[go: up one dir, main page]

WO2008034299A1 - A catalyst for converting hydrocarbons - Google Patents

A catalyst for converting hydrocarbons Download PDF

Info

Publication number
WO2008034299A1
WO2008034299A1 PCT/CN2006/002559 CN2006002559W WO2008034299A1 WO 2008034299 A1 WO2008034299 A1 WO 2008034299A1 CN 2006002559 W CN2006002559 W CN 2006002559W WO 2008034299 A1 WO2008034299 A1 WO 2008034299A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
weight
hydrocarbon conversion
phosphorus
catalyst
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2006/002559
Other languages
English (en)
French (fr)
Inventor
Yujian Liu
Huiping Tian
Xingtian Shu
Jun Long
Yibin Luo
Chaogang Xie
Zhenyu Chen
Liuzhou Zhao
Yuxia Zhu
Youbao Lu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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 Sinopec Research Institute of Petroleum Processing , China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to JP2009525892A priority Critical patent/JP5139433B2/ja
Priority to EP06791146.1A priority patent/EP2075068B1/en
Priority to CA2662077A priority patent/CA2662077C/en
Priority to KR1020097006562A priority patent/KR101359594B1/ko
Priority to BRPI0621984A priority patent/BRPI0621984B1/pt
Priority to US12/439,315 priority patent/US8716163B2/en
Publication of WO2008034299A1 publication Critical patent/WO2008034299A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J29/072—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/657—Pore diameter larger than 1000 nm
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0234—Impregnation and coating simultaneously
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • 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
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate or hypophosphite
    • 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

