[go: up one dir, main page]

WO2007019797A1 - Fludized bed catalyst for catalytic pyrolyzing - Google Patents

Fludized bed catalyst for catalytic pyrolyzing Download PDF

Info

Publication number
WO2007019797A1
WO2007019797A1 PCT/CN2006/002072 CN2006002072W WO2007019797A1 WO 2007019797 A1 WO2007019797 A1 WO 2007019797A1 CN 2006002072 W CN2006002072 W CN 2006002072W WO 2007019797 A1 WO2007019797 A1 WO 2007019797A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
molecular sieve
fluidized bed
catalytic cracking
zeolite
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/CN2006/002072
Other languages
English (en)
French (fr)
Inventor
Zaiku Xie
Guangwei Ma
Weimin Yang
Hui Yao
Jingxian Xiao
Liang Chen
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.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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 China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to KR1020087006339A priority Critical patent/KR101347189B1/ko
Priority to US12/063,598 priority patent/US20090288990A1/en
Publication of WO2007019797A1 publication Critical patent/WO2007019797A1/zh
Anticipated expiration legal-status Critical
Priority to US12/978,107 priority patent/US9480975B2/en
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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—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
    • B01J29/72—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
    • B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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

  • the present invention relates to a catalytic cracking fluidized bed catalyst, and more particularly to a fluidized bed catalyst for catalytic cracking of naphtha to ethylene propylene.
  • the most important method for producing ethylene propylene is steam pyrolysis.
  • the most used raw material is naphtha.
  • steam pyrolysis naphtha has the disadvantages of high reaction temperature, harsh process conditions, high requirements on equipment, especially furnace tube materials, and large loss.
  • catalytic cracking is the most attractive and most promising one.
  • the goal is to find a suitable cracking catalyst, to increase the selectivity of ethylene propylene, to lower the reaction temperature, and to have a certain flexibility in the yield of ethylene propylene.
  • U.S. Patent No. 6,221,104 and domestic patent CN1504540A use a weight of 10 - 70. /. Clay, 5 ⁇ 85 wt% inorganic oxide, 1 ⁇ 50 wt% molecular sieve catalyst, shows a good conversion to light olefins, especially ethylene, for various steam pyrolysis materials.
  • the molecular sieve used is a zeolite with a high silicon to aluminum ratio of 0 to 25 wt% or a ZSM molecular sieve having an MFI structure, which is impregnated with phosphorus/Al, Mg or Ca, and is basically a simple molecular sieve catalyst.
  • oxides are used as catalysts.
  • Ernie's Italian patent CN1317546A relates Chelmsford chemical reactor steam cracking catalyst is the 12CaO'7Al 2 0 3.
  • the raw material can be used with naphtha, operating temperature 720 ⁇ 800 * C, at 1.1 ⁇ 1 ⁇ 8 atmospheres, contact time 0.07 ⁇ 0.2 seconds, ethylene
  • the yield of propylene and propylene can reach 43%.
  • Chinese patent CN1480255A describes an oxide catalyst which uses naphtha as a raw material to catalytically crack ethylene propylene at 780, and the ethylene + propylene yield can reach 47%.
  • molecular sieves have received much attention as the main cracking catalyst, but examples of mixing with oxides have not been reported.
  • the technical problem to be solved by the present invention is that the prior art catalytic cracking process produces ethylene propylene oxime with high reaction temperature, low catalyst low temperature activity and poor selectivity, and provides a new catalytic cracking fluidized bed catalyst.
  • the use of the catalyst to catalytically crack naphtha to ethylene propionate not only lowers the catalytic cracking temperature, but also improves the selectivity of the catalyst.
  • a catalytic cracking fluidized bed catalyst comprising a carrier selected from at least one of Si0 2 , A1 2 O 3 , molecular sieves and composite molecular sieves and in atomic ratio
  • A is selected from at least one of rare earth elements
