EP3325458A1 - Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees - Google Patents
Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thioureesInfo
- Publication number
- EP3325458A1 EP3325458A1 EP16741608.0A EP16741608A EP3325458A1 EP 3325458 A1 EP3325458 A1 EP 3325458A1 EP 16741608 A EP16741608 A EP 16741608A EP 3325458 A1 EP3325458 A1 EP 3325458A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- groups
- chosen
- process according
- cyclic
- solvent
- 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- Withdrawn
Links
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
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
-
- 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 converting sugars and in particular hexoses to 5-hydroxymethylfurfural in the presence of new organic catalysts of the family of thioureas of low acidity and non-corrosive.
- 5-hydroxymethylfurfural is a compound derived from biomass that can be used in many fields as precursors of active ingredients in pharmacy, agrochemicals or specialty chemicals. His interest in recent years is in its use as a precursor of furanedicarboxylic acid (FDCA) which is used as a substitute for terephthalic acid as a monomer for the production of polyester fibers or convenience plastics.
- FDCA furanedicarboxylic acid
- the high acidity of each of these catalysts can be characterized by the numerical value of its pKa in a solvent.
- the pKa of the sulfuric and sulfonic acids are between 0 and 3.
- the pKa of the sulfuric and sulfonic acids are between -14 and -2.
- the invention therefore relates to a process for producing 5-hydroxymethylfurfural from sugars using organic catalysts based on thiourea family compounds, low acid and non-corrosive.
- organic catalyst is meant a molecule acting as a catalyst and containing exclusively non-metallic atoms selected for example from carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, silicon, fluorine, bromine, chlorine and iodine.
- An advantage of the present invention is to provide a process for converting sugars to 5-hydroxymethylfurfural using one or more organic catalysts of the thiourea family, said catalysts having a low acidity, being non-corrosive and being easily recyclable.
- the filler treated in the process according to the invention is a filler comprising at least one sugar, preferably chosen from oligosaccharides and monosaccharides, alone or as a mixture.
- sugar is meant any oligosaccharide or monosaccharide soluble in the reaction conditions contemplated by the invention.
- Monosaccharide more particularly denotes carbohydrates of general formula C 6 (H 2 O) 6 or C 6 H 12 0 6 .
- the preferred monosaccharides used as filler in the present invention are selected from glucose, mannose, fructose, alone or as a mixture.
- Oligosaccharide more particularly denotes a carbohydrate having the formula wherein n is an integer greater than 1, the monosaccharide units making up said oligosaccharide being identical or different, and / or a carbohydrate having the formula (0 6 ⁇ 1 ⁇ ⁇ + 2 ⁇ 5 ⁇ + ⁇ ) ( ⁇ 5 ⁇ 8 ⁇ + 2 ⁇ 4 ⁇ + ⁇ ) where m and n are integers greater than or equal to 1, the monosaccharide units making up said oligosaccharide being identical or different.
- the oligosaccharides are preferably chosen from oligomers of hexoses or pentoses and of hexoses, preferably from hexose oligomers, preferably with a degree of polymerization allowing them to be soluble in the reaction conditions envisaged by the invention. They can be obtained by partial hydrolysis of polysaccharides derived from renewable resources such as starch, inulin, cellulose or hemicellulose, possibly derived from lignocellulosic biomass. For example, the steam explosion of lignocellulosic biomass is a process of partial hydrolysis of cellulose and hemicellulose contained in lignocellulosic biomass producing a flux of oligo- and monosaccharides.
- the preferred oligosaccharides used as filler in the present invention are preferably selected from sucrose, lactose, maltose, isomaltose, inulobiosis, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, taken alone or as a mixture.
- the filler comprising at least one sugar used in the process according to the invention is chosen from cellobiose, fructose and glucose, taken alone or as a mixture.
- said filler is chosen from fructose and glucose, taken alone or as a mixture.
- said feedstock is contacted in the process according to the invention with at least one organic catalyst of the thiourea family in the presence of at least one solvent, said solvent being water or an organic solvent , alone or a mixture, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa.
