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WO2018107450A1 - Procédé électrochimique pour produire un composé propiolactone - Google Patents

Procédé électrochimique pour produire un composé propiolactone Download PDF

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WO2018107450A1
WO2018107450A1 PCT/CN2016/110261 CN2016110261W WO2018107450A1 WO 2018107450 A1 WO2018107450 A1 WO 2018107450A1 CN 2016110261 W CN2016110261 W CN 2016110261W WO 2018107450 A1 WO2018107450 A1 WO 2018107450A1
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Prior art keywords
process according
compound
group
propiolactone
chosen
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PCT/CN2016/110261
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English (en)
Inventor
Renate Schwiedernoch
Gérard Mignani
Mengjia WU
Armin T. Liebens
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Rhodia Operations
Centre National De La Recherche Scientifique
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Priority to PCT/CN2016/110261 priority Critical patent/WO2018107450A1/fr
Publication of WO2018107450A1 publication Critical patent/WO2018107450A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This invention provides an electrochemical process for producing a propiolactone compound comprising reacting a compound having at least one ethylenically unsaturated carbon-carbon double bond with carbon dioxide in the presence of an electrolyte, a solvent and a catalyst.
  • An active goal is to take this carbon-trapped in a waste product and reuse it to build useful chemicals.
  • WO13164172 discloses a technology related to production of chemical compounds from carbon dioxide. This invention combines two steps: carbon dioxide electrolysis and “oxidative carbonylation” reaction. According to this technology, carbon dioxide needs to be split into carbon monoxide and oxygen first and “oxidative carbonylation” reaction of carbon monoxide and oxygen together with substrate is followed. Disadvantageously, in order to well control the gas streams, the requirement for reaction equipment and difficulty in operation is increased.
  • the present invention provides an electrochemical process for the production of a propiolactone compound comprising reacting:
  • a first reactant being a compound having at least one ethylenically unsaturated carbon-carbon double bond
  • a second reactant being carbon dioxide, in the presence of an electrolyte, a solvent and a catalyst
  • the catalyst comprises metal clusters comprising at least one metal element in elemental form, wherein the metal element is chosen in the group consisting of (i) elements of group IA, IIA, IIIA, IVA, VA, VIA and VIIA of the Periodic Table, (ii) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB of the Periodic Table, (iii) lanthanides, (iv) actinides, and (v) any combination thereof.
  • present invention makes it possible to directly transfer from carbon dioxide to propiolactone compounds with high selectivity by a more simple process.
  • electrochemical process is a chemical reaction that either causes or is caused by the movement of electrical current.
  • hydrocarbyl refers to a monovalent hydrocarbon group, i.e. a group consisting of carbon atoms and hydrogen atoms, which group is connected to the remainder of the compound of formula (I) via a carbon-to-carbon single bond and may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic.
  • a "C 1-11 hydrocarbyl” denotes a hydrocarbyl having 1 to 11 carbon atoms.
  • alkyl refers to a monovalent saturated aliphatic (i.e. non-aromatic) acyclic hydrocarbon group which may be linear or branched and does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond.
  • alkenyl refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon double bond while it does not comprise any carbon-to-carbon triple bond.
  • alkynyl refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon triple bond and optionally one or more carbon-to-carbon double bonds.
  • cycloalkyl refers to a monovalent cyclic saturated aliphatic hydrocarbon group which does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond.
  • Non-limiting examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cycloalkenyl refers to a monovalent cyclic unsaturated aliphatic hydrocarbon group which comprises at least one carbon-to-carbon double bond and does not comprise any carbon-to-carbon triple bond.
  • Non-limiting examples of cycloalkyl groups are cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclohexadienyl.
  • aryl refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring.
  • Aryl may, for example, refer to phenyl, naphthyl or anthracenyl.
  • metals of group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB are often referred to as transition metals.
  • This group comprises the elements with atomic number 21 to 30 (Sc to Zn) , 39 to 48 (Y to Cd) , 72 to 80 (Hf to Hg) and 104 to 112 (Rf to Cn) .
  • Lides refer to metals with atomic number 57 to 71.
  • Actinides refer to the metals with the atomic number 89 to 103.
  • an “anode” is an electrode through which conventional current flows into a polarized electrical device.
  • a “cathode” is the electrode from which a conventional current leaves a polarized electrical device.
  • Propiolactone compound of present invention refers to a ⁇ -propiolactone compound, which is an organic compound with a four-membered ring.