Definitions

  • Low-carbon olefins (C 2 ⁇ C 4 olefins) are important petrochemical feedstocks.
  • Low-carbon olefins are produced from petroleum hydrocarbons, usually using gaseous hydrocarbons, naphtha, kerosene, light diesel oil and vacuum residue.
  • the conventional catalytic cracking process also produces low-carbon olefins while producing gasoline and light diesel oil, but the yield thereof is only 15% by weight or less of the raw material oil.
  • some patents use a composite oxide catalyst.
  • Zr0 2, Hf0 2 as a main component combined with A1 2 0 3, Cr 2 0 3, MnO, Fe 2 0 3 and an alkali metal or an alkaline earth metal oxide catalysts (US3725495, US3839485);
  • Another example containing a small amount of Fe 2 0 3 , Ti0 2 , CaO, MgO, Na 2 0, K 2 0 SiO 2 Al 2 O 3 catalyst SU550173, SU559946).
  • a zeolite-containing catalyst With the increasing use of zeolites in the petrochemical and petroleum processing fields, a third type of catalyst, a zeolite-containing catalyst, has emerged. In recent years, in order to improve the catalytic cracking processes to produce gasoline oct embankment value, it is added in the shape selective additive catalyst, as disclosed in US 37 58403 to ZSM-5 zeolite and a large pore zeolite (ratio between the two may be 1: 10 - 3: 1 ) As a catalyst for the active component, the catalyst is used to increase the octane number of the gasoline, and the yield of the C3 and C4 olefins is also increased, and the yield of the C3 to C4 olefin is about 10% by weight.
  • a composite zeolite catalyst comprising a zeolite having a MFI structure (five-membered high silica zeolite) and a zeolite having a pore diameter of more than 7 angstroms for use in petroleum hydrocarbon cracking to produce low-carbon olefins, wherein large pore boiling
  • the stone mainly Y-type zeolite
  • the stone cracks the feed to form steam and diesel
  • the MFI structure zeolite further cracks it into lower olefins (US3758403, CN1043520A, US500649, CN1026242C).
  • the MFI structure zeolite was further modified, such as transition metal modification (US5236880), phosphorus modification (CN1205307A, US6566293), rare earth modification (CN1085825A), phosphorus and rare earth modification. (CN1093101A, US5380690, CN1114916A, CN1117518A, CN1143666A), phosphorus and alkaline earth metal modification (CN1221015A, US6342153, CN1222558A, US6211104) and phosphorus and transition metal modification (CN1504540A).
  • transition metal modification US5236880
  • phosphorus modification CN1205307A, US6566293
  • rare earth modification CN1085825A
  • phosphorus and rare earth modification phosphorus and rare earth modification.
  • Beta zeolite has a 12-membered ring-crossing channel structure, a 12-membered ring with a one-dimensional channel parallel to the (001) crystal plane has a pore size of 0.75 to 0.57 nm, and another 12-membered ring of a two-dimensional channel parallel to the (100) crystal plane. The pore size is from 0.65 to 0.56 nm.
  • Beta zeolite is a high-silica zeolite that has been discovered so far only by its three-dimensional structure. Due to its structural specificity, it has both acid-catalyzed properties and structural selectivity, and has high thermal stability (lattice damage). Temperature is greater than 1200 °C), hydrothermal stability and wear resistance.
  • ⁇ zeolite Due to its unique structural characteristics, ⁇ zeolite has a good thermal and hydrothermal stability, acid resistance, coking resistance and catalytic activity in a series of catalytic reactions, and has rapidly developed into a new type of catalytic material in recent years.
  • the use of zeolite beta for the cracking of petroleum hydrocarbons to produce lower olefins has also been reported.
  • CN1103105A discloses a cracking catalyst for producing isobutylene and isoamylene, which is a composite catalyst composed of four active components and a carrier, the active component of which is modified by two different silicon-aluminum ratios of HZSM-5 and
  • the high silicon HZSM-5, USY and ⁇ zeolite are composed of a natural clay and an inorganic oxide.
  • the composition and content of the catalyst are as follows: (1) Modified HZSM-5 having a silica to alumina ratio of 20 to 100: 5- 25 wt%; (2) high silicon HZSM-5 having a silicon to aluminum ratio of 250 to 450: 1-5 wt%; (3) USY zeolite: 5 to 20 wt%; (4) ⁇ zeolite: 1 to 5 wt% (5) Natural clay: 30 to 60% by weight; (6) Inorganic oxide: 15 to 30% by weight.
  • the catalyst has the characteristics of producing isobutylene and isoamylene, and can also produce high-octane gasoline.
  • CN1057408A discloses a cracking catalyst containing a high silica zeolite which is composed of 10 to 30% by weight of modified high silica zeolite and 70 to 90% by weight of a carrier, and the modified high silica zeolite is contained (based on the weight of the zeolite) 0.01 ⁇ 3.0% by weight of phosphorus, 0.01 - 1.0% by weight of iron or 0.01 - 10% by weight of aluminum (excluding aluminum in the zeolite structure), and a ZSM molecular sieve having a silicon to aluminum ratio of more than 15, zeolite or mordenite, and the carrier is an inorganic oxide Or inorganic oxidation a mixture of kaolin and kaolin, which is used in the catalytic cracking of hydrocarbons to produce low-carbon olefins, and also produces gasoline and diesel.
  • a high silica zeolite which is composed of 10 to 30% by weight of modified high silica zeolite and 70 to 90% by weight of
  • CN1099788A discloses a cracking catalyst for producing C 3 ⁇ C 5 olefins, which comprises 10 to 50% of a Y-type zeolite having a unit cell constant of 2.450 nm, and 2 to 40% of which is selected from the group consisting of P, RE, Ca, Mg, H, Al, etc.
  • CN1145396A discloses a cracking catalyst for producing isobutylene and isoamylene, which is composed of three kinds of zeolite active components and a carrier (based on a catalyst): a five-membered high-silica zeolite containing a monument and a rare earth, 6 to 30% by weight 5 to 20% by weight of USY zeolite, 1 to 5% by weight of P zeolite, 30 to 60% by weight of clay and 15 to 30% by weight of inorganic oxide. /. .
  • the catalyst is characterized by the production of isobutylene and isoamylene, and can be combined with high-octane gasoline.
  • CN1354224A discloses a catalytic cracking catalyst for producing isoparaffin-rich gasoline, propylene and isobutane, which is composed of 0 to 70% by weight of clay, 5 to 90% by weight of inorganic oxide and 1 based on the weight of the catalyst. ⁇ 50% by weight of zeolite composition.
  • the zeolite is based on the weight of the zeolite (1) 20 to 75 wt% of silica to alumina ratio of 5 to 15, and RE 2 0 3 of rare earth content of 8 to 20 wt% of high silica Y zeolite and (2) 20 to 75 wt% of silica to alumina ratio of 16 to 50, RE 2 0 3 of rare earth content of 2 to 7 wt% of high silica Y zeolite and (3) 1 to 50 wt% of zeolite beta or mordenite Or a mixture of ZRP zeolites.
  • the use of the catalyst increases the content of isoparaffins in gasoline while increasing the production of propylene and isobutane, but the propylene yield is only slightly increased.
  • CN1504541A discloses a catalyst for catalytically cracking hydrocarbons to produce low-carbon olefins in parallel to produce aromatic hydrocarbons, comprising molecular sieves having a pore diameter of 0.45-0.7 nm, amorphous oxides, and at least two of phosphorus, alkaline earth metals, lithium and rare earths. Sex element.
  • the molecular sieve is a silica-alumina molecular sieve or a silica-alumina molecular sieve
  • the silico-alumina molecular sieve is ZSM-5, ZSM-11, mordenite or Beta zeolite
  • the siliceous aluminum molecular sieve is SAPO-5, SAPO-11 or SAPO-34
  • the active center of the catalyst can be modulated by the actual product needs, and the low-carbon olefin can be used as a main product, or the aromatic hydrocarbon can be produced at the same time as the olefin is produced.
  • CN1566275A discloses a molecular sieve-containing hydrocarbon cracking catalyst and a preparation method thereof, the catalyst comprising a molecular sieve, a heat resistant inorganic oxide and a metal component, with or without clay, the molecular sieve being the first zeolite and a mixture of the second zeolite, ⁇ one
  • the zeolite is a Y-type zeolite
  • the second zeolite is a zeolite having a silica to alumina molar ratio of 20 or more, the first zeolite is 1 to 50% by weight, and the second zeolite is 1 to 60% by weight.
  • the content of the heat resistant inorganic oxide is 2 to 80% by weight, the content of the clay is 0 to 80% by weight, and the content of the metal component is 0.1 to 30% by weight, and the metal component is substantially present in a reduced valence state.
  • the catalyst can produce more C 3 ⁇ C 5 olefins, has higher desulfurization activity, and has higher cracking activity.
  • the second zeolite is selected from the group consisting of zeolites having a ruthenium structure, zeolites having an MFI structure containing phosphorus, rare earths and/or alkaline earth metals, beta zeolites, beta zeolites containing traces, rare earths and/or alkaline earth metals, mordenite, phosphorus One or more of rare earth and/or alkaline earth metal mordenite.
  • US5006497 and US Pat. No. 5,055,176 disclose a multi-component catalyst comprising a matrix, a macroporous molecular sieve, an alkane cracking isomerization molecular sieve and an aromatization molecular sieve, wherein the macroporous molecular sieve may be selected from the group consisting of zeolite Y, DeAlY , USY, UHPY, VPI-5, Cylindrical Clay, SAPO-37, ⁇ and mixtures thereof, Alkane cracking isomerization molecules screened from hydrogen type ZSM-5, ZSM-11, ZSM-22, ZSM-35 and ZSM- 57.
  • the aromatization molecular sieve is GaZSM-5.
  • US20050070422 discloses a catalyst composition for catalytic cracking stimulation of a olefin comprising a first molecular sieve having a mesopore diameter, at least one ruthenium molecular sieve having a pore diameter smaller than a diameter of the first molecular sieve pore, optionally The third type of macroporous molecular sieve.
  • the first molecule was selected from ZSM-5, ZSM-11, ZSM-12, ZSM-57, ITQ-13 and MCM-22.
  • the second molecule was screened from ECR-42, ZSM-22, ZSM-35, ZSM-23, MCM-22, MCM-49, SAPO-11, SAPO-34 and SAPO-41.
  • the third molecule was screened from faujasite, L zeolite, VPI-5, SAPO-37, X zeolite, beta zeolite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, MCM-9, MCM-41. , MCM-41S, MCM-48, zeolite, USY, REY, REUSY, etc.
  • the catalyst is suitable for the production of propylene from cracked naphtha and heavy hydrocarbon oil.
  • the present invention has been made in view of the above state of the art, and an object thereof is to provide a hydrocarbon conversion catalyst which catalyzes the conversion of petroleum hydrocarbons to produce lower olefins.
  • the inventors have found through diligent research that when a hydrocarbon-converting catalyst contains a specific modified zeolite beta as a catalyst component, the selectivity of C 2 ⁇ 12 olefin can be remarkably improved, thereby facilitating low-carbon olefins ( Further cracking of C 2 -C 4 olefins is formed, whereby the lower olefin can be produced from hydrocarbons in a higher yield, thereby completing the present invention.
  • the present invention provides a hydrocarbon conversion catalyst comprising 1 to 60% by weight of a zeolite mixture and 5 to 99% by weight of a heat resistant inorganic oxide based on the total amount of the hydrocarbon conversion catalyst. And 0 to 70% by weight of the clay, wherein the zeolite mixture contains 1 to 75% by weight of zeolite beta modified by phosphorus and transition metal M, 25 to 99% by weight, based on the total of the zeolite mixture a zeolite of MFI structure and 0 to 74% by weight of a large pore zeolite; wherein, the anhydrous chemical expression of the zeolite modified by phosphorus and transition metal ruthenium is expressed by mass percentage of oxide: (0) ⁇ 0.3 ) Na 2 0- ( 0.5 - 10 ) ⁇ 1 2 0 3 ⁇ ( 1.3 ⁇ 10 ) ⁇ 2 0 5 ⁇ ( 0.7 - 15 ) M x O y - ( 64 ⁇ 97 )
  • the present invention relates to the following aspects:
  • a hydrocarbon conversion catalyst comprising, based on the total amount of the hydrocarbon conversion catalyst, 1 to 60% by weight of a zeolite mixture, 5 to 99% by weight of a heat resistant inorganic oxide, and 0 to 70% by weight a clay characterized in that, in the total amount of the zeolite mixture, the zeolite mixture contains 1 to 75% by weight of zeolite beta modified by a monument and a transition metal M, and 25 to 99% by weight of an MFI structure.
  • the hydrocarbon conversion catalyst according to aspect 1 characterized in that the catalyst contains 10 to 50% by weight of the zeolite mixture, and 10 to 70% by weight, based on the total amount of the hydrocarbon conversion catalyst. Heat resistant inorganic oxide and 0 to 60% by weight of the clay.
  • the hydrocarbon conversion catalyst according to aspect 3 characterized in that the anhydrous chemical expression of the beta zeolite modified by phosphorus and transition metal M is: (0 ⁇ 0.2) Na 2 0- (1 ⁇ 9) ⁇ 1 2 0 3 ⁇ ( 2 - 5 ) ⁇ 2 0 5 ⁇ ( 1 - 3 ) M x O y - ( 82 ⁇ 95 ) Si0 2 .
  • hydrocarbon conversion catalyst according to aspect 1 characterized in that said transition metal M is selected from one or more of Fe, Co, Ni and Cu.
  • the zeolite having the MFI structure is selected from the group consisting of rare earth-containing ZRP zeolite, phosphorus-containing ZRP zeolite, phosphorus- and rare-earth-containing ZRP zeolite, and phosphorus- and alkaline earth metal-containing ZRP.
  • the zeolite having the MFI structure is selected from the group consisting of rare earth-containing ZRP zeolite, phosphorus-containing ZRP zeolite, phosphorus- and rare-earth-containing ZRP zeolite, and phosphorus- and alkaline earth metal-containing ZRP.
  • the large pore zeolite is selected from the group consisting of cerium type zeolite, cerium type zeolite containing phosphorus and/or rare earth, ultra-stable cerium zeolite, and ultra-stable phosphorus and/or rare earth.
  • the large pore zeolite is selected from the group consisting of cerium type zeolite, cerium type zeolite containing phosphorus and/or rare earth, ultra-stable cerium zeolite, and ultra-stable phosphorus and/or rare earth.
  • the zeolites is selected from the group consisting of cerium type zeolite, cerium type zeolite containing phosphorus and/
  • the hydrocarbon conversion catalyst according to aspect 1 characterized in that the clay is one or more selected from the group consisting of kaolin, halloysite and montmorillonite.
  • the hydrocarbon conversion catalyst of the present invention is a zeolite mixture of a zeolite modified with phosphorus and a transition metal ruthenium and a zeolite having an MFI structure or a zeolite modified with a brick and a transition metal ruthenium, a zeolite having a ruthenium structure and a large pore zeolite.
  • the active component the zeolite zeolite is simultaneously modified by phosphorus and transition metal ruthenium, thereby improving the hydrothermal stability of the zeolite beta and promoting the cracking of diesel oil and heavy oil.
  • the catalysts provided by the present invention have enhanced hydrocarbon conversion capabilities, higher yields of lower olefins, and particularly higher propylene yields.
  • the present invention provides a hydrocarbon conversion catalyst comprising from 1 to 60% by weight of a zeolite mixture based on the total amount of the hydrocarbon conversion catalyst, 5 to 99% by weight of the heat resistant inorganic oxide and 0 to 70% by weight of the clay, characterized in that the zeolite mixture contains 1 to 75% by weight of phosphorus and transition based on the total amount of the zeolite mixture a metal M-modified zeolite beta, 25 to 99% by weight of a zeolite having an MFI structure, and 0 to 74% by weight of a large pore zeolite; wherein the anhydrous chemical expression of the zeolite beta modified by phosphorus and transition metal ruthenium The formula is expressed as mass percentage of oxide: (0-0.3) Na 2 0- (0.5-10) ⁇ 1 2 0 3 ⁇ (1.3- 10 ) ⁇ 2 0 5 ⁇ ( 0.7 ⁇
  • lower olefin refers to a C 2 ⁇ C 4 olefins
  • hydrocarbon refers to a petroleum hydrocarbons, unless specifically described.
  • the hydrocarbons are selected from one or more of hydrocarbons, gasoline, diesel oil, hydrogenated tail oil, and the like, or a mixed fraction of these petroleum fractions, and crude oil and residual oil may also be used as they are.
  • the catalyst contains 10-50% by weight of the zeolite mixture, 10 to 70% by weight of the heat resistant inorganic oxide and 0 ⁇ based on the total amount of the hydrocarbon conversion catalyst. 60% by weight of the clay.
  • modified P zeolite which is one of the essential components of the hydrocarbon conversion catalyst of the present invention will be described.
  • the preferred range is: (0 ⁇ 0.2) Na 2 0 (1 ⁇ 9 ) ⁇ 1 2 0 3 ⁇ (1.5-7) ⁇ 2 0 5 ⁇ ( 0.9 - 10 ) M x O y - ( 75 ⁇ 95 ) Si0 2
  • a more preferable range is (0 ⁇ 0.2) Na 2 0-( 1 - 9 ) ⁇ 1 2 0 3 ⁇ ( 2-5 ) ⁇ 2 0 5 ⁇ ( 1 - 3 )M s O y -( 82 ⁇ 95) Si0 2 .
  • the transition metal M is selected from one or more of Fe, Co, Ni and Cu, more preferably from Fe and/or Cu.
  • the zeolite having an MFI structure is a high silica zeolite having a pentasil structure selected from one or more of ZSM-5 and ZRP series zeolites, particularly selected from the group consisting of rare earth-containing zeolites.
  • ZRP zeolite (CN1052290A, CN1058382A, US5232675), phosphorus-containing ZRP zeolite (CN1194181A, US5951963), scaly and rare earth ZRP zeolite (CN114 74 20A), phosphorus and alkaline earth metal-containing ZRP zeolite (CN1211469A, CN1211470A, US6080698) and One or more of ZSP zeolites (CN1465527A, CN1611299A) containing prayer and transition metals.
  • the large pore zeolite is a zeolite having a pore structure of at least 0.7 nm ring opening, such as one or more selected from the group consisting of Y zeolite, L zeolite, ⁇ zeolite, ⁇ zeolite, mordenite and ZSM-18 zeolite.
  • Y zeolite L zeolite
  • ⁇ zeolite ⁇ zeolite
  • mordenite ZSM-18 zeolite.
  • cerium-type zeolites, cerium-type zeolites containing monuments and/or rare earths, ultra-stable cerium zeolites, and ultra-stable cerium zeolites containing phosphorus and/or rare earths may be selected.
  • the zeolite having the MFI structure and the large pore zeolite may be commercially available or may be prepared by various methods known in the art, and will not be described herein.
  • the ⁇ zeolite modified with phosphorus and a transition metal ruthenium can be produced by various methods, for example, (1) introducing a monument and the transition metal ruthenium in the process of synthesizing the beta zeolite, or (2) After synthesizing the beta zeolite, steps such as ammonium exchange, phosphorus modification, the transition metal ruthenium modification, and calcination treatment are employed to introduce phosphorus and the transition metal ruthenium.
  • the calcination process can also be carried out under a steam atmosphere
  • the modification process of the zeolite by introducing phosphorus and transition metal ruthenium can be carried out, for example, by impregnation or ion exchange according to a conventional method in the art.
  • the method of impregnation can be carried out in one of three ways:
  • the cake and the calculated amount of the aqueous solution of the phosphorus compound are uniformly beaten at room temperature to 95 ° C, and then dried, and then calculated with one or more selected from the group consisting of Fe, Co, Ni, Cu, Mn, Zn and Sn.
  • An aqueous solution of a compound of transition metal M is dried at room temperature to 95 Torr and dried, wherein the order of impregnation of the above two solutions may also be reversed;
  • Examples of the ion exchange method include the following methods.
  • the ammonium exchanged beta zeolite filter cake and the calculated amount of the phosphorus-containing compound aqueous solution are beaten at room temperature to 95 ° C, and then dried, and calcined at 400 to 800 ° C, and then calculated with the calculated amount
  • An aqueous solution of a compound of one or more transition metals M of Fe, Co, Ni> Cu, Mn, Zn and Sn is uniformly mixed at a solid-liquid ratio of 1: (5 to 20), and then stirred at 80 95 ° C. After 2 to 3 hours of filtration, the exchange can be repeated multiple times, and the sample obtained after the exchange is washed several times with water, and then dried.
  • the ammonium salt is an inorganic ammonium salt commonly used in the ammonium exchange treatment of the art, such as one selected from the group consisting of ammonium chloride, ammonium sulfate and ammonium nitrate or a mixture thereof.
  • the phosphorus-containing compound is selected from the group consisting of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate or a mixture thereof.
  • the compound containing one or more transition metals M selected from the group consisting of Fe, Co, Ni, Cu, Mn > Zn and Sn is selected from their corresponding water-soluble salts,
  • the water-soluble salt is selected from one or more of a sulfate, a nitrate and a chloride.
  • the drying or drying may be carried out in a conventional manner, and the drying or drying temperature may be from room temperature to 350 Torr, preferably from 100 to 200 °C.
  • the calcination temperature is a conventional calcination temperature, generally 400 to 800. C , preferred It is 450 ⁇ 700 °C.
  • the starting zeolite beta to be used is not particularly limited, and those which are conventionally used in the art may be used, or a commercially available product may be used, and it may be obtained by a method known in the art. .
  • the starting beta zeolite is a sodium beta zeolite. If the sodium-type zeolite contains an organic templating agent, the above operation should be carried out after removing the templating agent. Moreover, the sodium content of the sodium beta zeolite should be such as to satisfy the sodium content requirement in the anhydrous chemical expression of the finally obtained beta zeolite containing phosphorus and the transition metal ruthenium. If not required, the sodium in the starting sodium beta zeolite can be removed by ammonium exchange. From this point of view, the ammonium exchange step is not essential in the preparation of the modified beta zeolite.
  • the equipment and condition control methods and the like employed are also not particularly limited, and those conventional in the art can be employed.
  • the heat resistant inorganic oxide is not limited, but is preferably one or more selected from the group consisting of heat resistant inorganic oxides which are generally used as a cracking catalyst substrate and a binder component, and examples thereof include alumina and silica. And one or more of amorphous silicon aluminum.
  • heat resistant inorganic oxides and methods for their preparation are well known to those skilled in the art.
  • These heat resistant inorganic oxides may be commercially available or may be obtained from the precursor of the heat resistant inorganic oxide by a method known in the art.
  • the precursor of the heat-resistant inorganic oxide may be used as it is, instead of the heat-resistant inorganic oxide. Therefore, the term "heat resistant inorganic oxide” includes the heat resistant inorganic oxide itself and/or the precursor of these heat resistant inorganic oxides.
  • the heat resistant inorganic oxide precursor referred to herein means a substance capable of forming the heat resistant inorganic oxide during the preparation of the hydrocarbon conversion catalyst of the present invention.
  • the precursor of the alumina may be selected from the group consisting of hydrated alumina and/or aluminum sol; the hydrated alumina may be selected, for example, from boehmite (boehmite), pseudo-water soft aluminum.
  • boehmite boehmite
  • pseudo-water soft aluminum alumina trihydrate
  • the precursor of the silica may be selected from, for example, silica sol, silicone gel, and water glass.
  • the precursor of the silica may be selected from, for example, silica sol, silicone gel, and water glass.
  • the precursor of the amorphous silicon aluminum may be selected from the group consisting of a silica alumina sol, a mixture of a silica sol and an aluminum sol, and one or more of a silica-alumina gel.
  • a silica alumina sol a mixture of a silica sol and an aluminum sol
  • a silica-alumina gel a silica-alumina gel
  • a clay may also be contained.
  • the clay is not particularly limited, but is preferably one or more selected from the group consisting of clays which are usually used as an active component of a cracking catalyst, and examples thereof include kaolin, halloysite, montmorillonite, diatomaceous earth, and angstrom. One or more of Rock, saponite, rector, sepiolite, attapulgite, hydrotalcite and bentonite.
  • the clay is preferably selected from one or more of kaolin, halloysite and montmorillonite. These clays and their preparation methods are well known to those skilled in the art, and commercially available products thereof can also be used.
  • the method for producing the hydrocarbon-based conversion catalyst of the present invention includes the following methods, but the present invention is not limited thereto.
  • the heat resistant inorganic oxide and/or its precursor with water, and then adding or not adding the clay to the resulting slurry, at which point the remaining portion of the heat resistant inorganic may be further added thereto.
  • the oxide and/or its precursor are then added to the resulting slurry to form the modified zeolite beta.
  • the resulting slurry is dried and then calcined.
  • an acid is added to the resulting slurry before or after the addition of the clay, and the pH of the slurry is adjusted to 1 to 5.
  • the resulting slurry is aged at a temperature of 30 to 90 Torr for 0.1 to 10 hours; after the aging is completed, the remaining portion of the heat resistant inorganic oxide and/or its precursor are added.
  • the clay may be added before the aging step or after the aging step, and the order of addition of the clay has no effect on the performance of the hydrocarbon conversion catalyst of the present invention.
  • all or a part of the heat resistant inorganic oxide and/or its precursor may be added before the aging step, but in order to make the catalyst have better wear resistance, it is preferred.
  • a portion of the heat resistant inorganic oxide and/or its precursor is added prior to the aging step, and then the remaining portion of the heat resistant inorganic oxide and/or its precursor is added after the aging step is completed.
  • the weight ratio of the first added portion to the later added portion is 1: 0.1 to 10, more preferably 1: 0.1 to 5.
  • an acid is added thereto.
  • the acid is selected from one or more of water-soluble inorganic acids and organic acids, preferably one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, and a carboxylic acid having 1 to 10 carbon atoms. kind or several.
  • the acid is used in an amount such that the pH of the slurry is from 1 to 5, preferably from 1.5 to 4.
  • the aging condition is preferably aging at a temperature of 40 to 80 ° C for 0.5 to 8 hours.
  • the drying method and conditions of the slurry are well known to those skilled in the art.
  • the drying method may be air drying, drying, air drying or spray drying, preferably spray drying.
  • the drying temperature may be from room temperature to 400 ° C, preferably from 100 to 350 Torr.
  • To facilitate spray drying zero solids content of the slurry before drying is preferably 10 to 50 wt%, more preferably 20 to 50 wt. 0/0.
  • the calcination conditions are also known to those skilled in the art.
  • the calcination temperature is 400 to 700 ° C, preferably 450 to 650 ° C
  • the calcination time is at least 0.5 hours, preferably 0.5. ⁇ 100 hours, more preferably 0.5 to 10 hours.
  • the catalysts provided by the present invention have enhanced hydrocarbon conversion capabilities and higher low olefinic yields, particularly higher propylene yields.
  • Examples 1 to 10 illustrate zeolite beta modified with phosphorus and transition metal M and a process for the preparation thereof.
  • each of the modified zeolite ⁇ in the sample Na 2 0, Fe 2 0 3 , Co 2 0 3, NiO, CuO, Mn 2 0 3, ZnO, Sn0 2 the content of A1 2 0 3 and Si0 2 by X-ray fluorescence Method determination (see “Petrochemical Analysis Methods (RIPP Experimental Methods)", edited by Yang Cuiding, Science Press, 1990).
  • the anhydrous chemical expression of B10 is: 0.11Na 2 O'5.9Al 2 O 3 '4.1P 2 O 5 '1.0CuO'1.0Fe 2 O 3 '87.9SiO 2 .
  • Examples 11 to 20 illustrate the hydrocarbon conversion catalyst of the present invention and a preparation method thereof, and the raw materials used in the preparation of the catalyst are as follows:
  • the aluminum sol Qilu catalyst factory produces A1 2 0 3 content of 21.5 wt%; silica sol Beijing Chemical Plant, its silica content is 16.0 wt%.
  • the large pore zeolites used are all produced by Qilu Catalyst Factory, and their industrial grades are:
  • the physicochemical parameters are: unit cell constant is 2.446 nm, Na 2 0 content is 1.1 wt%, rare earth oxide RE 2 0 3 content is 2.0 wt%, wherein cerium oxide content is 1.06 wt%, cerium oxide content 0.26% by weight, the other rare earth oxide content is 0.68% by weight;
  • the weight of the Na 2 0 is 0. 36 % by weight
  • DASY6.0 physicochemical parameters are: unit cell constant is 2.451 nm, Na 2 0 content is I ⁇ 6 wt%, rare earth oxide RE 2 0 3 content is 6.2 wt%, wherein cerium oxide content is 3.29 wt%, oxidation The content of cerium is 0.81% by weight, and the content of other rare earth oxides is 2.10% by weight;
  • REHY physicochemical parameters are: unit cell constant is 2.465 nm, Na 2 0 content is 3.2 wt%, rare earth oxide RE 2 0 3 content is 7.0 wt%, wherein cerium oxide content is 3.71% by weight, cerium oxide content 0.91% by weight, other rare earth oxide content is 2.38 weight%.
  • the zeolites with MFI structure used are all produced by Qilu Catalyst Factory, and their industrial grades are:
  • the catalyst was prepared in the same manner as in Example 11 except that an equivalent amount of the modified ⁇ zeolite ⁇ 2 was used instead of Bl to obtain the catalyst C2 provided by the present invention.
  • the composition of C2 is shown in Table 1.
  • the catalyst was prepared in the same manner as in Example 11 except that an equivalent amount of the modified ⁇ zeolite ⁇ 4 was used instead of Bl to obtain the catalyst C3 provided by the present invention.
  • the composition of C3 is shown in Table 1.
  • the catalyst was prepared in the same manner as in Example 11 except that an equivalent amount of the modified ⁇ zeolite B10 was used instead of Bl to obtain a catalyst C4 provided by the present invention.
  • the composition of C4 is shown in Table 1. Comparative example 1
  • This comparative example illustrates a reference catalyst containing beta zeolite modified without phosphorus and transition metals and a process for its preparation.
  • a catalyst was prepared in the same manner as in Example 11 except that ⁇ zeolite (which was the same as in Example 1) which was not modified with phosphorus and a transition metal was used in place of B1 to obtain a reference catalyst CB1.
  • the composition of CB1 is shown in Table 1. Comparative example 2
  • This comparative example illustrates a reference catalyst containing no zeolite beta and a process for its preparation.
  • the catalyst was prepared as in Example 11 except that ⁇ zeolite was not added and it was ultra stable.
  • the amount of cerium zeolite used was 1.2 kg (dry basis) to obtain a reference catalyst CB2.
  • the composition of CB2 is shown in Table 1.
  • Examples 21 to 24 illustrate the catalytic performance of the hydrocarbon conversion catalyst provided by the present invention.
  • Catalysts C1 to C4 were aged at 800 and aged with 100% steam for 14 hours.
  • the reactor was charged in a small fixed fluidized bed reactor with a catalyst loading of 180 g and a reaction temperature of 560 ° C. 10, under the condition of heavy hourly space velocity of 4 hours -1, the mixture of vacuum gas oil and steam (the amount of water vapor is 25 wt% of vacuum gas oil) is used to evaluate the aging catalyst, vacuum gas.
  • the properties of the oil are shown in Table 3.
  • the evaluation results are shown in Table 4. Comparative Example 3-4
  • Comparative Examples 3-4 illustrate the catalytic performance of the reference catalyst.
  • Raw material oil name Vacuum gas oil normal pressure residue density (20 ⁇ ), g/cm 3 0.8764 0.8906 Viscosity (80 ° C), glutinous rice 2 / sec 12.06 24.84 Asphaltene, wt% - 0.8 Kang's carbon residue, weight % 0.93 4.3 Distillation range, . C
  • the results in Table 4 show that the heavy oil cracking ability of the hydrocarbon conversion catalyst provided by the present invention is increased by 1.3 to 2 percentage points compared to the reference catalyst CB1 which is aged under the same conditions and has the same zeolite content but the zeolite is not modified.
  • Examples 25 to 30 illustrate the catalytic performance of the hydrocarbon conversion catalysts provided by the present invention under different reaction conditions.
  • Catalysts C5 ⁇ C10 were aged at 800 C for 100 hours with 100% steam.
  • a small fixed fluidized bed reactor was used.
  • the amount of catalyst in the reactor was 180 g.
  • the aged catalyst was evaluated by passing through atmospheric residue.
  • the properties of atmospheric residue are shown in Table 3.
  • the reaction conditions and product distribution are shown in Table 5.
  • Example 25 Example 26 Case 27 Case 28 Case 29 Case 30 Catalyst C5 C6 C7 C8 C9 C10 Reaction temperature, °c 520 520 580 580 620 620 Agent oil weight ratio 10 10 10 10 10 10 Weight hourly space velocity, hour ' 1 10 10 15 15 20 20 The amount of water vapor is atmospheric residue

