WO2018204000A1 - Procédés de régénération de catalyseurs - Google Patents

Procédés de régénération de catalyseurs Download PDF

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WO2018204000A1
WO2018204000A1 PCT/US2018/025640 US2018025640W WO2018204000A1 WO 2018204000 A1 WO2018204000 A1 WO 2018204000A1 US 2018025640 W US2018025640 W US 2018025640W WO 2018204000 A1 WO2018204000 A1 WO 2018204000A1
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group
catalyst
metal
gaseous stream
reactor
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PCT/US2018/025640
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Jeremy W. BEDRAD
Larry L. Iaccino
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Exxonmobil Chemical Patents Inc.
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    • 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
    • B01J29/44—Noble metals
    • 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
    • B01J29/068—Noble metals
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
    • B01J38/44—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material and adding simultaneously or subsequently free oxygen; using oxyhalogen compound
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on 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
    • B01J2229/42—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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen

Definitions

  • the present invention relates to processes for regenerating catalysts comprising a Group 10 metal and a microporous crystalline aluminosilicate.
  • Supported noble metal e.g., platinum containing catalysts are widely utilized in hydrocarbon conversion processes. Such catalysts generally lose activity over time, in large part due to the formation of coke. When the activity of the catalyst is reduced to an unsatisfactory level, the catalyst must be discarded or more preferably, reconditioned or regenerated so that it can be reused.
  • Conventional catalyst regeneration methods typically comprise burning coke off the catalyst under oxidation conditions sufficient to remove substantially all of the coke from the catalyst.
  • these conventional oxidative coke removal methods generally result in agglomeration of the supported metal particles.
  • the present invention relates to processes for regenerating catalysts comprising a Group 10 metal and a microporous crystalline aluminosilicate that address the need for methods of regenerating high Group 10 metal-to-aluminum ratio materials.
  • the invention relates to processes for regenerating a deactivated catalyst comprising at least one Group 10 metal and a microporous crystalline aluminosilicate having a molar ratio of Group 10 metal to Al of greater than or equal to 0.007: 1.
  • the processes comprise an oxychlorination step comprising contacting the catalyst with a first gaseous stream comprising a chlorine source and an oxygen source under conditions effective for dispersing at least a portion of the at least one Group 10 metal on the surface of the catalyst and for producing a first Group 10 metal chlorohydrate.
  • the processes further comprise a chlorine stripping step comprising contacting the catalyst with a second gaseous stream comprising an oxygen source, and optionally a chlorine source, under conditions effective for increasing the O/Cl ratio of the first Group 10 metal chlorohydrate to produce a second Group 10 metal chlorohydrate.
  • the invention further relates to processes for the chemical conversion of a hydrocarbon feedstock.
  • Such processes comprise the step of contacting a hydrocarbon feedstock with a catalyst comprising at least one Group 10 metal and a microporous crystalline aluminosilicate having a molar ratio of Group 10 metal to Al of greater than or equal to 0.007:1 in a reaction zone to form a hydrocarbon reaction product.
  • the processes further comprise the steps of forming deactivated catalyst from the catalyst and regenerating the deactivated catalyst in accordance with the regeneration processes of this invention.
  • FIG. 1 shows the yield of cyclic Cs as a function of CO to Pt uptake values resulting from the performance evaluation of fresh, sintered, and regenerated catalyst compositions conducted in Example 3.
  • FIG. 2 shows the yield of cyclic C 5 against time-on-oil resulting from the performance evaluation of sintered and regenerated catalyst compositions conducted in Example 6.
  • FIG. 3A and FIG. 3B show the yield of cyclic C 5 against time-on-oil resulting from the performance evaluation of fresh and treated catalyst compositions conducted in Example 10.
  • Disclosed herein are processes useful in regenerating Group 10 metal-containing zeolite catalysts which have become deactivated during a hydrocarbon conversion processing step.
  • the present methods are particularly suitable in hydrocarbon conversion processes comprising the conversion of acyclic hydrocarbons to alkenes, cyclics, and/or aromatics.
  • hydrocarbon means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.
  • C n means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
  • light hydrocarbon means light paraffinic and/or olefinic hydrocarbons comprised substantially of hydrogen and carbon only and has one to no more than 4 carbon atoms.
  • saturated includes, but is not limited to, alkanes and cycloalkanes.
  • non-saturates includes, but is not limited to, alkenes, dialkenes, alkynes, cyclo- alkenes and cyclo-dialkenes.
  • cyclic hydrocarbon denotes groups such as the cyclopropane, cyclopropene, cyclobutane, cyclobutadiene, etc., and substituted analogues of these structures. These cyclic hydrocarbons can be single- or multi-ring structures. Preferably, the term “cyclic hydrocarbon” refers to non-aromatics.
  • cyclic C 5 or “cC 5” includes, but is not limited to, cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more thereof.
  • cyclic C 5 " or “cC 5” also includes alkylated analogs of any of the foregoing, e.g., methyl cyclopentane, methyl cyclopentene, and methyl cyclopentadiene. It should be recognized for purposes of the invention that cyclopentadiene (CPD) spontaneously dimerizes over time to form dicyclopentadiene (DCPD) via Diels-Alder condensation over a range of conditions, including ambient temperature and pressure.
  • CPD cyclopentadiene
  • DCPD dicyclopentadiene
  • acyclics includes, but is not limited to, linear and branched saturates and non-saturates.
  • alkane refers to non-aromatic saturated hydrocarbons with the general formula C n H(2n+2), where n is 1 or greater.
  • An alkane may be straight chained or branched. Examples of alkanes include, but are not limited to methane, ethane, propane, butane, pentane, hexane, heptane and octane.
  • Alkane is intended to embrace all structural isomeric forms of an alkane. For example, butane encompasses n-butane and isobutane; pentane encompasses n- pentane, isopentane and neopentane.
  • alkene refers to a branched or unbranched unsaturated hydrocarbon having one or more carbon-carbon double bonds.
  • a simple alkene comprises the general formula CnEhn, where n is 2 or greater. Examples of alkenes include, but are not limited to ethylene, propylene, butylene, pentene, hexene and heptene.
  • Alkene is intended to embrace all structural isomeric forms of an alkene. For example, butylene encompasses but-l-ene, (Z)-but-2-ene, etc.
  • aromatic means a planar cyclic hydrocarbyl with conjugated double bonds, such as, for example, benzene.
  • aromatic encompasses compounds containing one or more aromatic rings, including, but not limited to, benzene, toluene, and xylene, and polynuclear aromatics (PNAs), which include, but are not limited to, naphthalene, anthracene, chrysene, and their alkylated versions.
  • C 6+ aromatics includes compounds based upon an aromatic ring having six or more ring atoms, including, but not limited to, benzene, toluene, and xylene and polynuclear aromatics (PNAs) which include, but are not limited to, naphthalene, anthracene, chrysene, and their alkylated versions.
  • PNAs polynuclear aromatics
  • BTX includes, but is not limited to, a mixture of benzene, toluene, and xylene (ortho and/or meta and/or para).
  • coke includes, but is not limited to, a low hydrogen content hydrocarbon that is adsorbed on the catalyst composition.
  • C n+ means hydrocarbon(s) having at least n carbon atom(s) per molecule.
  • C n- means hydrocarbon(s) having no more than n carbon atom(s) per molecule.
  • C 5 feedstock includes a feedstock containing n-pentane, such as, for example, a feedstock which is predominately normal pentane and isopentane (also referred to as methylbutane), with smaller fractions of cyclopentane and neopentane (also referred to as 2,2-dimethylpropane).
  • Group 10 metal means an element in Group 10 of the Periodic Table and includes, but is not limited to, nickel, palladium, platinum, and a mixture of two or more thereof.
  • Group 11 metal means an element in Group 11 of the Periodic Table and includes, but is not limited to, copper, silver, gold, and a mixture of two or more thereof.
  • Group 1 alkali metal means an element in Group 1 of the Periodic Table and includes, but is not limited to, lithium, sodium, potassium, rubidium, cesium, and a mixture of two or more thereof, and excludes hydrogen.
  • Group 2 alkaline earth metal means an element in Group 2 of the Periodic Table and includes, but is not limited to, beryllium, magnesium, calcium, strontium, barium, and a mixture of two or more thereof.
  • rare earth metal means an element in the Lanthanide series of the Periodic Table, as well as scandium and yttrium.
  • the term rare earth metal includes, but is not limited to, lanthanum, praseodymium, neodymium, cerium, yttrium, and a mixture of two or more thereof.
  • molecular sieve of the MCM-22 family includes one or more of:
  • molecular sieves made from a common first degree crystalline building block unit cell which unit cell has the MWW framework topology
  • a unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure.
