TW201822884A - 催化劑系統及利用催化劑系統之方法 - Google Patents

催化劑系統及利用催化劑系統之方法 Download PDF

Info

Publication number
TW201822884A
TW201822884A TW106142734A TW106142734A TW201822884A TW 201822884 A TW201822884 A TW 201822884A TW 106142734 A TW106142734 A TW 106142734A TW 106142734 A TW106142734 A TW 106142734A TW 201822884 A TW201822884 A TW 201822884A
Authority
TW
Taiwan
Prior art keywords
catalyst
layer formed
catalyst system
oxide
mixtures
Prior art date
Application number
TW106142734A
Other languages
English (en)
Inventor
珍瑟瑞素克 安納特
蘇里 康凱特
Original Assignee
泰商Ｓｍｈ股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 泰商Ｓｍｈ股份有限公司 filed Critical 泰商Ｓｍｈ股份有限公司
Publication of TW201822884A publication Critical patent/TW201822884A/zh

Links

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/13—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/22—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/23—Calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/33—Indium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/36—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/37—Lanthanides
    • B01J2523/3706—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/37—Lanthanides
    • B01J2523/3787—Ytterbium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/43—Tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/67—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/68—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/69—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/70—Constitutive chemical elements of heterogeneous catalysts of Group VII (VIIB) of the Periodic Table
    • B01J2523/74—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/82—Metals of the platinum group
    • B01J2523/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/82—Metals of the platinum group
    • B01J2523/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/82—Metals of the platinum group
    • B01J2523/828—Platinum
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

本發明係關於一種催化劑系統及一種包含使烴進料接觸該催化劑系統之方法，該催化劑系統包含：(a)由第一催化劑形成之至少一個層，該第一催化劑包含承載於固體載體上之脫氫活性金屬；(b)由第二催化劑形成之至少一個層，該第二催化劑包含金屬氧化物；以及(c)由第三催化劑形成之至少一個層，該第三催化劑包含承載於無機載體上之過渡金屬；其中該由第二催化劑形成之至少一個層夾置於該由第一催化劑形成之至少一個層與該由第三催化劑形成之至少一個層之間。