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

一种烃类转化催化剂 技术领域
本发明关于一种含沸石的烃类转化催化剂， 更具体地说， 关于一 种能够催化裂化烃类生产 c2 - C4烯烃的含沸石烃类催化裂化催化剂。 背景技术
低碳烯烃 （C2 ~ C4烯烃）是重要的石油化工原料， 从石油烃类制 取低碳烯烃， 通常采用以气态烃、 石脑油、 煤油、 轻柴油及减压渣油 为原料的蒸汽裂解方法， 常规的催化裂化工艺在生产汽油和轻柴油的 同时也副产低碳烯烃， 但其产率仅占原料油的 15重量％以下。
采用催化裂化的方法， 从石油烃类生产低碳烯烃已有不少专利报 导， 在部分专利中使用的是金属负载型催化剂， 以 Si02、 A1203或其 它氧化物为载体， 所用金属元素多属 IIB、 VB、 VIIB和 VIII族金属 元素， 它们都具有加氢、 脱氢活性， 在高温和低压的裂化条件下表现 出脱氢活性， 因此加快低碳烯烃的生成 （US3541179、 US3647682 , DD225135, SU1214726 ) 。 使用此类催化剂时， 由于所负载金属的脱 氢性能， 在进行裂化反应的同时， 聚合结焦的副反应也相应加快， 使 催化剂上结炭较多， 因而只能采用沸程为 <220°C的轻质原料。
此外， 还有一部分专利使用的是复合氧化物催化剂。 如以 Zr02、 Hf02为主要成分， 辅以 A1203、 Cr203、 MnO、 Fe203以及碱金属或碱 土金属氧化物的催化剂（ US3725495、 US3839485 )；再如含少量 Fe203、 Ti02、 CaO、 MgO、 Na20、 K20 的 Si02 Al203催化剂 （SU550173、 SU559946 ) 。
随着沸石在石油化工和石油加工领域中日益广泛的应用， 出现了 第三类催化剂， 即含沸石的催化剂。 近年来， 为了提高催化裂化过程 生产的汽油的辛垸值，人们在催化剂中加入择形添加剂，如 US3758403 中公开了以 ZSM-5型分子筛和大孔沸石（两者比例可为 1: 10 - 3： 1 ) 为活性组分的催化剂， 采用此催化剂， 在提高汽油辛烷值的同时， 也 增加了 C3、 C4烯烃的收率， C3〜C4烯烃收率为 10重量％左右。
含具有 MFI结构的沸石 （五元环高硅沸石）和孔径大于 7 埃的 沸石的复合沸石催化剂用于石油烃裂解生产低碳烯烃时， 其中大孔沸 石 （主要是 Y型沸石）对原料进行裂化生成汽、 柴油， 而 MFI结构 沸石进一步将其裂化成低碳烯烃 （ US3758403、 CN1043520A、 US500649, CN1026242C ) 。 为提高催化剂对烯烃的选择性， 进一步 对 MFI结构沸石进行了改性， 如采用过渡金属改性（US5236880 ) 、 磷改性 （CN1205307A、 US6566293 ) 、 稀土改性 （CN1085825A ) 、 磷和稀土 改性 （ CN1093101A、 US5380690、 CN1114916A、 CN1117518A、 CN1143666A ) 、 磷和碱土金属改性 （ CN1221015A、 US6342153 , CN1222558A、 US6211104 ) 以及磷和过渡金属改性 ( CN1504540A ) 。
β沸石具有十二元环交叉孔道结构， 平行于 （001 ) 晶面的一维孔 道的 12元环孔径为 0.75 ~ 0.57nm, 另一个与 （100 ) 晶面平行的二维 孔道的 12 元环孔径为 0.65 ~ 0.56nm。 β 沸石是迄今为止所发现的唯 ——种大孔三维结构的高硅沸石， 由于其结构的特殊性， 兼具酸催化 特性和结构选择性，并且具有很高的热稳定性（晶格破坏温度大于 1200 °C ) 、 水热稳定性及耐磨性能。 由于独特的结构特征， 在一系列催化 反应中 β沸石具有良好的热和水热稳定性、 耐酸性、 抗结焦性和催化 活性， 近年来已迅速发展成为一种新型的催化材料。 将 β沸石用于石 油烃裂解生产低碳烯烃也有较多报导。
CN1103105A公开了一种多产异丁烯和异戊烯的裂化催化剂， 该 催化剂是由四种活性组分及载体组成的复合催化剂， 其活性组分由两 种不同硅铝比的改性 HZSM-5和高硅 HZSM-5、 USY和 β沸石构成， 载体由天然粘土和无机氧化物组成，该催化剂的组分和含量如下： （1 ) 硅铝比为 20〜100的改性 HZSM-5: 5-25重量％； ( 2 )硅铝比为 250〜450 的高硅 HZSM-5: 1-5重量％； ( 3 ) USY沸石： 5〜20重量％； ( 4 ) β沸石： 1〜5重量％; ( 5 ) 天然粘土： 30〜60重量％; ( 6 )无机氧化 物： 15〜30 重量％。 该催化剂具有多产异丁烯和异戊烯的特点， 同时 还可以联产高辛烷值汽油。
CN1057408A公开了一种含高硅沸石的裂化催化剂， 它由 10 ~ 30 重量％改性高硅沸石和 70 ~ 90 重量％载体组成， 该改性高硅沸石为 含（以沸石重量为基准） 0.01 ~ 3.0 重量％磷、 0.01 - 1.0 重量％铁或 0.01 - 10 重量％铝 （不包括沸石结构中的铝） ， 并且硅铝比大于 15 的 ZSM分子筛、 Ρ沸石或丝光沸石， 载体为无机氧化物或无机氧化 物和高岭土的混合物， 该催化剂用于烃类催化裂化过程生产低碳烯 烃， 并兼产汽油和柴油。
CN1099788A公开了一种多产 C3~C5烯烃的裂化催化剂， 由 10~ 50%晶胞常数 2.450nm的 Y型沸石、 2 ~ 40%选自 P、 RE、 Ca、 Mg、 H、 Al等改性的 ZSM-5 沸石、 β沸石及其混合物、 20~80%由高岭 土和铝粘结剂组成的半合成载体组成。 使用该催化剂不仅能提高 C3~ C5烯烃的收率， 其中 iC4 = +iC5 =的产率达 10~13重量％， 同时还可以 使汽油产率保持在 35 ~ 42重量％左右。
CN1145396A公开了一种多产异丁烯和异戊烯的裂化催化剂， 由 三种沸石活性组分和载体组成（以催化剂为基准计） ： 含碑和稀土的 五元环高硅沸石 6~30重量％、 USY沸石 5~20重量％、 P沸石 1~ 5重量％、 粘土 30~60重量％和无机氧化物 15~30重量。 /。。 该催化 剂具有多产异丁烯和异戊烯的特点， 同时可联产高辛烷值汽油。
CN1354224A公开了一种用于生产富含异构烷烃汽油、 丙烯及异 丁烷的催化裂化催化剂， 是由以催化剂重量为基准的 0~70重量％粘 土， 5~90重量％无机氧化物和 1~50 重量％的沸石组成。 其中的沸 石为以沸石重量为基准的 （1) 20~75 重量％的硅铝比为 5~15、 以 RE203计的稀土含量为 8~20重量％的高硅 Y沸石与 （2) 20~75重 量％的硅铝比为 16~50、 以 RE203计的稀土含量为 2~7重量％的高 硅 Y沸石和（3) 1-50重量％的 β沸石或丝光沸石或 ZRP沸石的混 合物。 使用该催化剂可提高汽油中异构烷烃的含量， 同时增产丙烯和 异丁烷， 但其丙烯产率仅略有增加。
CN1504541A公开了一种催化烃类裂解生产低碳烯烃并联产芳烃 的催化剂， 含有孔径为 0.45-0.7 纳米的分子筛、 无定形的氧化物以及 磷、 碱土金属、 锂和稀土中的至少两种改性元素。 其中分子筛为硅铝 分子筛或硅磷铝分子筛， 所述硅铝分子筛为 ZSM-5、 ZSM-11, 丝光 沸石或 Beta 沸石， 所述硅鱗铝分子筛为 SAPO-5、 SAPO-11 或 SAPO-34， 该催化剂的活性中心可以通过实际的产物需要进行调变， 可以以低碳烯烃为主要产物， 也可以在多产烯烃的同时联产芳烃。
CN1566275A公开了一种含分子筛的烃类裂化催化剂及其制备方 法， 所述催化剂含有分子筛、 耐热无机氧化物和一种金属组分， 含或 不含粘土， 所述分子筛为第一种沸石和第二种沸石的混合物， 笫一种 沸石为 Y型沸石， 第二种沸石为氧化硅与氧化铝的摩尔比为 20 以上 的沸石， 第一种沸石的含量为 1 ~ 50重量％、第二种沸石的含量为 1 ~ 60重量％,耐热无机氧化物的含量为 2 ~ 80重量％，粘土的含量为 0 ~ 80重量％， 金属组分的含量为 0.1 ~ 30重量％， 所述金属组分基本上 以还原价态存在。 该催化剂既能多产 C3 ~ C5烯烃， 又具有更高脱硫 活性， 而且还具有更高的裂化活性。 其中第二种沸石选自具有 ΜΪΊ 结构的沸石， 含磷、 稀土和 /或碱土金属的具有 MFI 结构的沸石， β 沸石、 含碑、 稀土和 /或碱土金属的 β沸石、 丝光沸石， 含磷、 稀土和 /或碱土金属的丝光沸石中的一种或几种。
US5006497和 US5055176公开了一种多组分催化剂及其催化裂化 方法， 所述催化剂含有基质、 大孔分子筛、 烷烃裂化异构化分子筛和 芳构化分子筛， 其中大孔分子筛可选自沸石 Y， DeAlY, USY, UHPY, VPI-5, 柱形粘土， SAPO-37, β及其混合物， 烷烃裂化异构化分子筛 选自氢型 ZSM-5, ZSM-11, ZSM-22, ZSM-35 和 ZSM-57, 芳构化 分子筛为 GaZSM-5。
US20050070422公开了一种用于催化裂化增产^烯的催化剂组合 物， 该催化剂包含具有中孔直径的第一种分子筛， 至少一个孔道直径 小于第一种分子筛孔道直径的笫二种分子筛， 可选的第三种大孔分子 筛。 其中， 第一种分子筛选自 ZSM-5, ZSM-11 , ZSM-12, ZSM-57, ITQ-13和 MCM-22。 第二种分子筛选自 ECR-42, ZSM-22, ZSM-35, ZSM-23, MCM-22, MCM-49, SAPO-11 , SAPO-34 和 SAPO-41。 第三种分子筛选自八面沸石， L沸石， VPI-5, SAPO-37, X沸石， β 沸石， ZSM-3 , ZSM-4 , ZSM-18 , ZSM-20 , MCM-9 , MCM-41 , MCM-41S, MCM-48, Υ型沸石， USY, REY, REUSY等。 该催化 剂适用裂化石脑油、 重质烃油生产丙烯。
随着对低碳烯烃需求量的进一步增加， 人们希望开发一种烃类转 化催化剂， 其具有更强的烃类转化能力， 更高的低碳烯烃产率， 特别 是更高的丙烯产率。 发明内容
本发明就是鉴于以上现有技术的发展状况而提出的， 其目的是提 供一种催化石油烃转化生产低碳烯烃的烃类转化催化剂。 本发明人通过刻苦的研究发现， 当烃类转化催化剂中包含特定的 改性 β沸石作为催化剂组分时， 可以使 C2〜( 12烯烃的选择性得到显著 提高， 从而有利于低碳烯烃 （C2~C4烯烃） 的进一步裂化生成， 由此 能够从烃类以更高的收率生产该低碳烯烃， 从而完成了本发明。
为了实现该目的， 本发明提供了一种烃类转化催化剂， 以该烃类 转化催化剂的总量为基准， 其含有 1 ~ 60重量％的沸石混合物、 5~99 重量％的耐热无机氧化物和 0~70重量％的粘土， 以所述沸石混合物 的总量计， 所述沸石混合物中含有 1~75重量％的由磷和过渡金属 M 改性的 β沸石、 25~99重量％的具有 MFI结构的沸石和 0~74重量 %的大孔沸石； 其中， 所述由磷和过渡金属 Μ 改性的 β 沸石的无水 化学表达式以氧化物所占的质量百分率表示时为： （ 0 ~ 0.3 ) Na20- ( 0.5 - 10 ) Α1203· ( 1.3 ~ 10 ) Ρ205· ( 0.7 - 15 ) MxOy- ( 64 ~ 97 ) Si02, 其中， 所述过渡金属 M选自 Fe、 Co, Ni、 Cu、 Mn、 Zn和 Sn 中的一种或几种， x表示所述过渡金属 M的原子数， y表示满足所述 过渡金属 M的氧化态所需的一个数。
具体而言， 本发明涉及以下方面的内容：
1. 一种烃类转化催化剂， 以该烃类转化催化剂的总量为基准， 其含有 1-60 重量％的沸石混合物、 5~99 重量％的耐热无机氧化物 和 0~70重量％的粘土， 其特征在于， 以所述沸石混合物的总量计， 所述沸石混合物中含有 1~75 重量％的由碑和过渡金属 M 改性的 β 沸石、 25~99重量％的具有 MFI结构的沸石和 0~74重量％的大孔 沸石， 其中， 所述由磷和过渡金属 Μ 改性的 β 沸石的无水化学表达 式以氧化物所占的质量百分率表示时为： （0~0.3) Na20- ( 0.5 - 10 ) Α1203· ( 1.3 ~ 10 ) Ρ205· ( 0.7 ~ 15 ) MxOy- ( 64-97) Si02, 其中， 所 述过渡金属 M选自 Fe、 Co、 Ni、 Cu、 Mn、 Zn和 Sn中的一种或几 种， x表示所述过渡金属 M的原子数， y表示满足所述过渡金属 M氧 化态所需的一个数。
2. 按照方面 1 的烃类转化催化剂， 其特征在于以所述烃类转化 催化剂的总量为基准， 所述催化剂含有 10~50 重量％的所述沸石混 合物、 10~70重量％的所述耐热无机氧化物和 0~60重量％的所述粘 土。
3. 按照方面 1 的烃类转化催化剂， 其特征在于所述的由磷和过 渡金属 M改性的 p沸石的无水化学表达式为： （ 0 ~ 0.2 ) Na20- ( 1 ~ ) Α1203· ( 1.5 - 7 ) Ρ205· ( 0.9 ~ 10 ) MxOy- ( 75 - 95 ) Si02。
4. 按照方面 3 的烃类转化催化剂， 其特征在于所述的由磷和过 渡金属 M改性的 β沸石的无水化学表达式为： （ 0 ~ 0.2 ) Na20- ( 1 ~ 9 ) Α1203· ( 2 - 5 ) Ρ205· ( 1 - 3 ) MxOy- ( 82 ~ 95 ) Si02。
5. 按照方面 1 的烃类转化催化剂， 其特征在于所述的过渡金属 M选自 Fe、 Co、 Ni和 Cu中的一种或几种。
6. 按照方面 5 的烃类转化催化剂， 其特征在于所述的过渡金属 M选自 Fe和 /或 Cu。
7. 按照方面 1 的烃类转化催化剂， 其特征在于所述具有 MFI结 构的沸石选自 ZSM-5和 Z P系列沸石中的一种或几种。
8. 按照方面 7的烃类转化催化剂， 其特征在于所迷具有 MFI结 构的沸石选自含稀土的 ZRP沸石、 含磷的 ZRP沸石、 含磷和稀土的 ZRP沸石、 含磷和碱土金属的 ZRP沸石以及含磷和过渡金属的 ZSP 沸石中的一种或几种。
9. 按照方面 1 的烃类转化催化剂， 其特征在于所述大孔沸石选 自八面沸石、 L沸石、 β沸石、 JQ沸石、 丝光沸石和 ZSM-18沸石中 的一种或几种。
10. 按照方面 9 的烃类转化催化剂， 其特征在于所述大孔沸石选 自 Υ型沸石、 含磷和 /或稀土的 Υ型沸石、 超稳 Υ沸石以及含磷和 /或 稀土的超稳 Υ沸石中的一种或几种。
11. 按照方面 1 的烃类转化催化剂， 其特征在于所述粘土选自高 岭土、 多水高岭土、 蒙脱土、 硅藻土、 埃洛石、 皂石、 累托土、 海泡 石、 凹凸棒石、 水滑石和膨润土中的一种或几种。
12. 按照方面 1 的烃类转化催化剂， 其特征在于所述粘土选自高 岭土、 多水高岭土和蒙脱土中的一种或几种。
本发明的烃类转化催化剂以由磷和过渡金属 Μ 改性的 β 沸石和 具有 MFI结构的沸石的沸石混合物或者由磚和过渡金属 Μ改性的 β 沸石、 具有 ΜΪΊ结构的沸石与大孔沸石的沸石混合物作为活性组分， 由于所述 β 沸石是被磷和过渡金属 Μ 同时改性的， 所以既提高了所 述 β沸石的水热稳定性并促进对柴油和重油的裂化， 又使其在应用于 烃类的催化裂化方法中时， C2〜( 12烯烃选择性得到显著提高， 而其中 的 c5~c12烯烃正是生成 c2〜c4烯烃的有效前驱体， 从而有利于通过具 有 MFI结构的沸石进一步裂化而生成 C2~C4烯烃。 因此， 本发明提 供的催化剂具有更强的烃类转化能力， 更高的低碳烯烃产率， 特别是 丙烯产率更高。 具体实施方式
为了能够以更高的收率从烃类生产低碳烯烃， 本发明提供了一种 烃类转化催化剂， 以该烃类转化催化剂的总量为基准， 其含有 1~60 重量％的沸石混合物、 5~99重量％的耐热无机氧化物和 0~70重量 %的粘土， 其特征在于， 以所述沸石混合物的总量计， 所述沸石混合 物中含有 1~75重量％的由磷和过渡金属 M改性的 β沸石、 25~99 重量％的具有 MFI结构的沸石和 0~74 重量％的大孔沸石； 其中， 所述由磷和过渡金属 Μ 改性的 β 沸石的无水化学表达式以氧化物所 占的质量百分率表示时为： (0-0.3) Na20- (0.5-10) Α1203· (1.3- 10 ) Ρ205· ( 0.7 ~ 15 ) MxOy- ( 64 ~ 97 ) Si02, 其中， 所述过渡金属 M 选自 Fe、 Co, Ni、 Cu、 Mn、 Zn和 Sn中的一种或几种， x表示所述 过渡金属 M的原子数， y表示满足所述过渡金属 M氧化态所需的一 个数。
