WO2018112779A1 - Process for the preparation of levulinate esters - Google Patents

Process for the preparation of levulinate esters Download PDF

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Publication number
WO2018112779A1
WO2018112779A1 PCT/CN2016/111225 CN2016111225W WO2018112779A1 WO 2018112779 A1 WO2018112779 A1 WO 2018112779A1 CN 2016111225 W CN2016111225 W CN 2016111225W WO 2018112779 A1 WO2018112779 A1 WO 2018112779A1
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Prior art keywords
alcohol
furfuryl alcohol
catalyst
process according
otf
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PCT/CN2016/111225
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French (fr)
Inventor
Alban CHAPPAZ
Francois Jerome
Karine De Oliveira Vigier
Eric Muller
Jonathan Lai
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Rhodia Operations
Le Centre National De La Recherche Scientifique
Universite De Poitiers
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Priority to PCT/CN2016/111225 priority Critical patent/WO2018112779A1/en
Publication of WO2018112779A1 publication Critical patent/WO2018112779A1/en

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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 polymer 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.
  • 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.
  • a first object of the invention is a process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol polymer with at least one other alcohol in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron and said furfuryl alcohol polymer being obtainable by condensation of furfuryl alcohol at a temperature of at least 50°C.
  • the furfuryl alcohol polymer is obtainable by condensation of furfuryl alcohol at a temperature ranging from 70°C to 170°C, more preferably from 80°C to 150°C, even more preferably from 90°C to 130°C.
  • the furfuryl alcohol polymer is obtainable by condensation of furfuryl alcohol in the presence of at least one solvent, preferably at least one alcohol solvent.
  • the alcohol solvent is identical to the other alcohol which will react with the furfuryl alcohol polymer for the synthesis of the levulinate ester.
  • the process comprises the following successive steps:
  • step b) condensation of the mixture obtained in step a) at a temperature of at least 50°C in order to obtain at least one furfuryl alcohol polymer
  • step d) 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 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 selected from SnCl 4 , SnX 1 X 2 X 3 (OTf) . xH 2 O and MX 1 X 2 (OTf) . xH 2 O wherein:
  • M represents a metal selected from Bi, Ga and Al,
  • 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;
  • OTf represents a triflate
  • X ranges from 0 to 10.
  • the catalyst is selected from SnCl 4 , Bi (OTf) 3 and BiCl 2 OTf, preferably from Bi (OTf) 3 and BiCl 2 OTf.
  • the catalyst is in the form of a hydrate.
  • the catalyst is present during the synthesis of the levulinate ester 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 initially introduced to obtain the furfuryl alcohol polymer.
  • the molar ratio water/metal of the catalyst during the synthesis of the levulinate ester 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 of the present invention allows obtaining levulinate esters with suitable yields.
  • 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 polymer with at least one other alcohol in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron and said furfuryl alcohol polymer being obtainable by condensation of furfuryl alcohol at a temperature of at least 50°C.
  • the furfuryl alcohol polymer used in the process of the invention is obtainable or obtained by condensation of furfuryl alcohol by heating at a temperature of at least 50°C, preferably ranging from 70°C to 170°C, more preferably from 80°C to 150°C, even more preferably from 90°C to 130°C.
  • the condensation of furfuryl alcohol is performed with a heating to reflux.
  • the condensation of furfuryl alcohol is performed in the presence of furfuryl alcohol in an amount ranging from 1 to 90%by weight, preferably from 2 to 75%by weight, more preferably from 5 to 50%by weight, based on the total weight of the condensation reaction medium.
  • the condensation of furfuryl alcohol is performed in the presence of a solvent, preferably an alcohol solvent.
  • a solvent preferably an alcohol solvent.
  • the alcohol solvent used for the preparation of the furfuryl alcohol polymer may be the “other alcohol” used for the synthesis of the levulinate ester.
  • the solvent (s) in particular the alcohol solvent (s) , represent (s) from 10 to 99%by weight, preferably from 25 to 98%by weight, more preferably from 50 to 95%by weight, based on the total weight of the solvents and furfuryl alcohol.
  • the condensation of furfuryl alcohol is performed in the presence of water.
  • the water is present during the condensation reaction of furfuryl alcohol in an amount such that during the reaction of synthesis of levulinate ester (s) , the molar ratio water/metal M (metal of the catalyst) ranges from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  • the furfuryl alcohol polymer comprises at least one compound among dimer, trimer and tetramer of furfuryl alcohol.
