EP0091221B1 - Dissolution et hydrolyse des hydrates de carbone - Google Patents

Dissolution et hydrolyse des hydrates de carbone Download PDF

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Publication number
EP0091221B1
EP0091221B1 EP19830301472 EP83301472A EP0091221B1 EP 0091221 B1 EP0091221 B1 EP 0091221B1 EP 19830301472 EP19830301472 EP 19830301472 EP 83301472 A EP83301472 A EP 83301472A EP 0091221 B1 EP0091221 B1 EP 0091221B1
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EP
European Patent Office
Prior art keywords
halide
aluminium
glucose
process according
hydrolysis
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Expired
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EP19830301472
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German (de)
English (en)
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EP0091221A3 (en
EP0091221A2 (fr
Inventor
Pudens Leonard Ragg
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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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 (3-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% 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.
  • EP-A-0.044.622 we describe and claim a process for the modification, solubilisation and/or hydrolysis of a glycosidically linked carbohydrate by treatment with a mixture comprising an aqueous inorganic acid and a halide of lithium, magnesium and/or calcium or a precursor of said halide.
  • the process of EP-A-0.044.622 is very successful. However easy separation of the metallic species from the organic products of the reaction cannot always be achieved by this process.
  • British Patent Specification No. 625688 proposes the use of aluminium chloride as a starch modifying agent and
  • British Patent Specification No. 718174 proposes a process for the enzymic modification of starch in which aluminium chloride is used.
  • the present invention we provide a process for the solubilisation and hydrolysis of a glycosidically linked carbohydrate to produce soluble oligosaccharides and/or glucose, in which the carbohydrate is contacted. with a mixture comprising an aqueous inorganic acid and a hydrated metal halide or a precursor of said halide at a temperature within the range 50° to 100°C, a reaction product is separated and metal ions are recovered from the separated product characterised in that the metal halide is an aluminium halide and the inorganic acid has a concentration within the range 0.5 to 5 molar.
  • the products of solubilisation and/or hydrolysis include oligosaccharides, as well as tri-, di- and monosaccharides.
  • 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.
  • the 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 carbohydrate-containing feedstocks:-
  • the process is applicable to glycosidically linked carbohydrates whether the glycosidic linkage is a (3-linkage as in cellulose, yeast glucan or laminarin, or an a-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, O-acetyl and pyruvate groups can also be treated by the process of the invention as can carbohydrates derived by carboxymethylation, acylation, hydroxyethylation 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 preferred.
  • the preferred hydrated aluminium halide is the hexahydrate AI 6) 3 - 6H 2 0.
  • 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°.
  • the conditions employed in the process of the present invention are similar to those employed in that of EP-A-0.044.622.
  • the relative proportions in which the two halides are present is preferably in the range 10:1 and 1:10 w/w.
  • 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.
  • Solid aluminium chloride AICI 3 . 6H 2 0 was added to concentrated hydrochloric acid and thereafter water was added to raise the volume and to give the required final concentrations.
  • Bottles containing solution of hydrochloric acid, aluminium chloride and starch were prepared and were allowed to stand for 15 minutes at room temperature. After this time the bottles were placed in a water bath at 70°C for 1 hour and thereafter the contents were analysed for D-glucose by the glucose oxidase method.
  • Figures 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 AI Cl 3 ⁇ 6H 2 0.
  • a solution of a mixture of 1 molar hydrochloric acid, 2 molar aluminium chloride (Al Cl 3 ⁇ 6H 2 0) 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 AI C13. 6H 2 0) 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. N.B.
  • a solution of a mixture of 2 molar hydrochloric acid, 2 molar aluminium chloride AI Cl 3 ⁇ 6H 2 0 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% AI 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)

Claims (9)

