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
  • 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
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  • 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
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/396—Distribution of the active metal ingredient
  • B01J35/398—Egg yolk like
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  • 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
  • B01J13/14—Polymerisation; cross-linking
  • B01J13/18—In situ polymerisation with all reactants being present in the same phase
  • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
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  • 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
  • B01J31/0281—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
  • B01J31/0298—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
  • B01J35/20—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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
• • 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
  • 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. It relates more particularly to a composition resulting from the dissolution of at least one Brönsted acid, denoted HB, in an ionic liquid medium comprising at least one organic cation Q + and one anion A ⁇ .
• 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 petrochemistry.
• solid catalysts such as zeolites or sulphonic resins can provide an improvement as regards the separation of the products and the recycling of the catalyst, but they often require higher reaction temperatures.
• An alternative approach for example described in patent FR 2829039, consists in implementing this type of reaction and catalyst in the form of a two-phase liquid-liquid system: The Lewis and/or Brönsted acid is immobilized in an ionic liquid phase Q + A-, which is little or not miscible with the products of the reaction. These can then be separated by decantation, and the catalytic phase can then be recycled and reused. Catalyst consumption is thus reduced.
• the viscosity of ionic liquids implies, for example, the implementation of a fairly high mechanical energy to ensure mixing between the two phases.
• the reaction selectivities can moreover be difficult to control, in particular because of the consecutive reactions linked to the partial miscibility of the primary products in the acidic ionic liquid. (One understands by consecutive reaction, a reaction where the reaction product reacts with the reactant to form a heavier and undesired product.)
• Another approach consists in implementing this type of reactions and catalysts in a continuous process, by example within a column-type reactor, in a fixed bed, with the immobilization of said catalytic composition in supported form.
• the immobilization can be done by covalent bonds between the ionic liquid and the support, or by physisorption via electrostatic interactions (Van der Waals, dipolar forces).
• the SILP type technology nevertheless has drawbacks: the electrostatic type bonds between the ionic liquid and the support are weak bonds, which can lead to a loss of ionic liquid by leaching over time. This type of implementation is therefore not very suitable for the immobilization of catalytic systems of interest to the present invention, for which the recycling of the catalyst in its entirety, or at least in large part, is desired.
• the object of the invention is therefore to improve the design of catalytic compositions operating in homogeneous liquid-liquid catalysis.
• the invention seeks in particular to improve their stability and/or their recyclability, or even to improve the yield and/or to improve the selectivity of the desired reactions.
• SUMMARY OF THE INVENTION The subject of the invention is first of all a catalytic composition in the form of a capsule whose walls of solid material define a closed volume which contains a liquid phase 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 Brönsted acid HB.
• capsules with a liquid core are very interesting, and “operate” in the following way: they are brought into contact with the reactant(s) in liquid form, for example in free suspension or in a fixed bed in a reactor. Their solid walls are chosen to be tight vis-à-vis the ionic liquid, but porous vis-à-vis the reagents and reaction products targeted: the reagents react by coming into contact with the ionic liquid of the capsules, forming reaction products which diffuse out of the capsules.
• the invention has thus developed capsules with a liquid core, which have many advantages: First of all, these capsules stabilize the catalytic formulation, they come to immobilize the Q + A- / HB system, without releasing the acid of Bronsted.
• these capsules are easily recyclable. They are also easy to implement in reactors operating continuously, in a traversed bed for example, or even in a fluidized bed. These capsules have very good pressure resistance (in particular at least up to 10 bars), which allows them to be used in processes which require the reagent to be liquefied (for example in the case of a dimerization reaction of isobutene). These capsules allow implementation in "heterogeneous" form of very viscous catalytic systems, in particular those based on formulations from ionic liquids. The solid capsules of the invention make it possible to implement them more easily, without having to consider their high viscosity.
• the concentration of Brönsted acid HB in the ionic liquid is between 0.05 and 40% by weight, in particular between 1 and 20% by weight.