  • furfuryl alcohol that can be used to obtain the furfuryl alcohol polymer 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 and a catalyst suitable for performing said reaction.
  • 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.
  • the furfuryl alcohol may be purified before condensation, by purification methods well known for the skilled person.
  • the condensation of furfuryl alcohol is performed in the substantially or totally absence of acid catalysts, such as metal chlorides, triflates, triflimidates, Aquivion, Nafion, sulfuric acid, hydrochloric acid, etc.
  • acid catalysts such as metal chlorides, triflates, triflimidates, Aquivion, Nafion, sulfuric acid, hydrochloric acid, etc.
  • other alcohol within the meaning of the present invention refers to an alcohol different from the furfuryl alcohol polymer and different from a furfuryl alcohol.
  • the other alcohol which reacts with the furfuryl alcohol polymer defined in the present application 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.
  • 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 or for preparing the furfuryl alcohol polymer.
  • the catalyst used for the synthesis of levulinate esters comprises at least one metal selected from bismuth, gallium, aluminum and tin, more preferably from bismuth and tin, even more preferably 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.
  • 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 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 SnCl 4 and catalysts comprising at least one metal M and at least one ligand OTf wherein
  • - M is selected from bismuth, gallium, aluminum, tin and iron, preferably from and bismuth, gallium, aluminum and tin, more preferably from bismuth and tin, even more 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 SnCl 4 , Bi (OTf) 3 , Bi (NTf 2 ) 3 , Ga (OTf) 3 , Al (OTf) 3 , Sn (OTf) 4 , 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.
  • 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 introduced to obtain the furfuryl alcohol polymer as defined in the present application.
  • the reaction of synthesis of levulinate esters 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.
  • a SnCl 4 catalyst may be in the form of SnCl 4 .5H 2 O or a AlCl 3 catalyst may be in the form of AlCl 3 .6H 2 O.
  • external water said water can be added before, during or after the condensation of furfuryl alcohol into furfuryl alcohol polymer and/or said external water can be added before or during the reaction of synthesis of the levulinate ester (s) .
  • the catalyst can also be in an anhydrous form.
  • the catalyst comprises triflate ligands
  • the catalyst will be preferably in an anhydrous form.
  • reaction medium By “reaction medium” , it is to be understood the medium wherein the reaction takes place.
  • the reaction medium comprises the furfuryl alcohol polymer, 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 polymer) and the catalyst of the conversion reaction.
  • the furfuryl alcohol polymer 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, the furfuryl alcohol polymer, and the other alcohol (s) used in the reaction medium for the synthesis of levulinate ester (s) .
  • the reaction for synthesizing levulinate esters 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:
  • step b) condensation of the mixture obtained in step a) at a temperature of at least 50°C,
  • the reaction mixture obtained in step a) comprises all the water used in the reaction.
  • the solvents used in step a) is alcohol solvents, and represent all the “other alcohol” used in the reaction for synthesizing levulinate esters. In this case, in step c) , no other alcohol is added.
  • the condensation step b) may be performed until the complete disappearance of the furfuryl alcohol, which can be followed for example by gas chromatography.
  • the solution obtained is cooled to a temperature ranging from 15°C to 40°C, preferably from 20 to 30°C.
  • the catalyst is then introduced (step c)) at this temperature.
  • the step d) of synthetizing is performed at a temperature ranging from 80°C to 200°C, preferably from 90°C to 180°C, more preferably from 110°C to 165°C, by for example a heating under reflux.
  • the process of the reaction may be a batch process or a continuous process.
  • 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.
  • furfuryl alcohol polymer in the conditions of the reaction, decomposes at least in part, into furfuryl alcohol which will react with the other alcohol to obtain the levulinate ester according to the following reaction:
  • ROH represents the other alcohol, as defined above.
  • 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 ( ⁇ 80 mg) 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 which provided information on yields and conversions.
  • the yield (or selectivity) in levulinate esters corresponds to the amount of levulinate esters expressed in molar percentage based on the molar amount of furfuryl alcohol initially introduced into the reaction medium.

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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 polymer with at least one other alcohol in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron and said furfuryl alcohol polymer being obtainable by condensation of furfuryl alcohol at a temperature of at least 50℃.

