EP2906521A1 - Procédé d'obtention d'alditols comportant cinq à six atomes de carbone - Google Patents

Procédé d'obtention d'alditols comportant cinq à six atomes de carbone

Info

Publication number
EP2906521A1
EP2906521A1 EP13792247.2A EP13792247A EP2906521A1 EP 2906521 A1 EP2906521 A1 EP 2906521A1 EP 13792247 A EP13792247 A EP 13792247A EP 2906521 A1 EP2906521 A1 EP 2906521A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
yield
acid
catalyst
bar
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Withdrawn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
EP13792247.2A
Other languages
German (de)
English (en)
Inventor
Ferdi SCHÜTH
Roberto Rinaldi
Niklas Meine
Jakob Hilgert
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP2906521A1 publication Critical patent/EP2906521A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/26—Hexahydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/20—Oxygen atoms
    • 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

  • the present invention relates to a process for the recovery of sugar alcohols having five to six carbon atoms in high yield from cellulosic materials.
  • the cellulosic starting materials e.g., microcrystalline cellulose, alpha-cellulose, wood and cellulosic residues such as sugarcane bagasse or wood chips
  • the acid-containing and preferably dried starting materials are brought into contact in a second step under the action of mechanical energy, so that the cellulose-containing materials are degraded into water-soluble products.
  • a third step from the water-soluble products in aqueous solution by hydrolytic hydrogenation by means of a metal-containing catalyst under high pressure hydrogen pressure and in high yield five to six carbon atoms containing sugar alcohols obtained.
  • biomass as a base material for fuels and for basic chemicals is currently the subject of extensive research.
  • Cellulose the main component of lignocellulosic biomass, is considered as a possible raw material. In order to obtain suitable and workable products, the cellulose must be broken up into smaller molecules.
  • WO 2009/061750 discloses a process for the preparation of soluble sugars from a cellulosic material.
  • the cellulosic material is contacted with a solid acid and milled together over an extended period of time to obtain a product of soluble sugars.
  • the solid acid used has the disadvantage that it is virtually consumed during the process, with the result that the catalytic activity decreases in the course of the process and also a recovery of the catalyst is not completely possible.
  • the conversion of cellulose-containing materials into water-soluble substances is not complete.
  • the inventors have found that those containing a catalytic amount of a strong acid (eg, HCl, H 2 S0 4 and others) can be replaced by a liquid or gaseous phase carried out impregnation, also referred to as impregnation according to the invention, the cellulose-containing starting materials is a very important step to obtain under the action of mechanical forces on the acid-coated and preferably dried starting materials completely water-soluble oligomers having molecular weights lower than 2000 daltons, the then directly, preferably without further treatment of a hydrogenation treatment in aqueous solution by means of a transition metal-containing catalyst can be subjected, and thus five to produce six carbon atoms containing sugar alcohols in high yield.
  • a strong acid eg, HCl, H 2 S0 4 and others
  • the present invention accordingly provides a process for obtaining sugar alcohols having five to six carbon atoms from cellulosic material or mixtures thereof, in which the cellulosic material is brought into intimate contact with an acid, carried out in a liquid or gaseous phase, in contact with the acid Acid-coated and preferably dried cellulose-containing material is subjected to a mechanical treatment to reduce the degree of polymerization of the cellulose-containing material, wherein the mechanical treatment is carried out at least until the degradation or cleavage products of cellulose-containing material to more than 60 wt .-%, preferably more than 70 wt .-%, especially more than 80 wt .-%, especially more than 90 wt .-%, based on the cellulose-containing material used are water-soluble, the resulting reaction product of a hydrogenation treatment with hydrogen in the presence of a catalyst with a content of transition metal selected from the metals of groups 3 to 10 of the Periodic Table (IUPAC) or mixtures thereof, preferably in aqueous
  • the cellulosic material is not limited to already purified celluloses or certain celluloses, even untreated natural products such as hay and spruce can with yields of at least 75% and 87% after 2 hours Milling, beech wood or sugar cane bagasse even with yields greater than 99% are converted into water-soluble products after 2 hours of milling, which can then be subjected to the hydrolytic hydrogenation treatment.
  • cellulose is used in the present application, this means that this is pure cellulose or cellulose-containing materials. It can be used both natural products such as wood, grasses, chemically pure celluloses and cellulose-containing materials.
  • an acid selected from inorganic acids, organic acids or mixtures thereof is used.
