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WO2018112776A1 - Process for the preparation of levulinate esters - Google Patents

Process for the preparation of levulinate esters Download PDF

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Publication number
WO2018112776A1
WO2018112776A1 PCT/CN2016/111220 CN2016111220W WO2018112776A1 WO 2018112776 A1 WO2018112776 A1 WO 2018112776A1 CN 2016111220 W CN2016111220 W CN 2016111220W WO 2018112776 A1 WO2018112776 A1 WO 2018112776A1
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WO
WIPO (PCT)
Prior art keywords
alcohol
catalyst
process according
furfuryl alcohol
otf
Prior art date
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PCT/CN2016/111220
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French (fr)
Inventor
Alban CHAPPAZ
Francois Jerome
Karine De Oliveira Vigier
Eric Muller
Jonathan Lai
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Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
Universite de Poitiers
Original Assignee
Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
Universite de Poitiers
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Application filed by Centre National de la Recherche Scientifique CNRS, Rhodia Operations SAS, Universite de Poitiers filed Critical Centre National de la Recherche Scientifique CNRS
Priority to PCT/CN2016/111220 priority Critical patent/WO2018112776A1/en
Priority to US16/472,716 priority patent/US10590060B2/en
Priority to PCT/CN2017/091021 priority patent/WO2018113240A1/en
Priority to EP17883597.1A priority patent/EP3558925B1/en
Priority to PCT/CN2017/091059 priority patent/WO2018113242A1/en
Publication of WO2018112776A1 publication Critical patent/WO2018112776A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

Definitions

  • the present invention relates to a process for the preparation of levulinate esters starting from furfuryl alcohol or from furfural in the presence of specific Lewis acid catalysts.
  • Levulinate esters such as alkyl levulinates
  • the acid-catalyzed ring opening of furfuryl alcohol in alcoholic media is a reaction of high interest yielding alkyl levulinates.
  • alkyl levulinates can be produced from furfuryl alcohol through an elegant 100%atom economical process. Furthermore, furfuryl alcohol is industrially produced in large scale from the manufacture of hemicellulosic biomass. The selectivity of the catalytic production of alkyl levulinates from furfuryl alcohol is rather low due to the dominant acid-catalyzed side polymerization of furfuryl alcohol leading to an important formation of tar.
  • HMF 5-hydroxymethylfurfural
  • WO 2010/102203 discloses a method for the preparation of alkyl levulinates starting from furfuryl alcohol and an alkanol in the presence of a protic acid such as hydrochloric acid or sulfuric acid.
  • a mixture alkyl levulinate/alkanol instead pure alkanol is used as a solvent for dilution of the furfuryl alcohol.
  • the catalysts used in this document are generally not easily recyclable since tarry products are formed when the concentration of furfuryl alcohol is increased.
  • the amount of furfuryl alcohol introduced in the process of said document is relatively low.
  • Yao-Bing Huang et al. discloses the conversion of furfuryl alcohol into alkyl levulinates catalyzed by metal salts comprising halogen or sulfated oxides, such as SnCl 4 catalysts. It has been observed that catalysts based on Sn provide a relatively low productivity. It was thus an object of the present invention to develop a process for converting furfuryl alcohol into levulinate esters with a catalytic system that permits to get very high selectivities and productivities.
  • a first object of the invention is a process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5%by weight, based on the total weight of the alcohols, and said catalyst comprising at least one metal selected from bismuth and gallium.
  • the catalyst further comprises at least one ligand selected from triflate, triflimidate, halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands; preferably the catalyst comprises at least one ligand selected from triflate, triflimidate and halogen.
  • the catalyst is of formula MX 1 X 2 (OTf) . xH 2 O wherein:
  • M represents a metal selected from Bi and Ga
  • X 1 , X 2 , and X 3 represent independently to each other a ligand, preferably selected from triflate, halogen, alkoxy, sulfate, nitrate, carboxylate, -N (SO 2 CF 3 ) 2 , alkyl, aryl and metal ligands, more preferably from triflate and halogen ligands; and OTf represents a triflate;
  • the catalyst is selected from Bi (OTf) 3 and BiCl 2 OTf.
  • the catalyst is in the form of a hydrate.
  • the furfuryl alcohol is present in a quantity ranging from 5 to 50%by weight, preferably from 7 to 40%by weight, more preferably from 10 to 25%by weight, based on the total weight of the alcohols.
  • the furfuryl alcohol is obtained from the reduction of furfural.
  • the process is performed in two steps, the first step being the reduction of furfural into furfuryl alcohol and the second step comprising the addition of the other alcohol for the reaction between furfuryl alcohol and the other alcohol.
  • the catalyst is present in an amount ranging from 0.05 to 20%mol, preferably ranging from 0.1 to 10%mol, more preferably ranging from 0.5 to 5%mol relative to the molar amount of furfuryl alcohol.
  • the molar ratio water/ (metal of the catalyst) ranges from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  • the other alcohol is selected from alcohols of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  • R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  • R comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
  • the other alcohol is in the form of a solution comprising only one alcohol or at least two different alcohols.
  • the process comprises the following steps:
  • reaction mixture comprising all or part of the catalyst, all or part of the water, and all or part of the other alcohol
  • the process further comprises a step of heating the reaction mixture obtained at the end of step a) to a temperature ranging from 80°C to 200°C, preferably from 100°C to 180°C, more preferably from 115°C to 165°C.