  • a compound having at least one ethylenically unsaturated carbon-carbon double bond refers to a compound of formula (I) :
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen or C 1-11 hydrocarbyl.
  • Said hydrocarbyl is preferably selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl, more preferably selected from alkyl, alkenyl, alkynyl, or aryl, and even more preferably selected from alkyl, alkenyl, or aryl.
  • Said alkyl preferably comprises 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 (i.e. 1, 2, 3 or 4) carbon atoms.
  • Said alkenyl preferably comprises 2 to 11 carbon atoms, more preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 (i.e. 2, 3 or 4) carbon atoms.
  • Said alkynyl preferably comprises 2 to 11 carbon atoms, more preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 (i.e. 2, 3 or 4) carbon atoms.
  • Said cycloalkyl preferably comprises 3 to 11 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 (i.e. 3, 4, 5 or 6) carbon atoms.
  • Said aryl is preferably selected from phenyl or naphthyl, and is more preferably phenyl.
  • said C 1-11 hydrocarbyl is preferably selected from C 1-11 alkyl (in particular, C 1-6 alkyl or C 1-4 alkyl) , C 2-11 alkenyl (in particular, C 2-6 alkenyl or C 2-4 alkenyl) , C 2-11 alkynyl (in particular, C 2-6 alkynyl or C 2-4 alkynyl) , C 3-11 cycloalkyl (in particular, C 3-6 cycloalkyl) , C 3-11 cycloalkenyl (in particular, C 3-6 cycloalkenyl) , phenyl or naphthyl.
  • C 1-11 alkyl in particular, C 1-6 alkyl or C 1-4 alkyl
  • C 2-11 alkenyl in particular, C 2-6 alkenyl or C 2-4 alkenyl
  • C 2-11 alkynyl in particular, C 2-6 alkynyl or C 2-4 alkynyl
  • said C 1-11 hydrocarbyl is selected from C 1-11 alkyl (in particular, C 1-6 alkyl or C 1-4 alkyl) , C 2-11 alkenyl (in particular, C 2-6 alkenyl or C 2-4 alkenyl) or phenyl.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen, C 1-11 alkyl, C 2-11 alkenyl, C 2-11 alkynyl, C 3-11 cycloalkyl, C 3-11 cycloalkenyl, phenyl or naphthyl, and are more preferably each independently selected from hydrogen, C 1-6 alkyl, C 2-6 alkenyl or phenyl, and are even more preferably each independently selected from hydrogen or linear C 1-4 alkyl.
  • At least one of R 1 , R 2 , R 3 and R 4 of formula (I) is hydrocarbyl and preferably alkyl and more preferably linear C 1-4 alkyl.
  • the compound of formula (I) comprises a total of 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms and even more preferably 2 to 12 carbon atoms.
  • the propiolactone compound according to the present invention may notably be a compound of formula (II) or formula (III) when compound of formula (I) is employed as starting reactant:
  • compound of formula (I) may be a compound having conjugated double bonds of formula (IV) :
  • R 5 , R 6 , R 7 , R 8 , R 9 and R 10 have the same meanings and preferred meanings as described and defined herein above for R 1 , R 2 , R 3 and R 4 .
  • the compound of formula (IV) comprises a total of 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms and even more preferably 6 to 12 carbon atoms.
  • At least one of R 5 , R 6 , R 7 , R 8 , R 9 and R 10 of formula (IV) is hydrocarbyl and preferably alkyl and more preferably linear C 1-4 alkyl.
  • the propiolactone compound according to the present invention may notably be a compound of formula (V) or formula (VI) when compound of formula (IV) is employed as starting reactant:
  • first reactant may be chosen in the group consisting of 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, isoprene, myrcene, styrene, alpha-methylstyrene and 1-pheny-l, 3-butadiene.
  • Preferred examples of propiolactone compound may be chosen in the group consisting of 3-methyl-3- (prop-1-en-2-yl) oxetan-2-one, 3- (4-methylpent-3-1-yl) -3-vinyloxetan-2-one, 3- (6-methylhepta-1, 5-dien-2-yl) oxetan-2-one, 3, 3-dimethyl-4- (3-methylenepent-4-en-1-yl) oxetan-2-one, 3-vinyloxetan-2-one, 3-methyl-3-vinyloxetan-2-one, 3- (prop-1-en-2-yl) oxetan-2-one, 3-methyl-3-phenyloxetan-2-one, 3-styryloxetan-2-one and 4-phenyl-3-vinyloxetan-2-one.