  • the acid is used in the process according to the invention in catalytic amounts.
  • the acid is used in an amount of 0.0001 to 1 mmol per g of cellulose.
  • the impregnation of the cellulosic substrates with a strong acid is carried out in a dilute acidic solution (0.0001 to 6 mol / l) of the acid in a low boiling point solvent (eg, dimethyl ether, diethyl ether, methyl ethyl ether, tert-butyl methyl ether, acetone , Pentane, hexane, heptane, supercritical carbon dioxide, ethyl acetate, methyl acetate, methanol, dichloromethane, etc.). or mixtures thereof, which can be easily removed in a next process step, for example by applying a negative pressure or supplying heat.
  • a low boiling point solvent eg, dimethyl ether, diethyl ether, methyl ethyl ether, tert-butyl methyl ether, acetone , Pentane, hexane, heptane, supercritical carbon dioxide, ethyl
  • the substrate may be treated with a gaseous acid.
  • cellulose or the cellulose-containing material may be exposed to gaseous HCl, S0 3 or other gaseous acids. If desired, however, it is also possible for a combination of the impregnation with the impregnation to take place by gaseous means, even with different acids
  • inorganic acid has a pKa value ⁇ 3, preferably the pKa value is between -14 and 2.
  • Suitable examples of inorganic acids are mineral acids such as sulfuric acid, sulfur dioxide, sulfur trioxide, hydrochloric acid, phosphoric acid, phosphotungstic acid and Nitric acid, with nitric acid being less preferred.
  • Particularly good conversion results are also obtained when the organic acid has a pKa value ⁇ 3, preferably the pKa value is between -14 and 2.
  • organic acids are benzenesulfonic acids and their derivatives, haloalkanoic acid, such as trifluoroacetic acid, or methanesulfonic acid, Trifluoroacetic acid and oxalic acid and derivatives thereof.
  • acids having a pKa value of less than -2 Preference is given to acids having a pKa value of less than -2.
  • the acid is not brought into direct contact with the cellulose, but in a first process step, the cellulose-containing material is impregnated with a solution of the acid in a suitable solvent and / or with a gaseous acid becomes.
  • those solvents which do not adversely affect the reaction are suitable, such as water and organic solvents such as diethyl ether, dichloromethane, ethanol, methanol, THF, acetone; Benzene, lighter hydrocarbons (eg, four to seven carbon atom-containing hydrocarbons) and any other polar or non-polar solvent in which the acid used is soluble, or which allows a good mixing of cellulose and acid in a dispersion, and which has a boiling point of 100 ° C and below has.
  • the solution or dispersion of the acid is mixed with the cellulose-containing material and optionally allowed to stand for some time from up to several hours, especially up to 2 hours.
  • the solvent is removed again, for example by filtration and / or evaporation.
  • a low-boiling solvent having a boiling point at normal pressure of 30 to 80 ° C is used as the solvent, this can be removed in a simple manner, either by gentle heating and / or by applying a negative pressure again.
  • the acid which usually has a higher boiling point, remains on the cellulosic material.
  • the mechanical treatment of the cellulose can be carried out in the presence of the acid. It has been found that the degree of conversion of the cellulose by impregnating the cellulosic material with inorganic and / or organic acid in the presence of a solvent can be substantially increased.
  • the acid-containing and preferably dried cellulose-containing material will have a residual moisture content of less than 20% by weight, especially less than 16% by weight, based on the total weight of the impregnated cellulose-containing material.
  • a cellulosic material is used which has a residual moisture in the range of 2 to 10 wt .-%, based on the total weight of the impregnated cellulose-containing material, which, if necessary, can be achieved by drying.
  • the mechanical treatment of the acid-containing and dried cellulose-containing substrates can be carried out, for example, by grinding, extruding or kneading.
  • mills those can be used which comminute the millbase using grinding media, such as.
  • vibrating mills stirred mills, stirred ball mills, ball mills, etc.
  • ball mills Particularly preferred are ball mills. All extruders known from the prior art can be used as extruders. If the method according to the invention is carried out in a ball mill, for example in a planetary ball mill, then turning times of 400 to 1200, preferably 800 to 1000, rpm have proven suitable.
  • the speed may also be lower for large-scale installations, but the person skilled in the art will be dependent determine the speed of the material used and the mill used so that an optimized result can be achieved.
  • the reaction time, d. H. the time in which the mechanical treatment is carried out is usually from 0.01 to 24 hours, with periods of 1, 5 to 12, especially 2 to 6 hours are sufficient to a mixture of products having a molecular weight lower than 2000 Da or to recover completely water-soluble products.