• the largest average dimension of the capsules, in particular their average diameter in the case of substantially spherical capsules, is generally between 1 and 1000 ⁇ m, in particular between 2 and 100 ⁇ m, or between 10 ⁇ m and 50 ⁇ m.
• the organic cation Q + can be a quaternary ammonium and/or a quaternary phosphonium and/or a trialkylsulfonium, and the anion A ⁇ is an anion forming with the cation Q + a liquid salt below 150°C.
• the anion A- can be chosen 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 ) 3 C- and carboranes.
• the anion A- is an anion forming with the cation Q + a liquid salt below 150°C.
• the Q + cation can in particular be chosen from the following compounds: for which R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different, linked or not, represent hydrogen or hydrocarbyl groups having from 1 to 12 carbon atoms, 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 according to the invention, 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 Brönsted acids used according to the invention are defined as being acid compounds capable of donating at least one proton. According to the invention, these Brönsted acids have the general formula HB, in which B represents an anion.
• the Brönsted acid HB comprises an anion B chosen from among the anions tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates, in particular methylsulfonate, perfluorosulfonate, 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 ) 3 C- and carborane.
• anion B chosen from among the anions tetrafluoroborate, tetraalkylbor
• the catalytic composition may comprise one or more of these Brönsted acids, therefore with different B anions.
• the Brönsted acid HB has the formula Q 2 + A 2 -, in which Q 2 + 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 term sulphonic acid or carboxylic acid function means a hydrocarbyl substituent having from 1 to 12 carbon atoms containing a sulphonic acid (-SO 3 H) or carboxylic acid (-CO 2 H) group grafted onto the cation Q2 +.
• compositions Q 2 + A 2 - mention may be made of 1-methyl-3-(2-ethylsulfonic)imidazolium trifluoromethylsulfonate, 1-ethyl-3-(2-ethylcarboxylic)imidazolium bistriflylamide, N-butyl-N-(2-ethylsulfonic) pyrrolidinium trifluoromethylsulfonate, N-ethyl-N-(2-ethylcarboxylic) bistriflylamide pyrrolidinium, (2-ethylsulfonic) triethylammonium trifluoromethylsulfonate and triphenyl(3-propylsulfonic) phosphonium paratoluenesulfonate.
• the solid material of the walls of the capsule can be obtained from solid particles chosen from silica particles, preferably functionalized with hydrophobic hydrocarbon groups, clay particles, preferably modified with organic or amphiphilic molecules, nanoparticles magnetic materials, in particular Fe3O4, carbon nanotubes, particles of graphene oxides, particles of synthetic polymers, 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, with possible addition to the particles of at least one surfactant.
• solid particles chosen from silica particles, preferably functionalized with hydrophobic hydrocarbon groups, clay particles, preferably modified with organic or amphiphilic molecules, nanoparticles magnetic materials, in particular Fe3O4, carbon nanotubes, particles of graphene oxides, particles of synthetic polymers, particles of material of natural origin
• the optional surfactant or each of the optional surfactants if there are several, can be of the ionic, cationic or anionic, non-ionic or amphoteric type.
• the solid material of the walls of the capsule is obtained by said particles and by a crust formed by adding a crosslinking agent, which makes it possible to bind the solid particles together.
• this crosslinking agent is chosen from at least one silicon compound of the orthosilicate or alkoxysilane type, in particular chosen from at least tetramethyl orthosilicate, tetraethyl orthosilicate, tetrabutyl orthosilicate, trimethoxysilane and triethoxysilane.
• This type of crosslinking agent is in fact capable of crosslinking by hydrolysis, and then serves as a base material for forming a solid crust.
• the solid particles are chosen based on silicon oxide optionally functionalized with hydrophobic groups, and the crust is obtained by hydrolysis of a crosslinking agent chosen from the orthosilicates or alkoxysilanes mentioned above. high.