在本发明上下文中， 所述术语 "低碳烯烃" 指的是 C2~C4烯烃， 而所述的术语 "烃类" 指的是石油烃类， 除非有特殊的说明。
所述烃类选自 烃类、 汽油、 柴油、 加氢尾油、 等石油馏分中 的一种或几种， 或这些石油馏分的混合馏分， 也可以直接使用原油和 渣油。 减压瓦斯油、 原油和渣油中的一种或几种的混合物。
在一个优选的实施方案中， 以该烃类转化催化剂的总量为基准， 该催化剂含有 10-50重量％的所述沸石混合物、 10~70重量％的所 述耐热无机氧化物和 0 ~ 60重量％所述粘土。
首先对作为本发明烃类转化催化剂必要组分之一的所述改性 P沸 石进行说明。
所述的由磷和过渡金属 M 改性的 β 沸石的无水化学表达式以氧 化物所占的盾量百分率表示时， 优选的范围是： （0~0.2) Na20 (1~ 9 ) Α1203· (1.5-7) Ρ205· ( 0.9 - 10 ) MxOy- ( 75 ~ 95 ) Si02, 更优选 的范围是（ 0 ~ 0.2 )Na20-( 1 - 9 )Α1203·( 2-5 )Ρ205·( 1 - 3 )MsOy-( 82 ~ 95 ) Si02。
在优选的实施方案中， 所述的过渡金属 M选自 Fe、 Co、 Ni和 Cu 中的一种或几种， 更优选选自 Fe和 /或 Cu。
本发明提供的烃类转化催化剂中， 所述具有 MFI结构的沸石为具 有 pentasil结构的高硅沸石， 选自 ZSM-5和 ZRP系列沸石中的一种或几 种， 特别是选自含稀土的 ZRP沸石 （CN1052290A、 CN1058382A, US5232675 ) 、 含磷的 ZRP沸石 ( CN1194181A、 US5951963 ) 、 含鱗 和稀土的 ZRP沸石 （CN1147420A ) 、 含磷和碱土金属的 ZRP沸石 ( CN1211469A, CN1211470A、 US6080698 ) 以及含祷和过渡金属的 ZSP沸石 （CN1465527A、 CN1611299A ) 中的一种或几种。
所述大孔沸石为具有至少 0.7 纳米环开口的孔状结构的沸石， 比 如选自 Y型沸石、 L沸石、 β沸石、 Ω沸石、 丝光沸石和 ZSM-18沸 石中的一种或几种， 特别是可选自 Υ型沸石、 含碑和 /或稀土的 Υ型 沸石、 超稳 Υ沸石以及含磷和 /或稀土的超稳 Υ沸石中的一种或几种。
另外， 所述具有 MFI 结构的沸石和所述大孔沸石可以采用市售 品， 也可以采用本领域公知的各种方法进行制备， 在此不赘述。
所述由磷和过渡金属 Μ 改性的 β 沸石可以采用各种方法进行制 备， 比如可以举出， （1 )在合成 β 沸石的过程中引入碑和所述过渡 金属 Μ， 或者（2 )在合成 β 沸石后采用铵交换、 磷改性、 所述过渡 金属 Μ改性及焙烧处理等步骤来引入磷和所述过渡金属 Μ。
举例而言， 所述由碑和过渡金属 Μ 改性的 β 沸石可以按照如下 方法制备。 即， 将常规晶化所得的钠型 β沸石按照 β沸石： 铵盐： Η20 = 1： ( 0.1 ~ 1 ) ： ( 5 - 10 ) 的重量比在室温至 100°C下交换 0.5 ~ 2 小时后过滤， 并将此交换过程重复 1 ~ 4次， 使 p沸石上的 Na20含量 小于 0·2 重量％， 然后， 采用浸渍或离子交换的方法， 在交换后的 p 沸石中引入磷和选自 Fe、 Co、 Ni、 Cu、 Mn、 Zn、 Sn 中的一种或几 种的过渡金属 M对该 β沸石进行改性，接着干燥之， 然后在 400 ~ 800 °C下焙烧 0.5 ~ 8小时， 该焙烧过程也可以在水蒸汽气氛下进行， 由此 就可以制备所述由磷和过渡金属 M改性的 β沸石。
在制备所述改性 β 沸石时， 所述的引入磷和过渡金属 Μ对该沸 石进行的改性过程比如可以按照本领域的常规方法采用浸渍或离子交 换方式进行。 其中， 所述浸渍的方法可以采用如下三种方式之一进行：
a. 将铵交换后的 P沸石滤饼与计算量的含碑化合物的水溶液在 室温至 95Ό下打浆均 后烘干， 在 400 ~ 800°C奈件下焙烧后， 再与 计算量的含选自 Fe、 Co, Ni> Cu、 Mn、 Zn和 Sn中的一种或几种过 渡金属 M的化合物的水溶液在室温至 95Ό下混合均匀， 然后干燥之； b. 将铵交换后的 p沸石滤饼与计算量的含磷化合物的水溶液在 室温至 95°C下打浆均匀后烘干， 再与计算量的含选自 Fe、 Co、 Ni、 Cu、 Mn、 Zn和 Sn中的一种或几种过渡金属 M的化合物的水溶液在 室温至 95Ό下混合均勾后干燥之， 其中也可以将上述两种溶液的浸渍 顺序颠倒； 和
c 将铵交换后的 β沸石滤饼与计算量的含磷化合物与含选自 Fe、 Co、 Ni、 Cu、 Mn、 Zn和 Sn 中的一种或几种过渡金属 M 的化合物 的混合水溶液在室温至 95 °C下混合均勾后干燥之。
所说的离子交换方式比如可以举出以下方法。
将铵交换后的 β沸石滤饼与计算量的含磷化合物的水溶液在室温 至 95°C下打浆均 后烘干， 在 400 ~ 800 °C条件下焙烧后， 再与计算 量的含选自 Fe、 Co, Ni> Cu、 Mn、 Zn和 Sn中的一种或几种过渡金 属 M的化合物的水溶液按 1: ( 5 ~ 20 )的固液比混合均匀后， 在 80 95°C下搅拌 2 ~ 3 小时后过滤， 该交换可重复多次， 将交换后所得样 品用水洗涤多次， 然后干燥即可。
在制备所述改性 β沸石时， 所说的铵盐为本领域铵交换处理中常 用的无机铵盐， 比如选自氯化铵、 硫酸铵和硝酸铵之一或它们的混合 物。
在制备所述改性 β沸石时， 所迷的含磷化合物选自磷酸、 磷酸氢 铵、 磷酸二氢铵和磷酸铵之一或其混合物。
在制备所述改性 β沸石时， 所说的含选自 Fe、 Co、 Ni、 Cu、 Mn> Zn和 Sn 中的一种或几种过渡金属 M的化合物选自它们相应的水溶 性盐， 而所说的水溶性盐选自硫酸盐、 硝酸盐和氯化盐中的一种或几 种。
在制备所述改性 β沸石时， 所述的干燥或烘干可以采用常规的方 式进行， 并且干燥或烘干温度可以是室温至 350Ό , 优选为 100 ~ 200 °C。 所述焙烧温度为常规的焙烧温度， 一般来说为 400 ~ 800。C , 优选 为 450 ~ 700°C。
在制备所述改性 P沸石时， 对所用的起始 β沸石并没有特别的限 定， 可以采用本领域常用的那些， 也可以采用市售品， 还可以按照本 领域公知的方法进行制备而获得。 在优选的实施方案中， 所述起始 β 沸石为钠型 β沸石。 如果所述钠型 β沸石中含有有机模板剂， 则应该 在脱除模板剂后再进行如上的操作。 而且， 该钠型 β沸石中的钠含量 应该保证符合最终得到的含有磷和所述过渡金属 Μ 的 β 沸石的无水 化学表达式中对钠含量的要求。 如果不符合要求， 可以采用铵交换的 方法除去该起始钠型 β沸石中的钠。 从这一角度来说， 在制备所述改 性 β沸石时， 所述铵交换步骤并不是必须的。
在制备所述改性 β 沸石时， 所采用的设备和条件控制方法等也没 有特别的限制， 可以采用本领域常规的那些。
接着， 对作为本发明烃类转化催化剂另一必要组分的耐热无机氧 化物进行说明。
对所述耐热无机氧化物没有限定， 但优选选自通常用作裂化催化 剂基质和粘结剂组分的耐热无机氧化物中的一种或几种， 比如可举出 氧化铝、 氧化硅和无定型硅铝中的一种或几种。 这些耐热无机氧化物 及其制备方法是本领域技术人 所公知的。 这些耐热无机氧化物可以 采用市售品， 也可以采用本领域公知的方法由所述耐热无机氧化物的 前身物制得。
另外， 在制备本发明的烃类转化催化剂时， 可以直接使用所述耐 热无机氧化物的前身物来代替所迷耐热无机氧化物。 因此， 术语 "耐 热无机氧化物" 包括耐热无机氧化物本身和 /或这些耐热无机氧化物的 前身物。
这里所说的耐热无机氧化物前身物指的是在本发明烃类转化催化 剂制备过程中能形成所述耐热无机氧化物的物质。 具体举例而言， 所 述氧化铝的前身物可选自水合氧化铝和 /或铝溶胶； 所述水合氧化铝比 如可以选自一水软铝石 （薄水铝石 ) 、 假一水软铝石 （拟薄水铝石） 、 三水合氧化铝和无定形氢氧化铝中的一种或几种； 而所述氧化硅的前 身物比如可选自硅溶胶、 硅凝胶和水玻璃中的一种或几种。 进一步地， 所述无定形硅铝的前身物可选自硅铝溶胶、 硅溶胶和铝溶胶的混合物 以及硅铝凝胶中的一种或几种。 这些耐热无机氧化物的前身物及其制 备方法也是本领域技术人员所公知的。
在本发明的烃类转化催化剂中， 作为任选组分， 还可以含有粘土。 对所述粘土没有特别的限定， 但优选选自通常用作裂化催化剂活性组 分的粘土中的一种或几种， 比如可举出高岭土、 多水高岭土、 蒙脱土、 硅藻土、 埃洛石、 皂石、 累托土、 海泡石、 凹凸棒石、 水滑石和膨润 土中的一种或几种。 粘土优选选自高岭土、 多水高岭土和蒙脱土中的 一种或几种。 这些粘土及其制备方法为本领域技术人员所公知， 也可 以采用其市售品。
作为本发明的烃类转化催化剂的制备方法， 可以举出以下方法， 但本发明并不限于此。
将全部或一部分所述耐热无机氧化物和 /或其前身物与水混合打 浆， 然后向所得浆液中加入或不加入所述粘土， 此时可以进一步向其 中加入剩余部分的所述耐热无机氧化物和 /或其前身物， 然后向所得浆 液中加入所述改性 β沸石， 混合打浆均勾后， 干燥得到的浆液， 然后 焙烧之。 其中， 在加入所述改性 β沸石之前， 在加入所述粘土之前或 之后， 还向所得浆液中加入酸， 将所述浆液的 ρΗ值调节为 1 ~ 5。 在 Η值达到规定范围之后， 在 30 ~ 90Ό的温度下老化所得浆液 0.1 ~ 10 小时； 所述老化结束后， 加入剩余部分的所述耐热无机氧化物和 /或其 前身物。
在本发明的烃类转化催化剂的制备方法中， 所述粘土可以在所述 老化步骤之前或所述老化步骤之后加入， 该粘土的加入顺序对本发明 烃类转化催化剂的性能没有影响。
在制备本发明提供的烃类转化催化剂时， 在老化步骤之前， 可以 加入全部或一部分所述耐热无机氧化物和 /或其前身物， 但为了使该催 化剂具有更好的耐磨性能， 优选在进行所述老化步骤之前， 先加入一 部分所述耐热无机氧化物和 /或其前身物， 然后在老化步骤结束之后再 加入剩余部分的所述耐热无机氧化物和 /或其前身物。 在后一种情况 中， 先加入的部分与后加入的部分的重量比为 1: 0.1 ~ 10， 更优选为 1： 0.1 ~ 5。
在制备本发明的烃类转化催化剂时， 为了调节浆液的 ρΗ值， 向 其中加入酸。 所述酸选自可溶于水的无机酸和有机酸中的一种或几 种， 优选选自盐酸、 硝酸、 磷酸以及碳原子数为 1 ~ 10 的羧酸中的一 种或几种。 所述酸的用量以使浆液的 pH值为 1 ~ 5， 优选为 1.5 ~ 4 为准。
在本发明的烃类转化催化剂的制备方法中， 所述老化的条件优选 为在温度 40 ~ 80 °C下老化 0·5 ~ 8小时。
所述浆液的干燥方法和条件为本领域技术人员所公知， 例如， 干 燥的方法可以是晾干、 烘干、 鼓风干燥或喷雾干燥， 优选喷雾干燥。 干燥温度可以是室温至 400°C， 优选为 100 ~ 350Ό。 为了便于喷零干 燥， 干燥前浆液的固含量优选为 10 ~ 50重量％， 更优选为 20 ~ 50重 量0 /0。
浆液干燥后， 所述焙烧条件也为本领域技术人员所公知， 一般来 说， 所述焙烧温度为 400 ~ 700°C , 优选为 450 ~ 650°C， 焙烧时间至 少为 0.5小时， 优选为 0.5 ~ 100小时， 更优选为 0.5 ~ 10小时。
本发明提供的催化剂具有更强的烃类转化能力以及更高的低碳烯 烃产率， 特别是更高的丙烯产率。 实施例
下面的实施例和对比例将对本发明做进一步的说明， 但并不因此 而限定本发明。
实施例 1 ~ 10说明由磷和过渡金属 M改性的 β沸石及其制备方 法。 其中， 各个改性 β沸石样品中 Na20、 Fe203、 Co203、 NiO、 CuO、 Mn203、 ZnO、 Sn02、 A1203和 Si02的含量用 X射线荧光法测定（参 见 《石油化工分析方法 （RIPP 实验方法） 》 ， 杨翠定等编， 科学出 版社， 1990年出版） 。
以下所用试剂， 除特别说明的以外， 均为化学纯试剂。 实施例 1
将 100g (干基） p 沸石 （齐鲁催化剂厂生产， Si02/Al203=25 ) 用 NH4C1溶液交换洗涤至 Na20含量低于 0.2重量％， 过滤得滤饼； 加入 6.8gH3P04 (浓度 85% )与 3.2gCu(N03)2'3H20溶于 90g水中， 与滤饼混合浸渍烘干； 所得样品在 550Ό焙烧处理 2 小时， 得到含磷 和过渡金属铜的改性 β 沸石 Bl。 B1 的无水化学表达式为： 0.1Na2O-8.2Al2O3-4.0P2O5-1.0CuO-86.7SiO2o 实施例 2
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2重量％ ,过滤得滤饼；加入 12.5gH3P04(浓度 85% )与 6.3gCu<¾ 溶于 90g水中， 与滤饼混合浸渍烘干； 所得样品在 550Ό焙烧处理 1 小时， 得到含碑和过渡金属铜的改性 β沸石 Β2。 Β2的无水化学表达 式为： 0.1Na2O'7.0Al2O3'6.9P2O5'3.5OiO'82.5SiO2。 实施例 3
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2重量％， 过滤得滤饼； 将 4.2gNH4H2P04溶于 60g水中， 与滤 饼混合浸渍烘干、 经 550TC焙烧处理 2小时； 将上述样品按固液比 1:5 的比例与浓度为 5%的 Cu(N03)2溶液在 80 ~ 90°C下交换 2小时，过滤， 再交换若干次， 直至达到目标量， 再在 550Ό焙烧处理 2 小时， 得到 含碑和过渡金属铜的改性 β 沸石 Β3。 Β3 的无水化学表达式为： 0,03Na2O 2.0Al2O3'2.5P2O5'2.1CuO'93.4SiO2。 实施例 4
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2 重量％， 过滤得滤饼； 加入 7.1gH3P04 (浓度 85% ) 与 8.1gFe(N03)3-9H20溶于 90g 水中， 与滤饼混合浸渍烘干； 所得样品 在 550°C焙烧处理 2小时， 得到含礫和过渡金属铁的改性 β沸石 Β4。 Β4 的 无 水 化 学 表 达 式 为 ： 0.1Na2O*6.0Al2O3'4.1P2O5'1.5Fe2O3'88.3SiO2。 实施例 5
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Ν 0含量低 于 0.2 重量％ , 过滤得滤饼； 加入 10.3gH3PO4 (浓度 85% ) 与 39.6gCo(N03) ·6Η20溶于 90g水中， 与滤饼混合浸渍烘干； 所得样品 在 550Ό焙烧处理 2小时， 得到含磷和过渡金属钴的改性 β沸石 Β5。 Β5 的 无 水 化 学 表 达 式 为 ： 0JNa，O'6.7Al7O 5.4I O 9.6C02O 78,2SiO2。 实施例 6
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2 重量％ , 过滤得滤饼； 加入 7.5gH3P04 (浓度 85% ) 与 6.7gNi(N03)2'6H20溶于 90g水中， 与滤饼混合浸渍烘干； 所得样品在 550Ό焙烧处理 2小时， 得到含磷和过渡金属镍的改性 β沸石 Β6。 Β6 的无水化学表达式为： 0.08Na2O'6.0Al2O3'4.3P2O5'1.8NiO'87.8SiO2。 实施例 Ί
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2 重量％， 过滤得滤饼； 加入 6.9gH3P04 (浓度 85% ) 与 16.1gMn(N03)2溶于 9(^水中， 与滤饼混合浸渍烘干； 所得样品在 550 °C焙烧处理 2小时， 得到含碑和过渡金属锰的改性 β沸石 Β7。 Β7的 无水化学表达式为： 0.09Na2O'1.9Al2O3'3.8P2O5'6.4Mn2O3'87.8SiO2。 实施例 8