  • Such crystal structures are discussed in the "Atlas of Zeolite Framework Types," Fifth edition, 2001, the entire content of which is incorporated as reference.); molecular sieves made from a common second degree building block, being a 2- dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
  • molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.
  • the stacking of such second degree building blocks may be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof;
  • molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
  • the MCM-22 family includes those molecular sieves having an X-ray diffraction pattern including d-spacing maxima at 12.4+0.25, 6.9+0.15, 3.57+0.07, and 3.42+0.07 Angstrom.
  • the X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
  • molecular sieve is used synonymously with the term “zeolite” or “microporous crystalline material.”
  • the term “selectivity” means the moles of carbon in the respective cyclic C 5 , CPD, Ci, and C2-4 formed divided by total moles of carbon in the pentane converted.
  • carbon selectivity to cyclic C5 of at least 30% means that at least 30 moles of carbon in the cyclic C5 is formed per 100 moles of carbon in the pentane converted.
  • conversion means the moles of carbon in the acyclic C5 feedstock that is converted to a product.
  • conversion of at least 70% of said acyclic C5 feedstock to a product means that at least 70% of the moles of said acyclic C5 feedstock was converted to a product.
  • Alpha Value is used as a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 3,354,078 and in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278, (1966); and Vol. 61, p. 395, (1980), each incorporated herein by reference.
  • the experimental conditions of the test used herein included a constant temperature of 538°C and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, p. 395, (1980).
  • deactivated catalyst refers to catalyst that has lost activity during the course of a hydrocarbon conversion process, e.g., due to the accumulation of coke and/or agglomeration of metal.
  • regenerated catalyst and “rejuvenated catalyst” refer to deactivated catalyst that has been treated to restore at least a portion of the lost activity. Regenerated catalyst is catalyst that has been treated in the presence of chlorine.
  • reactor system refers to a system including one or more reactors and all optional equipment used in the production of cyclopentadiene.
  • reactor refers to any vessel(s) in which a chemical reaction occurs. Reactor includes both distinct reactors, as well as reaction zones within a single reactor apparatus and, as applicable, reactions zones across multiple reactors. For example, a single reactor may have multiple reaction zones. Where the description refers to a first and second reactor, the person of ordinary skill in the art will readily recognize such reference includes two reactors, as well as a single reactor vessel having first and second reaction zones. Likewise, a first reactor effluent and a second reactor effluent will be recognized to include the effluent from the first reaction zone and the second reaction zone of a single reactor, respectively.
  • a reactor/reaction zone may be an adiabatic reactor/reaction zone or a diabatic reactor/reaction zone.
  • adiabatic refers to a reaction zone for which there is essentially no heat input into the system other than by a flowing process fluid.
  • a reaction zone that has unavoidable losses due to conduction and/or radiation may also be considered adiabatic for the purpose of this invention.
  • diabatic refers to a reactor/reaction zone to which heat is supplied by a means in addition to that provided by the flowing process fluid.
  • the term "moving bed” reactor refers to a zone or vessel with contacting of solids (e.g., catalyst particles) and gas flows such that the superficial gas velocity (U) is below the velocity required for dilute -phase pneumatic conveying of solid particles in order to maintain a solids bed with void fraction below 95%.
  • the solids e.g., catalyst material
  • the solids may slowly travel through the reactor and may be removed from the bottom of the reactor and added to the top of the reactor.
  • a moving bed reactor may operate under several flow regimes, including settling or moving packed-bed regime (U ⁇ U m f), bubbling regime (Umf ⁇ U ⁇ Umb), slugging regime (U m b ⁇ U ⁇ U c ), transition to and turbulent fluidization regime (U c ⁇ U ⁇ Utr), and fast-fluidization regime (U>Utr), where U m f is minimum fluidizing velocity, U m b is minimum bubbling velocity, U c is the velocity at which fluctuation in pressure peaks, and tr is transport velocity.
  • the term "settling bed” reactor refers to a zone or vessel wherein particulates contact with gas flows such that the superficial gas velocity (U) is below the minimum velocity required to fluidize the solid particles (e.g., catalyst particles), the minimum fluidization velocity (U m f), U ⁇ U m f, in at least a portion of the reaction zone, and/or operating at a velocity higher than the minimum fluidization velocity, while maintaining a gradient in gas and/or solid property (such as, temperature, gas, or solid composition, etc.) axially up the reactor bed by using reactor internals to minimize gas-solid back-mixing.
  • U superficial gas velocity
  • U m f minimum fluidization velocity
  • U m f minimum fluidization velocity
  • a settling bed reactor may be a "circulating settling bed reactor,” which refers to a settling bed with a movement of solids (e.g., catalyst material) through the reactor and at least a partial recirculation of the solids (e.g., catalyst material).
  • the solids e.g., catalyst material
  • the solids may have been removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned back to the reactor.
  • fluidized bed reactor refers to a zone or vessel with contacting of solids (e.g., catalyst particles) and gas flows such that the superficial gas velocity (U) is sufficient to fluidize solid particles (i.e., above the minimum fluidization velocity U m f) and is below the velocity required for dilute-phase pneumatic conveying of solid particles in order to maintain a solids bed with void fraction below 95%.
  • solids e.g., catalyst particles
  • U superficial gas velocity
  • cascaded fluid-beds means a series arrangement of individual fluid-beds such that there can be a gradient in gas and/or solid property (such as, temperature, gas, or solid composition, pressure, etc.) as the solid or gas cascades from one fluid-bed to another.
  • Locus of minimum fluidization velocity is given in, for example, Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2 nd Edition, Butterworth- Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2 nd Edition, Butterworth-Heinemann, Boston, 2010.
  • a fluidized bed reactor may be a moving fluidized bed reactor, such as a "circulating fluidized bed reactor,” which refers to a fluidized bed with a movement of solids (e.g., catalyst material) through the reactor and at least a partial recirculation of the solids (e.g., catalyst material).
  • the solids e.g., catalyst material
  • the solids may have been removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned back to the reactor.
  • the term "riser” reactor also known as a transport reactor refers to a zone or vessel (such as, vertical cylindrical pipe) used for net upwards transport of solids (e.g., catalyst particles) in fast-fluidization or pneumatic conveying fluidization regimes.
  • Fast fluidization and pneumatic conveying fluidization regimes are characterized by superficial gas velocities (U) greater than the transport velocity (Utr).
  • U superficial gas velocities
  • Utr transport velocity
  • Fast fluidization and pneumatic conveying fluidization regimes are also described in Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2 nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2 nd Edition, Butterworth-Heinemann, Boston, 2010.
  • a fluidized bed reactor such as a circulating fluidized bed reactor, may be operated as a riser reactor.
  • radiantly heated tubular or “fired tubes” reactor refers to a furnace and parallel reactor tube(s) positioned within a radiant section of the furnace.
  • the reactor tubes contain a catalytic material (e.g., catalyst particles), which contacts reactant(s) to form a product.
  • the term "convectively heated tubes” reactor refers to a conversion system comprising parallel reactor tube(s) containing a catalytic material and positioned within an enclosure. While any known reactor tube configuration or enclosure may be used, preferably the conversion system comprises multiple parallel reactor tubes within a convective heat transfer enclosure. Preferably, the reactor tubes are straight rather than having a coiled or curved path through the enclosure (although coiled or curved tubes may be used). Additionally, the tubes may have a cross section that is circular, elliptical, rectangular, and/or other known shapes. The tubes are preferentially heated with a turbine exhaust stream produced by a turbine burning fuel gas with a compressed gas comprising oxygen. In other aspects, the reactor tubes are heated by convection with hot gas produced by combustion in a furnace, boiler, or excess air burner. However, heating the reactor tubes with turbine exhaust is preferred because of the co-production of shaft power among other advantages.
  • the term "fixed bed” or "packed bed” reactor refers to a zone or vessel (such as, vertical or horizontal, cylindrical pipe or a spherical vessel) and may include transverse (also known as cross flow), axial flow, and/or radial flow of the gas, where solids (e.g., catalyst particles) are substantially immobilized within the reactor and gas flows such that the superficial velocity (U) is below the velocity required to fluidize the solid particles (i.e., below the minimum fluidization velocity U m f) and/or the gas is moving in a downward direction so that solid particle fluidization is not possible.
  • the superficial velocity (U) is below the velocity required to fluidize the solid particles (i.e., below the minimum fluidization velocity U m f) and/or the gas is moving in a downward direction so that solid particle fluidization is not possible.
  • cyclical refers to a periodic recurring or repeating event that occurs according to a cycle.
  • reactors e.g., cyclic fixed bed
  • reactors may be cyclically operated to have a reaction interval, a reheat interval, and/or a regeneration interval.