  • the process of the present invention permits to works with highly concentrated furfuryl alcohol solutions, as high as 5%or 10%by weight or even as high as 50%by weight of furfuryl alcohol in the reaction medium.
  • the process of the present invention allows obtaining a high yield, such as 94%yield of levulinate esters, as well as a high productivity.
  • the process of the present invention allows reducing the amount of by-products that can be formed during the reaction.
  • the produced levulinate esters are stable and can be conveniently recovered from the reaction medium, for example by distillation, and the catalyst can be recycled for a further conversion reaction.
  • the present invention is directed to a process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5%by weight, based on the weight of all alcohol, and said catalyst comprising at least one metal selected from bismuth and gallium.
  • the catalyst comprises at least one metal selected from bismuth.
  • the catalyst further comprises at least one ligand selected from triflate (OTf) , triflimidate (NTf 2 ) , halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands; preferably the catalyst comprises at least one ligand selected from triflate (OTf) , triflimidate (NTf 2 ) and halogen; more preferably the catalyst comprises at least one triflate ligand.
  • OTf triflate
  • NTf 2 triflimidate
  • halogen alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands
  • the catalyst can be in a dimeric form, including for example a Bi-Bi or Bi-Pd bound.
  • halogen ligands mention may be made of chloride, bromide, fluoride or iodide ligands, and preferably chloride ligands.
  • alkoxy ligands of formula –OR’ wherein R’ represents an alkyl radical comprising from 1 to 24 carbon atoms or an alkenyl radical comprising from 2 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic and can optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain.
  • the alkoxy ligand is selected from methoxy, ethoxy, propoxy, butoxy ligands.
  • Tf represents a triflyl group also named trifluoromethanesulfonyl (CF 3 SO 3 -) . Therefore, NTf 2 represents the triflimidate radical-N (SO 2 CF 3 ) 2 .
  • alkyl ligands mention may be made of alkyl or alkenyl radicals having from 1 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic.
  • Alkyl ligands may optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain.
  • the alkyl ligand is selected from methyl, ethyl, propyl, butyl, pentyl, cyclopentadienyl ligands.
  • aryl radicals having from 6 to 24 carbon atoms
  • said aryl radical can be substituted by one or more substituents, such as alkyl or alkenyl having from 1 to 12 carbon atoms, said aryl radical can be bicyclic.
  • the aryl radical is selected from phenyl, benzyl, naphthenyl.
  • carboxylate ligands include carboxylate of formula-OCOR” wherein R” represents an alkyl radical comprising from 1 to 24 carbon atoms or an alkenyl radical comprising from 2 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic and can optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain.
  • carboxylate ligands are selected from methanoate, acetate, propanoate, butanoate ligands.
  • the catalyst is selected from catalysts comprising at least one metal M and at least one ligand OTf wherein
  • - M is selected from bismuth and gallium, preferably from bismuth;
  • OTf is a triflate, also named trifluoromethanesulfonate (CF 3 SO 3 -) .
  • the catalyst may further comprise at least one organic ligand of type “L” , i.e. a neutral ligand that donate two electrons to the metal, the bond between these ligands and the metal is a coordinate bond.
  • organic ligand of type L mention may be made of phosphine ligands, in particular diphosphine ligands, such as 1, 2-bis (diphenylphosphino) ethane (DPPE) or diamine ligands, in particular bipyridine.
  • DPPE 1, 2-bis (diphenylphosphino) ethane
  • the presence of this kind of organic ligand may improve the selectivity towards levulinate esters and may allow introducing a higher amount of furfuryl alcohol in the reaction medium.
  • Ligands may also improve the solubility of the catalyst, the stability of the catalyst or the kinetics of the reaction.
  • the catalyst is selected from Bi (OTf) 3 , Bi (NTf 2 ) 3 , Ga (OTf) 3 , and BiCl 2 ( OTf) , more preferably from Bi (OTf) 3 and BiCl 2 ( OTf) .
  • Catalysts that can be used in the process of the invention are commercially available or may be synthesized by processes well known for the skilled person.
  • the catalyst used in the process of the invention may be unsupported (homogeneous catalysis) or supported (heterogeneous catalysis) .
  • a supported catalyst facilitates the process and the recovery of the catalyst at the end of the reaction and does not change the catalysis cycle or the role of the catalyst during the reaction.
  • the support may be any support well known by the skilled person in the art, such as silica, alumina, zeolites or titanium-based solids, or metal oxides such as bismuth oxides, gallium oxides, tin oxides, aluminum oxides or iron oxides.
  • polystyrene resins acid oxides, such as niobium oxides, zeolites or sulfonated charcoals.
  • the catalyst may also be immobilized in a liquid phase.
  • one or more other catalysts different from the (Lewis acid) catalysts defined above may be also present in the reaction medium.
  • said other catalysts are selected from Bronsted acids, in particular strong Bronsted acids, such as triflic acid, perfluorosulfonic acid or Nafion is well known by the skilled person and can be defined as a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.
  • the catalyst (s) is (are) present in an amount ranging from 0.05 to 5%mol, preferably ranging from 0.1 to 3%mol, more preferably ranging from 0.5 to 2%mol based on the molar amount of furfuryl alcohol.
  • the reaction takes place in the presence of a catalytic amount of water.
  • the reaction takes place with a molar ratio water/metal M (metal of the catalyst) ranging from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  • Water may for example be introduced into the reaction medium by an addition of (external) water or through the use of a catalyst in the form of a hydrate.
  • the catalyst can also be in an anhydrous form.