  • the mechanical treatment is carried out according to the invention at least until the degradation or cleavage products of the cellulose-containing material to more than 60% by weight, preferably more than 70 wt .-%, especially more than 80 wt .-%, especially more than 90 Wt .-%, based on the cellulose-containing material used are water-soluble. This is usually the case when the degree of polymerization of the cellulose fragments is less than 15 anhydroglucose units. This is achieved depending on the apparatus used for the mechanical treatment and the amount of cellulose-containing material used usually with a treatment time of 2 to 6 hours, this process time can be determined by those skilled in the knowledge of the system used and the cellulose-containing materials used.
  • the process of the present invention can achieve nearly quantitative conversions of the cellulosic materials to water-soluble products.
  • water-soluble cellulose oligomers, cellobiose and other products whereby the formation of by-products (eg, 5-hydroxymethylfurfural, furfural, levulinic acid, etc.) can be largely avoided.
  • cellulose cleavage products which are in powder form, especially after milling in a ball mill, are dissolved, optionally with separation of non-water soluble residues, in water and a hydrogenation treatment with hydrogen in the presence of a transition metal catalyst which is usually subjected to an amount of up to 10 wt .-%, transition metal based on the total weight of the transition metal used, subjected.
  • heating of an aqueous solution of the resulting degradation or cleavage products of the cellulose-containing material at a temperature of more than 80 ° C, especially between 100 ° and 200 ° C, in particular from 120 ° to 160 ° C, especially between 130 ° and 150 ° C, over a period of 0.5 to 24 hours, especially from 0.25 to 12 hours, in particular from 2 to 6 hours are carried out, any resulting solid residues are separated by filtration, and then the catalyst to the filtrate of the heat aqueous solution and the hydrogenation treatment in an autoclave at a hydrogen pressure of 10 to 100 bar, especially 30 to 70 bar, in particular 40 to 60 bar, at a temperature of more than 140 ° C, especially between 150 ° and 200 ° C, be carried out over a period of 0.25 to 24 hours, especially from 0.5 to 12 hours, in particular from 1 to 6 hours.
  • Metal oxides or mixed oxides of Si, W, V, Al, Ti, Ce, Zr, Sc, Y, Zr, Ta, Nb, Cr, Mo and / or lanthanides, or carbonaceous catalyst supports (eg activated carbons) are advantageous.
  • suitable carriers are metal oxides or mixed oxides of Si, W, V, Al, Ti, Ce, Zr, Sc, Y, Zr, Ta, Nb, Cr, Mo and / or lanthanides, or carbon-containing catalyst supports (eg activated carbons), such as Si0 2 , Al 2 0 3 , Ti0 2 , Zr0 2 , Nb 2 0 5 , W 2 0 5 , W0 3 , W 2 0 3 , W0 2 , Ce0 2 and mixed oxides or activated carbon thereof called.
  • the hydrogenation catalyst of the invention particularly comprises ruthenium present in reduced, highly dispersed form on a porous carbon support.
  • the catalyst comprises at least 0.1% by weight of Ru, based on the total weight of the catalyst, to ensure at least sufficient catalyst activity.
  • the metal loadings on the carbon support are 0.5 to 10.0 wt .-%, particularly 3 to 7 wt .-% ruthenium, based on the total weight of the catalyst.
  • the metal catalyst such as the Ru / C catalyst for the process according to the invention preferably an activation treatment at temperatures of more than 140 ° C, especially more than 160 ° C, and up to 250 ° C, at a hydrogen pressure of at least 40 bar, particularly at least 50 bar, over a period of 0.25 to 2 hours in an autoclave is subjected to a prehydrogenation of the catalyst and thus an improved activity for the hydrolytic hydrogenation of the cellulose cleavage products already at the beginning of Hydrogenation of the cleavage products to allow.
  • the catalyst in non-activated form, and the reactivity is increased in the hydrogenation in the process according to the invention.
  • the hydrolytic hydrogenation is thus carried out according to the invention especially at a pressure of 10 to 100 bar, especially 30 to 70 bar, in particular 40 to 60 bar and at a temperature of more than 140 ° C, especially between 150 ° and 200 ° C.
  • the reaction time in which the hydrolytic hydrogenation is carried out according to the process of the invention is usually from 0.25 to 24 hours, with periods of from 0.5 to 12, especially from 1 to 6 hours being usually sufficient.
  • the catalyst After completion of the hydrogenation, the catalyst can be filtered off and reused without causing a decrease in activity due to clogging of the catalyst pores by cellulose degradation products, as seen in prior art hydrogenation processes for cellulose.
  • Microcrystalline cellulose (Aldrich, 500 mg) was added to water (10 ml).
  • Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
  • the Mixture was heated to 160 ° C in an autoclave under a room temperature hydrogen pressure of 50 bar. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • Microcrystalline cellulose (1.20 g) was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
  • the mixture was placed in an autoclave under a room temperature hydrogen pressure of 50 bar
  • Reaction time started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filter cake was washed, dried and weighed.
  • the conversion was calculated by the weight difference of cellulose.