Description

催化劑系統及利用催化劑系統之方法
本發明係關於一種催化劑系統及一種用於利用該催化劑系統將包含飽和烴化合物之烴進料轉化成烯烴產物之方法。
烯烴、尤其係包括乙烯及丙烯在內之輕烯烴為珍貴之烴產物。該等烯烴適用於製備各種各樣之最終產物，包括環氧乙烷、環氧丙烷、乙苯、丙酮、酚、聚乙烯、聚丙烯、其他聚合物、以及其他石油化學產物。即使價格已隨時間波動，業內需求亦仍然持續增長。
為滿足工業需要，已使用許多方法來生產烯烴。然而，由例如烷烴等價值較低之原料生產烯烴通常在經濟上更吸引人。一種用於將飽和烷烴轉化成烯烴之傳統方法係熱裂解。此係一種高耗能方法，且產物選擇率難以進行調整及控制。
催化裂解係後來開發出的一種方法。利用適當之催化材料(通常為沸石系材料)，烴裂解可在不那麼嚴苛之操作條件下發生。
在此領域中，亦已知藉由利用適當催化劑進行脫氫 而將飽和烷烴轉化成烯烴之方法。脫氫方法主要將飽和烷烴轉化成具有對應數目個碳原子之烯烴。在脫氫與置換(metathesis)之間進行整合在技術上亦係可行的，且預期最終能提供滿足高度工業需求之不同烯烴產物分佈。
當實施脫氫-置換整合方法時，需要對眾多效應進行最佳化及控制，以達成所需效率。舉例而言，在脫氫與置換期間可能會發生多種副反應，例如，所生產乙烯、丙烯或丁烯之(再)氫化，而該等乙烯、丙烯或丁烯原本係烷烴轉化方法之較佳最終產物。此外，在存在氫之情況下，烷烴進料(例如丙烷)可發生氫解(hydrogenolysis)及裂解。
因此，本發明之目的係提供一種用於將包含飽和烴化合物之烴進料轉化成烯烴產物之催化劑系統以及一種利用該催化劑系統之相應方法，其中會以催化劑系統之高轉化率及穩定性來達成高的烯烴選擇率。
上述目的係藉由一種包含以下之催化劑系統來達成：(a)由第一催化劑形成之至少一個層，該第一催化劑包含承載於固體載體上之脫氫活性金屬；(b)由第二催化劑形成之至少一個層，該第二催化劑包含金屬氧化物；以及(c)由第三催化劑形成之至少一個層，該第三催化劑包 含承載於無機載體上之過渡金屬；其中該由第二催化劑形成之至少一個層夾置於該由第一催化劑形成之至少一個層與該由第三催化劑形成之至少一個層之間。
所提供之本發明催化劑系統中，該第一催化劑、該第二催化劑及該第三催化劑其中之每一者不同於另外二種催化劑。
該固體載體可不同於該無機載體。
進一步地，該脫氫活性金屬可不同於該過渡金屬。在代表性實施態樣中，第二組成物不包含脫氫活性金屬，具體而言，第二組成物不包含鉑、鈀、銠、鉻、或其混合物。
較佳地，以第二催化劑之重量計，金屬氧化物以通常至少90%、更常為至少95%之量存在於第二催化劑中。
在一個實施態樣中，由第二催化劑形成之至少一個層係由金屬氧化物組成。
在一個實施態樣中，該金屬氧化物包含以下、較佳由以下組成：氧化鎂、氧化鈣、或其混合物，更佳為氧化鎂。
在一個另一實施態樣中，該金屬氧化物包含以下、較佳由以下組成：混合的鎂-鋁氧化物、混合的鈣-鋁氧化物、或其混合物，更佳為混合的鎂-鋁氧化物。
較佳地，第二催化劑中混合的鎂-鋁氧化物及/或混 合的鈣-鋁氧化物分別衍生自以下、更佳地藉由分別對以下進行熱處理而得到：鎂-鋁層狀雙氫氧化物或鈣-鋁層狀雙氫氧化物。
第二催化劑之各化合物中之至少一者、較佳為全部可充當吸附劑。
在一個實施態樣中，本發明之催化劑系統被配置成使得由第一催化劑形成之至少一個層、由第二催化劑形成之至少一個層及由第三催化劑形成之至少一個層垂直堆疊。更佳地，該催化劑系統被配置成使得烴進給流首先接觸由第一催化劑形成之至少一個層。
催化劑系統中由第二催化劑形成之至少一個層之量應足以防止在由第一催化劑形成之至少一個層與由第三催化劑形成之至少一個層之間進行實體接觸。此量相依於複數個因子，其中包括由第一催化劑形成之至少一個層之量、由第三催化劑形成之至少一個層之量、以及容納催化劑系統之反應器之直徑。
在一個實施態樣中，由第一催化劑形成之至少一個層、由第二催化劑形成之至少一個層及由第三催化劑形成之至少一個層容納於同一反應器、較佳為固定床反應器中。