- the groups R 1 and R 2 can be independently selected from the families of groups. For example, R 1 may be chosen from aromatic groups and R 2 from cycloalkyl groups.
- R1 and R2 are chosen from the same grouping family, R1 and R2 may be identical or different.
- said groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom or not and alkyl, cyclic or non-cyclic groups, said groups R 1 and R 2 may be substituted or not and identical or different and, preferably, said groups R1 and R2 are chosen from aromatic groups that do not comprise heteroatoms.
- said groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom
- said heteroatom is preferably chosen from nitrogen, phosphorus and oxygen.
- said groups R1 and R2 are preferably chosen from pyridine, phosphole and furan groups.
- said groups R 1 and R 2 are chosen from aromatic groups containing no heteroatom, they are advantageously chosen from aromatic groups having from 6 to 14 carbon atoms, fused or otherwise.
- the aromatic groups having from 6 to 14 carbon atoms are chosen from phenyl, naphthyl, phenanthryl and anthryl groups and very preferably, said group is phenyl.
- R 1 and R 2 groups are chosen from linear or branched, cyclic or non-cyclic alkyl groups, they are advantageously chosen from alkyl groups having from 1 to 12 carbon atoms, and preferably having from 1 to 6 atoms. carbons, and cycloalkyl groups having 3 to 8 carbon atoms, and preferably having 5 to 8 carbon atoms.
- the non-cyclic alkyl groups having 1 to 12 carbon atoms, and preferably 1 to 6 linear or branched carbon atoms are chosen from methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl groups.
- the cycloalkyl groups having from 3 to 8 carbon atoms and preferably having from 5 to 8 carbon atoms are chosen from cyclopentyl, cyclohexyl, cycloheptyl and bicyclo [2.2.2] octyl groups.
- said groups R1 and R2 are chosen from alkyl groups comprising at least one heteroatom, cyclic or otherwise, said heteroatom is preferably chosen from nitrogen.
- Said groups are therefore advantageously chosen from alkyl and / or cycloalkyl groups which may comprise at least one tertiary amine function.
- they are advantageously chosen from N, N-dimethylethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine and aza-bicyclo [2.2.2] octyl.
- said groups R1 and R2 are substituted, they are preferably substituted with at least one group chosen from halogens, the groups -CX 3 with X being a halogen and preferably Fluorine, the nitro group - N0 2 , the -NHCOCH 3 group, the alkoxy groups, preferably chosen from methoxy and ethoxy groups and alkyl groups having 1 to 12 carbon atoms, linear or branched, preferably chosen from methyl, ethyl and propyl groups, butyl, pentyl and hexyl.
- said groups R1 and R2 are substituted with at least one group chosen from halogens, the groups -CX 3 with X being a halogen and preferably Fluorine and alkoxy groups, preferably the methoxy group.
- Said groups R1 and R2 may advantageously be mono- or disubstituted.
- thiourea 1 thiourea 2 In the DMSO, the pKa organic catalysts of the thiourea family are between 8 and 22. They are therefore much less acidic than the strong acids conventionally used for the dehydration of sugars, such as sulfuric acid or sulfuric acid. sulfonic acids whose pKa in DMSO are between 0 and 3. These acidity ranking data are from the literature and well known to those skilled in the art, for example reference may be made to the article of FG Bordwell et al. (J. Am Chem Soc, 1991, 13, 8398-8401). Process of transformation
- the process for transforming the feedstock comprising at least one sugar is carried out in a reaction enclosure in the presence of at least one solvent, said solvent being water or an organic solvent, alone or in mixing, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa.
- the process is therefore carried out in a reaction vessel comprising at least one solvent and wherein said feedstock is placed in the presence of at least one organic catalyst of the thiourea family according to the invention.
- the process operates in the presence of at least one solvent, said solvent being water or an organic solvent, alone or as a mixture.
