WO1998021217A1 - Procede de preparation de glucose a partir de materiaux fibreux vegetaux - Google Patents

Procede de preparation de glucose a partir de materiaux fibreux vegetaux Download PDF

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Publication number
WO1998021217A1
WO1998021217A1 PCT/JP1996/003319 JP9603319W WO9821217A1 WO 1998021217 A1 WO1998021217 A1 WO 1998021217A1 JP 9603319 W JP9603319 W JP 9603319W WO 9821217 A1 WO9821217 A1 WO 9821217A1
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WO
WIPO (PCT)
Prior art keywords
acid
fiber material
plant fiber
glucose
solvent
Prior art date
Application number
PCT/JP1996/003319
Other languages
English (en)
Japanese (ja)
Inventor
Seiji Hata
Original Assignee
Tsurunaga, Takehisa
Suzuki, Yasutaka
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 Tsurunaga, Takehisa, Suzuki, Yasutaka filed Critical Tsurunaga, Takehisa
Priority to PCT/JP1996/003319 priority Critical patent/WO1998021217A1/fr
Priority to AU75074/96A priority patent/AU7507496A/en
Publication of WO1998021217A1 publication Critical patent/WO1998021217A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides

Definitions

  • the present invention relates to a method for producing glucose from a plant fiber material by dissolving a plant fiber material such as cellulose in a solvent.
  • Plant fiber materials contain cellulose as a polysaccharide, and glucose, the basic constituent unit of cellulose, is expected to be used as a food or energy source. Therefore, if glucose can be produced efficiently by efficiently decomposing not only cereals but also plant fiber materials, it will lead to effective use of waste such as waste paper.
  • a hydrolysis method using an acid or an enzyme is known as a hydrolysis method using an acid or an enzyme. Examples of the acid hydrolysis method (hereinafter referred to as “acid method”) include various extraction methods using dilute sulfuric acid or concentrated sulfuric acid, and methods using hydrogen chloride in concentrated hydrochloric acid or in a gaseous state.
  • enzymatic hydrolysis method As an enzymatic hydrolysis method (hereinafter referred to as “enzymatic method”), there is a method in which wood fragments are pretreated with wood flour and then enzymatically reacted with cellulase.
  • enzymatic method Although various measures are taken for the reaction conditions, etc., the contact with the reaction solvent becomes insufficient because the cell mouth, which is the substrate to be hydrolyzed, is in a non-dissolved state. There is a disadvantage that the hydrolysis requires a long time.
  • Cellulose is a natural macromolecule in which glucose is bound to a / 3-1,4-glycosidic bond.
  • Cellulose fibers are water-insoluble, although glucose, which is a structural unit of cellulose, is inherently hydrophilic. This is thought to be due to the fact that the cellulose molecules associate and crystallize due to strong hydrogen bonds.
  • the yield of crystalline cellulose (Abicel, manufactured by Asahi Kasei Corporation) obtained by hydrolyzing the amorphous region of cellulose fibers with dilute sulfuric acid is 90%.
  • This crystalline cellulose is treated with, for example, 3N hydrochloric acid at room temperature. Even after one week, no significant change occurs even if the mixture is vigorously stirred. In addition, when this is boiled, partial hydrolysis is observed, but at the same time decomposition of produced glucose is observed. Thus, the crystalline region has high resistance to hydrolysis.
  • a polymer having an alcohol residue for example, polyvinyl alcohol
  • cellulose swells with alkali, it does not dissolve under mild conditions.
  • hydrazine and N-methylmorpholine oxide dissolve cellulose, but such solutions are not suitable for hydrolysis.
  • cellulose is difficult to dissolve in alkali due to its crystallinity.
  • hydrolysis by alcohol does not only require a long time, but also causes side reactions such as a peeling reaction to occur, thereby reducing the production of glucose. Decrease rate.
  • a method of dissolving with an organic solvent has been proposed, a method suitable for obtaining dalcose by subsequent hydrolysis has not been found.
  • the present invention has been made to solve the above-described problems, and has found that a plant-based fiber material including cellulose fibers can be easily dissolved by an aqueous solution of oxoacid of phosphorus, and the dissolved liquid is used to hydrolyze cellulose and the like.
  • the present invention provides a method for producing glucose with a high yield by hydrolyzing a plant fiber material with high efficiency and under relatively mild conditions. is there
  • a method for producing glucose according to the present invention is characterized in that a plant fiber material is dissolved in a solvent containing oxoacid of phosphorus.
  • the solvent contains at least one aqueous solution selected from the group consisting of phosphoric acid, phosphonic acid, phosphinic acid and metaphosphoric acid, and has a concentration of 70% by weight or more.
  • the dissolved solution is neutralized with an inorganic acid catalyst or an alkaline solution and then contacted with an enzyme to hydrolyze polysaccharides such as cellulose contained in the plant fiber material, It produces glucose.
  • the hydrolysis reaction catalyst is an inorganic acid catalyst comprising hydrogen halide or concentrated sulfuric acid, and hydrogen halide power is particularly preferred.
  • a metal halide salt can be added during or after dissolving the plant fiber material in a solvent to generate hydrogen halide as an acid catalyst. .
  • oxo acid of phosphorus examples include phosphoric acid, phosphonic acid, phosphinic acid and metaphosphoric acid, and a mixed solvent composed of any combination of these may be used.