• a subject of the invention is also a process for the preparation of the catalytic composition as described above.
• This process may comprise the following steps: (a) addition of Brönsted acid HB to the liquid comprising at least one organic cation Q + and one anion A- to obtain an ionic liquid denoted Q + A-/HB, (b ) addition of the ionic liquid Q + A-/HB in a liquid phase L1 of hydrocarbon(s) containing solid particles, in order to form a so-called Pickering emulsion comprising drops of the ionic liquid Q + A-/HB stabilized by the solid particles in the liquid phase L1 of hydrocarbon(s), (c) addition to the emulsion obtained in step (b) of a crosslinking agent, in order to bind the solid particles together to form solid walls surrounding the drops of ionic liquid Q + A-/HB in the form capsules of catalytic composition in suspension in the liquid phase L1.
• a subject of the invention is also the assembly comprising the encapsulated catalytic compositions described above, and the liquid phase L1 which was used for their preparation and in which the capsules are in suspension.
• Pickering emulsions are liquid/liquid dispersions stabilized by nanoparticles or aggregates of solid nanoparticles that accumulate at the interface between two immiscible liquids (usually water and oil) and prevent coalescence (see for example the publication Pickering, SU (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, BP, and Clint, JH (2003. Adv. Colloid Interface Sci.100, 503–546).
• 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 (see for example the publication Binks, B., and Lumsdon, S. ( 2000. Langmuir 16, 8622–8631).
• the capsules according to the invention are therefore prepared by going through an intermediate stage of forming such a so-called Pickering emulsion: instead of using as they are the drops of ionic liquid surrounded by solid particles, the invention creates from of these solid particles arranged around the drops a crust, a shell, a solid wall: thus encapsulated, the drops are more stable, easier to recycle and implement, they can also withstand higher pressure.
• the ionic liquid Q + A-/HB can also comprise water, in particular in a content of 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, and advantageously from 1 to 3% by weight. compared to the ionic liquid Q + A-/HB.
• the volume ratio between the ionic liquid Q + A-/HB and the liquid phase L1 of hydrocarbon(s) is preferably between 2:1 and 1:10, in particular between 1:1 and 1:5.
• the addition of the crosslinking agent can be done by prior solubilization of said crosslinking agent in a liquid phase L2 of hydrocarbon(s), and it is therefore the liquid phase L2 containing the crosslinking agent which is added to the emulsion.
• the solid particles can be chosen based on silicon compounds, in particular silica, preferably functionalized with hydrophobic hydrocarbon groups.
• the crosslinking agent may be chosen from at least one silicon compound of the orthosilicate or alkoxysilane type, in particular chosen from at least one of the compounds: tetramethyl orthosilicate, tetraethyl orthosilicate, tetrabutyl orthosilicate, trimethoxysilane or triethoxysilane.
• the optional presence of water in the ionic liquid can thus promote the crosslinking of the crosslinking agent, when the crosslinking takes place by hydrolysis.
• the mass ratio between the crosslinking agent and the solid particles is between 1 and 10, in particular between 1 and 6.
• Step (c) for crosslinking the solid particles is preferably carried out at a temperature between 30 and 60° C., in particular for 2 to 24 hours.
• the preparation process according to the invention may also comprise a step (d) of separating the capsules of catalytic composition from the liquid phase L1 (or from at least part of said liquid phase).
• the preparation process according to the invention may also comprise a step (e) of washing the capsules separated in step (d), in particular with an L3 solvent immiscible with the encapsulated catalytic composition, in particular non-aqueous, and preferably based on hydrocarbon(s).
• the quantity of solid particles is between 0.1 and 10% by weight, preferably 0.5 to 5% by weight, in particular from 1 to 3 % by weight, relative to the ionic liquid Q + A-/HB.
• 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).
• the liquid phase L1 used in step (b) comprises 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 or hydrocarbons having preferably 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.