将 100g (干基）晶化产品 β沸石用 NH4C1溶液交换洗涤至 Na20 含量低于 0.2重量％， 过滤得滤饼； 加入 2.5gH3P04 (浓度 85% ) 与 6.1gZn(N03)2-6H20 溶于 90g 水中， 与滤饼混合浸渍烘干； 所得样品 在 550Ό焙烧处理 2小时， 得到含磷和过渡金属锌的改性 β沸石 Β8。 Β8 的 无 水 化 学 表 达 式 为 ： 0.15Na2O-1.3Al2O3-1.5P2O5-1.6ZnO-95.8SiO2o 实施例 9
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2 重量。 /。 ， 过滤得滤饼； 加入 7.1gH3P04 (浓度 85% ) 与 4.2gSnCl4'5H20溶于 90g水中， 与滤饼混合浸渍烘干； 所得样品在 550 °C焙烧处理 2小时， 得到含麟和过渡金属锡的改性 β沸石 Β9。 Β9的 无水化学表达式为： 0.11Na2O'6.3Al2O3'4.1P2O5'1.7SnO2'87.8SiO2。 实施例 10
将 100g (干基） β沸石用 NH4C1溶液交换洗涤至 Na20含量低 于 0.2 重量％， 过滤得滤饼； 加入 7.1gH3P04 (浓度 85% ) 、 3.2gCu(N03)2-3H20和 5.3gFe(N03)3'9H20溶于 90g水中 , 与滤饼混合 浸渍烘干； 所得样品在 550TC焙烧处理 2 小时， 得到含磷和过渡金属 铜、 铁的改性 β 沸石 B10 。 B10 的无水化学表达式为： 0.11Na2O'5.9Al2O3'4.1P2O5'1.0CuO'1.0Fe2O3'87.9SiO2。 实施例 11 ~ 20说明本发明烃类转化催化剂及其制备方法， 在制 备所述催化剂过程中所采用的原料说明如下：
粘土：
多水高岭土 苏州瓷土公司工业产品， 其固含量为 71.6重量％; 高呤土 苏州高岭土公司工业产品， 其固含量为 76重量％; 蒙脱土 浙江丰虹粘土化工有限公司工业产品， 其固含量 为 95重量％。
耐热无机氧化物或其前身物：
拟薄水铝石 山东铝厂工业产品， 其固含量为 62.0重量％;
铝溶胶 齐鲁催化剂厂生产， 其 A1203含量为 21.5重量％; 硅溶胶 北京化工厂出品， 其氧化硅含量为 16.0重量％。 所用的大孔沸石均由齐鲁催化剂厂生产， 其工业牌号分别为：
DASY2.0, 物化参数为： 晶胞常数为 2.446纳米， Na20含量为 1.1 重量％， 稀土氧化物 RE203含量为 2.0重量％, 其中， 氧化镧含 量为 1.06重量％， 氧化铈含量为 0.26 重量％, 其它稀土氧化物含量 为 0.68重量 %；
USY, 物化参数为： 晶胞常数为 2.445 纳米， Na20含量为 0.36 重量％;
DASY0.0,物化参数为： 晶胞常数为 2.443纳米， Na20含量为 0.85 重量％；
DASY6.0, 物化参数为： 晶胞常数为 2.451纳米， Na20含量为 I·6 重量％， 稀土氧化物 RE203含量为 6.2重量％, 其中， 氧化镧含量为 3.29重量％， 氧化铈含量为 0.81重量％ , 其它稀土氧化物含量为 2.10 重量％;
REHY, 物化参数为： 晶胞常数为 2.465纳米， Na20含量为 3.2 重量％， 稀土氧化物 RE203含量为 7.0重量％, 其中， 氧化镧含量为 3.71重量％， 氧化铈含量为 0.91重量％， 其它稀土氧化物含量为 2.38 重量％。
所用的具有 MFI 结构的沸石均由齐鲁催化剂厂生产， 其工业牌 号分别为：
ZSP-2, 其中 SiO2/Al2O3=70, Na20含量为 0.03重量％， P205含 量为 4.9重量％ , Fe203含量为 2.1重量％；
ZRP-1, 其中 SiO2/Al2O3=30, Na20含量为 0.17重量％， 稀土氧 化物 RE203含量为 1.4重量％, 其中， 氧化镧含量为 0.84重量％， 氧 化铈含量为 0.18重量 % , 其它稀土氧化物含量为 0.38重量％；
ZSP-1, 其中 SiO2/Al2O3=30， Na20含量为 0.1 重量％， P205含 量为 2.0重量％ , Fe203含量为 0.9重量％ )
ZRP-5, 其中 SiO2/Al2O3=50， Na20含量为 0.05重量％， P205含 量为 4.0重量％ ) 实施例 11
将 6.3Kg 多水高岭土加入到 25.0Kg脱阳离子水中， 打浆， 再加 入 4.0Kg拟薄水铝石， 用盐酸将其 pH调至 2， 搅拌均匀， 在 70Ό下 静置老化 1小时， 加入 1.4Kg铝溶胶（老化前后加入的耐热无机氧化 物或其前身物的重量比为 1: 0.12 ) ， 搅拌均匀， 加入 0.6Kg (干基） 改性 β沸石 Bl、 0.6Kg (干基）超稳 Y沸石 DASY2.0和 1.5Kg (干 基）具有 MFI结构的沸石 ZSP-2 的混合物， 与水打浆得到的 7.7Kg 浆液， 搅拌均勾， 得到固含量为 22.5重量％的浆液， 将得到的浆液在 250°C的温度下喷雾干燥成型为直径为 20 ~ 150微米的颗粒， 在 550°C 下焙烧 2小时， 得到催化剂 Cl。 C1的组成见表 1。 实施例 12
按实施例 11 的方法制备催化剂， 不同的是用等量的改性 β 沸石 Β2代替 Bl， 得本发明提供的催化剂 C2。 C2的组成见表 1。 实施例 13
按实施例 11 的方法制备催化剂， 不同的是用等量的改性 β 沸石 Β4代替 Bl， 得本发明提供的催化剂 C3。 C3的组成见表 1。 实施例 14
按实施例 11 的方法制备催化剂， 不同的是用等量的改性 β 沸石 B10代替 Bl， 得本发明提供的催化剂 C4。 C4的组成见表 1。 对比例 1
本对比例说明含有未经磷和过渡金属改性的 β沸石的参比催化剂 及其制备方法。
按实施例 11 的方法制备催化剂， 不同的是用未经磷和过渡金属 改性的 β 沸石 （同实施例 1 )代替 B1, 得到参比催化剂 CB1。 CB1 的组成见表 1。 对比例 2
本对比例说明不含 β沸石的参比催化剂及其制备方法。
按实施例 11 的方法制备催化剂， 不同的是不加入 β 沸石， 超稳
Υ沸石的用量为 1.2Kg (干基） ， 得到参比催化剂 CB2。 CB2的组成 见表 1。
Figure imgf000019_0001
实施例 15
在 12.5Kg脱阳离子水中加入 4.0Kg拟薄水铝石， 用硝酸将其 pH 调至 2, 搅拌均匀， 在 50°C下静置老化 5小时， 得到老化后的产物。 在 2.5Kg脱阳离子水中， 加入 2.3Kg铝溶胶（老化前后加入的耐 热无机氧化物或其前身物的重量比为 1: 0.2 ) ， 再加入 4.0Kg高岭土 打浆， 搅拌均匀， 加入上述老化后的产物， 再加入 0.5Kg (干基） 改 性 β沸石 B3、 2.5Kg (干基）超稳 Y沸石 USY和 l.OKg (干基）具 有 MFI结构的沸石 ZRP-1的混合物，与脱阳离子水打浆得到的 11.4Kg 浆液， 搅拌均匀， 得到固含量为 27.2重量％的浆液， 在 220Ό下， 将 得到的浆液喷雾干燥成型为直径为 20 ~ 150微米的颗粒， 在 52(TC下 焙烧 4小时， 得到催化剂 C5。 C5的组成见表 2。 实施例 16
在 18.0Kg脱阳离子水中加入 3.9Kg高岭土和 l.lKg蒙脱土打浆， 再加入 4.0Kg拟薄水铝石 （耐热无机氧化物前身物均在老化前加入）， 用盐酸将其 pH调至 3， 搅拌均匀， 在 60 °C下静置老化 2小时， 加入 2.0Kg (干基）含碑和过渡金属钴的改性 β 沸石 B5、 0.5 g (干基） 含稀土氢 Y沸石 REHY和 l.OKg (干基）具有 MFI结构的沸石的混 合物， 与水打浆得到的 lO.OKg 浆液， 搅拌均匀， 得到固含量为 27.0 重量％的浆液，在 280Ό下，将得到的浆液喷雾干燥成型为直径为 20 ~ 150微米的颗粒， 于 580Ό焙下烧 2.5小时， 得到催化剂 C6D C6的组 成见表 2。 实施例 17
在 17.8Kg脱阳离子水中， 加入 4.2Kg 多水高岭土打浆， 再加入 4.0Kg拟薄水铝石， 用盐酸将其 pH调至 3.5， 搅拌均匀， 在 75Ό下静 置老化 0.5 小时， 加入 2.3Kg铝溶胶（老化前后加入的耐热无机氧化 物或其前身物的重量比为 1: 0.2 ) ， 搅拌均匀， 加入 l.OKg (干基） 含磷和过渡金属镍的改性 β沸石 B6、 1.0Kg(干基）超稳 Y沸石 DASY0.0 和 2.0Kg (干基）具有 MFI结构的沸石 ZSP-1的混合物， 与水打浆得 到的 11.4Kg浆液， 搅拌均匀， 得到固含量为 25.2重量％的浆液， 在 250°C下， 将得到的浆液喷雾干燥成型为直径为 20 ~ 150微米的颗粒， 于 600°C下焙烧 1小时， 得到催化剂 C7。 C7的组成见表 2。 实施例 18
在 20.0Kg脱阳离子水中， 加入 4.9Kg 多水高岭土打浆， 再加入 4.0Kg拟薄水铝石， 用盐酸将其 pH调至 3.5, 搅拌均匀， 在 75Ό下静 置老化 0.5小时， 加入 2.3Kg铝溶胶（老化前后加入的耐热无机氧化 物或其前身物的重量比为 1: 0.2 ) ， 搅拌均匀， 加入 0.2Kg (干基） 含磷和过渡金属锰的改性 P沸石 B7、0.8Kg(干基）超稳 Y沸石 DASY2.0 和 2.5Kg (干基）具有 MFI结构的沸石 ZSP-1的混合物， 与水打浆得 到的 lO.OKg浆液， 搅拌均匀， 得到固含量为 24.3重量％的浆液， 在 250 下， 将得到的浆液喷雾干燥成型为直径为 20 ~ 150微米的颗粒， 于 600°C下焙烧 1小时， 得到催化剂 C8。 C8的組成见表 2。 实施例 19
在 15.6Kg脱阳离子水中， 加入 3.5Kg 多水高岭土打浆， 再加入 4.0Kg拟薄水铝石， 用盐酸将其 pH调至 4， 搅拌均匀， 在 60Ό下静 置老化 1小时， 加入 4.7Kg铝溶胶（老化前后加入的耐热无机氧化物 或其前身物的重量比为 1: 0.4 ) ， 搅拌均匀， 加入 0.5Kg (干基） 的 改性 β沸石 B8、 0.5Kg (干基）超稳 Y沸石 DASY6.0和 3.0Kg (干 基）具有 MFI结构的沸石 ZRP-5的混合物， 与水打浆得到的 11.4Kg 浆液， 搅拌均匀， 得到固含量为 25.5重量％的浆液， 在 220°C下， 将 得到的浆液喷雾干燥成型为直径为 20 ~ 150微米的颗粒， 550°C焙烧 2 小时， 得到催化剂 C9。 C9的组成见表 2。 实施例 20
在 12.0Kg脱阳离子水中， 加入 3.2Kg拟薄水铝石打浆， 用盐酸 将其 pH调至 3，搅拌均匀，在 55Ό下静置老化 6小时，再加入 21.9Kg 硅溶胶， 和 2.3Kg铝溶胶（老化前后加入的耐热无机氧化物或其前身 物的重量比为 1: 2 ) ， 搅拌均匀， 加入 l.OKg (干基） 改性 β沸石 B9 和 3.0Kg (干基）具有 MFI结构的沸石 ZRP-5 的混合物， 与水打浆 得到的 11.4Kg浆液， 搅拌均匀， 得到固含量为 19.7重量％的浆液， 在 250°C下， 将得到的浆液喷雾干燥成型为直径为 20 ~ 150微米的颗 粒， 于 550Ό下焙烧 2小时， 得到催化剂 C10。 C10的组成见表 2。 实例编号 实施例 15 实施例 16 实施例 17 实施例 18 实施例 19 实施例 20 催化剂 C5 C6 C7 C8 C.9 C10 粘土：
种类 高岭土 高岭土 +蒙脱土 多水高岭土 多水髙岭土 多水高呤土 - 舍量， 重量％ 30 40 30 35 25
耐热无机氧化物：
种类 氧化铝 氣化铝 氣化铝 氧化铝 氧化铝 氧化铝 +氧化硅 含量， 重量％ 30 25 30 30 35 60 大孔沸石：
种类 USY EHY DASY0.0 DASY2.0 DASY6.0 - 含量， 重量％ 25 5 10 8 5
具有 ΜΠ结构的沸石：
种类 Z P-1 Z P-1 ZSP-] ZSP-1 ZRP-5 ZKP-S 含量， 重量％ 10 10 20 25 30 30
|3沸石：
种类 B5 B6 B7 B8
含量， 重量％ 20 10 2 5
改性元素种类及 P205, 5.4 P205, 4.3 Ρ205' 3.8 P205, 1.5
舍量， 重量％ Co203, 9.6 NiO, 1.8 Mn203, 6 L6ZnO, 1.6
实施例 21 ~ 24
Q C O
实施例 21 ~ 24说明本发明提供的烃类转化催化剂的催化性能。 将催化剂 C1 ~ C4在 800 , 用 100 %水蒸汽老化 14小时， 使用 小型固定流化床反应装置， 反应器中催化剂的装量为 180克， 在反应 温度为 560°C， 剂油重量比为 10, 重时空速为 4小时 -1的条件下， 通 入减压瓦斯油和水蒸汽的混合物 （水蒸汽的量为减压瓦斯油的 25 重 量％ )分别评价老化后的催化剂， 减压瓦斯油的性质见表 3， 评价结 果见表 4 对比例 3-4
对比例 3-4说明参比催化剂的催化性能。
按实施例 21 的方法使用相同的原料油分别评价参比催化剂 CB1 和 CB2， 结果见表 4 表 3
原料油名称 减压瓦斯油 常压渣油 密度 (20 Ό)，克 /厘米 3 0.8764 0.8906 粘度 (80°C)，亳米 2/秒 12.06 24.84 沥青质，重量％ - 0.8 康氏残炭，重量％ 0.93 4.3 馏程,。 C
IBP 246 282
10体积 % 430 370
30体积％ 482 482
50体积％ 519 553
70体积％ 573 ( 75.2体积％ ) -
90体积％ 一
FBP - -
表 4
Figure imgf000024_0001
表 4 的结果说明， 与在相同条件下老化且沸石含量相同、 但该沸 石未经改性的参比催化剂 CB1相比， 本发明提供的烃类转化催化剂的 重油裂化能力提高 1.3 ~ 2个百分点， 液化气产率提高 0.6 ~ 2.1个百分 点， 低碳烯烃 （C2= +C3= +C4 = ) 的产率提高 1~2个百分点； 与不含 β沸石的参比催化剂 CB2相比， 本发明提供的催化剂的重油裂化能力 提高 1.9~2.6个百分点， 液化气产率提高 1·0~2.5个百分点， 低碳烯 烃 （C2= +C3 = +C4 = ) 的产率提高 1.8 ~ 2.8个百分点。 实施例 25 - 30
实施例 25~30说明本发明提供的烃类转化催化剂在不同反应条 件下的催化性能。
将催化剂 C5~C10在 800C， 用 100%水蒸汽老化 17 小时， 使 用小型固定流化床反应装置， 反应器中催化剂的装量为 180克， 通入 常压渣油分别评价老化后的催化剂， 常压渣油的性质见表 3, 反应条 件和产品分布见表 5。 表 5
实 施 实 施 实 施 实 施 实 施 实 施 实施例编号
例 25 例 26 例 27 例 28 例 29 例 30 催化剂 C5 C6 C7 C8 C9 C10 反应温度， °c 520 520 580 580 620 620 剂油重量比 10 10 10 10 10 10 重时空速， 小时' 1 10 10 15 15 20 20 水蒸汽的量为常压渣油
12.5 12.5 25 25 37.5 37.5 的重量百分数， 重量％
转化率 79.5 78.9 85.6 83.4 86.5 86.6 产品分布， 重量％
干气 5.6 5.5 10.3 9.8 12.7 12.6 液化气 21.9 21.8 39.8 40.7 43.2 42.5 汽油 43.4 43.1 23.3 22.4 18.3 18.1 柴油 14.0 14.1 9.9 10.3 8.6 8.6 重油 6.5 7.0 4.5 6.3 4.9 4.8 焦炭 8.6 8.5 12.2 10.5 12.3 13.4 其中， 乙烯 1.5 1.4 5.2 5.1 6.8 6.8 其中， 丙稀 6.5 6.7 13.5 16.7 21.6 21.1 其中， 丁烯 6.2 7.0 12.8 12.5 14.3 14.6