  • Microcrystalline cellulose 500 mg was added to a 0.05 M sulfuric acid solution (10 ml).
  • Ruthenium on carbon 100 mg, 5% by weight of ruthenium was added as a catalyst.
  • the mixture was placed in an autoclave under a Room temperature hydrogen pressure of 50 bar heated to 160 ° C. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filter cake was washed, dried and weighed.
  • the conversion was calculated by the weight difference of cellulose.
  • the turnover was 13%.
  • the filtrate was analyzed by HPLC to determine product yield.
  • the yield of C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 5.6%, the yield of xylitol was 0.9%, other identified compounds together gave a yield of 0.7%.
  • the rotation frequency of the main disk was 800 rpm.
  • the resulting powder (500 mg) was added to 0.05 M sulfuric acid (10 ml).
  • Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst. The mixture was heated to 160 ° C in an autoclave under a room temperature hydrogen pressure of 50 bar. Upon reaching the
  • the autoclave was cooled in an ice-cooled water bath before it was opened.
  • the filtrate was analyzed by HPLC to determine product yield.
  • the yield of C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 44.7%, the yield of xylitol was 3.0%, other identified compounds together gave a yield of 0.5%.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before the Solvent was removed under reduced pressure. A sample of the powder so obtained was derivatized with phenyl isocyanate for GPC analysis.
  • the resulting powder (500 mg) was added to water (10 ml).
  • Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filter cake was washed, dried and weighed.
  • the conversion was calculated by the weight difference of cellulose.
  • the turnover was 32%.
  • the filtrate was analyzed by HPLC to determine product yield.
  • the yield for C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 9.0%, the yield for xylitol was 1.3%, other identified compounds together gave a yield of 0.8%.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 1 hour.
  • the rotation frequency of the main disk was 800 rpm.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the reaction mixture was filtered.
  • the filter cake was washed, dried and weighed.
  • the conversion was calculated by the weight difference of cellulose.
  • the turnover was 100%.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 3 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the reaction mixture was filtered.
  • the filter cake was washed, dried and weighed.
  • the conversion was calculated by the weight difference of cellulose.
  • the turnover was 100%.
  • ⁇ -cellulose (1.20 g) was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the thus-obtained powder (500 mg) was dissolved in 0.05 M sulfuric acid (10 ml). Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • ⁇ -cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure. A sample of the powder so obtained was derivatized with phenyl isocyanate for GPC analysis.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filter cake was washed, dried and weighed.
  • the conversion was calculated by the weight difference of cellulose.
  • the turnover was 100%.
  • the filtrate was analyzed by HPLC to determine product yield.
  • the yield for C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 85.9%, the yield for xylitol was 13.7%, other identified compounds together gave a yield of 0.4%.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filter cake was washed with water (60 ml) and acetone (60 ml), dried and used several times as a catalyst by addition to a freshly prepared solution of sulfuric acid-impregnated ground microcrystalline cellulose (500 mg) in water (10 ml ) was given.
  • the filtrate was analyzed by HPLC to determine product yield.
  • Example 12 Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • the catalyst was activated before the reaction.
  • ruthenium on carbon 100 mg, 5% by weight of ruthenium
  • the suspension was heated to 160 ° C. in an autoclave under a room temperature hydrogen pressure of 50 bar for 1 h.
  • the catalyst was filtered off, washed (60 ml of water, 60 ml of acetone) and dried before being added to the solution.
  • the reaction mixture was filtered. The filtrate was used to determine the
  • Sorbitan was 2.8%, the yield for xylitol was 3.7%, others identified
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product from J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was placed in a steel beaker with steel balls (6 steel balls, weight 3.95 g) in a Pulverisette P7 from Fritsch for 2
  • the rotation frequency of the main disk was 800 rpm.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 140 ° C for 1 hour. Upon reaching the reaction temperature was Measurement of the reaction time started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filtrate was analyzed by HPLC to determine product yield.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • the catalyst was activated before the reaction.
  • Ruthenium was suspended in water (10 ml). The suspension was heated to 160 ° C. in an autoclave under a room temperature hydrogen pressure of 50 bar for 1 h. The catalyst was filtered off, washed (60 ml of water, 60 ml of acetone) and dried before being added to the solution.