• the first liquid phase L1 is an unsaturated hydrocarbon
• it can be chosen from the products of the acid catalysis reaction implemented (alkylbenzene, di-isobutene, etc.)
• the liquid phases L2 and L3, when they are used, may contain the same hydrocarbons as the liquid phase: either at least phase L2 and/or phase L3 has the same composition as phase L1, or they are at least chosen from the hydrocarbons or mixtures of hydrocarbons mentioned above for the L1 phase.
• a subject of the invention is also an acid catalysis process which uses the catalytic composition in the form of capsules described above or prepared according to the preparation process described above.
• a subject of the invention is also an acid catalysis process, in which a catalytic composition is used in the form of a capsule whose walls of solid material define a closed volume which contains a liquid phase 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 Brönsted acid HB.
• the acid catalysis process can be implemented in a closed, semi-open or continuous system, with one or more reaction stages.
• It can be a process for alkylation of aromatic hydrocarbons, oligomerization of olefins, dimerization of isobutene, isomerization of n-olefins to iso-olefins, isomerization of n-paraffins to iso-paraffins, and alkylation of isobutane by olefins.
• 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, aryl, alkylaryl, alkoxy, aryloxy, cycloalkyl groups and/or by any group which does not interfere with the alkylation reaction, with 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.
• alkylbenzenes such as to
• the molar ratio between the alkylating agent and the aromatic hydrocarbon is preferably between 0.05 and 100, and preferably between 0.1 and 10.
• the temperature at which the aromatic alkylation is carried out may be between -50°C and 200°C, preferably being less than 100°C and in particular between -20°C and 50°C, in the presence or absence of the vapor phase.
• the reaction time is preferably between 1 minute and 10 hours.
• the acid catalysis process can be an olefin isomerization process, in particular of at least one olefin having from 4 to 30 carbon atoms.
• the acid catalysis process can be an isobutene dimerization process, starting from pure isobutene or as a mixture with other hydrocarbons, optionally in the presence of an alcohol or an ether.
• the temperature at which the dimerization is carried out is between -50°C and 200°C, preferably being below 100°C.
• the acid catalysis process can be carried out by reactive distillation.
• the acid catalysis process 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.
• the molar ratio between the iso-paraffin and the olefin is preferably 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 can be between -50 and 200°C, in particular between -20 and 30°C.
• FIG. 1 represents a scanning electron microscope image of capsules of catalytic composition prepared according to the invention.
• 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.
• the expressions “between ... and ...” and “between .... and ...” are equivalent and mean that the limit values of the interval are included in the range of values described.
• the object of the invention is a catalytic composition in the form of a capsule whose walls of solid material define a closed volume which contains a liquid phase 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 Brönsted acid HB, said catalytic composition being immobilized within capsules which comprise solid walls, also called “crust” and a liquid core.
• the non-aqueous liquid medium in which the Brönsted acid HB according to the invention is dissolved has the general formula Q + A- in which Q + represents a quaternary ammonium and/or a quaternary phosphonium and/or a trialkylsulfonium (III) and A- represents any known anion capable of forming with the cation Q + , a liquid salt at low temperature, i.e. below 150°C:
• R1, R2, R3, R4, R5 and R6 which are identical or different, bonded or not to each other, represent hydrogen, hydrocarbyl residues having from 1 to 12 carbon atoms, for example alkyl groups, saturated or unsaturated , cycloalkyls or aromatics, aryl or aralkyl, comprising from 1 to 12 carbon atoms, Among the R1, R2, R3, R4, R5 and R6 groups, mention will be made of the methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, butyl, tertiary, amyl, phenyl or benzyl;
• the ammonium and/or phosphonium cation is preferably chosen from the group formed by N-butylpyridinium, N-ethylpyridinium, 3-butyl-1-methylimidazolium, diethylpyrazolium, 3-ethyl-1-methylimidazolium, pyridin
• the A- anions that can be used in the context of the invention are preferably chosen from tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates (for example methylsulfonate), perfluoroalkylsulfonates (for example trifluoromethylsulfonate), fluorosulfonate, sulfates, phosphates, perfluoroacetates (for example trifluoroacetate), perfluorosulfonamides (for example bis-trifluoromethanesulfonyl amide (CF 3 SO 2 ) 2 N- fluorosulfonamides, perfluorosulfomethides (for example tris-trifluoromethanesulfonyl methylide (CF 3 SO 2 ) 3 C- and carboranes
• ionic liquids Q + A ⁇ that can be used according to the invention
• the Brönsted acids used according to the invention are defined as being acid compounds capable of donating at least one proton. According to the invention, these Brönsted acids have the general formula HB, in which B represents an anion.