  • the catalyst comprises triflate ligands
  • the catalyst will be preferably in an anhydrous form.
  • the catalyst is in an anhydrous form, when the catalyst is of formula MX 1 X 2 (OTf) . xH 2 O defined above, x is equal to zero.
  • reaction medium By “reaction medium” , it is to be understood the medium wherein the reaction takes place.
  • the reaction medium comprises the furfuryl alcohol, at least one other alcohol (different from furfuryl alcohol) , the catalyst (s) and water.
  • the reaction medium may further optionally comprise additional additives such as solvents different from the reactants of the conversion reaction.
  • the reaction medium is substantially free, or even totally free, of organic solvents different from the reactants (in particular different from the other alcohol reacting with the furfuryl alcohol) and the catalyst of the conversion reaction.
  • the conversion reaction of furfuryl alcohol to levulinate ester may be represented by the following equation:
  • ROH represents the other alcohol which reacts with the furfuryl alcohol.
  • furfuryl alcohol is obtained from the reduction of furfural.
  • the reduction of furfural may be represented by the following equation:
  • the reduction of furfural into furfuryl alcohol may be performed in the presence of hydrogen (or by hydrogen transfer) and a catalyst suitable for performing said reaction.
  • a catalyst suitable for performing said reaction are well known for the skilled person, among those catalysts for the reduction of furfural, mention may be made as an example of copper based catalysts.
  • the reduction may be performed in the presence of a solvent, said solvent may be for example the other alcohol which will be used in the reaction of conversion of furfuryl alcohol into levulinate ester.
  • Furfuryl alcohol and furfural may be commercially available.
  • Furfuryl alcohol may be of natural or synthetic origin.
  • the furfuryl alcohol may be purified before introduction into the reaction medium, by purification methods well known for the skilled person.
  • the furfuryl alcohol is present in a quantity of at least 5%by weight, preferably in an amount ranging from 5 to 50%by weight, more preferably from 7 to 40%by weight, even more preferably from 10 to 25%by weight, based on the total weight of all the alcohols present in the reaction medium.
  • all the alcohols refers to the furfuryl alcohol and the other alcohol (s) used in the reaction medium for the conversion of furfuryl alcohol into levulinate ester (s) .
  • the other alcohol which reacts with furfuryl alcohol may be selected from aliphatic alcohols or aromatic alcohols, preferably from aliphatic alcohols.
  • An aliphatic alcohol is a non-aromatic alcohol.
  • An aromatic alcohol comprises a OH function directly linked to an aryl ring.
  • An example of an aromatic alcohol is a phenol.
  • the other alcohol may be a monol or a polyol comprising for example from 2 to 5 OH functions or from 2 to 4 OH functions or from 2 to 3 OH functions, preferably the other alcohol is a monol, i.e. an alcohol comprising only one OH function.
  • the other alcohol is introduced through an alcoholic solution that may comprise one or several different alcohols, preferably the alcoholic solution comprises only one alcohol.
  • the alcoholic solution comprises a mixture of different alcohols
  • the levulinate esters obtained at the end of the reaction may be a mixture of different levulinate esters.
  • the other alcohol is selected from primary alcohols, i.e. compounds comprising at least the following radical: -CH 2 -OH.
  • the other alcohol is of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  • hydrocarbyl radical a radical comprising carbon atoms and hydrogen atoms, and optionally heteroatoms such as oxygen, nitrogen or sulfur. According to an embodiment, the hydrocarbyl radicals consist in carbon atoms and hydrogen atoms.
  • the other alcohol comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
  • the other alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol.
  • the other alcohol may be introduced in a stoichiometric amount in relation to the furfuryl alcohol or in excess, in particular if the other alcohol is also used as a solvent for example for preparing the catalyst in the reaction medium.
  • the reaction is performed at a temperature ranging from 80°C to 200°C, preferably from 100°C to 180°C, more preferably from 115°C to 165°C.
  • the reaction is generally performed at a pressure such that the reactants remain in a liquid state.
  • the reaction is performed at a pressure ranging from 0.5 to 5 bars, preferably from 1 to 3 bars, more preferably at atmospheric pressure.
  • the process of the invention comprises the following successive steps:
  • reaction mixture comprising all or part of the catalyst, all or part of the water, and all or part of the other alcohol
  • the reaction mixture obtained in step a) comprises all of the catalyst used in the reaction and/or all the water used in the reaction.
  • the reaction mixture, before step b) is heating to a temperature ranging from 80°C to 200°C, preferably from 100°C to 180°C, more preferably from 115°C to 165°C. This heating step may help for the preparation of the catalyst.
  • water is added into the reaction mixture before step b) and before the heating of said reaction mixture if any.
  • all the furfuryl alcohol is introduced during step b) .
  • furfuryl alcohol is mixed with the remaining part of the other alcohol before its introduction into the reaction mixture obtained in step a) .
  • the process of the reaction may be a batch process or a continuous process.
  • furfuryl alcohol may be sequentially or continuously introduced into the reaction mixture obtained at step a) .
  • the sequentially or continuously addition allows improving the selectivity towards levulinate esters and allows loading a higher amount of furfuryl alcohol into the reaction medium.
  • levulinate esters and other products can be recovered and isolated, for example by distillation.
  • the catalyst may be recycled for performing another reaction and another process.
  • reaction can be followed by gas chromatography or by HPLC (high performance liquid chromatography) or also by 1 H or 13 C NMR (Nuclear magnetic resonance) , according to well-known methods for the skilled person.