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 polymer 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.
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.
It was an object of the present invention to develop a process for converting furfuryl alcohol polymer into levulinate esters with a catalytic system that permits to get satisfying selectivities.
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 polymer with at least one other alcohol in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron and said furfuryl alcohol polymer being obtainable by condensation of furfuryl alcohol at a temperature of at least 50℃.
Preferably, the furfuryl alcohol polymer is obtainable by condensation of furfuryl alcohol at a temperature ranging from 70℃ to 170℃, more preferably from 80℃ to 150℃, even more preferably from 90℃ to 130℃.
According to an embodiment of the invention, the furfuryl alcohol polymer is obtainable by condensation of furfuryl alcohol in the presence of at least one solvent,  preferably at least one alcohol solvent. Preferably, the alcohol solvent is identical to the other alcohol which will react with the furfuryl alcohol polymer for the synthesis of the levulinate ester.
According to an embodiment of the invention, the process comprises the following successive steps:
a) providing a mixture comprising all or part of the furfuryl alcohol, all or part of the water, and all or part of the other alcohol, said mixture being substantially free or totally free of acid catalysts, such as the catalysts defined above,
b) condensation of the mixture obtained in step a) at a temperature of at least 50℃ in order to obtain at least one furfuryl alcohol polymer,
c) introducing the catalyst and optionally the remaining part of the other alcohol into the reaction mixture obtained after step b) ,
d) synthetizing the levulinate esters,
e) recovering the levulinate esters.
Preferably, step d) is performed at a temperature ranging from 80℃ to 200℃, preferably from 100℃ to 180℃, more preferably from 115℃ to 165℃.
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.
According to an embodiment, the catalyst is selected from SnCl4, SnX1X2X3 (OTf) . xH2O and MX1X2 (OTf) . xH2O wherein:
M represents a metal selected from Bi, Ga and Al,
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.
Preferably, the catalyst is selected from SnCl4, Bi (OTf) 3 and BiCl2OTf, preferably 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 catalyst is present during the synthesis of the levulinate ester 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 initially introduced to obtain the furfuryl alcohol polymer.
According to an embodiment of the invention, the molar ratio water/metal of the catalyst during the synthesis of the levulinate ester 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.
The process of the present invention allows obtaining levulinate esters with suitable yields.
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 polymer with at least one other alcohol in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron and said furfuryl alcohol polymer being obtainable by condensation of furfuryl alcohol at a temperature of at least 50℃.
The furfuryl alcohol polymer used in the process of the invention is obtainable or obtained by condensation of furfuryl alcohol by heating at a temperature of at least  50℃, preferably ranging from 70℃ to 170℃, more preferably from 80℃ to 150℃, even more preferably from 90℃ to 130℃.
According to an embodiment, the condensation of furfuryl alcohol is performed with a heating to reflux.
According to an embodiment, the condensation of furfuryl alcohol is performed in the presence of furfuryl alcohol in an amount ranging from 1 to 90％by weight, preferably from 2 to 75％by weight, more preferably from 5 to 50％by weight, based on the total weight of the condensation reaction medium.
According to an embodiment, the condensation of furfuryl alcohol is performed in the presence of a solvent, preferably an alcohol solvent. As an example, the alcohol solvent used for the preparation of the furfuryl alcohol polymer may be the “other alcohol” used for the synthesis of the levulinate ester. Preferably, the solvent (s) , in particular the alcohol solvent (s) , represent (s) from 10 to 99％by weight, preferably from 25 to 98％by weight, more preferably from 50 to 95％by weight, based on the total weight of the solvents and furfuryl alcohol.
According to an embodiment, the condensation of furfuryl alcohol is performed in the presence of water. Preferably, the water is present during the condensation reaction of furfuryl alcohol in an amount such that during the reaction of synthesis of levulinate ester (s) , the molar ratio water/metal M (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, the furfuryl alcohol polymer comprises at least one compound among dimer, trimer and tetramer of furfuryl alcohol.
According to an embodiment, furfuryl alcohol that can be used to obtain the furfuryl alcohol polymer is obtained from the reduction of furfural. The reduction of furfural may be represented by the following equation:
Figure PCTCN2016111225-appb-000001
The reduction of furfural into furfuryl alcohol may be performed in the presence of hydrogen 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 condensation, by purification methods well known for the skilled person.
According to an embodiment, the condensation of furfuryl alcohol is performed in the substantially or totally absence of acid catalysts, such as metal chlorides, triflates, triflimidates, Aquivion, Nafion, sulfuric acid, hydrochloric acid, etc.