  • Preferred reactions of the present invention are the following:
  • the catalyst comprises metal clusters comprising at least one metal element in elemental form, wherein the metal element is chosen in the group consisting of (i) elements of group IA, IIA, IIIA, IVA, VA, VIA and VIIA of the Periodic Table, (ii) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB of the Periodic Table, (iii) lanthanides, (iv) actinides, and (v) any combination thereof.
  • hydrogen is not included in metal element chosen in Group IA of the Periodic Table.
  • Carbon is not included in metal element chosen in Group IVA of the Periodic Table.
  • Nitrogen and phosphorus are not included in metal element chosen in Group VA of the Periodic Table.
  • Oxygen, sulfur and selenium are not included in metal element chosen in Group VIA of the Periodic Table.
  • the catalyst of present invention may comprise at least one metal element in elemental form chosen in the group consisting of elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB and any combination thereof.
  • the metal element could be chosen in the group consisting of nickel, cobalt, tin, iron, aluminum, chromium, platinum, palladium, rhodium, ruthenium, iridium, silver, gold, cerium, bismuth, manganese, rhenium and copper and more preferably chosen in the group consisting of nickel, cobalt, copper, iron and chromium.
  • the catalyst of present invention may comprise a metal alloy comprising at least two metal elements in elemental form, which is chosen in the group consisting of elements of groups IB, IIB, VIIIB.
  • the metal alloy may be notably chosen in the group consisting of Au-Fe, Au-Ni, Cu-Ni, Cu-Fe and Ni-Fe.
  • a metal alloy can be viewed as a solid metal-solid metal mixture wherein a primary metal acts as solvent while other metal (s) act (s) as solute; in a metal alloy and wherein the concentration of the metal solute does not exceed the limit of solubility of the metal solvent.
  • clusters refers to small, multiatom particles. Normally, any particle of somewhere between 2 and 3 ⁇ 10 7 atoms is considered a cluster.
  • number of metal atoms which form clusters of present invention could comprise 2 to 50000 atoms and preferably 3 to 3000 atoms.
  • the average particle diameter of metal clusters may be comprised from 1nm to 10nm and more preferably from 1.5nm to 3nm.
  • the average particle diameter of metal clusters may be up to 10nm as reported by Endeavour (1990) , 14, pp. 172-178 and J. Mol. Catal. A: Chem. (1999) , 145, pp. 1-44. Preferably, it may be comprised from 1nm to 10nm and more preferably from 1.5nm to 3nm as observed by transmission eletron microscopy (TEM) .
  • TEM transmission eletron microscopy
  • the sample of metal clusters could be obtained by the way described by J. Am. Chem. Soc, 116, 7401-7402. It is reported that the metal clusters could first be stabilized by an ionic liquid electrolyte in a solvent that has essentially no solubility to material obtained. Metal clusters of different particle size are then precipitated when they are controlled by variation of the current density.
  • the metal clusters may have any shape, i.e. they may e.g. be particulate or fibrous.
  • the term “particulate” in this respect is to be understood as referring to particles having a more or less isometric structure like spherical, substantially spherical, ovoidal or substantially ovoidal particles. Such particulate particles usually differ from acicular particles, platy particles as well as fibrous particles in the aspect ratio.
  • platy particles are well known by the persons skilled in the art. Typically, platy particles consist essentially of, or even consist of, particles having the shape of, or resembling to a plate, i.e. the particles are flat or substantially flat and their thickness is small in comparison with the other two dimensions.
  • acicular particles are also well known by the skilled in the art. Typically, acicular particles have the shape of, or resembling a needle.
  • the metal clusters having the shape of cuboctahedron.
  • Method for preparing the metal clusters is not particularly limited.
  • people having ordinary skill in the art could obtain metal clusters by some well-known methods, such as the ways disclosed by M.T. Reetz, W. Helbig, “Size-Selective Synthesis of Nanostructured Transition Metal Clusters” , J. Am. Chem. Soc. (1994) , 116, pp. 7401-7402; M.L. Rodriguez-Sanchez, M.J. Rodriguez, M.C. Blanco, J. Rivas, M.A. Lopez-Quintela, "Kinetics and mechanism of the formation of Ag nanoparticles by electrochemical techniques: a plasmon and cluster time-resolved spectroscopic study” , The journal of physical chemistry.