  • the process of the invention generally leads to a yield in levulinate ester of at least 40%mol, preferably at least 45%mol, more preferably at least 50%mol, even more preferably at least 55%mol, based on moles of furfuryl alcohol in the reaction medium.
  • Samples (0.1 g) were taken from the reaction mixture after different times and quenched with 1.1 g of isopropanol. An aliquot of the sample was filtered on Nylon Acrodisc 0.2 ⁇ m and analysed by GC without any further treatments.
  • the catalyst has been added in a proportion such that for each experiment, the catalyst represents 1%mol.
  • Furfuryl alcohol is present in an amount of 10%wt and the catalyst is present in an amount of 1%mol.
  • the yield (or selectivity) in butyl levulinate corresponds to the amount of butyl levulinate expressed in molar percentage based on the molar amount of furfuryl alcohol introduced into the reaction medium.
  • the productivity is the mol of butyl levulinate per mol of catalyst and per hour.
  • the Lewis acid catalysts based on Bi and Ga allow the production of butyl levulinates with a yield improved as compared to the acid catalysts based on In or Sc.
  • Previous works were limited to a furfuryl alcohol content of only 2 wt%solutions to achieve similar results.
  • the possibility to use a solution containing a higher amount of furfuryl alcohol is industrially more interesting in terms of operating costs.
  • the catalysts Bi (OTf) 3 and Ga (OTf) 3 based on Bi and Ga allow the production of butyl levulinates with a productivity improved as compared to catalysts based on Sn or Al.
  • the reaction can be performed with a relatively high amount of furfuryl alcohol. Indeed, with an amount of 30%by weight of furfuryl alcohol, the yield is still of 92%.

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Abstract

The present invention is directed to a process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5％ by weight, based on the total weight of the alcohols, and said catalyst comprising at least one metal selected from bismuth and gallium.

Description

PROCESS FOR THE PREPARATION OF LEVULINATE ESTERS TECHNICAL FIELD
The present invention relates to a process for the preparation of levulinate esters starting from furfuryl alcohol or from furfural in the presence of specific Lewis acid catalysts.
BACKGROUND ART
Levulinate esters, such as alkyl levulinates, are industrially relevant solvents or intermediates for the manufacture of pesticides, plasticizers, polymers or fuel additives. The acid-catalyzed ring opening of furfuryl alcohol in alcoholic media is a reaction of high interest yielding alkyl levulinates.
In contrast to the classical route involving 5-hydroxymethylfurfural (HMF) as a starting reagent or intermediate, alkyl levulinates can be produced from furfuryl alcohol through an elegant 100％atom economical process. Furthermore, furfuryl alcohol is industrially produced in large scale from the manufacture of hemicellulosic biomass. The selectivity of the catalytic production of alkyl levulinates from furfuryl alcohol is rather low due to the dominant acid-catalyzed side polymerization of furfuryl alcohol leading to an important formation of tar.
Document WO 2010/102203 discloses a method for the preparation of alkyl levulinates starting from furfuryl alcohol and an alkanol in the presence of a protic acid such as hydrochloric acid or sulfuric acid. A mixture alkyl levulinate/alkanol instead pure alkanol is used as a solvent for dilution of the furfuryl alcohol. The catalysts used in this document are generally not easily recyclable since tarry products are formed when the concentration of furfuryl alcohol is increased.
J.R. Kean and A.E. Graham, Catalysis Communications 59 (2015) 175-179, discloses a method for synthesizing alkyl levulinates from furfuryl alcohols using Indium (III) triflate catalysts. The amount of furfuryl alcohol introduced in the process of said document is relatively low.
To inhibit side polymerization reactions, previously reported homogeneous or heterogeneous catalytic processes are conducted under diluted conditions (furfuryl alcohol loading of 2-3 wt％) .
Yao-Bing Huang et al. (Green Chem. 2016, 18, 1516-1523) discloses the conversion of furfuryl alcohol into alkyl levulinates catalyzed by metal salts comprising halogen or sulfated oxides, such as SnCl4 catalysts. It has been observed that catalysts based on Sn provide a relatively low productivity. It was thus an object of the present invention to develop a process for converting furfuryl alcohol into levulinate esters with a catalytic system that permits to get very high selectivities and productivities.
SUMMARY OF THE INVENTION
A first object of the invention is a process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5％by weight, based on the total weight of the alcohols, and said catalyst comprising at least one metal selected from bismuth and gallium.
According to an embodiment of the invention, the catalyst further comprises at least one ligand selected from triflate, triflimidate, halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands； preferably the catalyst comprises at least one ligand selected from triflate, triflimidate and halogen.
Preferably, the catalyst is of formula MX1X2 (OTf) . xH2O wherein:
M represents a metal selected from Bi and Ga,
X1, X2, and X3 represent independently to each other a ligand, preferably selected from triflate, halogen, alkoxy, sulfate, nitrate, carboxylate, -N (SO2CF3) 2, alkyl, aryl and metal ligands, more preferably from triflate and halogen ligands； and OTf represents a triflate；
x ranging from 0 to 10.
According to an embodiment, the catalyst is selected from Bi (OTf) 3 and BiCl2OTf.
According to an embodiment of the invention, the catalyst is in the form of a hydrate.
According to an embodiment of the invention, the furfuryl alcohol is present in a quantity ranging from 5 to 50％by weight, preferably from 7 to 40％by weight, more preferably from 10 to 25％by weight, based on the total weight of the alcohols.
