WO1996017837A1 - Method for making hydroxymethylfurfural from aldohexose - Google Patents
Method for making hydroxymethylfurfural from aldohexose Download PDFInfo
- Publication number
- WO1996017837A1 WO1996017837A1 PCT/FR1995/001614 FR9501614W WO9617837A1 WO 1996017837 A1 WO1996017837 A1 WO 1996017837A1 FR 9501614 W FR9501614 W FR 9501614W WO 9617837 A1 WO9617837 A1 WO 9617837A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hmf
- catalyst
- liquid medium
- aldohexose
- ratio
- Prior art date
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Classifications
-
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Definitions
- the invention relates to a process for the manufacture of 5-hydroxymethyl furan-2-carboxaldehyde, more often designated hydroxymethylfurfural (HMF), from a liquid medium comprising at least one aldohexose and / or at least one oside capable of releasing at least an aldohexose.
- HMF can be manufactured in an organic medium (FR 2 669 635) or in an aqueous medium (WO 92/10486) from fructose or polyfructans.
- the synthesis of HMF can be obtained by heating the medium in the presence of a heterogeneous acid catalyst.
- the sugar solutions available on the market at low cost often include either osides (sucrose, inulin, starch, etc.) releasing at least one aldohexose by hydrolysis, or invert sugars obtained by hydrolysis of these osides, in the form of a mixture of simple sugars comprising a high proportion of aldohexose (s).
- osides sucrose, inulin, starch, etc.
- invert sugars obtained by hydrolysis of these osides in the form of a mixture of simple sugars comprising a high proportion of aldohexose (s).
- the known methods therefore require carrying out a prior or subsequent separation of the unprocessed sugars, and in particular of aldohexoses such as glucose.
- the invention aims to overcome these drawbacks by proposing a process for manufacturing HMF from a sweet liquid medium which can comprise any proportion of at least one aldohexose and in particular which consists of a solution or a syrup of 'aldohexose (s).
- the invention aims to propose a process for manufacturing HMF from a sugar solution or from a syrup which may comprise a high proportion of aldohexose (s) (such as glucose, galactose, annose or idose) and / or polysaccharide (s) (such as cellulose, starch, ...) and / or oligoholoside (s) (such as sucrose, lactose, maltose, cellobiose ...), with sufficiently high sugar processing and HMF production yields to envisage profitable industrial production.
- aldohexose such as glucose, galactose, annose or idose
- polysaccharide such as cellulose, starch,
- oligoholoside such as sucrose, lactose, maltose, cellobiose
- the invention aims in particular to propose a process for the manufacture of HMF from a sugar solution or from a syrup, the sugars of which consist solely of aldohexose (s) and / or of polysaccharide (s) and / or oligoholoside (s).
- the invention also aims to reduce the cost of preparing HMF by lowering the price of the raw material without increasing that of the process.
- the object of the invention is in particular to authorize the direct use of a greater variety of sugar solutions as a raw material for the manufacture of HMF, including sugar solutions extracted from natural products (Jerusalem artichokes, beets, canes sugar, corn, wheat ...) or sugar solutions from the hydrolysis of naturally occurring sugars (which include as many aldohexoses as ketohexoses and residual osides).
- the object of the invention is also to reduce or even eliminate the cost of the separation steps, and to increase the rate of conversion of the sugars into HMF.
- the invention aims in particular to propose such a manufacturing process in a single step, which can be carried out continuously, and producing a high purity HMF solution.
- the invention also aims to propose such a process for manufacturing HMF by heterogeneous acid catalysis and heating in a single step, rapid, low polluting, profitable whatever the size and capacity of the installation, in particular with large installations. and low or medium capacity.
- the invention relates to a process for the manufacture of hydroxymethylfurfural (HMF) from a liquid medium comprising at least one aldohexose and / or at least one oside capable of releasing at least one aldohexose, in which the liquid medium is heated to a temperature above 100 ° C. in the presence of an heterogeneous acid catalysis, characterized in that the liquid medium is put simultaneously in contact with at least two distinct acid catalysts, the first of which is an aluminosilicate in protonic form, and of an Si / Ai ratio of less than 4, in particular between 2 and 4, and the second of which is an aluminosilicate in protonic form, and with an Si / Ai ratio greater than 5.