  • the duration and/or order of the interval steps may change over time.
  • co-current refers to a flow of two streams (stream (a), stream (b)) in substantially the same direction. For example, if stream (a) flows from a top portion to a bottom portion of at least one reaction zone and stream (b) flows from a top portion to a bottom portion of at least one reaction zone, the flow of stream (a) would be considered co-current to the flow of stream (b). On a smaller scale within the reaction zone, there may be regions where flow may not be co-current.
  • counter-current refers to a flow of two streams (e.g., stream (a), stream (b)) in substantially opposing directions. For example, if stream (a) flows from a top portion to a bottom portion of the at least one reaction zone and stream (b) flows from a bottom portion to a top portion of the at least one reaction zone, the flow of stream (a) would be considered counter-current to the flow of stream (b). On a smaller scale within the reaction zone, there may be regions where flow may not be counter-current.
  • Catalyst compositions useful herein comprise a microporous crystalline aluminosilicate and a Group 10 metal. Suitable catalyst compositions are further characterized by having a Group 10 metal content- to- Al content molar ratio of greater than or equal to 0.007: 1, such as greater than or equal to 0.01 : 1, or greater than or equal to 0.05: 1, or greater than or equal to 0.1 : 1. For example, suitable catalysts compositions may have a Group 10 metal content-to-Al content molar ratio ranging from 0.007: 1 to 0.1: 1, or from 0.01 : 1 to 0.5: 1.
  • an aluminosilicate may have one or more metals present apart from aluminum.
  • an aluminosilicate may contain one or more metals from groups 8, 11, 13, and 14 of the Periodic Table of the Elements (preferably one or more of Fe, Cu, Ag, Au, B, Al, Ga, and or In) that are incorporated in the crystal structure during synthesis or impregnated post crystallization.
  • the microporous crystalline aluminosilicate has a constraint index in the range of 3 to 12.
  • Suitable aluminosilicates having a constraint index of 3 to 12 include and are selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM- 50, ZSM-57, ZSM-58, a MCM-22 family material and mixtures of two or more thereof.
  • the microporous crystalline aluminosilicate that has a constraint index in the range of 3 to 12 is ZSM-5.
  • ZSM-5 is described in U.S. Patent No. 3,702,886.
  • ZSM-11 is described in U.S. Patent No. 3,709,979.
  • ZSM-22 is described in U.S. Patent No. 5,336,478.
  • ZSM-23 is described in U.S. Patent No. 4,076,842.
  • ZSM-35 is described in U.S. Patent No. 4,016,245.
  • ZSM-48 is described in U.S. Patent No. 4,375,573.
  • ZSM-50 is described in U.S. Patent No. 4,640,829.
  • ZSM-57 is described in U.S. Patent No. 4,873,067.
  • ZSM-58 is described in U.S. Patent No. 4,698,217.
  • the MCM-22 family material is selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM- 10, EMM-10-P, EMM- 12, EMM- 13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30 and mixtures of two or more thereof.
  • Materials of the MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described in U.S. Patent No. 4,826,667), ERB-1 (described in European Patent No.
  • MCM-36 described in U.S. Patent No. 5,250,277
  • MCM-49 described in U.S. Patent No. 5,236,575
  • MCM-56 described in U.S. Patent No. 5,362,697
  • UZM-8 described in U.S. Patent No. 6,756,030
  • UZM-8HS described in U.S. Patent No. 7,713,513
  • the microporous crystalline aluminosilicate has a S1O2/AI2O3 molar ratio greater than 25, or greater than 50, or greater than 100, or greater than 400, or greater than 1,000, or in the range from 100 to 400, or from 100 to 500, or from 50 to 1000.
  • the Group 10 metal includes, or is selected from the group consisting of nickel, palladium, and platinum, preferably platinum.
  • the Group 10 metal content of said catalyst composition is at least 0.005 wt%, based on the weight of the catalyst composition.
  • the Group 10 content is in the range from 0.005 wt% to 10 wt%, or from 0.005 wt% up to 1.5 wt%, based on the weight of the catalyst composition.
  • the Group 10 metal is present in combination with an additional metal selected from Groups 8, 9, 11, and 13 of the Periodic Table of the Elements and the rare earth metals, such as Ga, In, Zn, Cu, Re, Mo, W, La, Fe, Ag, Rh, Pr, La, and/or oxides, sulfides, nitrides, and/or carbides of these metals.
  • the Group 10 metal is present in combination with a Group I alkali metal and/or a Group 2 alkaline earth metal.
  • Preferred additional metals are Group 11 metals.
  • the Group 11 metal is selected from the group consisting of Cu, Ag, Au, and mixtures of two or more thereof; preferably Cu or Ag.
  • the Group 11 metal content of the catalyst composition is such that the molar ratio of Group 11 metal to Group 10 metal is at least 0.01, based on the molar quantities of each in the catalyst composition.
  • the molar ratio of Group 11 metal to Group 10 metal is in the range from 0.1 to 10 or from 0.5 to 5 based on the molar quantities of each in the catalyst composition.
  • the Group 11 metal may be added to the catalyst composition during or after synthesis of the microporous crystalline molecular sieve as any suitable Group 11 metal compound.
  • a preferred Group 9 metal is Rh, which may form an alloy with the Group 10 metal.
  • the molar ratio of Rh to Group 10 metal is in the range from 0.1 to 5.
  • the rare earth metal is selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, and mixtures or combinations thereof.
  • the molar ratio of rare earth metal to Group 10 metal is in the range from 1 to 10.
  • the rare earth metal may be added to the catalyst composition during or after synthesis of the microporous crystalline molecular sieve as any suitable rare earth metal compound.
  • the catalyst composition has an Alpha Value (as measured prior to the addition of the Group 10 metal, preferably platinum, and/or prior to the addition of the optional Group 8- 13 metal, preferably, copper or silver) is less than 25, or in the range of greater than 1 to less than 25, preferably, less than 15, or in the range of greater than 1 to less than 15.
  • the Group 1 alkali metal is generally present as an oxide and the metal is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures of two or more thereof.
  • the Group 2 alkaline earth metal is generally present as an oxide and the metal is selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, and mixtures of two or more thereof.
  • the molar ratio of said Group 1 alkali metal to Al is at least 0.5, or at least 1, or in the from at least 1 up to 3, preferably at least 2, more preferably at least 3.
  • the molar ratio of said Group 2 alkaline earth metal to Al is at least 0.5, or at least 1, or from at least 1 up to 3, preferably at least 2, more preferably at least 3.
  • the catalyst compositions of this invention can be combined with a matrix or binder material to render them attrition resistant and more resistant to the severity of the conditions to which they will be exposed during use in hydrocarbon conversion applications.
  • Preferred binder materials comprise one or more of silica, titania, zirconia, metal silicates of Group 1 or Group 13 of the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, surface passivated alumina, and mixtures thereof.
  • suitable binder materials have a lower affinity for Group 10 metal particles, e.g., Pt, in comparison with the crystalline metallosilicate, e.g., aluminosilicate.
  • the combined compositions can contain 1 wt% to 99 wt% of the materials of the invention based on the combined weight of the matrix (binder) and material of the invention.
  • the relative proportions of microporous crystalline material and matrix may vary widely, with the crystal content ranging from 1 wt% to 90 wt% and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 wt% to 80 wt% of the composite.
  • the formulated catalyst composition may be made into one or more forms.
  • the formulated catalyst can be extruded to form an extrudate, particularly into a shaped extrudate having a geometric form.
  • the formulated catalyst composition may be made into a particle, such as, for example, a spray dried particle, an oil drop particle, a mulled particle, or a spherical particle.
  • the formulated catalyst composition may be made into a slurry.
  • the catalyst compositions can be made by the methods according to the Examples, below.
  • Feedstock useful herein generally comprises acyclic hydrocarbons, preferably acyclic C2-C10 hydrocarbons.
  • Acyclic C2-C10 hydrocarbons include, but are not limited to alkanes (e.g. , ethane, propane, butane, pentane, hexane, etc.), alkenes (e.g. , ethylene, propylene, butylene, etc.), alkynes (e.g. , ethyne, propyne, 1-butyne, 2-butyne, etc.), dialkenes (e.g. , 1,2-propadiene, 1,3-butadiene, 1,3-pentadiene, etc.) and combinations thereof.
  • An acyclic C2-C10 hydrocarbon feedstock, useful herein, is obtainable from crude oil or natural gas condensate.
  • the feedstock may preferably be an acyclic C5 feedstock and can include cracked C5 (in various degrees of unsaturation: alkenes, dialkenes, alkynes) produced by refining and chemical processes, such as fluid catalytic cracking (FCC), reforming, hydrocracking, hydrotreating, coking, and steam cracking.