  • metal salt may be reduced to metal clusters in situ while the reactants of invented process are present.
  • concentration of metal salt in the solvent may be preferably comprised from 0.00001 to 1mol/L and more preferably from 0.0001 to 0.01mol/L.
  • metal clusters could also be produced in situ by an electrode directly.
  • the active catalyst was produced by oxidizing electrode comprises metal element at a positive potential in order to produce metal ions in the solution. Then the metal ions were reduced to metal clusters at a negative potential.
  • the molar ratio of first reactant to catalyst of present invention may be comprised from 0.001 to 10 and preferably from 0.01 to 1.
  • the solvent of present invention is used to dissolve electrolyte and at least partially dissolve the first reactant.
  • Any suitable solvent such as water and organic solvent could be used.
  • organic solvent such as methanol, ethanol, propanol, acetone, acetonitrile, acetic acid, THF (tetrahydrofuran) , DMF (N, N-dimethylformamide) , DMSO (dimethylsulfoxide) , NMP (N-Methyl-2-pyrrolidone) , DMC (dimethyl carbonate) , NM (nitromethane) , PC (propylene carbonate) , EC (ethylene carbonate) and ionic liquids.
  • organic solvent such as methanol, ethanol, propanol, acetone, acetonitrile, acetic acid, THF (tetrahydrofuran) , DMF (N, N-dimethylformamide) , DMSO (dimethylsulfoxide) , NMP (N-Methyl-2-pyrrolidone) , DMC (dimethyl carbonate) , NM (nitromethane) ,
  • Said ionic liquid may be alkylammonium salt such as tetraalkylammonium halides, tetraalkylammonium perchlorates, tetraalkylammonium tetrafluoroborates.
  • the electrolyte may be organic or inorganic compounds.
  • Inorganic compounds are preferably alkali metal salt or alkaline earth metal salt.
  • Organic compounds could be ionic liquids, especially alkylammonium salt such as tetraalkylammonium halides, tetraalkylammonium perchlorates, tetraalkylammonium tetrafluoroborates.
  • inorganic compounds used as electrolyte notably are:
  • Halides such as lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide and potassium bromide, magnesium chloride, magnesium bromide.
  • Nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate.
  • Perchlorates such as lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate.
  • organic compounds used as electrolyte notably are:
  • Tetraalkylammonium halides such as tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetraoctyl ammonium bromide, tetraoctyl ammonium chloride.
  • the concentration of electrolyte in solvent may comprise preferably from 0.01wt%to 50 wt%and more preferably from 0.1 wt%to 5 wt%.
  • the invented process can further employ a stabilizer to metal clusters. It is understood that the stabilization can be accomplished in two precedented ways: electrostatic stabilization and steric stabilization.
  • Electrostatic stabilization occurs by the adsorption of ions to the often electrophilic metal surface. This adsorption creates an electrical double layer, which results in Coulombic repulsion force between individual particles.
  • Steric stabilization is achieved by surrounding the metal center by layers of material that are sterically bulky, such as polymers or surfactants. These large adsorbates provide a steric barrier which prevents close contact of the metal particle centers
  • the stabilizer of this invention is not particularly limited. Any stabilizer which can realize two precedented ways above mentioned can be used. It could notably be solvent or electrolyte molecules as mentioned above. In a specific embodiment, first reactant could be used as stabilizer.
  • the stabilizer could be chosen in the group consisting of THF (tetrahydrofuran) , DMF (N, N-dimethylformamide) , THT (tetrahydrothiophene) , alkylammonium salts such as tetraalkylammonium halides, tetraalkylammonium perchlorates, tetraalkylammonium tetrafluoroborate.
  • THF tetrahydrofuran
  • DMF N, N-dimethylformamide
  • THT tetrahydrothiophene
  • alkylammonium salts such as tetraalkylammonium halides, tetraalkylammonium perchlorates, tetraalkylammonium tetrafluoroborate.
  • the reaction may be carried out in the presence of an inert atmosphere such as N 2 , Ar.
  • atmospheres may be introduced to the reaction medium solely or in a form of mixture with carbon dioxide.
  • the gas pressure of present invention may be comprised between 10 bars and 200 bars and preferably between 20 bars and 50 bars.
  • the electrochemical reactor of present invention is not particularly limited. It should be understood by the people having ordinary skill in the art that conventional electrochemical reactor, which comprises at least one compartment, gas assemblies, anode-cathode assemblies could be used.