The expression “other alcohol” within the meaning of the present invention refers to an alcohol different from the furfuryl alcohol polymer and different from a furfuryl alcohol.
The other alcohol which reacts with the furfuryl alcohol polymer defined in the present application 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 or for preparing the furfuryl alcohol polymer.
Preferably, the catalyst used for the synthesis of levulinate esters comprises at least one metal selected from bismuth, gallium, aluminum and tin, more preferably from bismuth and tin, even more preferably 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.
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 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 SnCl4 and catalysts comprising at least one metal M and at least one ligand OTf wherein
- M is selected from bismuth, gallium, aluminum, tin and iron, preferably from and bismuth, gallium, aluminum and tin, more preferably from bismuth and tin, even more 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 SnCl4, Bi (OTf) 3, Bi (NTf2) 3, Ga (OTf) 3, Al (OTf) 3, Sn (OTf) 4, 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.
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 PCTCN2016111225-appb-000002
or 
Figure PCTCN2016111225-appb-000003
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 introduced to obtain the furfuryl alcohol polymer as defined in the present application.
The reaction of synthesis of levulinate esters 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. For example, a SnCl4 catalyst may be in the form of SnCl4.5H2O or a AlCl3 catalyst may be in the form of AlCl3.6H2O. If external water is added, said water can be added before, during or after the condensation of furfuryl alcohol into furfuryl alcohol polymer and/or said external water can be added before or during the reaction of synthesis of the levulinate ester (s) .
The catalyst can also be in an anhydrous form. When the catalyst comprises triflate ligands, the catalyst will be preferably in an anhydrous form.
By “reaction medium” , it is to be understood the medium wherein the reaction takes place. The reaction medium comprises the furfuryl alcohol polymer, 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 polymer) and the catalyst of the conversion reaction.
The furfuryl alcohol polymer 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, the furfuryl alcohol polymer, and the other alcohol (s) used in the reaction medium for the synthesis of levulinate ester (s) .
According to an embodiment, the reaction for synthesizing levulinate esters 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 mixture comprising all or part of the furfuryl alcohol, all or part of the water, and optionally all or part of the solvents, said mixture being preferably substantially free or totally free of catalysts, such as acid catalysts defined in the present invention,
b) condensation of the mixture obtained in step a) at a temperature of at least 50℃,
c) introducing the catalyst and optionally all or the remaining part of the other alcohol into the reaction mixture obtained after step b) ,
d) synthetizing the levulinate esters,
e) recovering the levulinate esters.
According to an embodiment of the invention, the reaction mixture obtained in step a) comprises all the water used in the reaction.
According to an embodiment of the invention, the solvents used in step a) is alcohol solvents, and represent all the “other alcohol” used in the reaction for synthesizing levulinate esters. In this case, in step c) , no other alcohol is added.
The condensation step b) may be performed until the complete disappearance of the furfuryl alcohol, which can be followed for example by gas chromatography.
According to an embodiment of the invention, after condensation step b) , the solution obtained is cooled to a temperature ranging from 15℃ to 40℃, preferably from 20 to 30℃. According to this embodiment, the catalyst is then introduced (step c)) at this temperature.
According to an embodiment of the invention, the step d) of synthetizing is performed at a temperature ranging from 80℃ to 200℃, preferably from 90℃ to 180℃, more preferably from 110℃ to 165℃, by for example a heating under reflux.
The process of the reaction may be a batch process or a continuous process.
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.
Without being bound by a theory, it is believed that the furfuryl alcohol polymer, in the conditions of the reaction, decomposes at least in part, into furfuryl alcohol which will react with the other alcohol to obtain the levulinate ester according to the following reaction:
Figure PCTCN2016111225-appb-000004
wherein ROH represents the other alcohol, as defined above.
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
Experimental protocol of the process of the invention
In a 50 mL glass reactor, 1.1 g of furfuryl alcohol, 2.6 mg of water (2 mol％) and 10.0 g of butanol were stirred and heated to reflux (117℃) . After 8 hours of condensation, around 80％mol of the initial fufuryl alcohol were consumed. The resulting solution was then cooled down to room temperature (23℃) . 66 mg of Bi (OTf) 3 (1mol％) were then added and the resulting mixture was stirred and heated at reflux (117℃) for another 9 hours.
During the reaction, samples (～80 mg) 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 which provided information on yields and conversions.
A yield in butyl levulinate of about 30％were obtained.
The yield (or selectivity) in levulinate esters corresponds to the amount of levulinate esters expressed in molar percentage based on the molar amount of furfuryl alcohol initially introduced into the reaction medium.