- HMF hydroxymethylfurfural
- said second catalyst is a zeolite chosen to transform ketohexoses - in particular fructose - into HMF with a transformation selectivity greater than 90% when it is used alone, under the operating conditions of the reaction (temperature, pressure , initial concentrations, flow rates, etc.), and said first catalyst is a zeolite whose acidity (in the sense of BRONSTED) is lower than that of said second catalyst.
- the second catalyst is chosen to transform the ketohexoses - in particular fructose - into HMF with a yield of HMF greater than 50% when it is used alone under the operating conditions of the reaction.
- the liquid medium is a concentrated aqueous solution, in particular a syrup, comprising more than 150 g / 1 of aldohexose (s) and / or of oside (s).
- said first catalyst is a zeolite, in particular a fau asite Y in protonic form.
- the Si / Ai ratio of this first catalyst is of the order of 2.5 to 3.
- said first catalyst advantageously has a three-dimensional structure having pores of around 7.5 ⁇ in diameter connected to cages of around 13 ⁇ in diameter arranged in cubic symmetry.
- said second catalyst is a zeolite, in particular an H-ordenite, and its Si / Ai ratio is of the order of 5 to 20, in particular of the order of 10.
- the liquid medium is heated to a temperature above 150 ° C and below 200 ° C, in particular of the order of 175 ° C.
- the method can be implemented continuously.
- the liquid medium is circulated continuously in at least one multi-stage reactor - in particular a pulsed column - in the presence of catalysts in cocurrent suspension of the liquid medium and the HMF is extracted continuously in a non-solvent. miscible with the liquid medium circulating against the current.
- the solvent is preferably an organic solvent, in particular MIBC (methyl isobutyl ketone).
- the pulsed columns are known vertical multicontact extraction or separation devices in which pulsations can be maintained (see for example the document "Pulsed Perforated-Plate Columns, DH Logsdail, MJ Slaten, Handbook of Solvent Extraction, Teh C.Lo Malcom HI Baird, Cari Hanson, Krieger Publishing Company, Malabar, Florida, 1991, 11-2, p 355-372, incorporated by reference in the present description. It should be noted that in a process according to the invention, the column not only as a separator, but also and above all as a continuous ultra-contact reactor. simultaneously in the pulsed column, in a single step, the reaction and the continuous selective extraction of the reaction product.
- the invention makes it possible to obtain ketoses continuously in a single step by isomerization of aldoses.
- the invention further relates to a method comprising in combination all or part of the features mentioned above or below.
- Other characteristics and advantages of the invention will appear on reading the following description which refers to the single appended figure which is a diagram of a column stage drawn from an installation for implementing a method according to the invention.
- This installation comprises a supply 1 of sugar solution, and supplies 2, 3 of acid catalysts.
- the feed 2 provides the first catalyst which is for example a faujasite Y in protonic form in powder of Si ⁇ 2 / Al2 ⁇ 3 ratio of 6.5 (ie an Si / Ai ratio of 3.25).
- This zeolite defines pores of 0.75 nanometer in diameter connected to cages of 1.3 nanometer in diameter in a symmetrical cubic structure.
- the feed 3 provides the second catalyst, which is for example formed of a mordenite in protonic form with an Si / Al ratio of the order of 10. This catalyst is also present in pulverulent form.
- the two catalysts are mixed in suspension with the sugar solution in a mixer 4.
- the mixture obtained is introduced into the upper part 5 of a pulsed column 6.
- the pulsed column 6 is temperature controlled. According to the invention, the temperature is above 150 ° C, in particular of the order of 175 ° C.
- an extraction solvent for the HMF produced.
- the sugar solution advantageously being an aqueous solution
- the extraction solvent used is advantageously MIBC.
