Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
  • B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0215—Sulfur-containing compounds
  • B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
  • B01J31/0224—Sulfur-containing compounds comprising sulfonyl groups being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0215—Sulfur-containing compounds
  • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
  • B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
  • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
  • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
  • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
  • B01J31/0288—Phosphorus
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
  • B01J31/0289—Sulfur
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
  • B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
  • B01J2523/51—Phosphorus
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
  • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
  • B01J2523/62—Sulfur
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
  • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
  • B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
  • B01J35/45—Nanoparticles

Definitions

• the present invention relates to a catalytic composition and its use in acid catalysis processes.
• the present invention also relates to acid catalysis processes using said composition, and more particularly the alkylation of aromatic hydrocarbons, the oligomerization of olefins, the isomerization of n-olefins to iso-olefins, the isomerization of n-paraffins to iso-paraffins, and the alkylation of isobutane by olefins.
• Acid catalysis reactions are very important industrial reactions, which find very varied applications in the field of refining and petrochemicals. We can refer in particular to the work of Christian Marcilly "Acid-base catalysis - Application to refining and petrochemicals" - July 2003 - Technip Editions, for more information on their subject.
• the conventional acid catalysts used for these transformations are very often Lewis and/or Bronsted acids.
• the most commonly used are hydrofluoric acid (HF), concentrated sulfuric acid (H2SO4), boron trifluoride (BF 3 ), aluminum trichloride (AICh).
• HF hydrofluoric acid
• H2SO4 concentrated sulfuric acid
• BF 3 boron trifluoride
• AICh aluminum trichloride
• the use of these acids has drawbacks, in particular because of the increasingly strict measures aimed at protecting the environment.
• HF which is toxic, volatile and corrosive
• Concentrated sulfuric acid on the other hand, is not very active and requires the use of large volumes of acid, which generate discharges, mainly inorganic salts, which must be brought up to environmental standards before being discharged.
• Consecutive reaction means a reaction where the reaction product reacts with the reagent to form a heavier and unwanted product.
• the aim of the invention is therefore to improve the catalytic compositions in the form of a two-phase liquid-liquid system.
• the invention seeks in particular to improve their stability and/or to improve the yield and/or the selectivity of the desired reactions.
• the invention firstly relates to a catalytic composition in the form of a so-called Pickering emulsion, said composition comprising a first non-aqueous liquid phase L1 comprising hydrocarbon compounds, in which drops of a second liquid phase L2 are stabilized by solid particles, said second liquid phase L2 comprising at least one ionic liquid of formula Q + A-, Q + being an organic cation and A- being an anion, and in which is dissolved a Bronsted acid HB.
• the liquid phase L2 can comprise a single ionic liquid, or several different ionic liquids in a mixture (then having a cation and/or an anion different from each other).
• the invention has thus chosen to put the two-phase liquid/liquid catalytic composition in the form of a Pickering emulsion in order to stabilize it.
• Pickering emulsions are in fact liquid/liquid dispersions stabilized by nanoparticles or aggregates of solid nanoparticles which accumulate at the interface between the two immiscible liquids (generally water and oil) and prevent coalescence (see for example the publication Pickering, S. U. (1907). J. Chem. Soc. Trans. 91, 2001-2021).
• the particles used to make Pickering emulsions are able to cling irreversibly to the interface between the two liquids, causing a stabilization of the emulsion much more effective than the adsorption of surfactants (see by example in Aveyard, R., Binks, B. P., and Clint, J. H. (2003)... Adv.
• the direction of the emulsion (water in oil or oil in water) is determined by the preferential wettability of the particles towards one or the other phase.
• the most wetting liquid vis-à-vis the particles will constitute the continuous phase of the emulsion, and the least wetting the dispersed phase (one can refer, for example, to the publication Binks, B., and Lumsdon , S. (2000. Langmuir 16, 8622-8631).
