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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
  • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
  • B01J29/46—Iron group metals or copper
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
  • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
  • B01J29/24—Iron group metals or copper
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
  • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
  • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
  • B01J29/68—Iron group metals or copper
• • 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
  • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
  • B01J2229/123—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to deactivate outer surface
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
  • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
  • B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst

Definitions

• the present invention relates to a process for the preparation of a catalyst based on a modified zeolite having small and / or pore means, that is to say having a maximum pore opening diameter of less than or equal to at 7 A, in order to obtain a catalyst advantageously used in various chemical conversion processes for hydrocarbons. More particularly, the invention also relates to the use of said catalyst containing said modified zeolite in a process for oligomerization of a light olefinic feedstock.
• zeolites with a shape selectivity such as zeolite ZSM-5 for the olefin oligomerization reaction has been known for a long time.
• the process for oligomerization of olefins of Mobil developed in the 1980s described inter alia in US Patents 4,150,062 and US 4,227,992 uses a ZSM-5 zeolite for the conversion of butenes to oligomers.
• the products obtained have a very low degree of connection and make jet fuel and diesel cuts of good qualities. This process gives very low yield in diesel cut (cut obtained after distillation of Poligomerate between 200 0 C - 36O 0 C), it is used mainly to produce jet fuel.
• US Pat. No. 4,402,867 describes a method for preparing a zeolite-based catalyst comprising a step of depositing in the aqueous phase at least 0.3% by weight of amorphous silica inside the pores of the zeolite.
• US Pat. No. 4,996,034 describes a process for substitution of aluminum atoms present in a zeolitic framework with silicon atoms, said process being carried out in one step in an aqueous medium using fluorosilicate salts.
• No. 4,451,572 describes the preparation of a zeolitic catalyst comprising a step of depositing organosilicic materials in the vapor or liquid phase, the targeted zeolites being large-pore zeolites, in particular zeolite Y.
• US Pat. No. 5,057,640 describes a process for the oligomerization of propylene using a catalyst containing a zeolite of Si / Al ratio greater than 12 and a stress index (Cl) of between 1 and 12 and in which at least 0.1 % by weight of silica with respect to weight of the zeolite was added.
• the catalyst referred to in this US Pat. No. 5,056,640 has an n-hexane adsorption of 1% less than on the starting material.
• the present invention relates to a process for the preparation of a catalyst containing at least one modified zeolite, said zeolite having, before being modified, a maximum pore opening diameter of less than or equal to 7 ⁇ , said process comprising at least: a) a step of introducing at least one metal chosen from the metals of groups VIB and VIII of the periodic table of elements on a support based on at least one protonated zeolite, b) a step of treating said zeolite in the presence of at least one molecular compound containing at least one silicon atom, said compound having a diameter greater than the maximum pore opening diameter of said zeolite is deposited on the outer surface of said zeolite in the gas phase, c) at least one heat treatment step.
• Said zeolite is preferably chosen from zeolites of structural type MEL, MFI, ITH, NES, EUO, ERI, IRON, CHA, MFS, MWW, MTT, TON and MOR.
• the present invention also relates to the use of said catalyst in a process for oligomerizing an olefinic feedstock containing hydrocarbon molecules having 2 to 12 carbon atoms per molecule.
• a catalyst comprising a modified zeolite, prepared according to a process comprising at least a) a step of introduction of at least one metal chosen from the metals of groups VIB and VIII of the classification periodic element on a support based on at least one protonated zeolite, b) a step of treating said zeolite in the presence of at least one molecular compound containing at least one silicon atom, said compound having a diameter greater than the diameter maximum opening pore of said zeolite, c) at least one heat treatment step, leads to improved catalytic performance, particularly in terms of yield and selectivity of the diesel cut in an oligomerization reaction of an olefinic feedstock containing hydrocarbon molecules having 2 to 12 carbon atoms per molecule, preferably 3 to 7 carbon atoms per molecule, and very preferably containing from 4 to 6 carbon atoms per molecule.
• Such a catalyst makes it possible to significantly increase the efficiency of the diesel cut relative to that obtained by using a catalyst of the state of the art.
• the cetane number which reflects the linearity of the hydrocarbon chains present in the diesel cut and which represents the quality of the diesel cut, is also advantageously improved compared with that usually presented by a diesel cut obtained by this reaction.