Claims

权 利 要 求
1. 一种烃类转化催化剂， 以该烃类转化催化剂的总量为基准， 其含有 1-60重量％的沸石混合物、 5~99 重量％的耐热无机氧化物 和 0~70重量％的粘土， 其特征在于， 以所述沸石混合物的总量计， 所述沸石混合物中含有 1~75 重量％的由磷和过渡金属 M 改性的 β 沸石、 25~99重量％的具有 MFI结构的沸石和 0~74重量％的大孔 沸石， 其中， 所述由磷和过渡金属 Μ 改性的 β 沸石的无水化学表达 式以氧化物所占的质量百分率表示时为： （0~0.3) Na20- (0.5-10) Α1203· ( 1.3 ~ 10 ) Ρ205· ( 0.7 ~ 15 ) MxOy- ( 64 ~ 97 ) Si02, 其中， 所 述过渡金属 M选自 Fe、 Co、 Ni Cu、 Mn、 Zn和 Sn中的一种或几 种， x表示所述过渡金属 M的原子数， y表示满足所述过渡金属 M氧 化态所需的一个数。
2. 按照权利要求 1 的烃类转化催化剂， 其特征在于以所述烃类 转化催化剂的总量为基准， 所述催化剂含有 10~50 重量％的所述沸 石混合物、 10 - 70重量％的所述耐热无机氧化物和 0 ~ 60重量％的所 述粘土。
3. 按照权利要求 1 的烃类转化催化剂， 其特征在于所述的由磷 和过渡金属 M改性的 β沸石的无水化学表达式为：（ 0 ~ 0.2 )Na20-( 1 - 9 ) Α1203· (1.5-7) P2Os- ( 0.9 - 10 ) MxOy- ( 75 ~ 95 ) Si02。
4. 按照权利要求 3 的烃类转化催化剂， 其特征在于所述的由磷 和过渡金属 M改性的 β沸石的无水化学表达式为：（ 0 ~ 0.2 )Na20 1 ~ 9 ) Α1203· (2-5) Ρ205· (1-3) MxOy- ( 82 ~ 95 ) Si02。
5. 按照权利要求 1 的烃类转化催化剂， 其特征在于所述的过渡 金属 M选自 Fe、 Co, Ni和 Cu中的一种或几种。
6. 按照权利要求 5 的烃类转化催化剂， 其特征在于所述的过渡 金属 M选自 Fe和 /或 CuQ
7. 按照权利要求 1的烃类转化催化剂， 其特征在于所述具有 MFI 结构的沸石选自 ZSM-5和 ZRP系列沸石中的一种或几种。
8. 按照权利要求 7的烃类转化催化剂， 其特征在于所述具有 MFI 结构的沸石选自含稀土的 ZRP沸石、 含磷的 ZRP沸石、 含磷和稀土 的 ZRP沸石、含磷和碱土金属的 ZRP沸石以及含磷和过渡金属的 ZSP 沸石中的一种或几种。
9. 按照权利要求 1 的烃类转化催化剂， 其特征在于所述大孔沸 石选自八面沸石、 L沸石、 β沸石、 Ω沸石、 丝光沸石和 ZSM-18沸 石中的一种或几种。
10. 按照权利要求 9 的烃类转化催化剂， 其特征在于所述大孔沸 石选自 Υ型沸石、 含碑和 /或稀土的 Υ型沸石、 超稳 Υ沸石以及含磷 和 /或稀土的超稳 Υ沸石中的一种或几种。
11. 按照权利要求 1 的烃类转化催化剂， 其特征在于所述粘土选 自高岭土、 多水高岭土、 蒙脱土、 硅藻土、 埃洛石、 皂石、 累托土、 海泡石、 凹凸棒石、 水滑石和膨润土中的一种或几种。
12. 按照权利要求 1 的烃类转化催化剂， 其特征在于所述粘土选 自高岭土、 多水高岭土和蒙脱土中的一种或几种。
PCT/CN2006/002559 2006-08-31 2006-09-28 A catalyst for converting hydrocarbons Ceased WO2008034299A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2009525892A JP5139433B2 (ja) 2006-08-31 2006-09-28 炭化水素転換触媒
EP06791146.1A EP2075068B1 (en) 2006-08-31 2006-09-28 A catalyst for converting hydrocarbons
CA2662077A CA2662077C (en) 2006-08-31 2006-09-28 A hydrocarbon conversion catalyst
KR1020097006562A KR101359594B1 (ko) 2006-08-31 2006-09-28 탄화수소 전환용 촉매
BRPI0621984A BRPI0621984B1 (pt) 2006-08-31 2006-09-28 catalisador para conversão de hidrocarboneto
US12/439,315 US8716163B2 (en) 2006-08-31 2006-09-28 Hydrocarbon conversion catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200610112734.4 2006-08-31
CN2006101127344A CN101134172B (zh) 2006-08-31 2006-08-31 一种烃类转化催化剂

Publications (1)

Publication Number Publication Date
WO2008034299A1 true WO2008034299A1 (en) 2008-03-27

Family

ID=39158620

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2006/002559 Ceased WO2008034299A1 (en) 2006-08-31 2006-09-28 A catalyst for converting hydrocarbons

Country Status (10)

Country Link
US (1) US8716163B2 (zh)
EP (1) EP2075068B1 (zh)
JP (1) JP5139433B2 (zh)
KR (1) KR101359594B1 (zh)
CN (1) CN101134172B (zh)
BR (1) BRPI0621984B1 (zh)
CA (1) CA2662077C (zh)
RU (1) RU2409422C2 (zh)
TW (1) TWI308589B (zh)
WO (1) WO2008034299A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010167349A (ja) * 2009-01-21 2010-08-05 Uop Llc 軽質オレフィン製造のためのｆｃｃ触媒
WO2010133643A3 (en) * 2009-05-19 2011-07-14 Shell Internationale Research Maatschappij B.V. Process for the manufacture of a formulated oxygenate conversion catalyst, formulated oxygenate conversion catalyst and process for the preparation of an olefinic product
CN101767029B (zh) * 2008-12-31 2012-06-27 中国石油化工股份有限公司 一种重油裂化催化剂及其应用
CN101773845B (zh) * 2009-01-08 2012-08-01 中国石油化工股份有限公司 一种重油裂化催化剂及其制备和应用方法
CN103007992A (zh) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 一种提高低碳烯烃浓度的裂化助剂
US9227181B2 (en) 2011-09-13 2016-01-05 Basf Corporation Catalyst to increase propylene yields from a fluid catalytic cracking unit