• the anions B are preferably chosen from tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates (for example methylsulfonate), perfluorosulfonates (for example trifluoromethylsulfonate), fluorosulfonate, sulfates, phosphates, perfluoroacetates (for example trifluoroacetate), perfluorosulfonamides (for example for example bis-trifluoromethanesulfonyl amide (CF 3 SO 2 ) 2 N-, fluorosulfonamides, perfluorosulfomethides (for example tris-trifluoromethanesulfonyl methylide (CF 3 SO 2 ) 3 C- and carboranes.
• alkylsulfonates for example methylsulfonate
• perfluorosulfonates for example tri
• the Brönsted acids used according to invention can be used alone or as a mixture
• the Brönsted acid HB can also have the general formula Q2 + A2 -, in which Q2 + represents an organic cation comprising at least one sulphonic acid or carboxylic acid function , and A2- represents an anion (specify that these are the same anions as A-)
• sulphonic acid or carboxylic acid function is meant a hydrocarbyl substituent having from 1 to 12 carbon atoms containing a sulphonic acid (-SO3H) or acid carboxylic acid (-CO 2 H) grafted onto the Q 2+ cation.
• compositions Q 2 + A 2 - which can be used, mention may be made of 1-methyl-3-(2-ethylsulfonic)imidazolium trifluoromethylsulfonate, 1-ethyl-3-(2-ethylcarboxylic)imidazolium bistriflylamide, N-butyl-N-(2-ethylsulfonic)pyrrolidinium trifluoromethylsulfonate, N-ethyl-N-(2-ethylcarboxylic)pyrrolidinium bistriflylamide, (2-ethylsulfonic)triethylammonium trifluoromethylsulfonate and triphenyl(3- propylsulfonic)phosphonium.
• the crust (or wall of the capsules) according to the invention consists of two elements: - on the one hand the solid particles used in the preparation of the Pickering emulsion.
• These particles are advantageously silica particles having an affinity for each of the two phases.
• the silica particles which are naturally hydrophilic due to the presence of groups silanols, are preferentially functionalized with hydrophobic hydrocarbon groups.
• modified silica particles different types of organic and inorganic particles can be used to stabilize Pickering emulsions, as detailed in the review article by Yang et al. ,2017), Front. Pharmacol.8:287.).
• clays which like silica, can be easily modified with organic or amphiphilic molecules, but also in a non-exhaustive way magnetic nanoparticles (Fe3O4), carbon nanotubes, graphene oxides, synthetic polymers, natural products such as hydroxyapatite, chitosan, cyclodextrin, dextran, cellulose nanocrystals or nanofibers, as well as food-grade biological particles such as starch, zein (corn protein), soy protein, wheat and even bacteria and yeasts. These particles come in various shapes and sizes (from a few nm to a few ⁇ m), can be used as such or in a mixture, and can be modified to change the surface properties (wettability).
• Fe3O4 magnetic nanoparticles
• carbon nanotubes graphene oxides
• synthetic polymers synthetic polymers
• natural products such as hydroxyapatite, chitosan, cyclodextrin, dextran, cellulose nanocrystals or nanofibers
• this agent cross-links by hydrolysis, creating a crust which binds the particles together.