- the extraction solvent is recovered which has flowed against the current and which is loaded with HMF.
- This solvent loaded with HMF is passed through an evaporator 8 which supplies at outlet 9 a concentrated solution of HMF free of sugars and by-products, and in particular free of aldohexoses.
- the residue of sugar solution not transformed into HMF is recovered with the catalysts in suspension.
- This mixture is passed through a filter 10 which makes it possible to separate the liquid and solid phases.
- the solid phase consisting of the catalysts is recycled directly or through a regeneration furnace 11, or by any other regeneration process, into the mixer 4.
- the liquid phase is discharged directly or to a purifier.
- this solution can be composed of sucrose or a solution of invert sugars (50% glucose and 50% fructose) or a solution of fructose and glucose comprising a higher proportion of glucose, or even d 'a pure glucose solution.
- the starting solution comprises osides
- hydrolysis of the osides into simple sugars aldohexoses or ketohexoses
- a molar conversion rate of glucose into HMF is obtained (number of moles of HMF in solution obtained / number of moles of initial glucose) of 8%.
- the molar rate of transformation of glucose into HMF and fructose is 15%.
- the molar rate of total transformation into HMF, fructose and mannose, is 17%.
- faujasite is added simultaneously in protonic form with an Si / Ai ratio equal to 3.25.
- the weight of faujasite used was half the weight of mordenite, or 5.4 g.
- a molar conversion rate of glucose into HMF of 10% is obtained.
- the molar rate of conversion of glucose into HMF and fructose is 28%.
- the total molar rate of transformation into HMF, fructose and mannose is 33%.
- EXAMPLE 3 This example is identical to Example 2, but a weight of faujasite identical to the weight of mordenite is used, ie 10.8 g.
- the molar rate of transformation into HMF is 13%.
- the molar rate of transformation into HMF and fructose is 34%.
- the total molar rate of transformation into HMF, fructose and mannose is 41%.
- This example is identical to Example 2, but a weight of faujasite is used which is twice the weight of mordenite, ie 21.6 g.
- the molar rate of transformation into HMF is 12%.
- the molar rate of transformation into HMF and fructose is 35.5%.
- the total molar rate of transformation into HMF, fructose and mannose is 43.5%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU43086/96A AU4308696A (en) | 1994-12-07 | 1995-12-06 | Method for making hydroxymethylfurfural from aldohexose |
EP95941779A EP0796255A1 (en) | 1994-12-07 | 1995-12-06 | Method for making hydroxymethylfurfural from aldohexose |
MXPA/A/1997/004211A MXPA97004211A (en) | 1994-12-07 | 1997-06-06 | Method for the elaboration hydroximethylphurfural apparate from aldohex |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR94/14959 | 1994-12-07 | ||
FR9414959A FR2727967A1 (en) | 1994-12-07 | 1994-12-07 | PROCESS FOR THE MANUFACTURE OF HYDROXYMETHYLFURFURAL FROM ALDOHEXOSE |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996017837A1 true WO1996017837A1 (en) | 1996-06-13 |
Family
ID=9469735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1995/001614 WO1996017837A1 (en) | 1994-12-07 | 1995-12-06 | Method for making hydroxymethylfurfural from aldohexose |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0796255A1 (en) |
AU (1) | AU4308696A (en) |
CA (1) | CA2207057A1 (en) |
FR (1) | FR2727967A1 (en) |