在一個實施態樣中，該催化劑系統由以下組成：(a)由第一催化劑形成之一個層，該第一催化劑包含承載於固體載體上之脫氫活性金屬；(b)由第二催化劑形成之一個層，該第二催化劑包含金屬氧化物；以及 (c)由第三催化劑形成之一個層，該第三催化劑包含承載於無機載體上之過渡金屬；其中由第二催化劑形成之層夾置於由第一催化劑形成之層與由第三催化劑形成之層之間。
在另一實施態樣中，該催化劑系統由以下組成：(a)由第一催化劑形成之第一層，該第一催化劑包含承載於固體載體上之脫氫活性金屬；(b)由第二催化劑形成之第二層，該第二催化劑包含金屬氧化物；(c)由第三催化劑形成之第三層，該第三催化劑包含承載於無機載體上之過渡金屬；(d)由第二催化劑形成之第四層，該第二催化劑包含金屬氧化物；以及(e)由第一催化劑形成之第五層，該第一催化劑包含承載於固體載體上之脫氫活性金屬；其中由第二催化劑形成之第二層夾置於由第一催化劑形成之第一層與由第三催化劑形成之第三層之間，且由第二催化劑形成之第四層夾置於由第三催化劑形成之第三層與由第一催化劑形成之第五層之間。
本發明之催化劑系統中可含有更多層，只要由包含承載於固體載體上之脫氫活性金屬之第一催化劑形成之層與由包 含承載於無機載體上之過渡金屬之第三催化劑形成之層始終藉由由包含金屬氧化物之第二催化劑形成之層彼此分隔開即可。
在一個實施態樣中，由第一催化劑形成之至少一個層與由第三催化劑形成之至少一個層間之重量比係在1：10至10：1、較佳地1：5至5：1、更佳地1：3至3：1、甚至更佳地1：2至2：1之範圍中。
脫氫活性金屬係指有效地將烴進行脫氫之金屬之群組。脫氫係其中自分子脫去氫之反應。在一個實施態樣中，該脫氫活性金屬選自鉑、鈀、銥、鉻、及其混合物，較佳地係鉑。
在一個實施態樣中，該固體載體選自氧化鋁、二氧化矽、二氧化鋯、二氧化鈦、氧化鎂、氧化鈣、及其混合物。
在另一實施態樣中，該固體載體包含混合的鎂-鋁氧化物、混合的鈣-鋁氧化物、或其混合物。
第一催化劑中亦可存在用以增強此第一催化劑之催化活性之另外的活性金屬，例如鉀、錫、鑭、銦、釔、鐿、錸、及其混合物，較佳地錫、銦、及其混合物。
在一個實施態樣中，基於第一催化劑之總重量，第一催化劑含有0.01重量%至25重量%之脫氫活性金屬，較佳地0.05重量%至20重量%之脫氫活性金屬，更佳地0.1重量%至5重量%之脫氫活性金屬。
在一個實施態樣中，於第一催化劑中，鉑係為脫氫活性金屬，Al2O3係固體載體，且錫及/或鉀係另外的活性金屬。
在另一實施態樣中，於第一催化劑中，鉑係脫氫活性金屬，SiO2及ZrO2係固體載體，且釔及/或鐿係另外的活性金屬。
在又一實施態樣中，於第一催化劑中，鉑係脫氫活性金屬，混合的鎂-鋁氧化物及/或混合的鈣-鋁氧化物係固體載體，且銦及/或錫係另外的活性金屬。
在一個實施態樣中，第一催化劑中混合的鎂-鋁氧化物及混合的鈣-鋁氧化物係衍生自鎂-鋁層狀雙氫氧化物或鈣-鋁層狀雙氫氧化物，較佳地可藉由使鎂-鋁層狀雙氫氧化物或鈣-鋁層狀雙氫氧化物在600℃至700℃、更佳地600℃至650℃之範圍中之溫度下超過2小時、更佳地3小時至10小時而獲得。
較佳地，以第一催化劑之重量計，第一催化劑中所存在的脫氫活性金屬、固體載體及另外的活性金屬之組合量係至少90%、更佳地至少95%。在特定實施態樣中，第一催化劑由脫氫活性金屬、固體載體及視需要另外的活性金屬組成。在一個實施態樣中，第三催化劑之過渡金屬選自鉬、鎢、錸、及其混合物。
過渡金屬較佳地係鎢，更佳地呈氧化鎢之形式。
在一個實施態樣中，無機載體選自氧化鋁、二氧化矽、二氧化鋯、二氧化鈦、沸石、及其混合物，較佳地係二氧化矽或二氧化矽與沸石之混合物。
在一個實施態樣中，第三催化劑包含承載於無機載體上之鎢，該無機載體包含二氧化矽與沸石之混合物。
較佳地，沸石選自ZSM-5、X-沸石、Y-沸石、β-沸石、MCM-22、鎂鹼沸石、及其混合物，更佳地係Y-沸石。
在另一較佳實施態樣中，第三催化劑更包含混合的金屬氧化物，更佳地混合的鎂-鋁氧化物、混合的鈣-鋁氧化物、或其混合物，其中該混合的金屬氧化物較佳與承載於無機載體上之過渡金屬進行物理混合。
在特別佳實施態樣中，第三催化劑含有承載於無機載體上與混合的鎂-鋁氧化物進行物理混合之氧化鎢，該無機載體包含二氧化矽與Y-沸石之混合物。