According to an embodiment, the furfuryl alcohol is obtained from the reduction of furfural. Preferably, the process is performed in two steps, the first step being the  reduction of furfural into furfuryl alcohol and the second step comprising the addition of the other alcohol for the reaction between furfuryl alcohol and the other alcohol.
According to an embodiment of the invention, the catalyst is present in an amount ranging from 0.05 to 20％mol, preferably ranging from 0.1 to 10％mol, more preferably ranging from 0.5 to 5％mol relative to the molar amount of furfuryl alcohol.
According to an embodiment of the invention, the molar ratio water/ (metal of the catalyst) ranges from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
According to an embodiment of the invention, the other alcohol is selected from alcohols of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals. Preferably, R comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
According to an embodiment of the invention, the other alcohol is in the form of a solution comprising only one alcohol or at least two different alcohols.
According to an embodiment of the invention, the process comprises the following steps:
a) providing a reaction mixture comprising all or part of the catalyst, all or part of the water, and all or part of the other alcohol,
b) introducing all or part of the furfuryl alcohol and optionally the remaining part of the other alcohol into the reaction mixture in order to synthesize the levulinate esters,
c) recovering the levulinate esters.
Preferably, the process further comprises a step of heating the reaction mixture obtained at the end of step a) to a temperature ranging from 80℃ to 200℃, preferably from 100℃ to 180℃, more preferably from 115℃ to 165℃.
The process of the present invention permits to works with highly concentrated furfuryl alcohol solutions, as high as 5％or 10％by weight or even as high as 50％by weight of furfuryl alcohol in the reaction medium.
The process of the present invention allows obtaining a high yield, such as 94％yield of levulinate esters, as well as a high productivity.
The process of the present invention allows reducing the amount of by-products that can be formed during the reaction.
The produced levulinate esters are stable and can be conveniently recovered from the reaction medium, for example by distillation, and the catalyst can be recycled for a further conversion reaction.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5％by weight, based on the weight of all alcohol, and said catalyst comprising at least one metal selected from bismuth and gallium.
Preferably, the catalyst comprises at least one metal selected from bismuth.
According to an embodiment of the invention, the catalyst further comprises at least one ligand selected from triflate (OTf) , triflimidate (NTf2) , halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands； preferably the catalyst comprises at least one ligand selected from triflate (OTf) , triflimidate (NTf2) and halogen； more preferably the catalyst comprises at least one triflate ligand.
Among metal ligands, mention may be made of Re, Pd, Fe, Ga, Sm, Co, Bi. Indeed, the catalyst can be in a dimeric form, including for example a Bi-Bi or Bi-Pd bound.
Among halogen ligands, mention may be made of chloride, bromide, fluoride or iodide ligands, and preferably chloride ligands.
Among alkoxy ligands, mention may be made of alkoxy ligands of formula –OR’ wherein R’ represents an alkyl radical comprising from 1 to 24 carbon atoms or an alkenyl radical comprising from 2 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic and can optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain. According to a specific embodiment, the alkoxy ligand is selected from methoxy, ethoxy, propoxy, butoxy ligands.
As is well known for the skilled person, “Tf” represents a triflyl group also named trifluoromethanesulfonyl (CF3SO3-) . Therefore, NTf2 represents the triflimidate radical-N (SO2CF3) 2.
Among alkyl ligands, mention may be made of alkyl or alkenyl radicals having from 1 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic. Alkyl ligands may optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain. According to a specific embodiment, the alkyl ligand is selected from methyl, ethyl, propyl, butyl, pentyl, cyclopentadienyl ligands.
Among aryl ligands, mention may be made of aryl radicals having from 6 to 24 carbon atoms, said aryl radical can be substituted by one or more substituents, such as alkyl or alkenyl having from 1 to 12 carbon atoms, said aryl radical can be bicyclic. According to a specific embodiment, the aryl radical is selected from phenyl, benzyl, naphthenyl.
Among carboxylate ligands, mention may be made of carboxylate of formula-OCOR” wherein R” represents an alkyl radical comprising from 1 to 24 carbon atoms or an alkenyl radical comprising from 2 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic and can optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain. According to a specific embodiment, carboxylate ligands are selected from methanoate, acetate, propanoate, butanoate ligands.
According to an embodiment of the invention, the catalyst is selected from catalysts comprising at least one metal M and at least one ligand OTf wherein
- M is selected from bismuth and gallium, preferably from bismuth；
- OTf is a triflate, also named trifluoromethanesulfonate (CF3SO3-) .
According to an embodiment of the invention, the catalyst may further comprise at least one organic ligand of type “L” , i.e. a neutral ligand that donate two electrons to the metal, the bond between these ligands and the metal is a coordinate bond. As an example of organic ligand of type L, mention may be made of phosphine ligands, in particular diphosphine ligands, such as 1, 2-bis (diphenylphosphino) ethane (DPPE) or diamine ligands, in particular bipyridine. The presence of this kind of organic ligand may improve the selectivity towards levulinate esters and may allow introducing a higher amount of furfuryl alcohol in the reaction medium. Ligands may also improve the solubility of the catalyst, the stability of the catalyst or the kinetics of the reaction.
According to an embodiment, the catalyst is selected from Bi (OTf) 3, Bi (NTf2) 3, Ga (OTf) 3, and BiCl2 (OTf) , more preferably from Bi (OTf) 3 and BiCl2 (OTf) .