WO (1) | WO1996017837A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008009933A1 (en) | 2008-02-18 | 2009-08-20 | Friedrich-Schiller-Universität Jena | Preparing 5-hydroxymethylfurfural, useful e.g. to manufacture pharmaceutical products such as fungicides, comprises thermally reacting carbohydrates in ionic liquid and discharging formed 5-hydroxymethylfurfural using extracting agent |
JP2013517288A (en) * | 2010-01-15 | 2013-05-16 | カリフォルニア インスティチュート オブ テクノロジー | Sugar isomerization |
US9255120B2 (en) | 2013-04-11 | 2016-02-09 | California Institute Of Technology | Conversion of glucose to sorbose |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB817139A (en) * | 1956-04-30 | 1959-07-22 | Quintin Pearson Peniston | Preparation of 5-hydroxymethyl 2-furfural |
GB876463A (en) * | 1959-02-25 | 1961-09-06 | Atlas Powder Co | Process for preparing hydroxymethyl furfural |
GB2058070A (en) * | 1979-09-05 | 1981-04-08 | Roquette Freres | Process for manufacturing 5-hydroxy-methyl-furfural |
FR2551754A1 (en) * | 1983-09-14 | 1985-03-15 | Roquette Freres | PROCESS FOR THE MANUFACTURE OF 5-HYDROXYMETHYLFURFURAL |
FR2663933A1 (en) * | 1990-06-27 | 1992-01-03 | Beghin Say Sa | New process for the preparation of 5-hydroxymethylfurfural from saccharides |
FR2669635A1 (en) * | 1990-11-22 | 1992-05-29 | Furchim | Process for the manufacture of high purity hydroxymethylfurfural (HMF) |
WO1992010486A1 (en) * | 1990-12-07 | 1992-06-25 | Commissariat A L'energie Atomique | Method for preparing 5-hydroxymethyl furfural by contact catalysis |
-
1994
- 1994-12-07 FR FR9414959A patent/FR2727967A1/en active Pending
-
1995
- 1995-12-06 WO PCT/FR1995/001614 patent/WO1996017837A1/en not_active Application Discontinuation
- 1995-12-06 CA CA002207057A patent/CA2207057A1/en not_active Abandoned
- 1995-12-06 EP EP95941779A patent/EP0796255A1/en not_active Withdrawn
- 1995-12-06 AU AU43086/96A patent/AU4308696A/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB817139A (en) * | 1956-04-30 | 1959-07-22 | Quintin Pearson Peniston | Preparation of 5-hydroxymethyl 2-furfural |
GB876463A (en) * | 1959-02-25 | 1961-09-06 | Atlas Powder Co | Process for preparing hydroxymethyl furfural |
GB2058070A (en) * | 1979-09-05 | 1981-04-08 | Roquette Freres | Process for manufacturing 5-hydroxy-methyl-furfural |
FR2551754A1 (en) * | 1983-09-14 | 1985-03-15 | Roquette Freres | PROCESS FOR THE MANUFACTURE OF 5-HYDROXYMETHYLFURFURAL |
FR2663933A1 (en) * | 1990-06-27 | 1992-01-03 | Beghin Say Sa | New process for the preparation of 5-hydroxymethylfurfural from saccharides |
FR2669635A1 (en) * | 1990-11-22 | 1992-05-29 | Furchim | Process for the manufacture of high purity hydroxymethylfurfural (HMF) |
WO1992010486A1 (en) * | 1990-12-07 | 1992-06-25 | Commissariat A L'energie Atomique | Method for preparing 5-hydroxymethyl furfural by contact catalysis |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008009933A1 (en) | 2008-02-18 | 2009-08-20 | Friedrich-Schiller-Universität Jena | Preparing 5-hydroxymethylfurfural, useful e.g. to manufacture pharmaceutical products such as fungicides, comprises thermally reacting carbohydrates in ionic liquid and discharging formed 5-hydroxymethylfurfural using extracting agent |
JP2013517288A (en) * | 2010-01-15 | 2013-05-16 | カリフォルニア インスティチュート オブ テクノロジー | Sugar isomerization |
US9255120B2 (en) | 2013-04-11 | 2016-02-09 | California Institute Of Technology | Conversion of glucose to sorbose |
Also Published As
Publication number | Publication date |
---|---|
AU4308696A (en) | 1996-06-26 |
FR2727967A1 (en) | 1996-06-14 |
CA2207057A1 (en) | 1996-06-13 |
EP0796255A1 (en) | 1997-09-24 |
MX9704211A (en) | 1997-09-30 |
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