 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate comprenant une etape d'hydrolyse acide preliminaire
WO2013107948A1 (fr) * 2012-01-18 2013-07-25 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate comprenant une etape d'hydrolyse acide preliminaire
WO2013107947A1 (fr) * 2012-01-18 2013-07-25 IFP Energies Nouvelles Procédé de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydraté permettant d'obtenir une fraction cellulosique et une fraction hémicellulosique

Also Published As

Publication number Publication date
JPS58190400A (ja) 1983-11-07
EP0091221B1 (de) 1987-09-09
DE3373493D1 (en) 1987-10-15
EP0091221A3 (en) 1985-03-13

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