• the use of the catalyst as described above in a process for oligomerizing an olefinic feed containing hydrocarbon molecules having from 2 to 12 carbon atoms per molecule, preferably from 3 to 7 carbon atoms per molecule, and very preferably containing from 4 to 6 carbon atoms per molecule allows the production of an oligomer of very good quality which can advantageously after distillation at the appropriate cutting point, be integrated in the diesel pool of a refinery.
• the present invention relates to a process for the preparation of a catalyst containing at least one modified zeolite, said zeolite having, before being modified, a maximum pore opening diameter of less than or equal to 7 ⁇ , said process comprising at least: a) a step of introducing at least one metal selected from the metals of groups VIB and VIII of the periodic table of elements on a support based on at least one protonated zeolite, b) a step of treating said zeolite in the presence of at least one molecular compound containing at least one silicon atom, said compound having a diameter greater than the maximum pore opening diameter of said zeolite is deposited on the outer surface of said zeolite in the gas phase; least one heat treatment step.
• the initial zeolite which has not yet been modified to be contained in the catalyst prepared according to the process of the invention, has a maximum pore opening diameter of less than or equal to 7 A and Preferred zeolite is selected from zeolites defined in the "Atlas of Zeolite Structure Types" classification, W. M Meier, DH Oison and Ch. Baerlocher, 5th revised edition, 2001, Elsevier "to which reference is made also the present application but may also be any zeolite having a maximum pore opening diameter of less than or equal to 7 A.
• the zeolites listed in the "Atlas of Zeolite Structure Types" are classified according to their structural type All zeolites having a maximum pore opening diameter of less than or equal to 7 A and preferably less than 6.5 A are suitable for carrying out the preparation process according to the invention and in particular for the implementation process step b) of the process according to the invention.
• the maximum pore opening diameter of a zeolite corresponds to the maximum dimension of the "ring dimensions" mentioned in the "Atlas of Zeolite Structure Types" for each of the structural types.
• the zeolite initially used, before being modified, to be contained in the catalyst prepared according to the process of the invention has either one or channels whose opening is defined by a ring with 10 oxygen atoms.
• a zeolite having at least channels whose opening is defined by a ring of 12 oxygen atoms (12 MR) is particularly suitable for carrying out the process for preparing the catalyst according to the invention provided that it has a maximum pore opening diameter less than or equal to 7 A.
• a zeolite of structural type MOR which has both channels whose opening is defined by an 8-atom oxygen ring (8 MR) and channels whose opening is defined by a ring of 12 oxygen atoms (12 MR) is suitable for carrying out the preparation process according to the invention.
• MOR structural type zeolites have a maximum pore opening diameter of 7.0 ⁇ .
• the zeolite modified according to the different steps of the process according to the invention, initially contains, that is to say, before being modified, at least silicon and aluminum in a proportion such that the Si / Si atomic ratio Ai is preferably between 2 and 200, more preferably between 5 and 100 and even more preferably between 8 and 80. It advantageously contains at least one other element W, different from silicon and aluminum, integrating tetrahedral form into the framework of the zeolite.
• said element W is chosen from iron, germanium, boron and titanium and represents a weight portion of between 5 and 30% of all the constituent atoms of the zeolitic framework other than the oxygen atoms.
• the zeolite then has a ratio (Si + W) / Al of between 2 and 200, preferably of between 5 and and 100 and very preferably between 8 and 80, W being defined as above.
• the zeolite modified according to the different steps of the process according to the invention is preferably chosen from zeolites of structural type MEL, MFI, ITH, NES, EUO, ERI, IRON, CHA, MFS, MWW, MTT, TON and MOR and of very preferably chosen from zeolites of structural type MFI, MOR and FER.
• zeolites of structural MEL type zeolite ZSM-11 is preferred.
• zeolites of structural type MFI zeolite ZSM-5 is preferred.
• zeolites of ITH structural type zeolite ITQ-13 is preferred (US 6,471,941).
• zeolites of structural NES type zeolite NU-87 is preferred.
• zeolites of EUO structural type zeolite EU-1 is preferred.
• zeolites of structural type ERI zeolite erionite is preferred.
• zeolites of structural type FER structural type ferrierite zeolites and ZSM-35 are preferred.
• zeolites of structural type CHA zeolite chabazite is preferred.
• zeolites of structural MFS type zeolite ZSM-57 is preferred.
• the MCM-22 zeolite is preferred.
• zeolites of MTT structural type zeolites of MTT structural type
• zeolite ZSM-23 is preferred.
• zeolites of structural type TON zeolite ZSM-22 is preferred.
• mordenite zeolite is preferred.
• the first step of the catalyst preparation process according to the invention is either step a) or step b).