• the invention has been able to demonstrate that the encapsulation of the ionic liquid phase Q + A _ containing Bronsted acid HB, in the form of droplets in a so-called "Pickering" emulsion makes it possible, in particular, to obtain a gain in very significant selectivity compared to the two-phase system previously described.
• the immobilization of the catalytic composition Q + A7HB within a Pickering emulsion leads to a whole series of other advantages, including a more efficient implementation of the catalytic formulation Q + A7HB, with, in particular, the reduction of liquid/liquid transfer problems and reduction of the energy consumption required to carry out this transfer.
• the immobilization of the catalytic composition Q + A7HB within a Pickering emulsion brings another advantage: the stabilization of the catalytic formulation Q + A7HB in the form of droplets, making it easily recyclable.
• the reaction can be carried out with an excess of continuous phase, with slight agitation, then the agitation is stopped and the emulsion is allowed to sediment, the upper phase containing the products is removed, and the mixture is recharged with a new continuous phase containing the reagent. In this case, the emulsion can then be recycled without being broken.
• PEOBS for "Pickering Emulsion Organic Biphasic System” or, in French, "biphasic organic system of Pickering emulsion”
• Another advantage of the invention it is possible to implement this system in a continuous reactor with a traversed bed.
• the organic cation Q + is a quaternary ammonium and/or a quaternary phosphonium and/or a trialkylsulfonium.
• the anion A- is an anion forming with the cation Q + a liquid salt below 150°C.
• the anion A- can in particular be chosen (alone or as a mixture of at least two of them) from tetrafluoroborate, tetraalkylborate, hexafluorophosphate, hexafluoroantimonate, alkylsulfonate, in particular methylsulfonate, perfluoroalkylsulfonate, in particular trifluoromethylsulfonate, fluorosulfonate, sulfate , phosphate, perfluoroacetate, in particular trifluoroacetate, perfluorosulfonamide, in particular bis-trifluoromethanesulfonyl amide (CF 3 SO 2 ) 2 N-fluorosulfonamide, perfluorosulfomethide, in particular tris-trifluoromethanesulfonyl methylide (CF 3 SO 2 ) 3C _ and carboranes.
• tetrafluoroborate tetraalky
• the Q + cation can be chosen from the following compounds (alone or as a mixture of at least two of them): for which R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different, linked or not to each other, represent hydrogen or hydrocarbyl groups having from 1 to 12 atoms of carbon, in particular alkyl, saturated or unsaturated, cycloalkyl or aromatic, aryl or aralkyl groups, comprising from 1 to 12 carbon atoms.
• ionic liquids Q + A _ of interest mention may be made of N-butylpyridinium hexafluorophosphate, N-ethylpyridinium tetrafluoroborate, butyl-3-methyl-1-imidazolium hexafluoroantimonate, butyl-3-methyl-1-imidazolium hexafluorophosphate, butyl-3-methyl-1-imidazolium trifluoromethylsulfonate, pyridinium fluorosulfonate, trimethylphenylammonium hexafluorophosphate, butyl-3-methyl-1 bis-trifluoromethylsulfonylamide -imidazolium, triethylsulfonium bis-trifluoromethylsulfonylamide, tributylhexylammonium bis-trifluoromethylsulfonylamide, butyl-3-methyl-1-imi
• the Bronsted acids used according to the invention are defined as being acid compounds capable of donating at least one proton.
• these Bronsted acids have the general formula HB, in which B represents an anion.
• the Bronsted acid HB comprises an anion B chosen from tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonate anions, in particular methylsulfonate, perfluorosulfonate, in particular trifluoromethylsulfonate, fluorosulfonate, sulfate, phosphate, perfluoroacetate, in particular trifluoroacetate, perfluorosulfonamide , in particular bis-trifluoromethanesulfonyl amide (CFsSOs ⁇ N-, fluorosulfonamide, perfluorosulfomethide, in particular tris-trifluoromethanesulf
• the catalytic composition may comprise one or more of these Bronsted acids, therefore with different B anions.