  • the reaction mixture was filtered.
  • the filtrate was analyzed by HPLC to determine product yield.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was obtained added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • Ruthenium on carbon (100 mg, 5 wt.% Ruthenium) was added as a non-activated catalyst.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 150 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filtrate was analyzed by HPLC to determine product yield.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened. The reaction mixture was filtered. The filtrate was analyzed by HPLC to determine product yield.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product from J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the reaction mixture was filtered.
  • the filtrate was analyzed by HPLC to determine product yield.
  • Example 20 Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the powder thus obtained (500 mg) was dissolved in water (10 ml).
  • the catalyst was activated before the reaction.
  • ruthenium on carbon 100 mg, 5% by weight of ruthenium
  • the suspension was heated to 200 ° C. in an autoclave under a room temperature hydrogen pressure of 50 bar for 1 h.
  • the catalyst was filtered off, washed (60 ml of water, 60 ml of acetone) and dried before being added to the solution.
  • the reaction mixture was filtered. The filtrate was used to determine the
  • Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product from J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 150 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • Beechwood sawdust was made into a powder with a kitchen mixer. The powder was sieved and the proportion of particles smaller than 250 ⁇ m was reused.
  • This powder (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
  • the powder (1.00 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 3 hours.
  • the rotation frequency of the main disk was 800 rpm.
  • the resulting powder (900 mg) was dissolved in water (9 ml). The solution was heated to 145 ° C. for 1 hour, the resulting solid was separated by filtration, and the filtrate from the combined mixtures was analyzed by HPLC.
  • the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 145 ° C for 1 hour. Upon reaching the reaction temperature was Measurement of the reaction time started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
  • the reaction mixture was filtered.
  • the filtrate was analyzed by HPLC to determine product yield.
  • the yield for the C6 compounds (sorbitol, mannitol and glucose) was calculated relative to the concentration of glucose and cellobiose in the reaction solution before the reaction.
  • the C6 sugar alcohol yield (sorbitol, mannitol) was 84.0%, the glucose yield was 13.4%.
  • the yield for xylitol (84.2%) and xylose (1 1, 7%) were calculated relative to the concentration of xylose in the reaction solution before the reaction.
  • By-products further identified were gycerin, 1,3-propanediol, methanol, levulinic acid, hydroxymethylfurfural and furfural and furanic acid.
  • Fig. 1 shows the degree of polymerization of the phenylcarbanylate derivatives of a-cellulose (1), MCC (2), a-cellulose ball-milled for 2 hours (3), MCC ball-milled for 2 hours (4), IMCC (5), IMCC for 1 h (6), 2 h (7) and 3 h ball-milled (8).
  • Fig. 2 shows the comparison of the performance of Ru / C and Ru / C * catalysts in the hydrolytic hydrogenation of IMCC ball-milled for 2 h.
  • Reaction conditions 500 mg of substrate, 10 ml of water, 100 mg of catalyst, 50 bar of H 2 ⁇ rt), 1 h.
  • Fig. 4 TEM images of the Ru / C catalysts: (a) before the reaction, (b) after a run and (c) after 6 runs. The illustration at the bottom right shows the Ru particle distribution of the catalyst samples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé d'obtention d'alditols comportant cinq à six atomes de carbone, avec un haut rendement, à partir de matériaux contenant de la cellulose. Dans une première étape, les matériaux de départ (par exemple cellulose monocristalline, cellulose alpha, bois et résidus contenant de la cellulose, comme par exemple de la bagasse de canne à sucre ou des copeaux de bois) sont mis en contact étroit avec un acide par imprégnation effectuée en phase liquide ou gazeuse. Dans une deuxième étape, les matériaux de départ traités à l'acide et séchés sont mis en contact sous l'effet d'une énergie mécanique, de sorte que les matériaux contenant de la cellulose sont décomposés en produits hydrosolubles. Ensuite, dans une troisième étape, des alditols comportant cinq à six atomes de carbone sont obtenus à partir des produits hydrosolubles en solution aqueuse, par hydrogénation hydrolytique au moyen d'un catalyseur contenant un métal, sous pression d'hydrogène, avec une haute sélectivité et un haut rendement.
EP13792247.2A 2012-10-09 2013-10-04 Procédé d'obtention d'alditols comportant cinq à six atomes de carbone Withdrawn EP2906521A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012109595.7A DE102012109595A1 (de) 2012-10-09 2012-10-09 Verfahren zur Gewinnung von Zuckeralkoholen mit fünf bis sechs Kohlenstoffatomen
PCT/DE2013/100350 WO2014056486A1 (fr) 2012-10-09 2013-10-04 Procédé d'obtention d'alditols comportant cinq à six atomes de carbone