Catalysts that can be used in the process of the invention are commercially available or may be synthesized by processes well known for the skilled person.
The catalyst used in the process of the invention may be unsupported (homogeneous catalysis) or supported (heterogeneous catalysis) . A supported catalyst facilitates the process and the recovery of the catalyst at the end of the reaction and does not change the catalysis cycle or the role of the catalyst during the reaction. The support may be any support well known by the skilled person in the art, such as silica, alumina, zeolites or titanium-based solids, or metal oxides such as bismuth oxides, gallium oxides, tin oxides, aluminum oxides or iron oxides. Among supports, mention may also be made of polystyrene resins, acid oxides, such as niobium oxides, zeolites or sulfonated charcoals.
The catalyst may also be immobilized in a liquid phase.
According to an embodiment, one or more other catalysts, different from the (Lewis acid) catalysts defined above may be also present in the reaction medium. Preferably, said other catalysts are selected from Bronsted acids, in particular strong Bronsted acids, such as triflic acid, perfluorosulfonic acid
Figure PCTCN2016111220-appb-000001
or
Figure PCTCN2016111220-appb-000002
Nafion is well known by the skilled person and can be defined as a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.
The combination of said Bronsted acid with the Lewis acid catalyst defined above and used in the process of the invention provides a synergistic effect for improving the selectivity towards the levulinate esters.
According to an embodiment, the catalyst (s) is (are) present in an amount ranging from 0.05 to 5％mol, preferably ranging from 0.1 to 3％mol, more preferably ranging from 0.5 to 2％mol based on the molar amount of furfuryl alcohol.
The reaction takes place in the presence of a catalytic amount of water. According to an embodiment, the reaction takes place with a molar ratio water/metal M (metal of the catalyst) ranging from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
Water may for example be introduced into the reaction medium by an addition of (external) water or through the use of a catalyst in the form of a hydrate.
The catalyst can also be in an anhydrous form. When the catalyst comprises triflate ligands, the catalyst will be preferably in an anhydrous form. When the catalyst is in an anhydrous form, when the catalyst is of formula MX1X2 (OTf) . xH2O defined above, x is equal to zero.
By “reaction medium” , it is to be understood the medium wherein the reaction takes place. The reaction medium comprises the furfuryl alcohol, at least one other alcohol (different from furfuryl alcohol) , the catalyst (s) and water. The reaction medium may further optionally comprise additional additives such as solvents different from the reactants of the conversion reaction.
According to an embodiment, the reaction medium is substantially free, or even totally free, of organic solvents different from the reactants (in particular different from the other alcohol reacting with the furfuryl alcohol) and the catalyst of the conversion reaction.
The conversion reaction of furfuryl alcohol to levulinate ester may be represented by the following equation:
Figure PCTCN2016111220-appb-000003
wherein ROH represents the other alcohol which reacts with the furfuryl alcohol.
According to an embodiment, furfuryl alcohol is obtained from the reduction of furfural. The reduction of furfural may be represented by the following equation:
Figure PCTCN2016111220-appb-000004
The reduction of furfural into furfuryl alcohol may be performed in the presence of hydrogen (or by hydrogen transfer) and a catalyst suitable for performing said reaction. Such catalysts are well known for the skilled person, among those catalysts for the reduction of furfural, mention may be made as an example of copper based catalysts. The reduction may be performed in the presence of a solvent, said solvent may be for example the other alcohol which will be used in the reaction of conversion of furfuryl alcohol into levulinate ester.
Furfuryl alcohol and furfural may be commercially available. Furfuryl alcohol may be of natural or synthetic origin.
According to an embodiment, the furfuryl alcohol may be purified before introduction into the reaction medium, by purification methods well known for the skilled person.
The furfuryl alcohol is present in a quantity of at least 5％by weight, preferably in an amount ranging from 5 to 50％by weight, more preferably from 7 to 40％by weight, even more preferably from 10 to 25％by weight, based on the total weight of all the alcohols present in the reaction medium.
The expression “all the alcohols” refers to the furfuryl alcohol and the other alcohol (s) used in the reaction medium for the conversion of furfuryl alcohol into levulinate ester (s) .
The other alcohol which reacts with furfuryl alcohol may be selected from aliphatic alcohols or aromatic alcohols, preferably from aliphatic alcohols.
An aliphatic alcohol is a non-aromatic alcohol. An aromatic alcohol comprises a OH function directly linked to an aryl ring. An example of an aromatic alcohol is a phenol.
The other alcohol may be a monol or a polyol comprising for example from 2 to 5 OH functions or from 2 to 4 OH functions or from 2 to 3 OH functions, preferably the other alcohol is a monol, i.e. an alcohol comprising only one OH function.
According to an embodiment, the other alcohol is introduced through an alcoholic solution that may comprise one or several different alcohols, preferably the alcoholic solution comprises only one alcohol. In the case wherein the alcoholic solution comprises a mixture of different alcohols, the levulinate esters obtained at the end of the reaction may be a mixture of different levulinate esters.
According to an embodiment, the other alcohol is selected from primary alcohols, i.e. compounds comprising at least the following radical: -CH2-OH.
According to an embodiment, the other alcohol is of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
By “hydrocarbyl radical” , it is to be understood a radical comprising carbon atoms and hydrogen atoms, and optionally heteroatoms such as oxygen, nitrogen or sulfur. According to an embodiment, the hydrocarbyl radicals consist in carbon atoms and hydrogen atoms.