• the Bronsted acid HB has the formula Q2 + A2 'in which O2 + represents an organic cation comprising at least one sulphonic acid or carboxylic acid function, and A 2 _ represents an anion, in particular the same anion as the anion A- of the ionic liquid.
• the expression sulphonic acid or carboxylic acid function means a hydrocarbyl substituent having from 1 to 12 carbon atoms containing a sulphonic acid (-SO3H) or carboxylic acid (-CO2H) group grafted onto the cation Q 2 + .
• compositions Q2 + A 2 _ of interest mention may be made of 1-methyl-3-(2-ethylsulfonic)imidazolium trifluoromethylsulfonate, 1-ethyl-3-(2-ethylcarboxylic)imidazolium bistriflylamide, N-butyl-N-(2-)trifluoromethylsulfonate ethylsulfonic acid) pyrrolidinium, N-ethyl-N-(2-ethylcarboxylic) pyrrolidinium bistriflylamide, (2-ethylsulfonic) triethylammonium trifluoromethylsulfonate and triphenyl(3-propylsulfonic) phosphonium paratoluene sulfonate.
• the first liquid phase L1 may comprise one or more saturated hydrocarbons, in particular of the linear or cyclic alkane type, and/or one or more unsaturated hydrocarbons, in particular of the olefin or aromatic compound type.
• Said hydrocarbon(s) preferably having between 3 and 20 carbon atoms, preferably between 5 and 9 carbon atoms.
• the first phase L1 comprises only one or more hydrocarbons.
• the first liquid phase L1 can be chosen from pentane, hexane, heptane, cyclohexane, methylcyclohexane, toluene, xylene, pure or as a mixture. Preferably, it is chosen from heptane, cyclohexane and methylcyclohexane.
• the first liquid phase L1 is an unsaturated hydrocarbon
• the products of the acid catalysis reaction used alkylbenzene, di-isobutene, etc.:
• the initial emulsion is a liquid emulsion ionic-HB / reaction product.
• the product then constitutes the continuous phase.
• the procedure can then consist in introducing the reagent (for example isobutene) into the continuous phase, the reaction takes place in the drops of ionic liquid as in the conventional case, the reaction products not being miscible with the phase ionic liquid, unlike the reactant which is soluble in both phases.
• the solid particles which are suitable for the invention can be of various shapes and sizes (for example from a few nanometers to a few microns, in the form of substantially spherical beads or not). They can be of a single type, or be used as a mixture of several types of particles. They can be modified to change their surface properties (in particular to modify their wettability).
• This surfactant can be of the anionic, cationic, non-ionic or amphoteric type.
• the solid particles can thus be chosen from: silica particles, preferably functionalized with hydrophobic hydrocarbon groups, clay particles, preferably modified with organic or amphiphilic molecules, magnetic nanoparticles, in particular FesC, carbon nanotubes, graphene oxide particles, synthetic polymer particles, such as polyethylene glycol (PEG), polystyrene (PS), polylactic acid (PLA), polycaprolactone (PCL), or latex particles, particles of material of natural origin chosen preferably from hydroxyapatite, chitosan, cyclodextrin, dextran, particles in the form of cellulose nanocrystals or nanofibers, particles of biological material, in particular of food grade, preferably chosen from starch, zein, soy proteins, bacteria and yeasts.
• synthetic polymer particles such as polyethylene glycol (PEG), polystyrene (PS), polylactic acid (PLA), polycaprolactone (PCL), or latex particles
• PEG polyethylene glycol
• PS polystyrene
• the ratio in the emulsion between the largest dimension of the drops and the largest dimension of the solid particles is at least 100.
• the largest dimension is understood to mean the diameter when the particles are substantially spherical).
• the largest dimension of the drops is between 1 ⁇ m and 1000 ⁇ m, preferably between 2 ⁇ m and 100 ⁇ m, in particular between 10 ⁇ m and 50 ⁇ m.
• the size of the drops is measured by optical microscopy (in particular by Olympus BX51 with analysis software for image analysis).