• Step b), whether before or after step a), is preferably followed immediately by step c).
• the zeolite used for carrying out the first step of the process for preparing the catalyst according to the invention that is to say employed for the implementation of step a) carried out in the presence of at least one metal of groups VIB and / or VIII of the periodic table of elements or for the implementation of step b) carried out in the presence of at least one molecular compound containing at least one silicon atom having a well-defined diameter, present in calcined form and contains at least one proton such that it is in its protonated form (hydrogen form H + ) in which the cation content other than H + is less than 30% of the total number of cations, preferably less than 20% and very preferably less than 15% based on the total number of cation on the zeolite.
• the zeolite to be modified is in its raw form of synthesis, still containing the structuring agent.
• organic material used to prepare it calcination may be carried out said zeolite at a temperature between 300 and 700 0 C, preferably between 400 and 600 0 C and if the zeolite contains one or more metal (s) alkali / alkaline earth, proceed to one or more ion exchange (s) (s) by a solution containing at least one ammonium salt, for example ammonium nitrate NH 4 NO 3 , so as to remove at least partly, preferably almost completely, an alkaline cation present in the zeolite.
• ammonium salt for example ammonium nitrate NH 4 NO 3
• a step of calcination under dry air flow, at a temperature generally between approximately 400 and 500 0 C, is then intended to generate the formation of protons in the zeolite by desorption of ammonia thus leading to the hydrogen form of the zeolite, ready for the implementation of the first step of the preparation process according to the invention.
• the zeolite used for carrying out the first step of the process for preparing the catalyst according to the invention is an acidic zeolite containing between 70 and 100%, preferably between 80 and 100% and very preferably between 85 and 100% proton form H + compensation cations, the rest of the cations being preferably chosen from the metals of groups IA and NA of the periodic table of elements, and more particularly said cation is chosen from Na + , Li + cations, K + , Rb + , Cs + , Ba 2+ and Ca 2+ .
• Step a) of the process for preparing the catalyst according to the invention is a step of introducing at least one metal chosen from the metals of groups VIB and VIII of the periodic table of the elements on a carrier based on minus a protonated zeolite.
• said metal chosen from metals of groups VIB and VIII of the periodic table of elements is chosen from nickel, iron, palladium, ruthenium and chromium, very preferably from nickel and chromium.
• the Group VIII metal is nickel. Of the Group VIB metals, chromium is preferred.
• the deposition of at least one metal chosen from Group VIB and VIII metals is generally carried out by dry impregnation, by excess impregnation or by ion exchange (s) according to methods well known to those skilled in the art, preferably by ion exchange (s).
• ion exchange introduction of nickel it is preferred to use an aqueous solution containing nickel under the oxidation state + 2, for example nickel sulphate.
• the weight content of the metal chosen in groups VIB and VIII, introduced on the zeolite support is advantageously between 0.01 and 10% by weight, and preferably between 0.1 and 5% by weight relative to the weight of the catalyst prepared according to method of the invention.
• the support based on at least one protonated zeolite consists entirely of said protonated zeolite, which has in terms of maximum pore opening diameter, structure and chemical composition, the characteristics described above.
• the support based on at least one protonated zeolite consists of said protonated zeolite shaped with a matrix and optionally a binder.
• the method for preparing the catalyst according to the invention comprises a step b) of selectivation of the zeolite, in its protonated form, said selectivation step can be carried out either before the step of introducing at least one metal of the groups VIB and / or VIII according to said step a) after said step a).
• selectivation is meant in the sense of the present invention, the neutralization of the acidity of the outer surface of each of the crystals of the zeolite.
• the neutralization of the acidity can be done by any method known to those skilled in the art. Conventional methods generally employ, for specific selectivation of acidic sites on the outer surface of zeolites, molecules whose kinetic diameter is greater than the pore opening diameter of the zeolite.
• step b) of selectivation consists in treating the zeolite, in its protonated form, possibly previously subjected to said step a), in the presence of at least one molecular compound containing at least one silicon atom whose diameter is greater than the maximum pore opening diameter of the zeolite to be treated according to step b).
• the process for preparing the catalyst according to the invention comprises only one step b).
• the molecules generally used to passivate or selectivize the outer surface of the zeolite are compounds containing atoms that can interact with the outer surface sites of each of the zeolite crystals.
• the molecules used according to the invention are organic or inorganic molecules containing one or more silicon atom (s).