甚至更佳的係衍生自鎂-鋁層狀雙氫氧化物前驅物之混合的鎂-鋁氧化物。
在一個實施態樣中，基於第三催化劑之總重量，第三催化劑含有1重量%至15重量%之過渡金屬，甚至更佳地5重量%至10重量%之過渡金屬。
在一個實施態樣中，第三催化劑更包含選自鋅、鎵、銦、鑭、及其混合物之摻雜劑。較佳地，摻雜劑被承載於無機載體上。
較佳地，基於第三催化劑之總重量，摻雜劑以0.1重量%至10重量%之量、更佳地以1重量%至5重量%之量存在於第三催化劑中。
較佳地，以第三催化劑之重量計，第三催化劑中所存在的過渡金屬、無機載體、混合的金屬氧化物及可選的摻雜劑 之組合量係至少90%、更佳地至少95%。在特定實施態樣中，第三催化劑由過渡金屬、無機載體、混合的金屬氧化物、及視需要摻雜劑組成。較佳藉由將脫氫活性金屬及可選的另外活性金屬之所有元素前驅物承載於固體載體上、隨後進行適合之熱處理來製備第一催化劑。
類似地，較佳藉由將過渡金屬及可選的摻雜劑之所有元素前驅物承載於無機載體上、隨後進行適合之熱處理來製備第三催化劑。
元素前驅物係為含有所需元素之起始化合物，該等所需元素可藉由適合之熱處理而在最終之烴轉化催化劑中被轉化成所需形式之元素。舉例而言，元素前驅物可包括元素之氧化物、鹵化物、烷氧化物、硝酸鹽、碳酸鹽、甲酸鹽、草酸鹽、胺、或氫氧化物。
更佳地，藉由將以溶液形式提供的脫氫活性金屬及可選的另外活性金屬之元素前驅物浸漬、較佳地同時浸漬(共浸漬)於固體載體上、隨後進行煆燒來製備第一催化劑。煆燒較佳係在氧化氣氛中於300℃至800℃之範圍中之溫度下實施達1小時至24小時，甚至更佳地於400℃至600℃之範圍中之溫度下實施達2小時至10小時。
此外，更佳地，藉由將以溶液形式提供的過渡金屬及可選的摻雜劑之元素前驅物浸漬、較佳循序地浸漬於無機載體上、隨後進行煆燒來製備第三催化劑。煆燒較佳係在氧化氣氛中於300℃至800℃之範圍中之溫度下實施達1小時至24小時，甚至更 佳地於400℃至600℃之範圍中之溫度下實施達2小時至10小時。
在一個實施態樣中，第一催化劑、第二催化劑及第三催化劑可呈粉末形式。在另一實施態樣中，第一催化劑、第二催化劑及第三催化劑亦可被形成為更適合於工業利用之形狀，例如，丸粒、片劑、擠出物、或球體。
在對第一催化劑、第二催化劑及第三催化劑進行成形時，可添加黏結材料以便於將粉末形成為所需形狀。可使用此項技術中已知的任何黏結材料。
上述目的進一步藉由一種方法來達成，該方法包含使包含飽和烴化合物之烴進給流接觸本發明之催化劑系統。
在一個實施態樣中，該烴進給流係藉由首先接觸該由第一催化劑形成之至少一個層，其次接觸該由第二催化劑形成之至少一個層，接著接觸該由第三催化劑形成之至少一個層而穿過該催化劑系統。
在一個實施態樣中，該烴進給流包含具有2至5個碳原子之至少一種烷烴，其較佳選自丙烷、正丁烷、及其混合物。在另一實施態樣中，該烴進給流包含選自乙烷、丙烷、丁烷、戊烷、及其混合物，較佳地選自丙烷、丁烷、及其混合物之烷烴，甚至更佳地，該烴進給流係丙烷。
可以廣泛之操作條件來操作本發明之方法。然而，某些特定範圍之操作條件可得到高的烯烴選擇率。
在一個實施態樣中，該方法係在200℃至800℃、較 佳地350℃至700℃、甚至更佳地450℃至650℃之範圍中之溫度下實施。
在另一實施態樣中，該方法係在0.01巴至10巴(表壓)、較佳地0.05巴至5巴(表壓)之範圍中之壓力下實施。
獲得所需產量之烯烴產物所需要的接觸時間相依於數種因子，例如操作溫度、操作壓力及催化劑活性。在一個實施態樣中，該方法係在0.01hr-1至20hr-1、較佳地0.05hr-1至5hr-1之範圍中之重量時空速度(weight hourly space velocity；WHSV)下實施。
在接觸烴進給流之前，可視需要對催化劑系統進行預處理。預處理條件可包含在高溫、較佳地250℃至850℃、更佳地400℃至750℃、甚至更佳地500℃至700℃下使催化劑系統接觸惰性氣體、氧化氣體、還原氣體、或其混合物。在一個較佳實施態樣中，預處理條件包含在500℃至700℃之範圍中之溫度下使催化劑接觸還原氣體、更佳地氫氣達大約0.5小時至8小時。