  • the reactor may be preferably a single compartment stainless steel reactor that allows running high pressure electrochemical synthesis under inert conditions.
  • Anode or cathode of present invention may comprise non-metal element, such as carbon in form of graphite, glassy carbon.
  • Anode or cathode of present invention may notably comprise at least one metal element in elemental form and/or at least one metal compound of at least one metal element, wherein the metal element is chosen in the group consisting of (i) elements of group IA, IIA, IIIA, IVA, VA, VIA and VIIA of the Periodic Table, (ii) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB of the Periodic Table, (iii) Lanthanides, and (iv) any combination thereof.
  • anode or cathode may comprise one and only one metal element in elemental form.
  • anode or cathode may comprise a mixture comprising at least two metal elements in elemental form.
  • anode or cathode may comprise a metal alloy comprising at least two metal elements in elemental form.
  • the metal compound comprised in anode or cathode may notably be metal oxides.
  • cathode may comprise at least one element chosen in the group consisting of C, Fe Ag, Ni, Ru, Ir, Os, Mn, La, Co, Ce and any combination thereof.
  • the cathode may comprise stainless steel.
  • anode may comprise at least one element chosen in the group consisting of C, Fe Pd, Pt, Ru, Au, Rh, Ir, Bi, Sn, B and any combination thereof.
  • the anode may comprise graphite or glassy carbon.
  • sacrificing electrode may be used in present invention, which may comprise element chosen in a group consisting of Al, Mg, Be, Zn, Fe, Ti and Pb.
  • the electrodes above mentioned could be made with porous substrate structures.
  • the anode substrates may comprise one or more conducting materials prepared in a sheet, foam, grid, cloth or other similar conductive and porous structure.
  • the substrate can be merely physically support the electrode materials above mentioned and transmit electrons, and/or it can be electrochemically active.
  • Anode substrates can include, for example, stainless steel net, nickel foam, sintered nickel powder, etched aluminum-nickel mixtures, carbon fibers, and carbon cloth.
  • carbon materials and stainless steel are used as an anode substrate.
  • Cathode substrates can include stainless steel, nickel foam, sintered nickel powder, etched aluminum-nickel mixtures, metal screens, carbon fibers, and carbon cloth.
  • separator In present invention, a separator or an ion-exchange membrane could be placed between anode and cathode.
  • separatator should be understood as a layer that provides a physical separation between the anode and the cathode and acts as an electrical insulator between the two conductive electrodes. It has pores big enough for the fuel or electrolyte solution to go through.
  • ion-exchange membrane should be understood as a layer transports dissolved ions across a conductive polymeric membrane.
  • potentiostat/galvanostat device or any DC regulated power supply could be used to control and measure the parameters, such as potential and current density.
  • Conventional reference electrode such as saturated calomel electrode, Ag/AgCl electrode, Ag ion electrode, solid Pt electrode should be employed when potentiostat/galvanostat device is used.
  • the potential of present invention to produce a propiolactone compound may be comprised from -0.0001V to -10V, and preferably from -1 to -3V.
  • the current density of present invention to produce propiolactone compound may be comprised from -0.01mA/cm 2 to -10 mA/cm 2 and preferably from -1 mA/cm 2 to -5 mA/cm 2 .
  • the reaction temperature of present invention may be comprised from -20°C to 100°C and preferably from 0°C to 40°C and more preferably from 10°Cand 30°C.
  • Example 1 preparation of Ni catalyst by reducing of NiBr 2
  • a single compartment high pressure stainless steel reactor was used and equipped with nickel foam cathode, aluminium anode and platinum wire as reference electrode.
  • 0.041 g NiBr 2 and 0.49 g 2 3-dimethyl-1, 3-butadiene was introduced and the reactor was closed and flushed with Ar.
  • the pressure was increased by adding CO 2 to 20 barg.
  • the electrodes were connected to the potentiostat.
  • the active catalyst was produced by reducing the nickel salt by electrochemistry. Therefore, a potential of -0.9V with a current density of -2.4 mA/cm 2 was applied for 3000 s.
  • the so in-situ produced active nickel species were immediately used for propiolactone synthesis. (see EXAMPLE 2)
  • the active clusters were not formed by adding a metal salt but rather by the electrode itself.
  • the same reactor and setup was used as described in example 1.