- the organic solvents are advantageously chosen from alcohols such as methanol, ethanol, propanols, butanols, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, esters such as ethyl formate and acetate.
- alcohols such as methanol, ethanol, propanols, butanols, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, esters such as ethyl formate and acetate.
- ethyl lactones such as ⁇ -valerolactone, ⁇ -butyrolactone, cyclic carbonates such as ethylene carbonate, propylene carbonate, nitriles such as acetonitrile, benzonitrile, amides such as dimethylformamide, diethylformamide, / V-methylpyrrolidone, sulfones such as dimethylsulfone, sulfolane, sulfoxides such as DMSO, ammonium salts such as choline chloride, alone or in admixture.
- the process according to the invention operates solely in the presence of organic solvent.
- said process according to the invention operates at a temperature between 50 ° C and 200 ° C and preferably between 50 ° C and 175 ° C, and at a pressure between 0.1 MPa and 8 MPa and preferred way between 0.1 and 5 MPa.
- the method can be operated according to different embodiments.
- the process can advantageously be implemented batchwise or continuously. It can be carried out in a closed reaction chamber or in a semi-open reactor.
- the organic catalyst (s) of the thiourea family are introduced into the reaction chamber in an amount corresponding to a mass ratio of filler / organic catalyst (s) of between 1 and 1000, preferably between 1 and 500. preferably between 1 and 100, preferably between 1 and 50.
- the filler is introduced into the process in an amount corresponding to a mass ratio solvent / filler of between 0.1 and 200, preferably between 0.3 and 100 and more preferably between 1 and 50.
- the hourly mass velocity (mass feed rate / mass of organic catalyst (s)) is between 0.01 hr -1 and 5 hr -1 , preferably between 0 and 02 h "1 and 2 h" 1.
- the catalyst can be easily recovered by precipitation, distillation, extraction or washing. It can also be recovered by passage over an ion exchange resin such as Amberlyst 15 or Amberlyst 31 and recycled after washing of this resin.
- an ion exchange resin such as Amberlyst 15 or Amberlyst 31 and recycled after washing of this resin.
- the products obtained and their mode of analysis The product of the reaction of the transformation process according to the invention is 5-hydroxymethylfurfural.
- reaction medium is analyzed by gas phase chromatography (GC) to determine the content of 5-HMF in the presence of an internal standard and by ion chromatography to determine the conversion of the charge in the presence of an external standard.
- GC gas phase chromatography
- Figure 1 is a graph showing the evolution of the yield of the 5-HMF reaction from a sugar charge under different catalytic conditions.
- glucose and fructose used as feed are commercial and used without further purification.
- 3,5-Trifluoromethylphenyl isothiocyanate, phenyl isothiocyanate, cyclohexylamine and p-anisidine used as precursors for the catalysts according to the invention are commercial and used without further purification.
- N-methylpyrrolidone, NMP in the examples, used as a solvent is commercial and used without further purification.
- the molar yield of thiourea is calculated by the ratio between the number of moles of thiourea obtained and the number of moles of isothiocyanate reagent involved.
- the molar yield of 5-HMF is calculated by the ratio of the number of moles of 5-HMF obtained to the number of moles of sugar filler engaged.
- the catalyst of Example 2 (0.044 g, 0.17 mmol) was added to a solution of fructose (2.0 g, 1 1, 10 mmol) in NMP (20 g).
- the mass ratio filler / catalyst is 45.5.
- the solvent / filler mass ratio is 10.
- the reaction medium is then stirred at 120 ° C. for 6 h.
- the conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography.
- the molar yield of 5-HMF after 6h is 59%.
- the catalyst of Example 1 (0.046 g, 0.12 mmol) was added to a mixture of fructose and glucose 50% w / wt% (2.0 g, 1 1, 10 mmol) in NMP (20 mmol). boy Wut).
- the mass ratio filler / catalyst is 43.5.
- the solvent / filler mass ratio is 10.
- the reaction medium is then stirred at 120 ° C. for 6 h.