Publications (1)

Publication Number Publication Date
EP2906521A1 true EP2906521A1 (fr) 2015-08-19

Family

ID=49596023

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13792247.2A Withdrawn EP2906521A1 (fr) 2012-10-09 2013-10-04 Procédé d'obtention d'alditols comportant cinq à six atomes de carbone

Country Status (10)

Country Link
US (1) US9206098B2 (fr)
EP (1) EP2906521A1 (fr)
JP (1) JP6212564B2 (fr)
BR (1) BR112015007740A2 (fr)
CA (1) CA2886756A1 (fr)
DE (1) DE102012109595A1 (fr)
EA (1) EA028770B1 (fr)
IN (1) IN2015DN02471A (fr)
MX (1) MX2015004447A (fr)
WO (1) WO2014056486A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018508485A (ja) * 2015-02-18 2018-03-29 ディーエスエム アイピー アセッツ ビー．ブイ． レブリン酸の連続水素化
CN105289601B (zh) * 2015-12-07 2018-01-02 中国科学院广州能源研究所 一种山梨醇水相加氢制取直链c5/c6烷烃催化剂及其制备方法
US10882804B2 (en) * 2018-09-14 2021-01-05 University Of South Carolina Methods and compositions for hydrodeoxygenation of carbohydrates and carbohydrate analogs
DE102019117437A1 (de) 2019-06-27 2020-12-31 Technische Universität Dresden Mechanochemisches Syntheseverfahren unter Verwendung eines katalytisch aktiven Formkörpers
DE102021106741A1 (de) 2021-03-18 2022-09-22 Ruhr-Universität Bochum, Körperschaft des öffentlichen Rechts Mechanochemisches Syntheseverfahren unter Verwendung eines katalytisch aktiven Formkörpers

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4619917B2 (ja) * 2005-10-14 2011-01-26 月島機械株式会社 リグノセルロースの前処理方法
JP4423432B2 (ja) * 2006-03-01 2010-03-03 国立大学法人北海道大学 セルロースの加水分解および／または加水分解物の還元用触媒およびセルロースから糖アルコールの製造方法
US8062428B2 (en) 2007-11-06 2011-11-22 University Of Central Florida Research Foundation, Inc. Solid acid catalyzed hydrolysis of cellulosic materials
GB0918821D0 (en) 2009-10-27 2009-12-09 Univ Leuven Kath Catalytic process for the production of alcohols from biomass-related feedstocks
JP5823756B2 (ja) * 2010-07-21 2015-11-25 国立大学法人北海道大学 糖アルコールの製造方法
DE102011012102A1 (de) * 2011-02-23 2012-08-23 Studiengesellschaft Kohle Mbh Verfahren zur säurekatalysierten Depolymerisation von Cellulose
EA023989B1 (ru) 2010-11-25 2016-08-31 Штудиенгезельшафт Коле Мбх Способ кислотно-катализируемой деполимеризации целлюлозы
DE102010052602A1 (de) * 2010-11-25 2012-05-31 Studiengesellschaft Kohle Mbh Verfahren zur säurekatalysierten Depolymerisation von Cellulose
US20120172588A1 (en) * 2010-12-30 2012-07-05 Ming Qiao Catalytic biomass deconstruction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2014056486A1 *