Families Citing this family (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009092282A1 (zh) * 2008-01-09 2009-07-30 China Petroleum & Chemical Corporation 含酸劣质原油转化催化剂及其制备方法和应用
EP2082801A1 (en) * 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Process for obtaining modified molecular sieves
US9079162B2 (en) 2008-04-28 2015-07-14 BASF SE Ludwigshafen Fe-BEA/Fe-MFI mixed zeolite catalyst and process for the treatment of NOX in gas streams
RU2548362C2 (ru) 2009-06-25 2015-04-20 Чайна Петролеум & Кемикал Корпорейшн Катализатор каталитического крекинга и способ повышения селективности катализатора(варианты)
CN101927198B (zh) * 2009-06-25 2013-06-05 中国石油化工股份有限公司 一种改善催化裂化催化剂选择性的处理方法
JP5152925B2 (ja) * 2009-09-24 2013-02-27 一般財団法人石油エネルギー技術センター 炭化水素油の接触分解触媒、炭化水素油の接触分解触媒の製造方法および炭化水素油の接触分解方法
BR112012025744A2 (pt) * 2010-04-08 2016-06-28 Basf Se catalisador, sistema de tratamento de gás de escape, e, processo para o tratamento de uma corrente de gás
CN102019200B (zh) * 2010-04-13 2013-01-16 卓润生 一种高活性的催化热裂解催化剂及其制备方法
KR101852143B1 (ko) * 2010-05-21 2018-04-25 피큐 코포레이션 ＮＯｘ 환원을 위한 신규한 금속―함유 제올라이트 베타
CN102452669B (zh) * 2010-10-22 2013-04-24 中国石油化工股份有限公司 一种含磷和过渡金属的mfi结构分子筛及其制备方法
BR112014007168B1 (pt) * 2011-10-12 2024-02-15 Indian Oil Corporation Ltd Processo para melhorar a tolerância ao níquel de catalisadores de craqueamento de hidrocarbonetos pesados
WO2013059164A2 (en) 2011-10-17 2013-04-25 Exxonmobil Research And Engineering Company Selective dehydration of alcohols to dialkylethers and integrated alcohol-to-gasoline processes
US8940652B2 (en) * 2011-11-04 2015-01-27 Basf Corporation Phosphorus modified cracking catalysts with enhanced activity and hydrothermal stability
JP2015516867A (ja) * 2012-03-16 2015-06-18 トリッシュラー、クリスツィアンＴＲＩＳＣＨＬＥＲ，Ｃｈｒｉｓｔｉａｎ 触媒、触媒の調製方法、ならびにオレフィン調製のための方法および装置における触媒の使用
RU2612973C2 (ru) * 2012-09-13 2017-03-14 Басф Корпорейшн Новый катализатор для увеличения выхода пропилена из установки крекинга с псевдоожиженным катализатором
JP5925100B2 (ja) * 2012-10-03 2016-05-25 本田技研工業株式会社 ポリプロピレン組成物の製造方法
CN103785460B (zh) * 2012-10-26 2016-01-20 中国石油化工股份有限公司 一种催化裂解催化剂及其制备方法
CN103785459B (zh) * 2012-10-26 2016-01-20 中国石油化工股份有限公司 一种催化裂解催化剂及其制备方法
KR20140080661A (ko) * 2012-12-13 2014-07-01 재단법인 포항산업과학연구원 고발열량의 합성천연가스 제조장치 및 그 제조방법
CA2893459C (en) * 2012-12-21 2021-03-16 Albemarle Europe Sprl Modified y-zeolite/zsm-5 catalyst for increased propylene production
JP5911446B2 (ja) * 2013-03-22 2016-04-27 コスモ石油株式会社 炭化水素油の接触分解触媒の製造方法
GB2521516B (en) * 2013-10-22 2021-04-21 China Petroleum & Chem Corp A metal modified Y zeolite, its preparation and use
JP6383636B2 (ja) * 2013-10-22 2018-08-29 中国石油化工股▲ふん▼有限公司 金属修飾されたｙ型ゼオライト、その製法およびその使用
CN104588054B (zh) * 2013-10-31 2017-06-30 中国石油化工股份有限公司 一种含磷和稀土的介孔催化材料
CN103537289B (zh) * 2013-11-07 2015-09-23 盐城工学院 一种低温scr脱硝催化剂制备方法
US9796932B2 (en) * 2013-12-19 2017-10-24 Basf Corporation FCC catalyst compositions containing boron oxide and phosphorus
KR101595826B1 (ko) * 2014-05-08 2016-02-22 한국화학연구원 함산소화물로부터 프로필렌 제조용 제올라이트 촉매 및 이의 제조방법
US9233360B1 (en) * 2014-09-10 2016-01-12 Chevron U.S.A. Inc. Stable support for Fischer-Tropsch catalyst
CN106140277B (zh) * 2015-04-16 2018-09-28 中国石油化工股份有限公司 一种改性β沸石及其制备方法
RU2586280C1 (ru) * 2015-04-23 2016-06-10 Федеральное государственное бюджетное научное учреждение "Научный центр проблем здоровья семьи и репродукции человека" Способ комплексной терапии функциональных нарушений пищеварения у детей дошкольного возраста
EP3135373A1 (en) * 2015-08-24 2017-03-01 INDIAN OIL CORPORATION Ltd. Preparation and composition of a fluid catalytic cracking catalyst additive with lower phosphate content for enhanced lpg yield
CN106607075B (zh) * 2015-10-21 2019-06-11 中国石油化工股份有限公司 制备烯烃与芳烃的流化床催化剂及应用
CN107974282B (zh) * 2016-10-21 2020-09-22 中国石油化工股份有限公司 一种生产低碳烯烃和轻芳烃的催化裂解方法
CN107974285B (zh) * 2016-10-21 2020-09-22 中国石油化工股份有限公司 一种生产低碳烯烃和轻芳烃的催化裂解方法
US10526546B2 (en) 2017-02-23 2020-01-07 Saudi Arabian Oil Company Systems and methods for cracking hydrocarbon streams utilizing cracking catalysts
US10494574B2 (en) * 2017-02-23 2019-12-03 Saudi Arabian Oil Company Systems and methods for cracking hydrocarbon streams such as crude oils utilizing catalysts which include zeolite mixtures
CN109701460B (zh) * 2017-10-26 2021-11-16 中国石油化工股份有限公司 加氢裂化催化剂在线循环再生的方法和系统
CN109701624B (zh) * 2017-10-26 2022-02-08 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法和重质原料油加氢裂化的方法
CN109701519B (zh) * 2017-10-26 2022-02-08 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法和重质原料油加氢裂化的方法
US10889768B2 (en) * 2018-01-25 2021-01-12 Saudi Arabian Oil Company High severity fluidized catalytic cracking systems and processes for producing olefins from petroleum feeds
CN108479846B (zh) * 2018-02-08 2019-12-31 中国石油大学(北京) 一种芳构化催化剂及其制备方法和再生方法及芳构化方法
CN108906117A (zh) * 2018-07-06 2018-11-30 郑州三希新材料科技有限公司 一种新型可视变色的空气净化材料及其制备方法
CN111097507B (zh) * 2018-10-26 2023-01-13 中国石油化工股份有限公司 催化剂及其制备方法和应用及含硫轻质原料油吸附脱硫和烃类转化的方法
US10899971B2 (en) * 2019-02-13 2021-01-26 Exxonmobil Research And Engineering Company Stabilization of zeolite beta for FCC processes
CN110075911A (zh) * 2019-05-20 2019-08-02 南京工业大学 一种用于c10+重质芳烃加氢脱烷基的催化剂及其制备方法
CN110479361A (zh) * 2019-09-03 2019-11-22 四川润和催化新材料股份有限公司 一种降油浆和多产低碳烯烃的助剂及其制备方法与应用
MX2022006890A (es) * 2019-12-09 2022-07-11 Coolbrook Oy Integracion de calor en una instalacion de procesamiento de hidrocarburos.
US11225612B2 (en) 2020-03-27 2022-01-18 Saudi Arabian Oil Company Catalyst and process for catalytic steam cracking of heavy distillate
RU2740476C1 (ru) * 2020-04-30 2021-01-14 Федеральное государственное бюджетное образовательное учреждение высшего образования «Московский государственный университет имени М.В.Ломоносова» (МГУ) Способ получения титано-алюмо-силикатного цеолита типа zsm-12
CN113797962B (zh) * 2020-06-17 2023-01-13 中国石油化工股份有限公司 一种催化裂化助剂及其制备方法和应用
CN114425376B (zh) * 2020-09-27 2024-03-12 中国石油化工股份有限公司 一种含mfi沸石的烃类转化催化剂及其制备方法
CN113070095B (zh) * 2021-04-09 2023-03-28 陕西延长石油（集团）有限责任公司 一种轻烃催化裂解制低碳烯烃催化剂及其制备方法
US11827521B2 (en) 2021-12-14 2023-11-28 Industrial Technology Research Institute Method for selectively chemically reducing CO2 to form CO
US20240416329A1 (en) * 2023-06-14 2024-12-19 Saudi Arabian Oil Company Methods of forming zeolite compositions and catalyst compositions
WO2025061791A1 (en) 2023-09-18 2025-03-27 Basf Se Method and system for providing a catalyst composition

Citations (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3541179A (en) 1966-11-10 1970-11-17 Japan Gasoline Process for manufacturing olefins by catalytic partial oxidation of hydrocarbons
US3647682A (en) 1968-10-23 1972-03-07 Union Carbide Corp Olefin production by the catalytic treatment of hydrocarbons
US3725495A (en) 1969-12-23 1973-04-03 Toksoe H Catalytic steam cracking of hydrocarbons and catalysts therefor
US3758403A (en) 1970-10-06 1973-09-11 Mobil Oil Olites catalytic cracking of hydrocarbons with mixture of zsm-5 and other ze
US3839485A (en) 1969-12-23 1974-10-01 Haldor Topsoe As Catalytic steam cracking of hydrocarbons and catalysts therefor
SU550173A1 (ru) 1975-06-10 1977-03-15 Предприятие П/Я Р-6830 Способ приготовлени катализатора дл пиролиза углеводородного сырь
SU559946A1 (ru) 1975-06-10 1977-05-30 Предприятие П/Я Р-6830 Способ получени непредельных углеводородов
DD225135A1 (de) 1984-06-25 1985-07-24 Adw Ddr Verfahren zur thermokatalytischen spaltung von kohlenwasserstoffen
SU1214726A1 (ru) 1984-11-01 1986-02-28 Институт неорганической и физической химии АН АзССР Способ получени низкомолекул рных олефинов
CN1043520A (zh) 1988-12-21 1990-07-04 中国石油化工总公司石油化工科学研究院 一种生产低碳烯烃的裂解催化剂
US5006497A (en) 1988-12-30 1991-04-09 Mobil Oil Corporation Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products
CN1052290A (zh) 1989-11-30 1991-06-19 中国石油化工总公司石油化工科学研究院 含稀土的五元环结构高硅沸石及合成
US5055176A (en) 1988-12-30 1991-10-08 Mobil Oil Corporation Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products
CN1057408A (zh) 1990-06-20 1992-01-01 中国石油化工总公司石油化工科学研究院 含高硅沸石的裂解催化剂
CN1058382A (zh) 1990-07-23 1992-02-05 中国石油化工总公司石油化工科学研究院 含稀土五元环结构高硅沸石的制备方法
US5232579A (en) * 1991-06-14 1993-08-03 Mobil Oil Corporation Catalytic cracking process utilizing a zeolite beta catalyst synthesized with a chelating agent
US5232675A (en) 1991-02-28 1993-08-03 Research Institute Of Petroleum Processing Rare earth-containing high-silica zeolite having penta-sil type structure and process for the same
US5236880A (en) 1989-12-11 1993-08-17 W. R. Grace & Co.-Conn. Catalyst for cracking of paraffinic feedstocks
CN1085825A (zh) 1992-10-22 1994-04-27 中国石油化工总公司 制取高质量汽油、丙烯、丁烯的烃转化催化剂
CN1093101A (zh) 1993-03-29 1994-10-05 中国石油化工总公司 制取低碳烯烃的裂解催化剂
CN1026242C (zh) 1991-11-05 1994-10-19 中国石油化工总公司 制取高质量汽油和烯烃的烃转化催化剂
CN1099788A (zh) 1993-08-28 1995-03-08 中国石油化工总公司石油化工科学研究院 多产烯烃的裂化催化剂
CN1103105A (zh) 1993-11-23 1995-05-31 中国石油化工总公司石油化工科学研究院 一种多产异丁烯和异戊烯的裂化催化剂
CN1114916A (zh) 1994-07-15 1996-01-17 中国石油化工总公司 制取低碳烯烃的多沸石催化剂
CN1117518A (zh) 1994-08-22 1996-02-28 中国石油化工总公司 制取低碳烯烃的双沸石催化剂
CN1143666A (zh) 1996-02-08 1997-02-26 中国石油化工总公司 多产异构烯烃及汽油的裂化催化剂
CN1145396A (zh) 1995-08-28 1997-03-19 中国石油化工总公司 一种多产异丁烯和异戊烯的裂化催化剂
CN1147420A (zh) 1995-10-06 1997-04-16 中国石油化工总公司 具有mfi结构含磷和稀土的分子筛
CN1205307A (zh) 1998-07-13 1999-01-20 徐邦舜 氯化钡、碳酸镁联合生产方法
CN1211470A (zh) 1997-09-17 1999-03-24 中国石油化工总公司 多产乙烯和丙烯的五元环分子筛组合物
CN1211469A (zh) 1997-09-17 1999-03-24 中国石油化工总公司 一种五元环分子筛组合物的制备方法
US5905051A (en) * 1997-06-04 1999-05-18 Wu; An-Hsiang Hydrotreating catalyst composition and processes therefor and therewith
CN1221015A (zh) 1997-12-23 1999-06-30 中国石油化工总公司 重油催化热裂解层柱粘土催化剂及其制备
CN1222558A (zh) 1997-10-15 1999-07-14 中国石油化工集团公司 催化热裂解制取低碳烯烃催化剂
US6080698A (en) 1997-09-17 2000-06-27 China Petrochemical Corporation Pentasil-type molecular sieve containing composition and its preparation method
US6211104B1 (en) 1997-10-15 2001-04-03 China Petrochemical Corporation Catalyst for catalytic pyrolysis process for the production of light olefins and the preparation thereof
CN1354224A (zh) 2000-11-17 2002-06-19 中国石油化工股份有限公司 生产富含异构烷烃汽油、丙烯及异丁烷的催化裂化催化剂
US6566293B1 (en) 1999-11-22 2003-05-20 Akzo Nobel N.V. Catalyst composition with high efficiency for the production of light olefins
CN1465527A (zh) 2002-06-27 2004-01-07 中国石油化工股份有限公司 一种含磷和过渡金属的mfi结构分子筛
CN1504541A (zh) 2002-12-03 2004-06-16 中国科学院大连化学物理研究所 烃类催化裂解制烯烃并联产芳烃催化剂及制法和应用
CN1504540A (zh) 2002-11-29 2004-06-16 中国石油化工股份有限公司 一种石油烃裂解制取低碳烯烃的催化剂
CN1566275A (zh) 2003-06-30 2005-01-19 中国石油化工股份有限公司 一种含分子筛的烃类裂化催化剂及其制备方法
US20050070422A1 (en) 2003-09-25 2005-03-31 Tan-Jen Chen Multi component catalyst and its use in catalytic cracking
CN1611299A (zh) 2003-10-31 2005-05-04 中国石油化工股份有限公司 一种含磷和金属组分的mfi结构分子筛及其应用