- the conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography.
- the molar yield of 5-HMF after 6h is 58%.
- the catalyst of Example 2 (0.044 g, 0.17 mmol) is added to a mixture of fructose and glucose 50% w / wt% (2.0 g, 1 1, 10 mmol) in NMP (20 mg / ml). boy Wut).
- the mass ratio filler / catalyst is 45.5.
- the solvent / filler mass ratio is 10.
- the reaction medium is then stirred at 120 ° C. for 6 h.
- the conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography.
- the molar yield of 5-HMF after 6 hours is 60%. Comparative Example 7 Transformation of fructose without catalyst (non-compliant)
- the kinetics of reaction is faster and the yield of 5-HMF is greater in the case of the use of weakly organic organic catalysts of the thiourea family according to the invention compared to a strong sulfonic acid such as Amberlyst 15, namely about 60% molar yield of 5-HMF in the presence of thiourea against 45% for the acidic resin Amberlyst 15 after 6 hours of reaction.
- a strong sulfonic acid such as Amberlyst 15, namely about 60% molar yield of 5-HMF in the presence of thiourea against 45% for the acidic resin Amberlyst 15 after 6 hours of reaction.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Saccharide Compounds (AREA)
- Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Furan Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1557052A FR3039150B1 (fr) | 2015-07-24 | 2015-07-24 | Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees |
PCT/EP2016/067126 WO2017016924A1 (fr) | 2015-07-24 | 2016-07-19 | Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3325458A1 true EP3325458A1 (fr) | 2018-05-30 |
Family
ID=54545260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16741608.0A Withdrawn EP3325458A1 (fr) | 2015-07-24 | 2016-07-19 | Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees |
Country Status (8)
Country | Link |
---|---|
US (1) | US10239852B2 (fr) |
EP (1) | EP3325458A1 (fr) |
JP (1) | JP2018526342A (fr) |
KR (1) | KR20180034422A (fr) |
CN (1) | CN108137524A (fr) |
BR (1) | BR112018000195A2 (fr) |
FR (1) | FR3039150B1 (fr) |
WO (1) | WO2017016924A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3076554B1 (fr) | 2018-01-10 | 2020-09-18 | Ifp Energies Now | Procede de production de 5-hydroxymethylfurfural |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7393963B2 (en) * | 2004-12-10 | 2008-07-01 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
US9199956B2 (en) * | 2012-01-03 | 2015-12-01 | Council Of Scientific & Industrial Research | Process for chemical conversion of cellulose isolated from aromatic spent biomass to hydroxymethyl furfural |
-
2015
- 2015-07-24 FR FR1557052A patent/FR3039150B1/fr not_active Expired - Fee Related
-
2016
- 2016-07-19 BR BR112018000195A patent/BR112018000195A2/pt not_active IP Right Cessation
- 2016-07-19 EP EP16741608.0A patent/EP3325458A1/fr not_active Withdrawn
- 2016-07-19 US US15/747,343 patent/US10239852B2/en not_active Expired - Fee Related
- 2016-07-19 JP JP2018502816A patent/JP2018526342A/ja active Pending
- 2016-07-19 KR KR1020187002190A patent/KR20180034422A/ko unknown
- 2016-07-19 CN CN201680043452.5A patent/CN108137524A/zh active Pending
- 2016-07-19 WO PCT/EP2016/067126 patent/WO2017016924A1/fr unknown
Also Published As
Publication number | Publication date |
---|---|
KR20180034422A (ko) | 2018-04-04 |
US10239852B2 (en) | 2019-03-26 |
CN108137524A (zh) | 2018-06-08 |
US20180370937A1 (en) | 2018-12-27 |
FR3039150A1 (fr) | 2017-01-27 |
JP2018526342A (ja) | 2018-09-13 |
BR112018000195A2 (pt) | 2018-09-11 |
FR3039150B1 (fr) | 2017-07-28 |
WO2017016924A1 (fr) | 2017-02-02 |
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