Also Published As

Publication number Publication date
US9206098B2 (en) 2015-12-08
MX2015004447A (es) 2015-06-24
WO2014056486A1 (fr) 2014-04-17
DE102012109595A1 (de) 2014-04-24
JP2015535855A (ja) 2015-12-17
CA2886756A1 (fr) 2014-04-17
JP6212564B2 (ja) 2017-10-11
BR112015007740A2 (pt) 2018-04-24
IN2015DN02471A (fr) 2015-09-04
EA201500401A1 (ru) 2015-11-30
EA028770B1 (ru) 2017-12-29
US20150274618A1 (en) 2015-10-01

Similar Documents

Publication Publication Date Title
EP2906521A1 (fr) Procédé d'obtention d'alditols comportant cinq à six atomes de carbone
EP2473467B1 (fr) Procédé pour la préparation catalytique d'acide formique
EP2574609B1 (fr) Procédé de fabrication de liaisons de furane à partir de matières premières renouvelables
EP0616846B1 (fr) Procédé de préparation d'un catalyseur d'hydrogénation à base de métal precieux déposé sur charbon actif
EP1399255A2 (fr) Catalyseurs au ruthenium sur support a base de silice pour l'hydrogenation des saccharides
EP2643485B1 (fr) Procédé de dépolymérisation de cellulose, catalysée par de l'acide
EP2666540A1 (fr) Procédé d'hydrodésoxygénation catalytique de dérivés de furane et/ou d'huiles de pyrolyse, le catalyseur correspondant et son procédé de préparation.
JP2013542920A (ja) セルロースの同時の加水分解および水素化
DE112012005560T5 (de) Verfahren zur chemischen Umwandlung von Cellulose isoliert aus aromatischer verbrauchter Biomasse zu Hydroxymethylfurfural
DE102016224073A1 (de) Verbessertes HMF-Herstellungsverfahren
US10883151B2 (en) Solid catalysts
EP0001425A1 (fr) Catalyseur au ruthénium sur support, son procédé de préparation et son utilisation comme catalyseur d'hydrogénation
EP2981626B1 (fr) Procédé de dégradation de biomasse lignocellulosique
EP2294230A1 (fr) Décomposition de matériaux contenant des hydrates de carbone avec des catalyseurs inorganiques
DE69706682T2 (de) Verfahren zur hydrierung von ungesättigten verbindungen auf pflanzlicher basis und zur regenerierung eines verwendeten katalysators
WO2022189198A1 (fr) Procédé et catalyseur pour la production de blocs de construction phénoliques à partir de lignine
DE102018208510A1 (de) Salz- und Säuregemisch-katalysierte HMF-Herstellung
DE102010052602A1 (de) Verfahren zur säurekatalysierten Depolymerisation von Cellulose
EP1572354B1 (fr) Catalyseur supporte contenant du rhenium et procede d'hydrogenation de composes carbonyles en phase liquide au moyen dudit catalyseur
AT526076B1 (de) Verfahren zur Herstellung von Lävulinsäure aus Fructose
DE2908993A1 (de) Verfahren zur gewinnung aus zellulosematerialien und verwendung zur gewinnung von glucose
DE102011012102A1 (de) Verfahren zur säurekatalysierten Depolymerisation von Cellulose
EP1769006B1 (fr) Procede de preparation de balles d'avoine pour la production de xylane
CN116083658A (zh) 一种分步选择性降解木质纤维素制备木糖、葡萄糖和木质素的方法
DE19619075A1 (de) Verfahren zum Herstellen von Hydroxymethylfurfural aus Aldohexose

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150414

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MEINE, NIKLAS

Inventor name: RINALDI, ROBERTO

Inventor name: HILGERT, JAKOB

Inventor name: SCHUETH, FERDI

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20180124

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20180605