  • FCC fluid catalytic cracking
  • the acyclic C5 feedstock useful in the process of this invention comprises pentane, pentene, pentadiene and mixtures of two or more thereof.
  • the acyclic C5 feedstock comprises at least 50 wt%, or 60 wt%, or 75 wt%, or 90 wt% n-pentane, or in the range from 50 wt% to 100 wt% n- pentane.
  • the acyclic C5 hydrocarbon feedstock optionally does not comprise C 6 aromatic compounds, such as benzene.
  • C 6 aromatic compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, and preferably at zero wt%.
  • the acyclic C 5 hydrocarbon feedstock optionally does not comprise benzene, toluene, or xylene (ortho, meta, or para).
  • any benzene, toluene, or xylene (ortho, meta, or para) compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, and preferably at zero wt%.
  • the acyclic C 5 hydrocarbon feedstock optionally does not comprise C 6+ aromatic compounds.
  • C 6+ aromatic compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, and preferably at zero wt%.
  • the catalyst regeneration processes of this disclosure are generally employed in hydrocarbon conversion processes that comprise contacting a hydrocarbon feedstock with any one of the aforementioned catalyst compositions in at least one reaction zone to form a hydrocarbon reaction product.
  • suitable hydrocarbon conversion processes include: the conversion of acyclic C 5 hydrocarbons to cyclic C 5 hydrocarbons; the conversion of acyclic C 6+ hydrocarbons to aromatic C 6+ hydrocarbons; the conversion of C2-C5 hydrocarbons to C 6+ aromatics; and/or the dehydrogenation of paraffins to olefins and/or dienes.
  • suitable hydrocarbon conversion processes can be conducted in a wide range of reactor configurations.
  • Particularly preferred reactor configurations include convectively heated tubes (as described in USSN 62/250,674, filed November 4, 2015); fired tubes (as described in USSN 62/250,693, filed November 4, 2015); a riser reactor (as described in USSN 62/250,682, filed November 4, 2015); a circulating fluidized bed or a circulating settling bed with counter-current flow (as described in USSN 62/250,680, filed November 4, 2015); a cyclic fluidized bed reactor or a cyclic fixed bed reactor (as described in USSN 62/250,677, filed November 4, 2015); and/or an electrically heated reactor.
  • suitable hydrocarbon conversion processes can be conducted in a single reaction zone or in a plurality of reaction zones, such as an adiabatic reaction zone followed by a diabatic reaction zone (as described in USSN 62/250,697, filed November 4, 2015).
  • a particularly preferred hydrocarbon conversion process is the conversion of acyclic C5 hydrocarbons to cyclic C5 hydrocarbons, the process comprising the steps of contacting said feedstock and, optionally, hydrogen under acyclic C5 conversion conditions in the presence of any one of the aforementioned catalyst compositions to form said product.
  • the acyclic C 5 hydrocarbon(s) contained in the C 5 feedstock is fed into a first reactor loaded with a catalyst, where the acyclic C 5 hydrocarbons contact the catalyst under conversion conditions, whereupon at least a portion of the acyclic C 5 hydrocarbon(s) molecules are converted into CPD molecules, and a reaction product containing CPD and, optionally, other cyclic hydrocarbons (e.g., C 5 cyclic hydrocarbons such as cyclopentane and cyclopentene) exits the first reactor as a first reactor hydrocarbon effluent.
  • C 5 cyclic hydrocarbons such as cyclopentane and cyclopentene
  • a hydrogen co-feedstock comprising hydrogen and, optionally, light hydrocarbons, such as Ci- CA hydrocarbons, is also fed into the first reactor (as described in USSN 62/250,702, filed November 4, 2015).
  • at least a portion of the hydrogen co-feedstock is admixed with the C 5 feedstock prior to being fed into the first reactor. The presence of hydrogen in the feed mixture at the inlet location, where the feed first comes into contact with the catalyst, prevents or reduces the formation of coke on the catalyst particles.
  • the product of the process for conversion of an acyclic C 5 feedstock comprises cyclic C 5 compounds.
  • the cyclic C 5 compounds comprise one or more of cyclopentane, cyclopentene, cyclopentadiene, and includes mixtures thereof.
  • the cyclic C 5 compounds comprise at least 20 wt%, or 30 wt%, or 40 wt%, or 50 wt% cyclopentadiene, or in the range of from 10 wt% to 80 wt%, alternately 20 wt% to 70 wt% of cyclopentadiene.
  • the acyclic C 5 conversion conditions include at least a temperature, a partial pressure, and a weight hourly space velocity (WHSV).
  • the temperature is in the range of 400°C to 700°C, or 450°C to 800°C, or in the range from 500°C to 650°C, preferably, in the range from 500°C to 600°C.
  • the partial pressure is in the range of 3 psia to 100 psia at the reactor inlet (21 to 689 kPa-a), or in the range from 3 psia to 50 psia (21 to 345 kPa-a), preferably, in the range from 3 psia to 20 psia (21 to 138 kPa-a).
  • the weight hourly space velocity is in the range from 1 hr 1 to 50 hr 1 , or in the range from 1 hr 1 to 20 hr 1 .
  • Such conditions include a molar ratio of the optional hydrogen co-feed to the acyclic Cs hydrocarbon in the range of 0 to 3 (e.g., 0.01 to 3.0), or in the range from 0.5 to 2.
  • Such conditions may also include co-feed C1-C4 hydrocarbons with the acyclic C5 feed.
  • this invention relates to a process for conversion of n-pentane to cyclopentadiene comprising the steps of contacting n-pentane and, optionally, hydrogen (if present, typically 3 ⁇ 4 is present at a molar ratio of hydrogen to n-pentane of 0.01 to 3.0) with one or more catalyst compositions, including but not limited to the catalyst compositions described herein, to form cyclopentadiene at a temperature of 400°C to 700°C, a partial pressure of 3 psia to 100 psia at the reactor inlet (21 to 689 kPa-a), and a weight hourly space velocity of 1 hr 1 to 50 hr 1 .
  • the use of the catalyst compositions of this invention provides a conversion of at least 10%, or at least 20%, or at least 30%, or in the range of from 20% to 50%, of said acyclic C 5 feedstock under acyclic C 5 conversion conditions of an n-pentane containing feedstock with equimolar 3 ⁇ 4, a temperature in the range of from 400°C to 500°C, or 450°C, an n-pentane partial pressure of 5 psia (35 kPa-a), or 7 psia (48 kPa-a), or from 4 psia to 6 psia at the reactor inlet (28 to 41 kPa-a), and an n-pentane weight hourly space velocity of 2 hr 1 , or between 1 hr 1 and 5 hr 1 .
  • any one of the catalyst compositions of this invention provides a carbon selectivity to cyclic Cs compounds of at least 10%, or at least 20%, or at least 30%, or in the range from 20% to 50%, under acyclic Cs conversion conditions including an n-pentane feedstock with equimolar 3 ⁇ 4, a temperature in the range of 400°C to 500°C, or 450°C, an n- pentane partial pressure between 3 psia and 10 psia (21 to 69 kPa-a), and an n-pentane weight hourly space velocity between 10 hr 1 and 20 hr 1 .
  • any one of the catalyst compositions of this invention provides a carbon selectivity to cyclopentadiene of at least 20%, or at least 30%, or at least 40%, or at least 50%, or in the range from 30% to 50%, under acyclic C 5 conversion conditions including an n- pentane feedstock with equimolar 3 ⁇ 4, a temperature in the range of 550°C to 600°C, an n- pentane partial pressure of 7 psia (48 kPa-a), or 5 psia (35 kPa-a), or from 4 psia to 6 psia (28 to 41 kPa-a), and an n-pentane weight hourly space velocity of 2 hr 1 , or between 1 hr 1 and 5 hr 1 .
  • Fluids inside the first reactor are essentially in gas phase.
  • a first reactor hydrocarbon effluent preferably in gas phase, is obtained.
  • the first reactor hydrocarbon effluent may comprise a mixture of the following hydrocarbons, among others: heavy components comprising more than 8 carbon atoms such as multiple -ring aromatics; C 8 , C 7 , and Ce hydrocarbons such as one-ring aromatics; CPD (the desired product); unreacted Cs feedstock material such as n-pentane; Cs by-products such as pentenes (1-pentene, 2-pentene, e.g.), pentadienes (1,3-pentadiene; 1 ,4-pentadiene, e.g.), cyclopentane, cyclopentene, 2-methylbutane, 2-methyl-l-butene, 3-methyl-l-butene, 2-methyl-l,3- butadiene, 2,2-dimethylpropane, and
  • the first reactor hydrocarbon effluent may comprise CPD at a concentration of C(CPD)1 wt%, based on the total weight of the C5 hydrocarbons in the first reactor hydrocarbon effluent; and al ⁇ C(CPD)1 ⁇ a2, where al and a2 can be, independently, 15, 16, 18, 20, 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, 38, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 as long as al ⁇ a2.