• the content of solid particles with respect to the second liquid phase L2 can be chosen from 0.1 to 10% by weight, in particular from 0.5 to 5% by weight, preferably from 1 to 3% by weight.
• the volume ratio between the second liquid phase L2 and the first liquid phase L1 is preferably between 2:1 and 1:10, preferably between 1:1 and 1:5.
• the catalytic composition according to the invention preferably has a concentration of Bronsted acid HB within the second liquid phase L2 of between 0.05 and 40.0% by weight, preferably between 0.1 and 5% by weight.
• a subject of the invention is also a method for preparing the catalytic composition as described above, and which comprises the following steps:
• the invention also relates to an acid catalysis process, which uses the catalytic composition as described above.
• the invention also relates to an acid catalysis process, which uses a catalytic composition in the form of a so-called Pickering emulsion, said composition comprising a first non-aqueous liquid phase L1 comprising hydrocarbon compounds, in which drops of a second liquid phase L2 are stabilized by solid particles, said second liquid phase L2 comprising at least one ionic liquid of formula Q + A-, Q + being an organic cation and A- being an anion, and in which an acid is dissolved by Bronsted HB.
• a catalytic composition in the form of a so-called Pickering emulsion
• said composition comprising a first non-aqueous liquid phase L1 comprising hydrocarbon compounds, in which drops of a second liquid phase L2 are stabilized by solid particles, said second liquid phase L2 comprising at least one ionic liquid of formula Q + A-, Q + being an organic cation and A- being an anion, and in which an acid is dissolved by Bronsted HB.
• the acid catalysis process according to the invention preferably takes place as follows: reagents are introduced in liquid or gaseous form into the catalytic composition, they interact with/solubilize in the drops of the second liquid phase L2 to convert into soluble reaction products in the first liquid phase L1. And the reaction products are then extracted from said first liquid phase L1, depending on the case, by breaking the emulsion of the catalytic composition, for example by performing a centrifugation, or without having to break the emulsion by operating sequentially , using, for example, the PEOBS technique mentioned above.
• the acid catalysis process according to the invention can be implemented in a closed, semi-open or continuous system, with one or more reaction stages.
• the acid catalysis process according to the invention can be a process for the alkylation of aromatic hydrocarbons, for the oligomerization of olefins, for the dimerization of isobutene, for the isomerization of n-olefins to iso-olefins, for the isomerization of n-paraffins to isoparaffins, and alkylation of isobutane by olefins.
• the acid catalysis process according to the invention can be an alkylation process:
• aromatic hydrocarbons chosen from monocyclic aromatics, in particular benzene, and alkylbenzenes such as toluene, ethylbenzene, xylene, mesitylene, durene or polycyclics, in particular naphthalene, alkylnaphthalenes and anthracene, said aromatic hydrocarbons possibly being substituted by one or more alkyl groups, aryl, alkylaryl, alkoxy, aryloxy, cycloalkyl and/or by any group which does not interfere with the alkylation reaction,
• At least one alkylating agent in the form of olefins having a number of carbon atoms from 2 to 20, these olefins being preferably chosen from ethylene, butenes, hexene-1, octene-1 , decene-1, dodecene-1, tetradecene-1, alone or as a mixture.
• olefins can be obtained, for example, in processes for the production of alpha-olefins by oligomerization of ethylene or in processes for the dehydrogenation of paraffins.
• olefins can be used pure or diluted, in particular in an alkane.
• the molar ratio between the alkylating agent and the aromatic hydrocarbon can range from 0.05 to 100, and preferably from 0.1 to 10.
• the temperature at which the aromatic alkylation is carried out is preferably between -50°C and 200°C, being preferably less than 100°C and in particular between -20°C and 50°C.
• the aromatic alkylation can take place in the presence or absence of the vapor phase, and the reaction pressure is preferably the autogenous pressure.
• the duration of the aromatic alkylation reaction is preferably between 1 minute and 10 hours.