According to an embodiment, the other alcohol comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
According to an embodiment, the other alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol.
The other alcohol may be introduced in a stoichiometric amount in relation to the furfuryl alcohol or in excess, in particular if the other alcohol is also used as a solvent for example for preparing the catalyst in the reaction medium.
According to an embodiment, the reaction is performed at a temperature ranging from 80℃ to 200℃, preferably from 100℃ to 180℃, more preferably from 115℃ to 165℃.
The reaction is generally performed at a pressure such that the reactants remain in a liquid state. Preferably, the reaction is performed at a pressure ranging from 0.5 to 5 bars, preferably from 1 to 3 bars, more preferably at atmospheric pressure.
According to an embodiment, the process of the invention comprises the following successive steps:
a) providing a reaction mixture comprising all or part of the catalyst, all or part of the water, and all or part of the other alcohol,
b) introducing all or part of the furfuryl alcohol and optionally the remaining part of the other alcohol into the reaction mixture in order to synthesize the levulinate esters,
c) recovering the levulinate esters.
According to an embodiment of the invention, the reaction mixture obtained in step a) comprises all of the catalyst used in the reaction and/or all the water used in the reaction.
According to an embodiment of the invention, the reaction mixture, before step b) , is heating to a temperature ranging from 80℃ to 200℃, preferably from 100℃ to 180℃, more preferably from 115℃ to 165℃. This heating step may help for the preparation of the catalyst.
According to an embodiment of the invention, water is added into the reaction mixture before step b) and before the heating of said reaction mixture if any.
According to an embodiment of the invention, all the furfuryl alcohol is introduced during step b) .
According to an embodiment, furfuryl alcohol is mixed with the remaining part of the other alcohol before its introduction into the reaction mixture obtained in step a) .
The process of the reaction may be a batch process or a continuous process. Indeed, furfuryl alcohol may be sequentially or continuously introduced into the reaction mixture obtained at step a) . The sequentially or continuously addition allows improving the selectivity towards levulinate esters and allows loading a higher amount of furfuryl alcohol into the reaction medium.
At the end of the reaction, levulinate esters and other products can be recovered and isolated, for example by distillation.
The catalyst may be recycled for performing another reaction and another process.
The reaction can be followed by gas chromatography or by HPLC (high performance liquid chromatography) or also by 1H or 13C NMR (Nuclear magnetic resonance) , according to well-known methods for the skilled person.
The process of the invention generally leads to a yield in levulinate ester of at least 40％mol, preferably at least 45％mol, more preferably at least 50％mol, even more preferably at least 55％mol, based on moles of furfuryl alcohol in the reaction medium.
The following examples show the effectiveness of the process and further explain the process of the present invention.
EXAMPLES
General description of the process of the present examples
In a typical experiment, a 100 mL glass reactor containing water (0.10 mmol, 1 eq. as compared to the metal of the catalyst) , the catalyst (0.10 mmol, 1mol％) and 5.78 g of butanol were stirred and heated to reflux (118℃) . Then a solution containing 1.0 g of furfuryl alcohol (10.2 mmol) and 3.0 g of butanol (40.4 mmol) was introduced in the reactor.
Samples (0.1 g) were taken from the reaction mixture after different times and quenched with 1.1 g of isopropanol. An aliquot of the sample was filtered on Nylon Acrodisc 0.2 μm and analysed by GC without any further treatments.
The catalyst has been added in a proportion such that for each experiment, the catalyst represents 1％mol.
Example 1: Comparison of different catalysts
Furfuryl alcohol is present in an amount of 10％wt and the catalyst is present in an amount of 1％mol.
For each experiment, 1 equivalent of water, as compared to the metal M of the catalyst, has been added with the catalyst before heating.
The yield (or selectivity) in butyl levulinate corresponds to the amount of butyl levulinate expressed in molar percentage based on the molar amount of furfuryl alcohol introduced into the reaction medium.
The productivity is the mol of butyl levulinate per mol of catalyst and per hour.
In the tables below, the following abbreviations have been used:
BL ＝ butyl levulinate
cata ＝ catalyst
FFA ＝ furfuryl alcohol
Table 1: Characteristics of the process for different catalysts
Figure PCTCN2016111220-appb-000005
As illustrated in table 1, the Lewis acid catalysts based on Bi and Ga allow the production of butyl levulinates with a yield improved as compared to the acid catalysts based on In or Sc. Previous works were limited to a furfuryl alcohol content of only 2 wt％solutions to achieve similar results. The possibility to use a solution containing a higher amount of furfuryl alcohol is industrially more interesting in terms of operating costs.
Additionally, the catalysts Bi (OTf) 3 and Ga (OTf) 3 based on Bi and Ga allow the production of butyl levulinates with a productivity improved as compared to catalysts based on Sn or Al.
Example 2: Process with different amounts of furfuryl alcohol
The same procedure has been conducted with Bi (OTf) 3 as catalyst but with different amounts of fulfuryl alcohol following two protocols, one in batch wherein all the FAA is added at the beginning, and the second wherein the FAA is added dropwise over 2h. The characteristics of the process are indicated in table 2 below.
For each experiment, 1 equivalent of water, as compared to the catalyst, has been added.
Table 2: Characteristic of the process for different amounts of furfuryl alcohol
Figure PCTCN2016111220-appb-000006
As illustrated in table 2, the reaction can be performed with a relatively high amount of furfuryl alcohol. Indeed, with an amount of 30％by weight of furfuryl alcohol, the yield is still of 92％.