  • the first reactor hydrocarbon effluent may comprise acyclic diolefins at a total concentration of C(ADO)l wt%, based on the total weight of the C5 hydrocarbons in the first reactor hydrocarbon effluent; and bl ⁇ C(ADO)l ⁇ b2, where bl and b2 can be, independently, 20, 18, 16, 15, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, or 0.5, as long as bl ⁇ b2.
  • a high CPD to acyclic diolefin molar ratio in the first reactor hydrocarbon effluent can be achieved such that C(CPD)l/C(ADO)l > 1.5, preferably 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, 2.6, 2.8, 3.0, 3.2, 3.4, 3.5, 3.6, 3.8, 4.0, 5.0, 6.0, 8.0, 10, 12, 14, 15, 16, 18, or 20.
  • the high ratio of C(CPD)l/C(ADO)l significantly reduces CPD loss as a result of Diels- Alder reactions between CPD and acyclic dienes in subsequent processing steps, and therefore, allows the processes of the present invention to achieve high DCPD yield and high DCPD purity for the subsequently produced DCPD fractions.
  • the total absolute pressure and temperature of the first reactor hydrocarbon effluent should be maintained at levels such that the dimerization of CPD to form DCPD is substantially avoided, and the Diels-Alder reactions between CPD and acyclic dienes are substantially inhibited.
  • a low partial pressure of CPD and/or a low partial pressure of hydrogen in the reaction mixture favors the conversion of acyclic C 5 hydrocarbons.
  • the total partial pressure of C 5 hydrocarbons and hydrogen in the first reactor effluent at the outlet is desired to be lower than atmospheric pressure.
  • the total overall pressure of the first reactor effluent is desirably sub-atmospheric, in order to achieve a level of satisfactory conversion from acyclic C5 hydrocarbons to CPD.
  • the activity of the catalyst generally gradually declines to form a deactivated catalyst due to the accumulation of carbonaceous or coke material and/or agglomeration of metal on the catalyst material during the reaction.
  • a regeneration cycle is advantageously performed to produce a regenerated catalyst having restored or substantially restored catalyst activity, typically by removing at least a portion of coke material from the catalyst composition.
  • regenerated catalyst has activity restored to at least 50% of the activity of the catalyst prior to deactivation, more preferably at least 60%, more preferably at least 80%.
  • Regenerated catalyst also preferably has restored or substantially restored catalyst selectivity, e.g., selectivity restored to at least 50% of the selectivity of the catalyst prior to deactivation, more preferably at least 60%, more preferably at least 80%.
  • catalyst selectivity e.g., selectivity restored to at least 50% of the selectivity of the catalyst prior to deactivation, more preferably at least 60%, more preferably at least 80%.
  • a regeneration cycle is employed when the catalyst composition comprises >1 wt% coke, such as >5 wt% coke, such as >10 wt% coke, or even >20 wt% coke.
  • Regeneration is carried out in at least one regeneration zone.
  • the regeneration zone(s) may be located in situ in the reaction zone or ex situ in one or more separate vessels apart from the reaction zone.
  • in situ regeneration methods are employed when the reactor configuration of the hydrocarbon conversion process is a fixed bed system, such as a heated tubular reactor.
  • regeneration is carried out in a separate regeneration zone when the reactor configuration of the hydrocarbon conversion process is a moving bed system, e.g., a circulating fluidized bed or a circulating settling bed.
  • a typical regeneration cycle begins by discontinuing contact of the hydrocarbon feedstock with the catalyst composition in the reaction zone or by transfer of the catalyst composition to a separate regeneration zone.
  • combustible hydrocarbon gas including feedstock or reactor product
  • a purge gas for example, N 2
  • the purging step may be proceeded by a step of contacting the catalyst with a 3 ⁇ 4 containing stream for partial, reductive removal of coke.
  • the following regeneration steps including at least oxychlorination and chlorine stripping, are then performed.
  • Regeneration of the catalyst material may occur as a continuous process or may be done batch wise.
  • a regeneration cycle typically requires less than 10 days, preferably less than 3 days to complete.
  • a regeneration cycle may be periodically performed between once every 6 days to once every 180 days, preferably between once every 10 days to once every 40 days.
  • regeneration of the catalyst comprises a first step to remove deposited carbonaceous or coke material from the catalyst, i.e., a coke removal step.
  • Coke removal can be performed by any process known in the art, including reductive and oxidative removal methods.
  • Reductive removal is preferably performed by contacting the catalyst with a gaseous stream comprising hydrogen under conditions effective to remove at least a portion of coke from the catalyst.
  • Oxidative removal is preferably performed by contacting the catalyst with a gaseous stream comprising an oxygen source, and optionally a chlorine source, under conditions effective to remove at least a portion of coke from the catalyst.
  • a preferred oxygen source is air, which is preferably diluted to reduce the O2 concentration to between 0.5 mol% and 10 mol%.
  • at least a portion of the Group 10 metal may be converted to a metal oxide.
  • at least a portion of the Group 10 metal is typically present in reduced form and/or as a metal oxide.
  • At least 10 wt% (>10 wt%) of coke material present at the start of the coke removal step is removed, such as between 10 wt% to 100 wt%.
  • the harsh conditions, e.g. high temperature, employed during coke removal typically result in agglomeration of the Group 10 metal particles and at least partial removal of the Group 10 metal particles from the pores of the crystalline aluminosilicate.
  • regeneration of the catalyst comprises an oxychlorination step subsequent to coke removal under conditions effective for dispersing at least a portion of the at least one Group 10 metal on the surface of the catalyst.
  • "catalyst surface” specifically includes area within the microporous structure of the catalyst composition.
  • the oxychlorination step is further effective to convert at least a portion of the Group 10 metal present in reduced and/or metal oxide to produce a Group 10 metal chlorohydrate.
  • the Group 10 metal chlorohydrate can be represented by Formula I:
  • M is a Group 10 metal
  • x is an integer ranging from 0 to 4
  • y is an integer ranging from 2 to 6, wherein the sum of x and y ranges from 4 to 6, and wherein a is an integer ranging from -2 to 0.
  • the metal chlorohydrate of Formula I is a mobile species that can relocate to different binding sites of the support. This relocation is believed to effectively decrease the average Group 10 metal particle size and increases the total Group 10 metal surface area (i.e., available active sites), regenerating the catalyst activity.
  • the oxychlorination step typically comprises contacting the catalyst with a gaseous stream comprising a chlorine source and an oxygen source.
  • the chlorine source may be selected from the group consisting of HC1, Ch, chlorinated hydrocarbons, e.g., CHCb, C2H4CI2, or C3H6CI2, and mixtures thereof, preferably HC1 and/or Ch.
  • the chlorine source may be present in the gaseous stream at a concentration ranging from 10 vppm to 50,000 vppm based on the total volume of the gaseous stream, such as 100 to 30,000 vppm, preferably from 500 vppm to 20,000 vppm.
  • a preferred oxygen source is air, which is preferably diluted to reduce the O2 concentration to between 0.5 mol% and 10 mol%.
  • the gaseous stream further comprises water at a concentration of 500 to 20,000 vppm based on the total volume of the gaseous stream.
  • at least a portion of, typically a majority of, e.g, 50 vol% or more, preferably 80 vol% of more, ideally 90 vol% or more, e.g., 100 vol% of the gaseous stream employed during oxychlorination is withdrawn from the regeneration zone to form an effluent.
  • Oxychlorination can be conducted under any combination of process conditions effective for dispersing at least a portion of the at least one Group 10 metal on the surface of the catalyst and for producing a Group 10 metal chlorohydrate.
  • Preferred temperature and pressure conditions include a temperature ranging from 400°C to 750°C, more preferably from 450°C to 550°C; and a total pressure ranging up to 100 bar, e.g., from 0.1 bar to 100 bar, more preferably from 1 bar to 10 bar, ideally at or atmospheric pressure.
  • Preferred flow rate conditions for the chlorine source and the oxygen source in the gaseous stream are those resulting in the following preferred partial pressure ranges in the effluent: a base 10 logarithm of chlorine partial pressure (log(PCl2)) in the range from -15.0 to 5.0, more preferably from - 5.0 to 3.0; and a base 10 logarithm of oxygen partial pressure (log(P02)) ranging from -5.0 to 2.0, more preferably from -3.0 to 1.0.
  • each component of the gaseous stream is fed to the regeneration zone within 30% of its chemical equilibrium concentration, more preferably within 20% of its chemical equilibrium concentration.