• the acid catalysis process according to the invention can be an olefin isomerization process, in particular of at least one olefin having from 4 to 30 carbon atoms.
• the acid catalysis process according to the invention can be a process for the dimerization of isobutene, starting from pure isobutene or as a mixture with other hydrocarbons, optionally in the presence of an alcohol or of an ether.
• isobutene The possible origins of isobutene are diverse. The most common are the dehydrogenation of isobutane, the dehydration of tert-butyl alcohol.
• the isobutene can also come from a C4 cut of FCC ("Fluid Catalytic Cracking") or from steam cracking. In the latter case, isobutene can be used as a mixture with n-butenes, isobutane and butane.
• FCC Fluid Catalytic Cracking
• the process according to the invention then has the additional advantage of making it possible to convert the isobutene selectively, without it having to be separated from the other constituents of the cut.
• Another advantage of the process according to the invention is that the co- isobutene-butene dimerization may be limited. Isobutene can also come from a biobased alcohol dehydration process.
• the temperature at which the isomerization or dimerization is carried out is preferably between -50°C to 200°C, preferably being less than 100°C.
• the isomerization or dimerization process can advantageously be carried out by reactive distillation.
• the acid catalysis process according to the invention may be a process for the alkylation of iso-paraffin, in particular isobutane, by olefins, said olefins being chosen from at least one of the following olefins: ethylene, butenes, hexene-1, octene-1, decene-1, dodecene-1, tetradecene-1, alone or as a mixture.
• olefins can be obtained in processes for the production of alpha-olefins by oligomerization of ethylene or in processes for the dehydrogenation of paraffins.
• olefins can be used pure or as a mixture.
• the iso-paraffin and the olefin can be introduced (into the catalytic composition) separately or as a mixture.
• the molar ratio between the iso-paraffin and the olefin is advantageously between 2/1 and 100/1, preferably between 10/1 and 50/1, in particular between 5/1 and 20/1.
• the temperature at which the iso-paraffin alkylation is carried out is preferably between -50 and 200°C, in particular between -20 and 30°C.
• the coalescence stability of the catalytic composition emulsion is evaluated by an optical method based on multiple light scattering.
• the analysis of the transmission and backscattering signals of light (wavelength 880 nm) is carried out using a Turbiscan device marketed by the company Formulaction.
• the technique makes it possible to highlight the phenomena of sedimentation, creaming and possible coalescence.
• the apparatus is used to verify that there is no coalescence of the dispersed phase of the emulsion and to confirm the stability of the emulsion to coalescence.
• the various embodiments presented can be used alone or in combination with each other, without limitation of combination.
• the various ranges of parameters for a given stage such as the pressure ranges and the temperature ranges can be used alone or in combination.
• a preferred range of pressure values can be combined with a more preferred range of temperature values.
• Example 1 (comparative): Dimerization of isobutene in a two-phase system
• the internal standard is a compound inert with respect to the chemical reaction carried out, which is introduced in a known quantity into the reaction medium. It makes it possible to measure the quantity of products formed after reaction, by gas chromatography, in the following way (schematically): the chromatographic area of the internal standard peak is measured, which corresponds to the mass that was introduced initially, then the area of the products, and by rule of three we deduce the mass of these products). Then, 44 g of a liquid feed containing 12% by weight of isobutene and 88% by weight of n-heptane, ie 5.28 g of isobutene, are introduced at ambient temperature. Stirring is then started (reaction time zero).
• the catalytic test is carried out in the same way as in Example 1, except that the reaction time is increased to 60 min. Isobutene conversion is 88%. The selectivity for dimerization (trimethyl-2,4,4-pentenes) and trimerization (C12) products is respectively 51% and 49%.
• Example 3 (according to the invention): Preparation of the Pickering emulsion [BMI][NTf 2 ]/HNTF 2 /SiO 2 /heptane
• solid silica particles which here are silica fume particles with the commercial reference Aerosil R972, marketed by the company EVONIK.