• This agent can advantageously be a silica compound of the orthosilicate or alkoxysilane type. It may be, in a non-exhaustive manner, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrabutyl orthosilicate, trimethoxysilane or triethoxysilane.
• the invention also provides a method for preparing capsules with a liquid core making it possible to encapsulate a catalytic formulation Q+A-/HB, and comprising the following steps: Bronsted acid HB and water are added to the ionic liquid Q + A- under magnetic stirring. The solid particles are dispersed in the hydrocarbon phase with magnetic stirring, or using a rotor-stator system of the type of the system marketed under the name Ultra-Turrax.
• the ionic liquid solution containing Bronsted acid and water, denoted Q + A-/HB, is preferably added drop by drop to the hydrocarbon phase (liquid phase L1) containing the solid particles under a strong agitation, allowing the particles to settle at the interface between the droplets of ionic liquid and the hydrocarbon phase, and forming a Pickering emulsion of the ionic liquid in hydrocarbon type.
• the dispersive energy is provided by any type of system providing energy to generate emulsification (rotor stator, propeller stirrer, static mixer, colloid mill, membrane system, ultrasonic stirring, microfluidic system, etc.).
• the assembly is placed in a rotary system of the rotary evaporator type, and heated to the temperature allowing the hydrolysis of the precursor to be carried out, for the appropriate time.
• the compositions of phases L1 and L2 are identical.
• the upper hydrocarbon phase containing the residual precursor is then removed by sampling, the capsules with a liquid core thus obtained are washed several times with a hydrocarbon solvent immiscible with the encapsulated ionic liquid.
• the quantity of solid particles used to manufacture the Pickering emulsion is generally located in the range of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 1% to 3% with respect to the dispersed phase, namely the ionic liquid Q + A-/HB.
• the quantity of water introduced into the dispersed phase namely the ionic liquid Q + A-/HB, is located in the range of 0.1 to 10% by mass, more preferably from 0.5% to 5% with respect to the dispersed phase, namely the ionic liquid Q + A-/HB.
• the volume ratio between the dispersed phase, namely the ionic liquid Q + A-/HB, and the hydrocarbon phase (phases L1 + L2) is between 2:1 and 1:10, preferably between 1:1 and 1: 5.
• the concentration of Bronsted acid HB within the ionic liquid Q + A ⁇ is generally between 0.05 and 40.0% by mass, preferably between 1 and 20%.
• the stirring speed ensured by the rotor-stator system to manufacture the Pickering emulsion is generally between 1000 and 20000 rpm, preferably between 2000 and 18000 rpm, very preferably between 5000 and 15000 rpm. minute.
• the mass ratio between the silica precursor and the solid particles is generally between 1 and 10, preferably between 2 and 6.
• the manufacture of the crust of the capsules by hydrolysis of the precursor is carried out in a rotary system of the rotary evaporator type, at a temperature between 30 and 60°C, for a heating time of between 2 and 24 h.
• the preferred liquid-core capsules according to the invention have a number-average diameter of between 1 ⁇ m and 1000 ⁇ m, preferably between 2 ⁇ m and 100 ⁇ m.
• the average size of the capsules is measured by optical microscopy (Olympus BX51 with analySIS software for image analysis) or by scanning electron microscopy (SEM, ZEISS Supra 40 device).
• the catalytic composition as defined above is used more particularly in acid catalysis processes, in particular processes for the alkylation of aromatic hydrocarbons, for the oligomerization of olefins, for the dimerization of isobutene, isomerization of n-olefins to iso-olefins, isomerization of n-paraffins to iso-paraffins, and alkylation of isobutane by olefins.
• the acid catalysis process using the catalytic compositions defined above consists of an aromatic alkylation process.
• the aromatic hydrocarbons considered according to the invention are monocyclic or polycyclic aromatics such as naphthalene, alkylnaphthalenes and anthracene.