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514179A (en) * 1966-09-12 1970-05-26 Bell & Howell Co Stabilized optical system and method of stabilizing images
DE2251635A1 (de) 1972-10-20 1974-05-02 Saunders Roller Box Tool Co Lt Werkzeugtraeger mit rollenabstuetzung
GB8820358D0 (en) * 1988-08-26 1988-09-28 Shell Int Research Process for catalytic cracking of hydrocarbon feedstock
US5194412A (en) 1991-01-22 1993-03-16 W. R. Grace & Co.-Conn. Catalytic compositions
AU652222B2 (en) 1991-03-12 1994-08-18 Mobil Oil Corporation Preparation of cracking catalysts, and cracking process using them
US5126298A (en) * 1991-03-12 1992-06-30 Mobil Oil Corp. Cracking catalysts comprising clays with different particle sizes, and method of preparing and using the same
AU642817B2 (en) 1991-06-14 1993-10-28 Mobil Oil Corporation A method of synthesizing zeolite beta
US5380590A (en) * 1992-09-16 1995-01-10 Teijin Limited Water-dispersible aromatic polyester, aqueous dispersion thereof and polyester film coated therewith which permits fast adhesion
AU683486B2 (en) * 1993-07-16 1997-11-13 Mobil Oil Corporation Catalyst system and process for catalytic cracking
CN1034586C (zh) * 1993-11-05 1997-04-16 中国石油化工总公司 多产低碳烯烃的催化转化方法
US5387723A (en) * 1994-01-12 1995-02-07 Texaco Chemical Inc. One-step synthesis of methyl t-butyl ether from t-butanol using β-zeolite catalysts modified with lithium plus rare earths
US5853566A (en) * 1995-11-28 1998-12-29 Shell Oil Company Zeolite-beta containing catalyst compositions and their use in hydrocarbon conversion processes for producing low boiling point materials
CN1059133C (zh) 1997-03-24 2000-12-06 中国石油化工总公司 具有mfi结构的含磷分子筛
US6210562B1 (en) * 1997-10-15 2001-04-03 China Petrochemical Corporation Process for production of ethylene and propylene by catalytic pyrolysis of heavy hydrocarbons
DE69910885T2 (de) * 1998-05-06 2004-05-19 Institut Français du Pétrole, Rueil-Malmaison Katalysator auf Basis von Beta-Zeolith mit Promotorelement und Verfahren zum Hydrocracken
CA2332299C (en) 1998-05-15 2008-01-29 Bulldog Technologies U.S.A., Inc. Alkaline phosphate-activated clay/zeolite catalysts
US7084087B2 (en) * 1999-09-07 2006-08-01 Abb Lummus Global Inc. Zeolite composite, method for making and catalytic application thereof
US6726834B2 (en) 1999-10-22 2004-04-27 Intevep, S.A. Process for catalytic cracking of a hydrocarbon feed with a MFI aluminisilcate composition
JP3489048B2 (ja) * 2000-02-01 2004-01-19 日産自動車株式会社 排気ガス浄化用触媒
CN1108356C (zh) * 2000-10-26 2003-05-14 中国石油化工股份有限公司 一种高活性高中油性加氢裂化催化剂及其制备方法
US6538169B1 (en) * 2000-11-13 2003-03-25 Uop Llc FCC process with improved yield of light olefins
US20030204121A1 (en) * 2002-04-30 2003-10-30 Miller Stephen J. Process for aromatics alkylation employing zeolite beta prepared by the in-extrudate method
CA2506470C (en) * 2002-11-18 2010-10-26 Ict Co., Ltd. Exhaust gas purifying catalyst and method for purifying exhaust gas
US6791002B1 (en) * 2002-12-11 2004-09-14 Uop Llc Riser reactor system for hydrocarbon cracking
CN1261216C (zh) * 2003-05-30 2006-06-28 中国石油化工股份有限公司 一种含分子筛的烃类裂化催化剂及其制备方法
KR20060023175A (ko) * 2003-06-26 2006-03-13 할도르 토프쉐 에이/에스 탄화수소 전환 공정 및 촉매
CN1333044C (zh) * 2003-09-28 2007-08-22 中国石油化工股份有限公司 一种烃油裂化方法
RU2238298C1 (ru) * 2003-09-30 2004-10-20 Закрытое акционерное общество "Нефтехимия" Способ переработки углеводородного сырья и катализатор для его осуществления
WO2005094992A1 (fr) * 2004-03-31 2005-10-13 China Petroleum & Chemical Corporation Catalyseur contenant un zeolite pour la conversion d'hydrocarbures et son elaboration, et procede de conversion d'huile d'hydrocarbure avec ce catalyseur
TWI277648B (en) * 2004-07-29 2007-04-01 China Petrochemical Technology A cracking catalyst for hydrocarbons and its preparation
US20060040823A1 (en) * 2004-08-18 2006-02-23 Stockwell David M Catalyst for NOx and/or SOx control
US20060174231A1 (en) * 2005-01-31 2006-08-03 Dong Wei Method and an apparatus for using code written in a language that is not native to the computer system to invoke a procedure written in a programming language that is native to the computer system
CN100425534C (zh) * 2005-05-31 2008-10-15 中国石油化工股份有限公司 一种改性β沸石

Patent Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3541179A (en) 1966-11-10 1970-11-17 Japan Gasoline Process for manufacturing olefins by catalytic partial oxidation of hydrocarbons
US3647682A (en) 1968-10-23 1972-03-07 Union Carbide Corp Olefin production by the catalytic treatment of hydrocarbons
US3725495A (en) 1969-12-23 1973-04-03 Toksoe H Catalytic steam cracking of hydrocarbons and catalysts therefor
US3839485A (en) 1969-12-23 1974-10-01 Haldor Topsoe As Catalytic steam cracking of hydrocarbons and catalysts therefor
US3758403A (en) 1970-10-06 1973-09-11 Mobil Oil Olites catalytic cracking of hydrocarbons with mixture of zsm-5 and other ze
SU550173A1 (ru) 1975-06-10 1977-03-15 Предприятие П/Я Р-6830 Способ приготовлени катализатора дл пиролиза углеводородного сырь
SU559946A1 (ru) 1975-06-10 1977-05-30 Предприятие П/Я Р-6830 Способ получени непредельных углеводородов
DD225135A1 (de) 1984-06-25 1985-07-24 Adw Ddr Verfahren zur thermokatalytischen spaltung von kohlenwasserstoffen
SU1214726A1 (ru) 1984-11-01 1986-02-28 Институт неорганической и физической химии АН АзССР Способ получени низкомолекул рных олефинов
CN1043520A (zh) 1988-12-21 1990-07-04 中国石油化工总公司石油化工科学研究院 一种生产低碳烯烃的裂解催化剂
US5055176A (en) 1988-12-30 1991-10-08 Mobil Oil Corporation Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products
US5006497A (en) 1988-12-30 1991-04-09 Mobil Oil Corporation Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products
CN1052290A (zh) 1989-11-30 1991-06-19 中国石油化工总公司石油化工科学研究院 含稀土的五元环结构高硅沸石及合成
US5236880A (en) 1989-12-11 1993-08-17 W. R. Grace & Co.-Conn. Catalyst for cracking of paraffinic feedstocks
CN1057408A (zh) 1990-06-20 1992-01-01 中国石油化工总公司石油化工科学研究院 含高硅沸石的裂解催化剂
CN1058382A (zh) 1990-07-23 1992-02-05 中国石油化工总公司石油化工科学研究院 含稀土五元环结构高硅沸石的制备方法
US5232675A (en) 1991-02-28 1993-08-03 Research Institute Of Petroleum Processing Rare earth-containing high-silica zeolite having penta-sil type structure and process for the same
US5232579A (en) * 1991-06-14 1993-08-03 Mobil Oil Corporation Catalytic cracking process utilizing a zeolite beta catalyst synthesized with a chelating agent
CN1026242C (zh) 1991-11-05 1994-10-19 中国石油化工总公司 制取高质量汽油和烯烃的烃转化催化剂
CN1085825A (zh) 1992-10-22 1994-04-27 中国石油化工总公司 制取高质量汽油、丙烯、丁烯的烃转化催化剂
CN1093101A (zh) 1993-03-29 1994-10-05 中国石油化工总公司 制取低碳烯烃的裂解催化剂
US5380690A (en) 1993-03-29 1995-01-10 China Petro-Chemical Corporation Cracking catalyst for the production of light olefins
CN1099788A (zh) 1993-08-28 1995-03-08 中国石油化工总公司石油化工科学研究院 多产烯烃的裂化催化剂
CN1103105A (zh) 1993-11-23 1995-05-31 中国石油化工总公司石油化工科学研究院 一种多产异丁烯和异戊烯的裂化催化剂
CN1036320C (zh) * 1993-11-23 1997-11-05 中国石油化工总公司石油化工科学研究院 一种制备异丁烯和异戊烯的裂化催化剂
CN1114916A (zh) 1994-07-15 1996-01-17 中国石油化工总公司 制取低碳烯烃的多沸石催化剂
CN1117518A (zh) 1994-08-22 1996-02-28 中国石油化工总公司 制取低碳烯烃的双沸石催化剂
CN1145396A (zh) 1995-08-28 1997-03-19 中国石油化工总公司 一种多产异丁烯和异戊烯的裂化催化剂
CN1055105C (zh) * 1995-08-28 2000-08-02 中国石油化工总公司 一种多产异丁烯和异戊烯的裂化催化剂
CN1147420A (zh) 1995-10-06 1997-04-16 中国石油化工总公司 具有mfi结构含磷和稀土的分子筛
CN1143666A (zh) 1996-02-08 1997-02-26 中国石油化工总公司 多产异构烯烃及汽油的裂化催化剂
US5905051A (en) * 1997-06-04 1999-05-18 Wu; An-Hsiang Hydrotreating catalyst composition and processes therefor and therewith
US6080698A (en) 1997-09-17 2000-06-27 China Petrochemical Corporation Pentasil-type molecular sieve containing composition and its preparation method
CN1211469A (zh) 1997-09-17 1999-03-24 中国石油化工总公司 一种五元环分子筛组合物的制备方法
CN1211470A (zh) 1997-09-17 1999-03-24 中国石油化工总公司 多产乙烯和丙烯的五元环分子筛组合物
US6211104B1 (en) 1997-10-15 2001-04-03 China Petrochemical Corporation Catalyst for catalytic pyrolysis process for the production of light olefins and the preparation thereof
CN1222558A (zh) 1997-10-15 1999-07-14 中国石油化工集团公司 催化热裂解制取低碳烯烃催化剂
US6342153B1 (en) 1997-12-23 2002-01-29 China Petrochemical Corporation Pillared clay catalysts for heavy oil catalytic pyrolisis process and the preparation method thereof
CN1221015A (zh) 1997-12-23 1999-06-30 中国石油化工总公司 重油催化热裂解层柱粘土催化剂及其制备
CN1205307A (zh) 1998-07-13 1999-01-20 徐邦舜 氯化钡、碳酸镁联合生产方法
US6566293B1 (en) 1999-11-22 2003-05-20 Akzo Nobel N.V. Catalyst composition with high efficiency for the production of light olefins
CN1354224A (zh) 2000-11-17 2002-06-19 中国石油化工股份有限公司 生产富含异构烷烃汽油、丙烯及异丁烷的催化裂化催化剂
CN1465527A (zh) 2002-06-27 2004-01-07 中国石油化工股份有限公司 一种含磷和过渡金属的mfi结构分子筛
CN1504540A (zh) 2002-11-29 2004-06-16 中国石油化工股份有限公司 一种石油烃裂解制取低碳烯烃的催化剂
CN1504541A (zh) 2002-12-03 2004-06-16 中国科学院大连化学物理研究所 烃类催化裂解制烯烃并联产芳烃催化剂及制法和应用
CN1566275A (zh) 2003-06-30 2005-01-19 中国石油化工股份有限公司 一种含分子筛的烃类裂化催化剂及其制备方法
US20050070422A1 (en) 2003-09-25 2005-03-31 Tan-Jen Chen Multi component catalyst and its use in catalytic cracking
CN1611299A (zh) 2003-10-31 2005-05-04 中国石油化工股份有限公司 一种含磷和金属组分的mfi结构分子筛及其应用

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767029B (zh) * 2008-12-31 2012-06-27 中国石油化工股份有限公司 一种重油裂化催化剂及其应用
CN101773845B (zh) * 2009-01-08 2012-08-01 中国石油化工股份有限公司 一种重油裂化催化剂及其制备和应用方法
JP2010167349A (ja) * 2009-01-21 2010-08-05 Uop Llc 軽質オレフィン製造のためのｆｃｃ触媒
WO2010133643A3 (en) * 2009-05-19 2011-07-14 Shell Internationale Research Maatschappij B.V. Process for the manufacture of a formulated oxygenate conversion catalyst, formulated oxygenate conversion catalyst and process for the preparation of an olefinic product
CN102438749A (zh) * 2009-05-19 2012-05-02 国际壳牌研究有限公司 配制含氧化合物转化催化剂的制造方法、配制含氧化合物转化催化剂和制备烯烃产物的方法
US9227181B2 (en) 2011-09-13 2016-01-05 Basf Corporation Catalyst to increase propylene yields from a fluid catalytic cracking unit
CN103007992A (zh) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 一种提高低碳烯烃浓度的裂化助剂
CN103007992B (zh) * 2011-09-22 2015-04-29 中国石油化工股份有限公司 一种提高低碳烯烃浓度的裂化助剂

Also Published As

Publication number Publication date
US20090325786A1 (en) 2009-12-31
CN101134172B (zh) 2010-10-27
KR101359594B1 (ko) 2014-02-07
JP5139433B2 (ja) 2013-02-06
BRPI0621984B1 (pt) 2015-12-22
KR20090049616A (ko) 2009-05-18
JP2010501341A (ja) 2010-01-21
CA2662077A1 (en) 2008-03-27
CA2662077C (en) 2014-06-03
BRPI0621984A2 (pt) 2011-12-20
TWI308589B (en) 2009-04-11
RU2009110506A (ru) 2010-10-10
EP2075068B1 (en) 2018-02-28
CN101134172A (zh) 2008-03-05
RU2409422C2 (ru) 2011-01-20
EP2075068A1 (en) 2009-07-01
TW200815577A (en) 2008-04-01
EP2075068A4 (en) 2012-01-11
US8716163B2 (en) 2014-05-06

Similar Documents

Publication Publication Date Title
WO2008034299A1 (en) A catalyst for converting hydrocarbons
JP5221540B2 (ja) 炭化水素を触媒転換するための方法
CA2563262C (en) A zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst
JP3927704B2 (ja) 軽質オレフィンの生産のための接触式熱分解プロセスのための触媒およびその調製
TWI647011B (zh) 含磷ｆｃｃ觸媒
US20100311569A1 (en) Catalyst and a method for cracking hydrocarbons
WO2006128374A1 (fr) Zeolites bêta modifiees
WO2022063290A1 (zh) 一种含mfi沸石的烃类转化催化剂及其制备方法
WO2018026313A1 (ru) Способ приготовления катализатора крекинга с щелочноземельными элементами
CN104946301B (zh) 一种提高低碳烯烃浓度的催化转化方法
RU2372142C2 (ru) Цеолитсодержащий катализатор конверсии углеводородов, способ его приготовления и способ превращения углеводородных нефтепродуктов с использованием этого катализатора
CN1323136C (zh) 一种烃油转化方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06791146

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2662077

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2009525892

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006791146

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 581/MUMNP/2009

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1020097006562

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2009110506

Country of ref document: RU

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12439315

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0621984

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20090227