• the protonated zeolite, possibly previously subjected to said step a) is subjected to a treatment step in the presence of at least one molecular compound containing at least a silicon atom.
• Said step b) allows the deposition of a layer of said molecular compound containing at least one silicon atom on the outer surface of the zeolite which will be transformed after step c) into an amorphous silica layer on the outer surface of each of the crystals of the zeolite.
• the molecular compound containing at least one silicon atom is chosen from compounds of formula Si-R 4 and Si 2 -Re where R may be either hydrogen, an alkyl, aryl or acyl group, an alkoxy group (O-R 1 ), a hydroxyl group (-OH) or a halogen, preferably an alkoxy group (OR 1 ) .
• the group R may be either identical or different.
• the molecular compound containing at least one silicon atom used in step b) of the process according to the invention may be a compound of silane, disilane, alkylsilane, alkoxysilane or siloxane type.
• said molecular compound has a composition of general formula Si- (OR ') 4 where R' is an alkyl, aryl or acyl group, preferably an alkyl group and very preferably an ethyl group.
• Said molecular compound used for the implementation of step b) of the process according to the invention has a diameter greater than the maximum pore opening diameter of the zeolite and preferably comprises at most two silicon atoms per molecule.
• the tetraethylorthosilicate (TEOS) molecular compound of formula Si (OCH 2 CH 3 ) 4 which has a diameter equal to 9.6 ⁇ , is very advantageous for carrying out step b) of the process according to the invention.
• TEOS is advantageous when it is a question of treating a structural type zeolite MOR having a maximum pore opening diameter of 7 ⁇ , a zeolite of structural type MFI having a maximum pore opening diameter of 5.6 ⁇ or a zeolite of structural type FER having a maximum pore opening diameter of 5.4 ⁇ .
• step b) of the process according to the invention which consists in treating the protonated zeolite, possibly previously subjected to step a), in the presence of at least one molecular compound containing at least one silicon atom is carried out by depositing said compound on the outer surface of the zeolite.
• step b) is carried out by depositing said molecular compound containing at least one silicon atom in the gas phase.
• Step b) according to the process of the invention is carried out in a fixed bed reactor.
• the zeolite Prior to the gas phase deposition (CVD) reaction in said fixed bed reactor, the zeolite is preferably activated. Activation of the zeolite in the fixed bed reactor is carried out under oxygen, in air or under an inert gas, or in a mixture of air and inert gas or oxygen and inert gas.
• the activation temperature of the zeolite is advantageously between 100 and 600 ° C., and very advantageously between 300 and 55 ° C.
• the molecular compound containing at least one silicon atom to be deposited on the outer surface of each of the crystals of the zeolite is sent into the vapor phase reactor, said molecular compound being diluted in a carrier gas which can be either hydrogen (H 2 ), or air, or Argon (Ar), either helium (He) or again nitrogen (N 2 ), preferably the carrier gas is an inert gas selected from Ar, He, and N 2 .
• Said molecular compound containing at least one silicon atom is deposited on the outer surface of said zeolite in the vapor phase, in the absence of any hydrocarbon compound.
• the temperature of the zeolite bed during the deposition is preferably between 10 and 300 ° C., and very preferably between 50 and 200 ° C.
• the partial pressure, in the gas phase, of the molecular compound to be deposited on the surface is preferably between 0.001 and 0.5 bar, and very preferably between 0.01 and 0.2 bar
• the duration of the deposit is preferably between 10 minutes and 10 hours and very preferably between 30 minutes and 5 hours and even more preferably between 1 and 3 hours.
• the molecular compound containing at least one silicon atom is decomposed by a heat treatment which is carried out at a temperature preferably between 200 and 700 ° C, more preferably between 300 and 500 ° C.
• Said heat treatment step is carried out under air, under oxygen, under hydrogen, under nitrogen or under argon or under a mixture of nitrogen and argon.
• the duration of this treatment is advantageously between 1 and 5 hours.
• an amorphous silica layer is deposited on the outer surface of each of the crystals of the zeolite.
• the inner surface of each of the crystals of the zeolite is preferably free of a deposit of an amorphous silica layer.
• the maximum pore opening diameter of the modified zeolite, present in the catalyst prepared according to the process of the invention is preferably unchanged compared with that of the initial zeolite still unmodified. Consequently, the modified zeolite contained in the catalyst prepared according to the process of the invention preferably has a maximum pore opening diameter of less than or equal to 7 ⁇ and preferably less than 6.5 ⁇ .