• Monocyclic aromatics are benzene and alkylbenzenes (toluene, ethylbenzene, xylene, mesitylene, durene, etc.).
• alkylating agents which can be used are olefins having a number of carbon atoms from 2 to 20. These olefins are more particularly ethylene, as well as butenes, hexene-1, octene-1, decene-1, dodecene-1, tetradecene-1, alone or as a mixture, as obtained for example in processes for the production of alpha-olefins by oligomerization of ethylene or in dehydrogenation processes paraffins.
• olefins can be used pure or diluted in an alkane.
• the molar ratio between the olefin 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 ranges, for example, from -50° C. to 200°C; it is advantageously below 100°C and preferably from -20°C to 50°C.
• the reaction can take place in the presence or absence of the vapor phase and the pressure is the autogenous pressure;
• the reaction time which depends on the temperature, is between 1 minute and 10 hours. It is adjusted so as to find a good compromise between conversion and selectivity.
• the acid catalysis process using the catalytic compositions defined above consists of a process for the dimerization of isobutene.
• the dimerization process according to the invention applies to isobutene pure or mixed with other hydrocarbons.
• the origins of isobutene are diverse. However, 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.
• the process according to the invention then has the additional advantage of making it possible to selectively convert the isobutene 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 isobutene-butene co-dimerization can be limited. Isobutene can also come from a biobased alcohol dehydration process.
• the dimerization reaction can be carried out in the presence of an alcohol or an ether.
• the temperature at which the dimerization reaction is carried out ranges, for example, from ⁇ 50° C. to 200° C.; it is advantageously less than 100°C.
• the dimerization reaction can be carried out using a reactive distillation technique.
• the acid catalysis process using the catalytic compositions defined above consists of a process for the alkylation of isobutane by olefins.
• the olefins which can be used in the isobutane alkylation process are chosen more particularly from ethylene, butenes, hexene-1, octene-1, decene-1, dodecene-1, tetradecene- 1, alone or as a mixture, as obtained for example in the processes for the production of alpha-olefins by oligomerization of ethylene or in the paraffin dehydrogenation processes. These olefins can be used pure or as a mixture.
• the iso-paraffin and the olefin can be introduced separately or as a mixture.
• the molar ratio between the iso-paraffin and the olefin is for example from 2/1 to 100/1 and more advantageously from 10/1 to 50/1, preferably from 5/1 to 20/1.
• the temperature at which the aliphatic alkylation reaction is carried out ranges, for example, from ⁇ 50° C. to 200° C.; preferably, it is from -20°C to +30°C.
• the acid catalysis process using the catalytic compositions defined above consists of an olefin isomerization process.
• the process for isomerization of the double bond of olefins described according to the invention applies to olefins having from 4 to 30 carbon atoms, pure or in a mixture.
• the temperature at which the isomerization reaction is carried out ranges, for example, from ⁇ 50° C. to 200° C.; it is advantageously less than 100°C.
• the isomerization reaction can be carried out using a reactive distillation technique. The invention will be described in more detail using the non-limiting examples below.
• Example 1 Resistance to pressure of a Pickering emulsion in a fixed bed 5.6 g of 1-Butyl-3-Methylimidazolium bis(trifluoromethanesulfonyl)imide ([BMI] [NTf 2 ]), 0.014g of HNTf 2 acid and a few milligrams of 4-nitroaniline, a dye which has a yellow color in this mixture.
• This mixture is denoted Phase 1. 5.13 g of n-heptane, then 0.145 g of silica particles (Aerosil R972, marketed by the company Evonik), are introduced into another beaker, under an inert atmosphere.
• Phase 2 This mixture is denoted Phase 2.
• Phase 1 The Phase 1 mixture is poured drop by drop into the beaker containing the n-heptane and the silica (Phase 2), with continuous application of a dispersion energy provided by a rotor-stator system (UltraTurrax, 10000 rpm).
• a rotor-stator system UltraTurrax, 10000 rpm.