Claims (15)

  1. A process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5％ by weight, based on the total weight of the alcohols, and said catalyst comprising at least one metal selected from bismuth and gallium.
  2. The process according to claim 1, wherein the catalyst further comprises at least one ligand selected from triflate, triflimidate, halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands, preferably selected from triflate, triflimidate and halogen.
  3. The process according to claim 1 or 2, wherein the catalyst is of formula MX1X2 (OTf) . xH2O wherein:
    M represents a metal selected from Bi and Ga,
    X1, X2, and X3 represent independently to each other a ligand, preferably selected from triflate, halogen, alkoxy, sulfate, nitrate, carboxylate, -N (SO2CF3) 2, alkyl, aryl and metal ligands, more preferably from triflate and halogen ligands；
    OTf represents a triflate； and
    x ranges from 0 to 10.
  4. The process according to any one of claims 1 to 3, wherein the catalyst is selected from Bi (OTf) 3 and BiCl2OTf, preferably from Bi (OTf) 3.
  5. The process according to any one of claims 1 to 4, wherein the catalyst is in the form of a hydrate.
  6. The process according to any one of claim 1 or 5, wherein furfuryl alcohol is present in a quantity ranging from 5 to 50％ by weight, preferably from 7 to 40％ by weight, more preferably from 10 to 25％ by weight, based on the total weight of the alcohols.
  7. The process according to any one of claims 1 to 6, wherein the furfuryl alcohol is obtained from the reduction of furfural.
  8. The process according to claim 7, wherein said process is performed in two steps, the first step being the reduction of furfural into furfuryl alcohol and the second step comprising the addition of the other alcohol for the reaction between furfuryl alcohol and the other alcohol.
  9. The process according to any one of claims 1 to 8, wherein the catalyst is present in an amount ranging from 0.05 to 20％mol, preferably ranging from 0.1 to 10％mol, more preferably ranging from 0.5 to 5％mol relative to the molar amount of furfuryl alcohol.
  10. The process according to any one of claims 1 to 9, wherein the molar ratio water/metal of the catalyst ranges from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  11. The process according to any one of claims 1 to 10, wherein the other alcohol is selected from alcohols of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  12. The process according to claim 11, wherein R comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
  13. The process according to any one of claims 1 to 12, wherein the other alcohol is in the form of a solution comprising only one alcohol or at least two different alcohols.
  14. The process according to any one of claims 1 to 13, comprising the following steps:
    a) providing a reaction mixture comprising all or part of the catalyst, all or part of the water, and all or part of the other alcohol,
    b) introducing all or part of the furfuryl alcohol and optionally the remaining part of the other alcohol into the reaction mixture in order to synthesize the levulinate esters,
    c) recovering the levulinate esters.
  15. The process according to claim 14, further comprising a step of heating the reaction mixture obtained at the end of step a) to a temperature ranging from 80℃ to 200℃, preferably from 100℃ to 180℃, more preferably from 115℃ to 165℃.
PCT/CN2016/111220 2016-12-21 2016-12-21 Process for the preparation of levulinate esters Ceased WO2018112776A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/CN2016/111220 WO2018112776A1 (en) 2016-12-21 2016-12-21 Process for the preparation of levulinate esters
US16/472,716 US10590060B2 (en) 2016-12-21 2017-06-30 Process for the preparation of levulinate esters
PCT/CN2017/091021 WO2018113240A1 (en) 2016-12-21 2017-06-30 Process for the preparation of levulinate esters
EP17883597.1A EP3558925B1 (en) 2016-12-21 2017-06-30 Process for the preparation of levulinate esters
PCT/CN2017/091059 WO2018113242A1 (en) 2016-12-21 2017-06-30 Process for preparation of levulinate esters

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Publication number Priority date Publication date Assignee Title
CN113181932A (en) * 2021-05-11 2021-07-30 昆明理工大学 Bifunctional biomass carbon-based catalyst and application thereof in catalytic preparation of levulinate
EP3954676A1 (en) * 2020-08-14 2022-02-16 GFBiochemicals IP Assets B.V. A process for the conversion of furfuryl alcohol into a levulinate ester
WO2023094511A1 (en) 2021-11-26 2023-06-01 Basf Se Process for forming alkyl ester of levulinic acid

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WO2007023173A1 (en) * 2005-08-26 2007-03-01 Shell Internationale Research Maatschappij B.V. A process for the conversion of furfuryl alcohol into levulinic acid or alkyl levulinate
CN105646227A (en) * 2014-11-14 2016-06-08 上海交通大学 A method of preparing levulinates by utilizing furfuryl alcohol

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WO2007023173A1 (en) * 2005-08-26 2007-03-01 Shell Internationale Research Maatschappij B.V. A process for the conversion of furfuryl alcohol into levulinic acid or alkyl levulinate
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3954676A1 (en) * 2020-08-14 2022-02-16 GFBiochemicals IP Assets B.V. A process for the conversion of furfuryl alcohol into a levulinate ester
CN113181932A (en) * 2021-05-11 2021-07-30 昆明理工大学 Bifunctional biomass carbon-based catalyst and application thereof in catalytic preparation of levulinate
CN113181932B (en) * 2021-05-11 2023-08-15 昆明理工大学 A bifunctional biomass carbon-based catalyst and its application in catalytic preparation of levulinate
WO2023094511A1 (en) 2021-11-26 2023-06-01 Basf Se Process for forming alkyl ester of levulinic acid

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