• the metal chosen from the metals of groups VIB and VIII may be introduced either substantially completely onto the matrix, partly on the zeolite and partly on the matrix, or, preferably, almost completely on the zeolite, this being done, in the manner known to those skilled in the art, by the appropriate choice of parameters used during said deposition, such as for example the nature of the precursor of said metal.
• step a) of the process according to the invention consists solely of said protonated zeolite (first embodiment of the invention).
• step a)) whose characteristics in terms of maximum pore opening diameter, structure, chemical composition are in accordance with what has been said above in the present description, the metal chosen from metals of groups VIB and VIII is introduced directly onto the protonated zeolite which is preferably in the form of a powder.
• the shaping of the protonated zeolite with a matrix and optionally a binder is carried out during a step d).
• Said step d) of shaping can take place either directly after step a) of introduction of the metal on the protonated zeolite and prior to the implementation of steps b) and c) of the process of the invention or after the steps a), b) and c) of the process according to the invention is again after the implementation of said steps b) and c) and before the implementation of said step a) when said steps b) and c) of the according to the invention are carried out before step a).
• the matrix used for the shaping of the protonated zeolite is an amorphous or poorly crystallized porous mineral matrix of oxide type.
• alumina silica, silica-alumina, clays, in particular natural clays such as kaolin or bentonite, magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates and coal.
• a matrix among the aluminates Preferably, the matrix is an alumina in all its forms known to those skilled in the art, and preferably gamma alumina.
• the shaping of said zeolite with at least one matrix is generally such that the catalyst is in the form of cylindrical or multi-lobed extrusions such as bilobed, trilobed, straight-lobed or twisted, but may possibly be such that the catalyst is in the form of crushed powders, tablets, rings, balls, wheels.
• the conditions for shaping the zeolite, the choice of the matrix, optionally the preliminary grinding of the zeolite, the peptization process, the addition of pore-forming agents, the mixing time, the extrusion pressure if the catalyst is extruded, the speed and the drying time are determined for each matrix according to the well-known rules of the skilled person.
• the shaping of the zeolite with at least one matrix as described above can be carried out at different stages of the process according to the invention. More particularly, when the support based on said zeolite used during step a) consists of said zeolite shaped with a matrix, the shaping is carried out prior to the implementation of step a) of the process of the invention.
• the shaping is carried out either directly after said step a) and before the implementation of steps b ) and c), or after the implementation of said steps b) and c) and before the implementation of said step a) when said steps b) and c) precede said step a), or even after the implementation steps a), b) and c).
• one of the preferred methods for preparing the catalyst according to the invention consists in exchanging a protonated zeolite with at least one metal chosen from Group VIB and VIII metals, preferably with nickel under its +2 oxidation state.
• Said ion exchange step is followed by a step of activating the zeolite at a temperature of between 300 and 55O 0 C and then the zeolite is treated at a temperature of between 50 and 200 ° C. in the presence of tetraethylorthosilicate (TEOS) vapor deposited on the outer surface of said zeolite.
• TEOS tetraethylorthosilicate
• the TEOS is decomposed by a heat treatment generally carried out at a temperature between 300 and 500 ° C in air.
• a zeolite modified in protonated form and having an amorphous silica layer on its external surface is thus obtained.
• Said modified zeolite is then shaped by extrusion by mixing it in a wet matrix gel (generally obtained by mixing at least one acid and a matrix powder), for example alumina, for a period of time necessary to obtaining a good homogeneity of the dough thus obtained, for example for about ten minutes, and then passing said dough through a die to form extrudates, for example having a diameter of between 0.4 and 4 mm inclusive preferably between 0.4 and 2.5 mm inclusive and more preferably between 0.8 and 2.0 mm inclusive.
• the extrudates thus shaped then undergo drying for a few hours at about 120 ° C.
• the catalyst prepared according to the process of the invention and comprising a modified zeolite in hydrocarbon chemical conversion processes and in particular in a process for oligomerization of an olefinic feed containing hydrocarbon molecules having 2 to 12 carbon atoms per molecule.
• the feedstock used for carrying out said oligomerization process contains hydrocarbon molecules containing from 3 to 7 carbon atoms per molecule, and very preferably containing from 4 to 6 carbon atoms per molecule.
• the catalyst prepared according to the process of the invention is treated according to said steps a), b) and c) ex-situ: it is introduced into the reactor to carry out the oligomerization of hydrocarbon molecules containing from 3 to 7 carbon atoms per molecule once said steps a), b) and c) of the process for preparing the catalyst according to the invention have been carried out.