• a Pickering [BMI][NTf 2 ]/HNTF 2 /SiO 2 /heptane emulsion is thus obtained.
• a piece of glass wool is introduced then a layer of fine sand (2.5 g).
• Example 2 (according to the invention): Preparation of capsules containing the catalytic system [BMI][NTf 2 ]/[BMI][BF 4 ]/HNTF2 16.9 g of 1-Butyl are introduced into a beaker under an inert atmosphere.
• Phase 1 -3-Methylimidazolium bis(trifluoromethanesulfonyl)imide ([BMI][NTf 2 ]), 4.5g of 1-Butyl-3-Methylimidazolium tetrafluoroborate [BMI][BF 4 ], 3.0g of HNTf 2 and 0 acid, 6g of water.
• BMI 1-Butyl-3-Methylimidazolium tetrafluoroborate
• Phase 2 silica fume (Aerosil R972, marketed by Evonik) is dispersed in 27.3 mL (18.7 g) of n-heptane with magnetic stirring.
• Phase 2 The Phase 1 mixture is poured drop by drop into the beaker containing the n-heptane and the silica (Phase 2), with continuous application of a dispersion energy provided by a rotor-stator system (UltraTurrax, 10000 rpm).
• a rotor-stator system UltraTurrax, 10000 rpm
• TMOS tetramethyl orthosilicate
• FIG. 1 is an image of the capsules thus prepared, obtained by Scanning Electron Microscopy (SEM, ZEISS Supra 40 apparatus), by observation in secondary electrons. It can be seen that the capsules are rather in the form of substantially spherical beads, the mean diameter of which measured by SEM is 15 ⁇ m.
• Example 3 Resistance to pressure of capsules with a liquid core in a fixed bed In the bottom of the tubular reactor described in Example 4, a piece of glass wool is introduced then a layer of fine sand (2 .5g). A quantity of 13 g of capsules synthesized according to Example 2 is taken up with a little heptane and deposited above the bed of sand. The upper volume of the reactor is then supplemented with heptane.
• the reactor is closed and connected at the inlet to a ballast containing n-heptane, maintained at a pressure of 10 bar.
• the valve is opened and the liquid charge is introduced into the reactor.
• the pressure is adjusted by means of a regulator placed upstream of the reactor, and a pressure regulator placed at the outlet of the reactor.
• the pressure is gradually increased to around 8 bar.
• the effluent collected is transparent (absence of dye), which reflects the fact that the catalytic composition thus implemented remains well confined inside the column reactor, within the capsules. The capsules therefore resist a pressure of approximately 8 bar.
• Example 4 Dimerization of isobutene in a fixed bed using the capsules described in example 2
• a tubular stainless steel reactor 10 cm long and 1 cm internal diameter is used for the implementation of the capsules in isobutene dimerization.
• the reactor is closed and connected at the inlet to a ballast containing a mixture of 15% by mass of isobutene, 5% by mass of n-butane and 80% by mass of n-heptane, maintained at a pressure of 10 bar.
• the valve is opened, and the liquid charge is introduced into the reactor.
• the pressure is adjusted by means of a regulator placed upstream of the reactor, and a pressure regulator placed at the outlet of the reactor. A pressure of 4 bar is thus applied.
• the outlet valve located downstream of the pressure regulator is open to continuously collect the effluents leaving the reactor.
• the effluents sampled are then analyzed by gas phase chromatography (PONA column) after treatment with sodium hydroxide (0.1 M) to eliminate any traces of acid and drying over MgS0 4 .
• Isobutene conversion is measured using the butane present in the charge as an internal standard.
• 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.
• the selectivity dimerization products (C8 olefins) and trimerization (C12) is respectively 69% and 31%.
• the sample taken after 5 hours shows a mass conversion of isobutene of 95%.
• the selectivity for dimerization (C8 olefins) and trimerization (C12) products is 66% and 34%, respectively. After 5 hours, the effluent is still transparent.

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