• the second liquid phase L2 is prepared: a mixture consisting of 5.6 g of 1-Butyl-3-Methylimidazolium bis(trifluoromethanesulfonyl)imide ([BMI][NTf2]) and 0.014g of HNTf2 acid.
• This mixture (second liquid phase L2) is poured drop by drop into the beaker containing the n-heptane (first liquid phase L1) and the silica particles, with continuous application of dispersion energy provided by a rotor-stator system ( UltraTurrax device, marketed by the company IKA, 10,000 rpm).
• a rotor-stator system UltraTurrax device, marketed by the company IKA, 10,000 rpm.
• the Pickering emulsion thus obtained contains 2.5% by weight of silica particles relative to the dispersed ionic liquid phase (L2).
• the emulsion thus produced has an average droplet size in number of 20 ⁇ m, with a minimum diameter of 9 ⁇ m and a maximum diameter of 54 ⁇ m. No coalescence was detected by the Turbiscan device according to the method described above.
• Example 4 Dimerization of isobutene using the Pickering emulsion system described in example 3
• This sample is analyzed by gas phase chromatography (PONA column) after treatment with sodium hydroxide (0.1 M) to eliminate any traces of acid and drying over MgS04.
• PONA column gas phase chromatography
• Isobutene conversion is 35%.
• the selectivity for dimerization (trimethyl-2,4,4-pentenes) and trimerization (C12) products is 91% and 9%, respectively.
• Example 5 Dimerization of isobutene using the Pickering emulsion system described in Example 3
• the catalytic test is carried out in the same way as in Example 4, except that the reaction time is increased to 60 min. Isobutene conversion is 88%. The selectivity for dimerization (trimethyl-2,4,4-pentenes) and trimerization (C12) products is 74% and 26%, respectively.
• Table 1 below shows all the results obtained on the basis of Examples 1 to 5. It highlights the very significant impact of the invention on the control of the selectivity for dimerization product: in fact, the comparative examples have a dimer selectivity/trimer selectivity ratio of at most 1.50 (example 1), whereas the examples according to the invention have a ratio of at least 2.84 (example 5) up to 10 (example 4), therefore a selectivity at least almost doubled.
• Example 6 Dimerization of an isobutene/1-butene mixture in a two-phase system
• the Fisher-Porter tube is opened to remove a few ml of the supernatant organic phase. This is analyzed by gas phase chromatography (PONA column) after treatment with sodium hydroxide (0.1 M) to eliminate any traces of acid and drying over MgS04. Isobutene conversion is 32%, while 1-butene conversion is only 5.4%. The selectivity for dimerization (trimethyl-2,4,4-pentenes) and trimerization (C12) products is 67% and 33%, respectively.
• Example 7 Dimerization of an isobutene/1-butene mixture in a Pickering emulsion
• the pressure is evacuated, the gaseous phase is recovered in a bladder and analyzed by gas chromatography on an Alumina Plot column.
• the Fisher-Porter tube is opened to remove a few ml of the supernatant organic phase. This is analyzed by gas phase chromatography (PONA column) after treatment with sodium hydroxide (0.1 M) to eliminate any traces of acid and drying over MgS04.
• PONA column gas phase chromatography
• the conversion of isobutene is 34% while the conversion of 1-butene is only 5.1%.
• the selectivity for dimerization (trimethyl-2,4,4-pentenes) and trimerization (C12) products is 93% and 7%, respectively.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Dispersion Chemistry (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=80933159

Family Applications (1)

Country Status (4)

Family Cites Families (5)

• 2021
  • 2021-12-21 FR FR2114086A patent/FR3130643A1/fr active Pending
• 2022
  • 2022-12-12 WO PCT/EP2022/085454 patent/WO2023117553A2/fr not_active Ceased
  • 2022-12-12 US US18/721,931 patent/US20250050319A1/en active Pending
  • 2022-12-12 EP EP22835719.0A patent/EP4452486A2/de active Pending

Also Published As

Similar Documents

Legal Events