  • the gaseous stream comprises a mixture of oxygen, HCl, Ch, and H2O, wherein each of these mixture components is fed to the regeneration zone within 20% of its chemical equilibrium concentration.
  • K eq can be determined as a function of temperature in accordance with the following equation:
  • At least a portion of the effluent withdrawn during the oxychlorination step is recycled to the regeneration zone.
  • the gaseous stream comprises a mixture of oxygen, HCl, Ch, and H2O
  • a portion of HCl and/or H2O is typically removed from the recycled portion of the effluent prior to supplying the recycled stream to the regeneration zone.
  • supplemental O2 and/or Ch may be added to the recycled portion of the effluent prior to supplying the recycled stream to the regeneration zone.
  • the catalyst is typically subjected to a reduction step immediately following oxychlorination. It has presently been found that the activity of the regenerated catalyst compositions of this disclosure can be improved by employing a chlorine stripping step subsequent to oxychlorination under conditions effective for increasing the O/Cl ratio of the Group 10 metal chlorohydrate.
  • increasing the O/Cl ratio of the Group 10 metal chlorohydrate it is meant that the chlorine content of the metal chlorohydrate is reduced and the oxygen concentration of the metal chlorohydrate is increased.
  • increasing the O/Cl ratio refers to increasing the value of x and decreasing the value of y.
  • the chlorine stripping step converts the first metal chlorohydrate of Formula I to produce a second metal chlorohydrate of Formula II:
  • M is a Group 10 metal
  • z is an integer ranging from 2 to 5
  • w is an integer ranging from 1 to 4, wherein the sum of z and w ranges from 4 to 6, and wherein b is an integer ranging from -2 to 0, wherein z > x and wherein w ⁇ y.
  • z may be greater than x by an integer ranging from 1 to 5
  • w may be less than y by an integer ranging from 1 to 5.
  • z may be greater than x by an integer of 1, 2, or 3, while w may be less than y by an integer of 1, 2, or 3.
  • the metal chlorohydrate of Formula II is has higher surface affinity than the metal chlorohydrate of Formula I, resulting in higher dispersion of the Group 10 metal upon reduction performed subsequent to oxychlorination.
  • the chlorine stripping step typically comprises contacting the catalyst with a gaseous stream comprising an oxygen source, optionally in combination with a chlorine source and/or a water source.
  • the chlorine source may be selected from the group consisting of HC1, Ch, chlorinated hydrocarbons, e.g., CHCI3, C2H4CI2, or C3H6CI2, and mixtures thereof, preferably HC1 and/or Ck.
  • a preferred oxygen source is air, which is preferably diluted to reduce the O2 concentration to between 0.5 mol% and 10 mol%.
  • the gaseous stream employed during chlorine stripping has the same composition as the gaseous stream employed during oxychlorination.
  • the temperature and/or total pressure is adjusted to achieve the desired O/Cl ratio increase.
  • at least a portion of, typically a majority of, e.g, 50 vol% or more, preferably 80 vol% of more, ideally 90 vol% or more, e.g., 100 vol%, of the gaseous streams present in the regeneration zone during chlorine stripping is withdrawn from the regeneration zone to form an effluent.
  • Chlorine stripping can be conducted under any combination of process conditions effective for increasing the O/Cl ratio of the Group 10 metal chlorohydrate.
  • Preferred temperature and pressure conditions include a temperature ranging from 400°C to 750°C, more preferably from 450°C to 550°C; and a total pressure ranging up to 100 bar, e.g., from 0.1 bar to 100 bar, more preferably from 1 bar to 10 bar, ideally at or atmospheric pressure.
  • Preferred flow rate conditions for the oxygen source and the optional chlorine source in the gaseous stream are those resulting in the following preferred partial pressure ranges in the effluent: log(PCi2) in the range from -15.0 to 5.0, more preferably from -5.0 to 3.0; and log(P02) ranging from -5.0 to 2.0, more preferably from -3.0 to 1.0.
  • the gaseous stream employed during chlorine stripping has the same composition as the gaseous stream employed during oxychlorination
  • chlorine stripping is typically conducted at the same or similar process conditions as oxychlorination with the exception that the temperature is typically reduced by 20°C to 200°C.
  • purge gas e.g. N 2
  • purge gas is generally reintroduced to purge oxidant gases from the regeneration zone.
  • the catalyst is generally chemically reduced to convert the Group 10 metal to elemental form.
  • this reduction is achieved by contacting the catalyst with a gaseous stream comprising from 10 vol% to 100 vol% hydrogen at a temperature within the range of 100°C to 650°C.
  • the gaseous stream preferably contains less than 100 vppm, more preferably less than 10 vppm, of each of the following components: CO, CO2, H2O, and/or hydrocarbon.
  • the reduced catalyst is sulfided by contacting the catalyst with a sulfur containing gaseous stream.
  • the sulfur containing gaseous stream has a sulfur concentration of 100 to 1,000 vppm.
  • a preferred sulfur containing gaseous stream is a mixture of H2S and 3 ⁇ 4. The sulfur containing gaseous stream is generally contacted with the catalyst at a flow rate and period of time sufficient to deposit from 10 to 1,000 ppm by weight of S on the catalyst.
  • the hydrocarbon conversion processes may further comprise periodically performing one or more rejuvenation cycles to remove at least a portion of incrementally deposited coke material accumulated on the catalyst material.
  • incrementally deposited coke refers to the amount of coke that is deposited on the catalyst during a conversion cycle.
  • a rejuvenation cycle is employed when the catalyst composition comprises >1 wt% incrementally deposited coke, such as >5 wt% incrementally deposited coke, or >10 wt% incrementally deposited coke.
  • a rejuvenation cycle may be advantageously performed >10 minutes, e.g., >30 minutes, >2 hours, >5 hours, >24 hours, >2 days, >5 days, >20 days, after beginning the specified hydrocarbon conversion process.
  • performing a rejuvenation cycle lengthens the amount of time the catalyst can maintain adequate activity before the next regeneration cycle.
  • the hydrocarbon conversion processes may comprise >1 e.g., >2, >5 or >20 rejuvenation cycles between each regeneration cycle.
  • Rejuvenation is carried out in at least one rejuvenation zone.
  • the rejuvenation zone(s) may be located in situ in the reaction zone or ex situ in one or more separate rejuvenation zones apart from the reaction zone.
  • in situ rejuvenation methods are employed when the reactor configuration of the hydrocarbon conversion process is a fixed bed system, such as a heated tubular reactor.
  • rejuvenation is carried out in a separate rejuvenation zone when the reactor configuration of the hydrocarbon conversion process is a moving bed system, e.g., a circulating fluidized bed or a circulating settling bed.
  • a typical rejuvenation cycle begins by discontinuing contact of the hydrocarbon feedstock with the catalyst composition in the reaction zone or by transfer of the catalyst composition to a separate rejuvenation zone.
  • combustible hydrocarbon gas including feedstock or reactor product, is purged from the catalyst composition using a purge gas, for example, N 2 .
  • the purging step may be proceeded by a step of contacting the catalyst with a H 2 containing stream for partial, reductive removal of coke.
  • rejuvenation of the catalyst is preferably achieved using a mild oxidation step, and optionally at least one hydrogen treatment.
  • the mild oxidation step generally comprises contacting the catalyst composition with an oxygen-containing gaseous stream under conditions effective to remove at least a portion of incrementally deposited coke material on the catalyst.
  • these conditions include a temperature range of 250°C to 500°C, and a total pressure of 0.1 bar to 100 bar, preferably at or atmospheric pressure.
  • the oxygen-containing gaseous stream is typically supplied to the rejuvenation zone(s) at a total WHSV in the range from 1 to 10,000.
  • the source of oxygen may be, for example, 0 2 , O3, nitrogen oxides, CO2, and mixtures of any of the foregoing.
  • the concentration of oxygen in the gaseous stream is in the range from 0.1 to 20% by volume for O2, O3, and/or nitrogen oxides, preferably from 0.5 to 5%.
  • concentration of oxygen in the gaseous stream may further comprise a non-reactive substance (e.g., N 2 , CO).
  • purge gas e.g. N 2
  • purge gas is generally reintroduced to purge oxidant gases from the rejuvenation zone.
  • the catalyst is typically reduced to convert the noble metal oxide formed during rejuvenation to the elemental metal. Subsequent to reduction, the rejuvenation cycle is complete and flow of hydrocarbon feedstock may be resumed or the catalyst transferred back to the reaction zone.
  • rejuvenation is effective at removing at least 10 wt% (> 10 wt%) of incrementally deposited coke material. Between 10 wt% to 100 wt%, preferably between 90 wt% to 100 wt% of incrementally deposited coke material is removed.