1. Procédé de dissolution et d'hydrolyse d'un hydrate de carbone à liaisons glycosidiques pour produire des oligosaccharides solubles et/ou du glucose, selon leqeul l'hydrate de carbone est mis en contact avec un mélange comprenant un acide inorganique aqueux et un halogénure métallique hydraté ou un précurseur de celui-ci, à une température dans la gamme de 50 à 100°C, un produit de réaction est séparé et des ions métalliques sont récupérés à partir du produit séparé, caractérisé en ce que l'halogénure métallique est un halogénure d'aluminium et l'acide inorganique a une concentration dans la gamme de 0,5 à 5 M.
2. Procédé suivant la revendication 1 de dissolution et d'hydrolyse de cellulose, pour produire une cellodextrine, de cellotriose, du cellobiose et/ou du glucose.
3. Procédé suivant la revendication 1 de dissolution et d'hydrolyse d'amidon, pour produire du D-glucose ou un mélange de sucres contenant du D-glucose.
4. Procédé suivant l'une quelconque des revendications 1 à 3, dans lequel l'acide inorganique est l'acide chlorhydrique.
5. Procédé suivant l'une quelconque des revendications 1 à 4, dans lequel l'halogénure d'aluminium hydraté ou un précurseur de celui-ci, est le chlorure d'aluminium hexahydraté AICI3,6H20.
6. Procédé suivant l'une quelconque des revendications 1 à 5, dans lequel il y a, en plus de l'halogénure d'aluminium hydraté ou d'un précurseur de celui-ci, un halogénure de lithium, de calcium et/ou de magnésium ou un précurseur d'un tel halogénure.
7. Procédé suivant l'une quelconque des revendications 1 à 6, dans lequel l'hydrate de carbone est mis en contact avec le mélange à une température dans la gamme de 50° à 90°C.
8. Procédé suivant la revendication 7, dans lequel la température est dans la gamme de 65° à 75°C.
9. Procédé suivant la revendication 6, dans lequel le mélange contient deux halogénures métalliques, un halogénure d'aluminium hydraté et un halogénure de lithium, de calcium ou de magnésium, les proportions relatives des deux halogénures étant dans la gamme de 10:1 à 1:10 en p/p.
EP19830301472 1982-04-05 1983-03-16 Dissolution et hydrolyse des hydrates de carbone Expired EP0091221B1 (fr)

Applications Claiming Priority (2)

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

Publications (3)

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EP0091221A2 EP0091221A2 (fr) 1983-10-12
EP0091221A3 EP0091221A3 (en) 1985-03-13
EP0091221B1 true EP0091221B1 (fr) 1987-09-09

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EP19830301472 Expired EP0091221B1 (fr) 1982-04-05 1983-03-16 Dissolution et hydrolyse des hydrates de carbone

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EP (1) EP0091221B1 (fr)
JP (1) JPS58190400A (fr)
DE (1) DE3373493D1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0187422A3 (fr) * 1985-01-08 1988-07-13 Shell Internationale Researchmaatschappij B.V. Procédé de traitement de biomasse à la vapeur, produit obtenu, son utilisation, et le réacteur
US4637835A (en) * 1985-06-28 1987-01-20 Power Alcohol, Inc. Methods of hydrolyzing cellulose to glucose and other (poly)saccharides
US6423145B1 (en) * 2000-08-09 2002-07-23 Midwest Research Institute Dilute acid/metal salt hydrolysis of lignocellulosics
BRPI0500470A (pt) * 2005-02-11 2006-09-26 Acquaquimica Ltda processo de preparação de compostos carbonilados a partir de produto vegetal e compostos carbonilados resultantes
EP2100972A1 (fr) 2008-03-13 2009-09-16 BIOeCON International Holding N.V. Procédé pour convertir les polysaccharides dans un hydrate de sel fondu
WO2010106055A1 (fr) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Procédé de transformation de polysaccharides dans un hydrate de sel fondu inorganique
EP2408782A1 (fr) 2009-03-17 2012-01-25 BIOeCON International Holding N.V. Procede pour la conversion de polysaccharides dans un hydrate de sel fondu inorganique
WO2010106052A1 (fr) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Procédé de transformation de polysaccharides dans un hydrate de sel fondu inorganique
WO2010106053A2 (fr) 2009-03-17 2010-09-23 Bioecon International Holding N.V. Processus de conversion de polysaccharides en hydrate de sel fondu inorganique
WO2011035978A1 (fr) 2009-09-23 2011-03-31 Basf Se Oligosaccharides et leur préparation par hydrolyse acide d'amidon
JP2011206044A (ja) * 2009-09-30 2011-10-20 Sekisui Chem Co Ltd セルロース糖化方法
FR2963008B1 (fr) * 2010-07-23 2013-01-04 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
FR2979913B1 (fr) * 2011-09-08 2015-01-16 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avrc un sel de fer hydrate
FR2985736B1 (fr) * 2012-01-18 2020-01-10 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
FR2985737B1 (fr) * 2012-01-18 2020-01-10 IFP Energies Nouvelles Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate comprenant une etape d'hydrolyse acide preliminaire

Family Cites Families (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
US3085038A (en) * 1958-10-15 1963-04-09 Res And Mechanical Applic S P Production of cellulose furfural and fodder from agricultural waste

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Publication number Publication date
EP0091221A3 (en) 1985-03-13
EP0091221A2 (fr) 1983-10-12
DE3373493D1 (en) 1987-10-15
JPS58190400A (ja) 1983-11-07

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