  • These oxo acids of phosphorus act not as acids as so-called proton donors but as solvents such as cellulose. This is evident from the fact that phosphoric acid and the like are different from sulfuric acid and the like, and the same glucose as cellulose has a low solubility and low solubility in starch with ⁇ -1,4-darcoside linkage. That is, a plant fiber material such as cellulose can be dissolved in an oxoacid-based solvent of phosphorus without being substantially decomposed.
  • the concentration of the oxo acid of phosphorus used in the present invention is desirably 0% by weight or more, and particularly preferably in the range of 70 to 85% by weight. Also, the amount of these used is not particularly limited, but it is usually preferable to use 5 to 15% by weight of the plant fiber material to be dissolved.
  • the dissolution can be carried out at room temperature, but may be carried out by heating to a temperature of up to 60 ° C., preferably in the range of 30 to 60 ° C.
  • a dissolution method an ordinary method such as a stirring and mixing method is used, and is not particularly limited.
  • the lysate obtained as described above is neutralized with an inorganic acid catalyst (excluding phosphorus oxo acid) or an alkaline solution and then brought into contact with an enzyme to hydrolyze the plant fiber material. Let it break down.
  • an inorganic acid catalyst excluding phosphorus oxo acid
  • an enzyme to hydrolyze the plant fiber material. Let it break down.
  • the inorganic acid catalyst to be used those having a small amount of water are preferable in order to prevent the formation of a white precipitate due to addition, contact and the like.
  • Hydrogen halide or sulfuric acid is suitably used, and a mixture thereof may be used, but hydrogen halide is particularly preferably used. Note that an aqueous hydrochloric acid solution that easily produces a white precipitate is not preferable.
  • Hydrogen halide can be used as a gas state, and examples thereof include hydrogen chloride gas, hydrogen bromide gas, and hydrogen fluoride gas.
  • a particularly preferred inorganic acid catalyst is hydrogen chloride gas. The amount of inorganic acid catalyst used is based on the amount of vegetable fiber material used.
  • an enzyme may be used for the hydrolysis.
  • the same hydrolysis effect as when using an inorganic acid catalyst can be obtained by an enzymatic reaction using cellulose.
  • the hydrolysis is carried out while adding an enzyme solution after neutralizing the solution of the plant fiber material with a catalyst solution of an inorganic acid or a solution of the inorganic acid with an alkali solution.
  • the reaction temperature is not particularly limited, but it is preferable to carry out the reaction under relatively mild temperature conditions of 40 to 80 ° C.
  • gaseous hydrogen halide add hydrogen halide by blowing gas into the solution.
  • the hydrolysis reaction depends on the amount of the plant fiber material to be used, but usually can be completed in 30 minutes to 3 hours.
  • a metal halide to the solution during or after dissolving the plant fiber material in the solvent, and to generate hydrogen halide as an acid catalyst simultaneously with the dissolution.
  • hydrolysis can be performed in the same manner as when an acid catalyst is added. Since the metal halide is dissolved in the solution to generate the corresponding hydrohalic acid, there is an advantage that an easy-to-handle metal salt can be used instead of directly using a difficult-to-handle hydrogen halide gas.
  • metal salts include halogens such as sodium, lithium, magnesium, and aluminum. Compounds.
  • lithium chloride, magnesium chloride, aluminum chloride, and the like are used to generate hydrogen chloride
  • lithium bromide and the like are used to generate hydrogen bromide to generate hydrogen fluoride.
  • lithium fluoride or the like is used.
  • metal halide salts may be added during or after dissolution of the plant fiber material with the oxo acid-based solvent of phosphorus.
  • the reaction mixture is filtered using an ion exchange resin or an ion exchange membrane, and the filtrate is concentrated to obtain glucose crystals.
  • a reverse osmosis method an ultrafiltration method, an electrodialysis method, or the like can be used.
  • paper, wood, etc. not to mention cellulose itself, can be used, preferably in the form of finely pulverized powder.
  • a plant fiber material containing cellulose fibers is efficiently hydrolyzed under relatively mild reaction conditions in which no force, no secondary decomposition occurs, and good darcos is obtained. It can be produced with a high yield.
  • Example 1 According to the procedure of Example 1, 3 g of waste paper powder was dissolved in 30 g of an 85% phosphoric acid aqueous solution. Thereafter, a hydrolysis reaction and post-treatment were carried out according to the same procedure as in Example 1 except that 3 ml of concentrated sulfuric acid was added to this solution instead of lithium chloride, to obtain 2.4 g of glucose.
  • Distilled water (1 Om1) was added to waste paper powder (10 g), and distilled water was sufficiently absorbed in the waste paper powder. Then, 30 g of an 85% phosphoric acid aqueous solution was added and kneaded sufficiently. This kneaded material was heated to 50 to 60 ° C., and kneading was continued to obtain a paste. After the paste was cooled to room temperature, the mixture was sufficiently stirred while blowing hydrogen chloride gas. This was placed in a closed container, heated to 80 ° C, and stirring was continued in that state while degassing. After completion of the hydrolysis reaction was confirmed in the same manner as in Example 3, post-treatment was performed to obtain crude glucose 7.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