Claims (15)

  1. A process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol polymer with at least one other alcohol in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron and said furfuryl alcohol polymer being obtainable by condensation of furfuryl alcohol at a temperature of at least 50℃.
  2. The process according to claim 1, wherein the furfuryl alcohol polymer is obtainable by condensation of furfuryl alcohol at a temperature ranging from 70℃ to 170℃, more preferably from 80℃ to 150℃, even more preferably from 90℃ to 130℃.
  3. The process according to claim 1 or 2, wherein the furfuryl alcohol polymer is obtainable by condensation of furfuryl alcohol in the presence of at least one solvent, preferably at least one alcohol solvent.
  4. The process according to claim 3, wherein the alcohol solvent is identical to the other alcohol which will react with the furfuryl alcohol polymer for the synthesis of the levulinate ester.
  5. The process according to claim 4, comprising the following successive steps:
    a) providing a mixture comprising all or part of the furfuryl alcohol, all or part of the water, and all or part of the other alcohol, said mixture being substantially free or totally free of acid catalysts, such as the catalysts defined in claim 1,
    b) condensation of the mixture obtained in step a) at a temperature of at least 50℃ in order to obtain at least one furfuryl alcohol polymer,
    c) introducing the catalyst and optionally the remaining part of the other alcohol into the reaction mixture obtained after step b) ,
    d) synthetizing the levulinate esters,
    e) recovering the levulinate esters.
  6. The process according to claim 5, wherein step d) is performed at a temperature ranging from 80℃ to 200℃, preferably from 100℃ to 180℃, more preferably from 115℃ to 165℃.
  7. The process according to any one of claims 1 to 6, 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.
  8. The process according to any one of claims 1 to 7, wherein the catalyst is selected from SnCl4, SnX1X2X3 (OTf) . xH2O and MX1X2 (OTf) . xH2O wherein:
    M represents a metal selected from Bi, Ga and Al,
    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.
  9. The process according to any one of claims 1 to 8, wherein the catalyst is selected from SnCl4, Bi (OTf) 3 and BiCl2OTf, preferably from Bi (OTf) 3 and BiCl2OTf.
  10. The process according to any one of claims 1 to 9, wherein the catalyst is in the form of a hydrate.
  11. The process according to any one of claims 1 to 10, wherein the catalyst is present during the synthesis of the levulinate ester 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 initially introduced to obtain the furfuryl alcohol polymer.
  12. The process according to any one of claims 1 to 11, wherein the molar ratio water/metal of the catalyst during the synthesis of the levulinate ester ranges from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  13. The process according to any one of claims 1 to 12, wherein the other alcohol is selected from alcohols of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  14. The process according to claim 13, wherein R comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
  15. The process according to any one of claims 1 to 14, wherein the other alcohol is in the form of a solution comprising only one alcohol or at least two different alcohols.
PCT/CN2016/111225 2016-12-21 2016-12-21 Process for the preparation of levulinate esters WO2018112779A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023094511A1 (en) 2021-11-26 2023-06-01 Basf Se Process for forming alkyl ester of levulinic acid

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US20070049771A1 (en) * 2005-08-26 2007-03-01 Van De Graaf Wouter D Process for the conversion of furfuryl alcohol into levulinic acid or alkyl levulinate
US20150045576A1 (en) * 2013-08-08 2015-02-12 Battelle Memorial Institute Methods of making alkyl lactates and alkyl levulinates from saccharides
CN104497299A (en) * 2014-11-20 2015-04-08 济南圣泉集团股份有限公司 Method for preparing low dissociation furfuryl alcohol binder
CN104959154A (en) * 2015-07-09 2015-10-07 南京林业大学 Catalyst for preparing levulinate ester and method for preparing levulinate ester by using catalyst

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Publication number Priority date Publication date Assignee Title
US20070049771A1 (en) * 2005-08-26 2007-03-01 Van De Graaf Wouter D Process for the conversion of furfuryl alcohol into levulinic acid or alkyl levulinate
US20150045576A1 (en) * 2013-08-08 2015-02-12 Battelle Memorial Institute Methods of making alkyl lactates and alkyl levulinates from saccharides
CN104497299A (en) * 2014-11-20 2015-04-08 济南圣泉集团股份有限公司 Method for preparing low dissociation furfuryl alcohol binder
CN104959154A (en) * 2015-07-09 2015-10-07 南京林业大学 Catalyst for preparing levulinate ester and method for preparing levulinate ester by using catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023094511A1 (en) 2021-11-26 2023-06-01 Basf Se Process for forming alkyl ester of levulinic acid

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