於在操作條件下接觸烴進給流之後，某些有毒之物質、重烴及焦炭可能會沈積於催化劑系統之表面上。此通常影響催化劑混合物之活性而使其隨時間逐漸下降。可對用過之催化劑系統執行適合之再生，以至少部分地恢復其活性。
在一實施態樣中，烴轉化方法包含再生步驟，其中該再生步驟包括在高溫下使催化劑系統接觸氧化劑。應謹慎地控制再生步驟，以避免使催化劑過熱及破壞催化劑之結構。在一實 施態樣中，再生步驟係在200℃至700℃、較佳地300℃至600℃之範圍中之溫度下實施。在不受限制之情況下，可採用其他已知的再生技術。
自以上對本發明之詳細說明可理解，在一個實施態樣中，第一催化劑、第二催化劑及第三催化劑彼此不同。
已根據以上揭露內容製備並測試了本發明之多種催化劑系統。發明人已意外地發現，利用本發明催化劑系統之烴轉化方法之特色在於，以催化劑系統之良好穩定性達成令人滿意之程度的烷烴轉化率、烯烴選擇率。
實驗結果
實施例1(比較例)
藉由在空氣中於620℃下對Mg-Al-CO3層狀雙氫氧化物進行煆燒達8小時以獲得混合的鎂-鋁氧化物載體、然後將氯鉑酸之溶液及硝酸銦水合物之溶液浸漬於載體上來製備催化劑A。然後，將所獲得混合物在110℃下進行乾燥並在620℃下進行煆燒。所得催化劑A含有承載於Mg-Al氧化物載體上之0.3重量%之Pt、0.6重量%之In。
藉由以偏鎢酸銨水合物之溶液進行浸漬、然後在110℃下進行乾燥達3小時來製備含有7重量%之W、4重量%之Y-沸石、10重量%之Mg-Al氧化物及餘重之SiO2的催化劑B。然後，將 所得材料與Mg-Al-CO3層狀雙氫氧化物混合，隨後在空氣中於550℃下進行煆燒達2小時。
將4克催化劑B、隨後1.5克催化劑A裝載至¾英吋不銹鋼反應器中。在氫氣中於580℃下對所得催化劑床進行預處理達30分鐘。然後，使催化劑床冷卻至570℃，之後以大約0.5hr-1之重量時空速度將丙烷進給通過催化劑床，其中丙烷首先接觸催化劑A。
將來自反應器之流出物送至氣相層析(Gas Chromatography；GC)設備，以量測產物分佈。此測試之結果顯示於表1中。
實施例2
使用在實施例1中所述之方法來製備催化劑A及催化劑B。
將4克催化劑B、隨後1克氧化鈣及隨後1.5克催化劑A裝載至¾英吋不銹鋼反應器中。
如在實施例1中所述來使所得催化劑床進行預處理與在反應測試條件下進行測試。此測試之結果顯示於表1中。
實施例3
使用在實施例1中所述之方法來製備催化劑A及催化劑B。
將4克催化劑B、隨後1克氧化鎂及隨後1.5克催化劑A裝載至¾英吋不銹鋼反應器中。
如在實施例1中所述來使所得催化劑床進行預處理與在反應測試條件下進行測試。此測試之結果顯示於表1中。
實施例4
藉由在空氣中於620℃下對Mg-Al-CO3層狀雙氫氧化物進行煆燒達8小時以獲得混合的鎂-鋁氧化物載體、然後將氯鉑酸之溶液及氯化錫水合物之溶液浸漬於載體上來製備催化劑C。然後，將所獲得混合物在110℃下進行乾燥並在620℃下進行煆燒。所得催化劑C含有承載於Mg-Al氧化物載體上之0.3重量%之Pt、0.6重量%之Sn。
如在實施例1中所述來製備催化劑B。
將4克催化劑B、隨後1克氧化鈣及隨後1.5克催化劑C裝載至¾英吋不銹鋼反應器中。
如在實施例1中所述來使所得催化劑床進行預處理與在反應測試條件下進行測試。此測試之結果顯示於表1中。
實施例6(比較例)
使用在實施例1中所述之方法來製備催化劑A及催化劑B。
將4克催化劑B、隨後1.5克催化劑A裝載至¾英吋不銹鋼反應器中。
如在實施例1中所述、但以大約0.2hr-1之重量時空速度來使所得催化劑床進行預處理與在反應測試條件下進行測試。 此測試之結果顯示於表2中。
實施例7
使用在實施例1中所述之方法來製備催化劑A及催化劑B。
將0.7克催化劑B、隨後1克氧化鎂、隨後4克催化劑A、隨後1克氧化鎂及隨後1.5克催化劑A裝載至¾英吋不銹鋼反應器中。
如在實施例6中所述來使所得催化劑床進行預處理與在反應測試條件下進行測試。此測試之結果顯示於表2中。
表2
前述說明及申請專利範圍中所揭露之特徵可單獨地及以任意組合形式成為用於以多種形式達成本發明之材料。