  • the process for producing cyclic Cs compounds of this invention comprises one or more cyclic Cs compositions.
  • Such composition comprises one or more cyclic Cs compounds.
  • These cyclic C 5 compounds include and are selected from the group consisting of cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, pentene, pentadiene, and mixtures of two or more thereof.
  • the cyclic C 5 compounds may be reacted with a substrate to form a product.
  • the substrate comprise a double bond.
  • Such product includes is one or more of a Diels Alder reaction derivative of cyclopentadiene, cyclic olefin copolymers, cyclic olefin polymers, polycyclopentene, ethylidene norbornene, EPDM rubber, alcohols, plasticizers, blowing agents, solvents, octane enhancers, gasoline, unsaturated polyester resins, hydrocarbon resin tackifiers, formulated epoxy resins, polydicyclopentadiene, metathesis polymers of norbornene or substituted norbornenes or dicyclopentadiene, tetracyclodocene, or any combination of two or more thereof.
  • the Diels Alder reaction derivatives of cyclopentadiene is or comprises norbornene or substituted norbornenes.
  • the product may be made into a useful article.
  • Such article comprise any of the products made or derived from the process of this invention.
  • the article may be one or more of wind turbine blades, composites containing glass or carbon fibers, and formulated adhesives.
  • Pulse CO chemisorption was performed at 35°C on a Thermo Scientific TPDRO 1100 instrument.
  • the sample was first reduced in 5%H2/N2 (20 niL/min) at 250°C for 15 minutes.
  • the sample ( ⁇ 0.1 g) was then placed in a temperature controlled chamber set at 35°C.
  • 20%CO/He ⁇ 10 micromoles of CO was pulsed over the sample (10 pulses with 7 minute interval between pulses). Pulses were detected by a thermal conductivity detector, with a moisture trap placed between the sample and the detector to collect any moisture.
  • a synthesis mixture with ⁇ 22% solids was prepared from 8,800 g of deionized (DI) water, 600 g of 50% NaOH solution, 26 g of 43% Sodium Aluminate solution, 730 g of n- propyl amine 100% solution, 40 g of ZSM-5 seed crystals, and 3,190 g of Ultrasil PMTM modified silica were mixed in a 5-gal pail container and then charged into a 5-gal autoclave after mixing.
  • the synthesis mixture had the following molar composition:
  • the synthesis mixture was mixed and reacted at 230°F (110°C) at 350 rpm for 48 hours.
  • the resulting reaction slurry was discharged and stored in a 5-gal pail container.
  • the XRD pattern of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
  • the SEM of the as-synthesized material shows that the material was composed of mixture of large crystals with size of ⁇ 1-2 micron.
  • the resulting ZSM-5 crystals had a S1O2/AI2O3 molar ratio of ⁇ 498, total surface area(SA)/(micropore SA + mesopore SA) of 468 (422 + 45) m 2 /g, and a sodium content of ⁇ 0.37 wt%.
  • a portion of the synthesized material was calcined for 6 hours in nitrogen at 900°F (482°C). After cooling, the sample was re -heated to 900°F (482°C) in nitrogen and held for three hours. The atmosphere was then gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise increments. Each step was held for 30 minutes. The temperature was increased to 1000°F (540°C), the oxygen content was increased to 16.8%, and the material was held at 1000°F (540°C) for 6 hours. After cooling, ⁇ 5015 ppm Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide. The resulting catalyst composition was dried overnight at 250°F (121°C), and lastly calcined in air at 610°F (321 °C) for 1 hour. The catalyst composition powder was pressed, crushed, and sieved to obtain 20-40 mesh particle size.
  • Example 2 Sintering and Regeneration of Example 1 Catalyst Composition
  • Example 1 The synthesized ZSM-5 catalyst composition of Example 1 was sintered at 650°C for 2 hours under flowing air to induce Pt agglomeration on the zeolite support. As shown in Table 2 below, the sintered material exhibited a 35% decrease in CO uptake from that of the fresh catalyst, demonstrating the expected decrease in active sites resulting from agglomeration of the noble metal.
  • a sample of the sintered material was regenerated by a two-step procedure comprising an oxychlorination step followed by a chlorine stripping step, while a second sample was regenerated via oxychlorination in the absence of a subsequent chlorine stripping step.
  • the oxychlorination step was performed by holding the material at 550°C for 1 hour under flowing air and 1,2-dichloropropane (DCP, 40 ⁇ ).
  • the chlorine stripping step was performed by calcining the oxychlorinated material in air at 550°C for 1 hour.
  • the regenerated catalyst samples were then cooled in air to room temperature over 4 hours and reduced in the presence of hydrogen.
  • Table 2 shows that the two-step regeneration procedure, comprising oxychlorination followed by chlorine stripping, resulted in a 21% increase in CO uptake as compared to the sintered material.
  • Table 2 further shows that the oxychlorinated material that was not subjected to a chlorine stripping step did not adsorb CO at an appreciable level.
  • the catalyst composition was then tested for performance with a feed of n-pentane, 3 ⁇ 4, and balance He, typically at 550- 600°C, 5.0 psia (35 kPa-a) C5H12, 1.0 molar H 2 :C 5 Hi 2 , 14.7 hr 1 WHSV, and 30 psig (207 kPa) total.
  • Catalyst composition stability and regenerability were tested post initial tests at 550 to 600°C by treatment with H 2 (200 mL/min, 30 psig (207 kPa), 650°C) for 5 hours then retesting performance at 600 °C.
  • FIG. 1 shows the total cyclo-product (cyclopentane, cyclopentene, and cyclopentadiene) yield for the fresh, sintered, and oxychlorinated catalyst. Yield was not demonstrated to be a strong function of CO:Pt in this range, but the data show that Pt can be re-dispersed via oxychlorination, and that the resultant material is still very active for CPD production.
  • a synthesis mixture with ⁇ 22% solids was prepared from 8,800 g of deionized (DI) water, 600 g of 50% NaOH solution, 26 g of 43% Sodium Aluminate solution, 730 g of n- propyl amine 100% solution, 20 g of ZSM-5 seed crystals, and 3,190 g of SipernatTM 340 specialty silica were mixed in a 5-gal pail container and then charged into a 5-gal autoclave after mixing.
  • the synthesis mixture had the following molar composition:
  • the synthesis mixture was mixed and reacted at 210°F (99°C) at 350 rpm for 72 hours.
  • the resulting reaction slurry was discharged and stored in a 5-gal pail container.
  • the XRD pattern of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
  • the SEM of the as-synthesized material showed that the material was composed of mixture of crystals with size of - 0.5 - 1 micron.
  • the resulting ZSM-5 crystals had a S1O2/AI2O3 molar ratio of ⁇ 467 and a sodium content of ⁇ 0.25 wt%.
  • An aqueous mixture was prepared for extrusion using 65 wt% of the as-synthesized zeolite support and 35 wt% of a silica binder composed of 50 wt% LudoxTM LS silica and 50 wt% AerosilTM 200 silica. This mixture was extruded into 1/16" (0.16 cm) diameter cylinders and dried. This extrudate was then calcined for 6 hours in nitrogen at 900°F (480°C). After cooling, the sample was re -heated to 900°F (480°C) in nitrogen and held for three hours. The atmosphere was then gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise increments.
  • Example 5 Sintering and Regeneration of Example 4 Catalyst Composition
  • Example 4 The synthesized extrudate catalyst composition of Example 4 was sintered at 700°C for 4 hours under flowing air to induce Pt agglomeration on the zeolite support. As shown in Table 3 below, the sintered material exhibited a 70% decrease in hydrogen chemisorption from that of the fresh catalyst, demonstrating the expected decrease in active sites resulting from agglomeration of the noble metal.
  • the sintered material was regenerated by a two-step procedure comprising an oxychlorination step followed by a chlorine stripping step.
  • the sintered material (0.25 g) was dried in flowing nitrogen (800 ml/min, 40 psia (280 kPa)) at 250°C for 2 hours. The temperature was then ramped to the desire oxychlorination temperature (500°C or 550°C) over 2 hours in nitrogen.
  • Oxychlorination was performed by continuously feeding an oxychlorination mixture comprising O2, HQ, Ck, and H2O over the sintered material for 1 hour under a variety of conditions, as shown in Table 3.
  • Chlorine stripping was performed by flowing an oxygen-containing gaseous stream comprising 2 vol% oxygen over the oxychlorinated catalyst at the oxychlorination temperature for 30 minutes. Nitrogen (800 ml/min, 40 psia (280 kPa)) was then flowed over the catalyst at 500°C to purge the material prior to reducing the material in flowing hydrogen (500 ml/min) at 500°C for 4 hours.