• the feed used in the oligomerization process according to the invention contains from 20 to 100% by weight, and preferably from 25 to 80% by weight of olefins.
• Possible sources for the olefinic feedstock used in the oligomerization process of the invention are the light cut of the fluid catalytic cracking (FCC), the steam cracker and the etherification unit effluents.
• FCC fluid catalytic cracking
• Said oligomerization process is preferably carried out under the following operating conditions: the total pressure is between 0.1 and 10 MPa and preferably between 0.3 and 7 MPa, the temperature is between 40 and 600 ° C. and preferentially between 100 and 400 ° C., the hourly space velocity (WH) is between 0.01 and 100 h -1 and preferably between 0.4 and 20 h -1 .
• the oligomerization process corresponds to an addition limited to essentially 2 to 6 monomers or base molecules, said monomers being olefins.
• Example 1 Preparation of a catalyst based on a modified zeolite ZSM-5.
• the zeolite is stripped for 2 h at 150 ° C. to evacuate the unreacted TEOS.
• the decomposition of TEOS is under air at 45O 0 C for 3 hours.
• a modified zeolite Z1, in protonated form, of structural type MFI and having an amorphous silica layer on its external surface is thus obtained.
• Zeolite Z1 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 450 ° C. under dry air, a catalyst which contains 60% by weight of zeolite modified with Z1 and 40% by weight. alumina.
• Example 2 Preparation of a catalyst based on a modified MOR zeolite.
• the zeolite is stripped for 2 hours at 150 ° C. to evacuate the unreacted TEOS.
• the decomposition of TEOS is under air at 450 ° C for 3 hours.
• a zeolite modified Z2, in protonated form, of structural type MOR and having an amorphous silica layer on its external surface is thus obtained.
• Zeolite Z2 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 450 ° C. in dry air, a catalyst which contains 60% by weight of modified zeolite Z2 and 40% by weight. alumina.
• Example 3 Preparation of a catalyst based on a modified FER zeolite.
• the zeolite is stripped for 2 hours at 150 ° C. to evacuate the unreacted TEOS.
• the decomposition of TEOS is under air at 450 ° C for 3 hours.
• a zeolite modified Z3, in protonated form, of structural type FER and having an amorphous silica layer on its external surface is thus obtained.
• Zeolite Z3 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 450 ° C. under dry air, a catalyst which contains 60% by weight of zeolite modified with Z3 and 40% by weight. alumina.
• Example 4 Preparation of a catalyst based on a ZSM-5 zeolite not exchanged with a metal.
• Zeolite Z4 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 45 ° C. in dry air, a catalyst which contains 60% by weight of zeolite Z4 and 40% by weight of water. alumina.
• Example 5 Preparation of a catalyst based on a non-metal exchanged zeolite MOR.
• Zeolite Z5 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 450 ° C. in dry air, a catalyst which contains 60% by weight of zeolite Z5 and 40% by weight of alumina.
• Example 6 (comparative): Preparation of a catalyst based on an iron zeolite not exchanged with a metal.
• Zeolite Z6 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 450 ° C. under dry air, a catalyst which contains 60% by weight of zeolite Z6 and 40% by weight of water. alumina.
• Example 7 Preparation of a catalyst based on a modified MFI zeolite.
• the temperature of the reactor is then reduced to 15O 0 C, then a partial pressure of 0.15 bar of TEOS [ If (OCH 2 CH 3 ) 4 ] is added to the nitrogen stream.
• TEOS If (OCH 2 CH 3 ) 4 ] is added to the nitrogen stream.
• the zeolite is stripped for 2 hours at 150 ° C. to evacuate the unreacted TEOS.
• the decomposition of TEOS is under air at 450 ° C. for 3 hours.
• a modified zeolite Z7, in protonated form, of structural type MFI and having an amorphous silica layer on its external surface is thus obtained.
• Zeolite Z7 is then shaped by extrusion with an alumina gel so as to obtain, after drying at 120 ° C. and calcination at 450 ° C. under dry air, a catalyst which contains 60% by weight of Z7 modified zeolite and 40% by weight. alumina.
• Example 8 Catalytic Evaluation of Catalysts Based on Z1, Z2 Modified Zeolites Z3 and Z7 and based zeolites Z4, Z5 and Z6 in oligomerization of light olefins.
• Table 1 Performance of catalysts based on the MFI zeolite.
• Catalyst Catalyst Catalyst Converter based on Z1 base Z4 base Z7
• Table 2 Performance of catalysts based on the FER zeolite.

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