Claims (15)

  1. 一種催化劑系統，包含：(a)由第一催化劑形成之至少一個層，該第一催化劑包含承載於固體載體上之脫氫活性金屬；(b)由第二催化劑形成之至少一個層，該第二催化劑包含金屬氧化物；以及(c)由第三催化劑形成之至少一個層，該第三催化劑包含承載於無機載體上之過渡金屬；其中該由第二催化劑形成之至少一個層夾置於該由第一催化劑形成之至少一個層與該由第三催化劑形成之至少一個層之間。
  2. 如請求項1所述之催化劑系統，其中該金屬氧化物包含氧化鎂、氧化鈣、或其混合物。
  3. 如請求項1或2所述之催化劑系統，其中該由第一催化劑形成之至少一個層與該由第三催化劑形成之至少一個層間之重量比係在1：10至10：1之範圍中。
  4. 如請求項1或2所述之催化劑系統，其中該脫氫活性金屬選自鉑、鈀、銥、鉻、及其混合物。
  5. 如請求項1或2所述之催化劑系統，其中該固體載體選自氧化鋁、二氧化矽、二氧化鋯、二氧化鈦、氧化鎂、氧化鈣、及其混合物。
  6. 如請求項1或2所述之催化劑系統，其中該第一催化劑更包含選 自鉀、錫、鑭、銦、釔、鐿、錸、及其混合物之另外的活性金屬。
  7. 如請求項1或2所述之催化劑系統，其中該第一催化劑含有0.01重量%至25重量%之該脫氫活性金屬。
  8. 如請求項1或2所述之催化劑系統，其中該過渡金屬選自鉬、錸、鎢、及其混合物。
  9. 如請求項1或2所述之催化劑系統，其中該無機載體選自氧化鋁、二氧化矽、二氧化鋯、二氧化鈦、沸石、及其混合物。
  10. 如請求項1或2所述之催化劑系統，其中該第三催化劑更包含混合的鎂-鋁氧化物、混合的鈣-鋁氧化物、或其混合物。
  11. 一種方法，包含使烴進給流接觸如請求項1至10中任一項所述之催化劑系統。
  12. 如請求項11所述之方法，其中該烴進給流係藉由首先接觸該由第一催化劑形成之至少一個層，其次接觸該由第二催化劑形成之至少一個層，接著接觸該由第三催化劑形成之至少一個層而穿過該催化劑系統。
  13. 如請求項11或12所述之方法，其中該烴進給流包含選自乙烷、丙烷、丁烷、戊烷、及其混合物之烷烴。
  14. 如請求項11或12所述之方法，其中該方法係在200℃至800℃之範圍中之溫度下實施。
  15. 如請求項11或12所述之方法，其中該催化劑系統係藉由使該催化劑系統在接觸該烴進給流之前在250℃至850℃之範圍中之 溫度下接觸惰性氣體、氧化氣體、還原氣體、或其混合物而被預處理。
TW106142734A 2016-12-13 2017-12-06 催化劑系統及利用催化劑系統之方法 TW201822884A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
??16203704.8 2016-12-13
EP16203704.8A EP3335791B1 (en) 2016-12-13 2016-12-13 Catalyst system and process utilizing the catalyst system