  • Example 6 On-Oil Testing of Example 5 Catalyst Composition
  • the catalyst composition was then tested for performance with a feed of n-pentane, 3 ⁇ 4, and balance He, at 575°C, 7.0 psia (48 kPa-a) C5H12, 1.0 molar H 2 :C 5 Hi 2 , 30 hr 1 WHSV, and 60 psia (410 kPa) total.
  • FIG. 2 shows the total cyclic C5 yield for the sintered (Sample C) and both regenerated catalysts (Samples A & B) against time-on-oil. Cyclization activity was regenerated to 130% and 150% of the original, sintered activity.
  • a sample of the zeolite support material synthesized in Example 1 in sodium form was calcined for 6 hours in nitrogen at 900°F (482°C). After cooling, the sample was re -heated to 900°F (482°C) in nitrogen and held for 3 hours. The atmosphere was then gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise increments. Each step was held for 30 minutes. The temperature was increased to 1000°F (540°C), the oxygen content was increased to 16.8%, and the material was held at 1000°F (540°C) for 6 hours.
  • Rh was added via incipient wetness impregnation using an aqueous solution of rhodium(III) nitrate hydrate.
  • the Rh impregnated catalyst was dried at 250°F (121°C) for 4 hours.
  • ⁇ 0.53 wt% Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide.
  • the resulting catalyst composition was dried at 250°F (121°C) for ⁇ 18 hours, and lastly calcined in air at 610°F (321°C) for 1 hour.
  • the catalyst composition powder was pressed, crushed, and sieved to obtain 20-40 mesh particle size.
  • a sample of the zeolite support material synthesized in Example 1 in sodium form was calcined for 6 hours in nitrogen at 900°F (482°C). After cooling, the sample was re -heated to 900°F (482°C) in nitrogen and held for 3 hours. The atmosphere was then gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise increments. Each step was held for 30 minutes. The temperature was increased to 1000°F (540°C), the oxygen content was increased to 16.8%, and the material was held at 1000°F (540°C) for 6 hours.
  • the material (0.25 g) was mixed with SiC (5 g) and loaded into a 0.56" (1.4 cm) ID, 33.5" (85 cm) long quartz reactor.
  • the catalyst was dried in flowing nitrogen (800 seem, 40 psia (280 kPa)) over 2 hours at 250°C. The temperature was then ramped to 500°C over 2 hours in nitrogen.
  • Oxychlorination was performed by continuously feeding an oxychlorination mixture comprising 0 2 (10 vol%, 3.97 P 02 ), HC1 (2800 ppm, 0.11 PHCI), Cl 2 (2200 ppm, 0.09 PCL2) and H 2 0 (5000 ppm, 0.20 Pmo) over the material for 1 hour at 500°C.
  • Chlorine stripping was performed by flowing an oxygen-containing gaseous stream comprising 2 vol% oxygen over the oxy chlorinated catalyst at the oxychlorination temperature for 30 minutes. Nitrogen (800 ml/min, 40 psia (280 kPa)) was then flowed at 500°C to purge the material prior to reducing the material in flowing hydrogen (500 ml/min) at 500°C for 4 hours.
  • Example 10 On-Oil Testing of Catalyst Compositions of Examples 7-9
  • FIG. 3 A shows the total cyclic C 5 yield for the fresh and treated Pt/Rh catalyst against time-on-oil
  • both the Pt/Rh and Pt/La catalyst compositions subjected to the oxychlorination and chlorine stripping procedure demonstrated cyclization activity near that of the fresh catalyst.
  • a process for regenerating a deactivated catalyst comprising at least one Group 10 metal and a microporous crystalline aluminosilicate having a molar ratio of Group 10 metal to Al of greater than or equal to 0.007: 1 in a regeneration zone comprising the steps of a) supplying a first gaseous stream comprising a chlorine source and an oxygen source to the regeneration zone; b) contacting the catalyst with the first gaseous stream under conditions effective for dispersing at least a portion of the at least one Group 10 metal on the surface of the catalyst and for producing a first Group 10 metal chlorohydrate; c) withdrawing at least a portion of the first gaseous stream from the regeneration zone to form a first effluent; d) supplying a second gaseous stream comprising an oxygen source, and optionally a chlorine source, to the regeneration zone; e) contacting the catalyst produced in step b) with the second gaseous stream under conditions effective for increasing the O/Cl ratio of the first Group 10 metal chlor
  • catalyst further comprises one or more additional metals selected from the group consisting of Group 1 metals, Group 2 metals, Group 8 metals, Group 9 metals, Group 11 metals, rare earth metals, and mixtures or combinations thereof.
  • microporous crystalline aluminosilicate is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, an MCM-22 family material, and mixtures or combinations thereof.
  • the microporous crystalline aluminosilicate comprises ZSM-5.
  • the catalyst further comprises a binder comprising one or more of silica, titania, zirconia, metal silicates of Group 1 or Group 13 of the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, surface passivated alumina, and mixtures thereof.
  • a-0 contacting the catalyst with a third gaseous stream under conditions effective to remove at least a portion of coke from the catalyst, wherein the third gaseous stream comprises at least one of: i. an oxygen source, and optionally a chlorine source; and/or ii. hydrogen.
  • step g) comprises contacting the catalyst with a fourth gaseous stream comprising 10 vol% to 100 vol% hydrogen based on the total volume of the fourth gaseous stream at a temperature ranging from 200°C to 650°C.
  • a process for the chemical conversion of a hydrocarbon feedstock comprising the steps of I. contacting a hydrocarbon feedstock with a catalyst comprising at least one Group 10 metal and a microporous crystalline aluminosilicate in a reaction zone to form a hydrocarbon reaction product, wherein the molar ratio of Group 10 metal to Al in the catalyst is greater than or equal to 0.007:1; II. forming deactivated catalyst from the catalyst; and III. regenerating the deactivated catalyst in accordance with the process of any one of numbered embodiments 1 to 21.
  • compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein.
  • compositions, element or group of elements are considered synonymous with the term “including.”
  • transitional phrase “comprising” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

L'invention concerne des procédés de régénération de catalyseurs comprenant au moins un métal du groupe 10 et un aluminosilicate cristallin microporeux ayant un rapport molaire du métal du groupe 10 à Al supérieur ou égal à 0,007 : 1, et des procédés de conversion d'hydrocarbures comprenant de tels procédés de régénération. Selon un aspect, les procédés de régénération comprennent une étape d'oxychloration consistant à mettre en contact le catalyseur avec un premier flux gazeux comprenant une source de chlore et une source d'oxygène dans des conditions efficaces pour disperser au moins une partie dudit métal du groupe 10 sur la surface du catalyseur et pour produire un premier chlorohydrate de métal du groupe 10. Les procédés comprennent en outre une étape de décapage au chlore consistant à mettre en contact le catalyseur avec un second flux gazeux comprenant une source d'oxygène, et éventuellement une source de chlore, dans des conditions efficaces pour augmenter le rapport O/Cl du premier chlorohydrate de métal du groupe 10 pour produire un second chlorohydrate de métal du groupe 10.
PCT/US2018/025640 2017-05-03 2018-04-02 Procédés de régénération de catalyseurs WO2018204000A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013546A (en) * 1974-07-19 1977-03-22 Texaco Inc. Removing metal contaminant from regenerated catalyst in catalytic cracking process
US5776849A (en) * 1983-11-10 1998-07-07 Exxon Research & Engineering Company Regeneration of severely deactivated reforming catalysts
US20080154079A1 (en) * 2006-12-20 2008-06-26 Saudi Basic Industries Corporation Regeneration of platinum-germanium zeolite catalyst
WO2011056917A1 (fr) * 2009-11-06 2011-05-12 Shell Oil Company Procédé de régénération de catalyseurs de la conversion d'hydrocarbures
US20120083637A1 (en) * 2010-09-30 2012-04-05 Clem Kenneth R Regeneration of Metal-Containing Catalysts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013546A (en) * 1974-07-19 1977-03-22 Texaco Inc. Removing metal contaminant from regenerated catalyst in catalytic cracking process
US5776849A (en) * 1983-11-10 1998-07-07 Exxon Research & Engineering Company Regeneration of severely deactivated reforming catalysts
US20080154079A1 (en) * 2006-12-20 2008-06-26 Saudi Basic Industries Corporation Regeneration of platinum-germanium zeolite catalyst
WO2011056917A1 (fr) * 2009-11-06 2011-05-12 Shell Oil Company Procédé de régénération de catalyseurs de la conversion d'hydrocarbures
US20120083637A1 (en) * 2010-09-30 2012-04-05 Clem Kenneth R Regeneration of Metal-Containing Catalysts

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