  • the active catalyst was produced by oxidizing the nickel electrode for about one hour at a potential range of +1V and +1.5V in order to produce Ni ions in the solution. Then the nickel ions were reduced by electrochemistry for 2000s. A potential of -1.2V with a current density of -2.4 mA/cm 2 was applied.
  • Example 4 Electrochemical Lactone formation in presence of nickel clusters prepared by Ni electrode
  • the electrochemical reaction was carried out similar to EXAMPLE 2 but without previous metal catalyst synthesis.
  • the single compartment high pressure stainless steel reactor was equipped with nickel foam cathode, aluminium anode and platinum wire as reference electrode.
  • 0.52 g 2 3-dimethyl-1, 3-butadiene was introduced and the reactor was closed and flushed with Ar.
  • the pressure was increased by adding CO 2 to 30 barg. Once the pressure is stable and the reactor cooled down to 30°C, the electrodes were connected to the potentiostat.
  • the nickel catalyst was firstly produced as described in EXAMPLE 1 followed by stirring the reaction solution for 96hs.
  • the reactor was equipped with a nickel foam cathode, an aluminium anode and a platinum wire as reference electrode.
  • 0.077 g NiBr 2 is introduced and the reactor closed and flushed with Ar.
  • the electrodes were connected to the potentiostat.
  • the active catalyst was produced by reducing the nickel salt by electrochemistry.
  • an iron salt was used as catalyst precursor.
  • the single compartment high pressure stainless steel reactor was equipped with nickel foam cathode, aluminium anode and platinum wire as reference electrode.
  • 0.083 g FeBr 3 and 0.43 g 2, 3-dimethyl-1, 3-butadiene were introduced and the reactor was closed and flushed with Ar.
  • the pressure was increased by adding CO 2 to 25 barg. Once the pressure was stable and the reactor cooled down to 20°C, the electrodes were connected to the potentiostat.
  • the active catalyst was produced by reducing the iron salt by electrochemistry. Therefore, a potential range between -1.2V and -1.45V and a current density of -2.4 mA/cm 2 were applied for 3000 s. The so in-situ produced active iron species were immediately used for propiolactone synthesis.
  • the propiolactone synthesis was followed directly by applying a potential range between -2.5V and -1.9V at a current density of -2.6 mA/cm 2 for 74 hs.
  • the work-up followed as described in EXAMPLE 2. Only propiolactone was formed.
  • the active nickel catalyst was firstly produced by electrochemical reduction of NiBr 2 as described in EXAMPLE 1. Then the reactor was pened and as well as the nickel cathode as the aluminium anode exchanged with new electrodes. Then the reactor was closed and the propiolactone synthesis carried out as described in EXAMPLE 2.
  • the reactor was filled with 66 ml DMF, 14 ml N4444Br solution (0.24 g/ml) , 0.031g NiBr 2 and 0.48 g 2, 3-dimethyl-1, 3-butadiene. After flushing with Argon the pressure was increased to 25 barg CO 2 . After exchanging the electrodes, the reactor was again filled with 25barg CO 2 . Only propiolactone was formed.

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Abstract

La présente invention concerne un procédé électrochimique de production d'un composé propiolactone comprenant la réaction d'un composé ayant au moins une double liaison carbone-carbone éthyléniquement insaturée avec du dioxyde de carbone en présence d'un électrolyte, d'un solvant et d'un catalyseur. La présente invention permet de transférer directement du dioxyde de carbone à un composé propiolactone avec une sélectivité élevée au moyen d'un procédé plus simple.
PCT/CN2016/110261 2016-12-16 2016-12-16 Procédé électrochimique pour produire un composé propiolactone WO2018107450A1 (fr)

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CN112517020A (zh) * 2020-12-17 2021-03-19 哈尔滨工业大学 一种纳米Cu-Ce合金催化剂的制备方法和应用
US11001549B1 (en) 2019-12-06 2021-05-11 Saudi Arabian Oil Company Electrochemical reduction of carbon dioxide to upgrade hydrocarbon feedstocks
US12018392B2 (en) 2022-01-03 2024-06-25 Saudi Arabian Oil Company Methods for producing syngas from H2S and CO2 in an electrochemical cell

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US11001549B1 (en) 2019-12-06 2021-05-11 Saudi Arabian Oil Company Electrochemical reduction of carbon dioxide to upgrade hydrocarbon feedstocks
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US12018392B2 (en) 2022-01-03 2024-06-25 Saudi Arabian Oil Company Methods for producing syngas from H2S and CO2 in an electrochemical cell

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