Publications (1)

Publication Number Publication Date
TW201822884A true TW201822884A (zh) 2018-07-01

Family

ID=57569913

Family Applications (1)

Application Number Title Priority Date Filing Date
TW106142734A TW201822884A (zh) 2016-12-13 2017-12-06 催化劑系統及利用催化劑系統之方法

Country Status (6)

Country Link
US (1) US11285461B2 (zh)
EP (2) EP3335791B1 (zh)
ES (1) ES2804725T3 (zh)
PL (1) PL3335791T3 (zh)
TW (1) TW201822884A (zh)
WO (1) WO2018108443A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112074345A (zh) * 2018-02-05 2020-12-11 Smh有限公司 在由链烷烃生产轻烯烃中用于调节接触状态的催化剂、体系和方法
CN111085199A (zh) * 2019-12-26 2020-05-01 四川润和催化新材料股份有限公司 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5243120A (en) * 1991-10-30 1993-09-07 Shell Oil Company Process for the production of olefins
US5905051A (en) * 1997-06-04 1999-05-18 Wu; An-Hsiang Hydrotreating catalyst composition and processes therefor and therewith
EP1622719A1 (en) * 2003-02-05 2006-02-08 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7361622B2 (en) * 2005-11-08 2008-04-22 Rohm And Haas Company Multi-staged catalyst systems and process for converting alkanes to alkenes and to their corresponding oxygenated products
DE102005032723A1 (de) * 2005-07-13 2007-01-18 Süd-Chemie AG Mehrschichtkatalysator auf Niobbasis zur katalytischen Umsetzung von Kohlenwasserstoffen
CN101348409B (zh) * 2007-07-19 2011-06-15 中国石油化工股份有限公司 一种生产低碳烯烃的方法
AU2011201715B8 (en) * 2010-04-15 2014-08-21 China Petroleum & Chemical Corporation A process for selective oxidative dehydrogenation of a hydrogen-containing co mixed gas
GB201220912D0 (en) * 2012-11-21 2013-01-02 Johnson Matthey Plc Oxidation catalyst for treating the exhaust gas of a compression ignition engine
PL3238819T3 (pl) * 2015-03-20 2021-08-02 SMH Co., Ltd. Sposób metatezy olefin

Also Published As

Publication number Publication date
EP3335791B1 (en) 2020-04-08
EP3335791A1 (en) 2018-06-20
US20190314788A1 (en) 2019-10-17
PL3335791T3 (pl) 2020-10-19
US11285461B2 (en) 2022-03-29
EP3554687A1 (en) 2019-10-23
ES2804725T3 (es) 2021-02-09
WO2018108443A1 (en) 2018-06-21

Similar Documents

Publication Publication Date Title
KR100967597B1 (ko) 탈수소화 촉매 조성물
US11286218B2 (en) Hydrocarbon conversion process
TW201822884A (zh) 催化劑系統及利用催化劑系統之方法
TW201703856A (zh) 催化劑與使用該催化劑的烴轉化製程
US11383225B2 (en) Hydrocarbon conversion catalyst system
CN110072613B (zh) 催化剂体系和用于使用该催化剂体系转化烃进料的方法
US11318445B2 (en) Hydrocarbon conversion catalyst