L'utilisation d'oxo acides de phosphore en tant que solvants permet la dissolution de matériaux fibreux végétaux difficiles à dissoudre. Du glucose peut être préparé en grande quantité selon les étapes suivantes: un matériau fibreux végétal est dissout dans un solvant contenant de l'oxo acide de phosphore, la solution obtenue est neutralisée par un catalyseur acide inorganique ou une solution alcaline puis elle est mise au contact d'un enzyme de façon que les polysaccharides contenus dans le matériau fibreux végétal soient efficacement hydrolysés, dans des conditions propres à ne pas provoquer de décomposition secondaire. Le solvant utilisé pour dissoudre les matériaux fibreux végétaux comprend de préférence une solution aqueuse contenant au moins un élément choisi dans le groupe constitué d'acide phosphorique, d'acide phosphonique, d'acide phosphinique et d'acide métaphosphorique, la concentration dudit solvant s'élevant à au moins 70 % en poids.
PCT/JP1996/003319 1996-11-12 1996-11-12 Procede de preparation de glucose a partir de materiaux fibreux vegetaux WO1998021217A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP1996/003319 WO1998021217A1 (fr) 1996-11-12 1996-11-12 Procede de preparation de glucose a partir de materiaux fibreux vegetaux
AU75074/96A AU7507496A (en) 1996-11-12 1996-11-12 Process for the preparation of glucose from vegetable fibrous materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1996/003319 WO1998021217A1 (fr) 1996-11-12 1996-11-12 Procede de preparation de glucose a partir de materiaux fibreux vegetaux

Publications (1)

Publication Number Publication Date
WO1998021217A1 true WO1998021217A1 (fr) 1998-05-22

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PCT/JP1996/003319 WO1998021217A1 (fr) 1996-11-12 1996-11-12 Procede de preparation de glucose a partir de materiaux fibreux vegetaux

Country Status (2)

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AU (1) AU7507496A (fr)
WO (1) WO1998021217A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61500002A (ja) * 1983-08-25 1986-01-09 パ−ソンズ　アンド　ウイツトモア，インコ−ポレイテイド ミクロビスポラ・ビスポラ・ルトガ−スｐ＆ｗ株を用いるセルロ−ス性基質のグルコ−スへの転換方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61500002A (ja) * 1983-08-25 1986-01-09 パ−ソンズ　アンド　ウイツトモア，インコ−ポレイテイド ミクロビスポラ・ビスポラ・ルトガ−スｐ＆ｗ株を用いるセルロ−ス性基質のグルコ−スへの転換方法

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AU7507496A (en) 1998-06-03

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