  • B is selected from at least one of pre-, ⁇ , ⁇ , VHB, VIB, I A and ⁇ A; a has a value ranging from 0.01 to 0.5;
  • the value of b ranges from 0.01 to 0.5;
  • c ranges from 0.01 to 0.5
  • X is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst
  • the molecular sieve is at least one selected from the group consisting of ZSM-5, Y zeolite, ⁇ zeolite, MCM-22, SAPO-34 and mordenite, and the composite molecular sieve is ZSM- 5 , Y zeolite, P zeolite, MCM-22, SAPO-34. Or a composite in which at least two molecular sieves in the mordenite are co-grown;
  • the molecular sieve in the catalyst is used in an amount of from 0 to 60% by weight of the catalyst.
  • the value of a is preferably in the range of 0.01 to 0.3; the value of b is preferably in the range of 0.01 to 0.3; and the value of c is preferably in the range of 0 ⁇ 01 to 0 ⁇ 3 .
  • Preferred side of rare earth elements The case is at least one selected from the group consisting of La and Ce.
  • a preferred embodiment of the cyclo element is at least one selected from the group consisting of Fe, Co and Ni; a preferred embodiment of the IB element is at least one selected from the group consisting of Cu and Ag; a preferred embodiment of the lanthanum element is Zn; a preferred embodiment of the VHB element A preferred embodiment of the Mn; VIB element is selected from the group consisting of Cr, Mo, and mixtures thereof; a preferred embodiment of the IA element is at least one selected from the group consisting of Li, Na, and K; and a preferred embodiment of the lanthanum element is selected from the group consisting of Mg, Ca, and Ba. And at least one of Sr.
  • the molecular sieve preferred embodiment is at least one selected from the group consisting of ZSM-5, Y, mordenite and beta zeolite, and the composite molecule is selected from at least ZSM-5/mordenite, ZSM-5/germanium zeolite and ZSM-5/ ⁇ zeolite.
  • the molecular sieve and the composite molecular sieve have a silicon-aluminum molar ratio of SiO 2 /Al 2 0 3 preferably in the range of 10 to 500, more preferably in the range of 20 to 300; and the molecular sieve in the catalyst is preferably used in a weight percentage of 10% by weight of the catalyst. ⁇ 60%, preferably 20-50%.
  • the catalytic cracking fluidized bed catalyst of the present invention is used for catalytic cracking of heavy oil, light diesel oil, light gasoline, catalytic cracked gasoline, gas oil, condensate, carbon tetraolefin or carbon pentaolefin.
  • the catalytic cracking fluidized bed catalyst of the present invention is prepared by using the corresponding nitrate, oxalate, or oxide as the raw material of the material A.
  • Class B elements use the corresponding nitrates, oxalates, acetates or solubles! 3 ⁇ 4 compound.
  • the gravel element used is derived from phosphoric acid, triammonium phosphate, diammonium phosphate, and ammonium dihydrogen phosphate.
  • the active element may be impregnated on the molecular sieve, or may be directly mixed with the molecular sieve to form.
  • the catalyst was prepared in such a manner that a slurry containing each component element and a carrier was heated and refluxed for 5 hours in a water bath of 70 to 80 Torr, followed by spray drying.
  • the obtained powder was calcined in a muffle furnace at a temperature of 600 to 750 Torr and a calcination time of 3 to 10 hours.
  • the invention adopts at least one of SiO 2 , A1 2 3 3 , molecular sieve or composite molecular sieve having acidity, shape selectivity and high specific surface area as a cracking aid, which is favorable for cracking of hydrocarbon raw materials by a positive carbon ion mechanism.
  • relatively low temperature 580 ⁇ 650 ⁇
  • it achieves good catalytic cracking effect and obtains high ethylene propylene yield. , achieved good technical results.
  • naphtha (see Table 1 for specific indicators) was used as a raw material.
  • the reaction temperature ranges from 580 to 650 Torr
  • the catalyst load is 0.5 to 2 grams of naphtha per gram of catalyst per hour
  • the water/naphtha weight ratio is from 0.5 to 3:1.
  • the fluidized bed reactor has an inner diameter of 39 mils and a reaction pressure of 0 to 0.2 MPa.
  • the slurry B was heated on a 70-80 Torr water bath, and 15 g of the above-mentioned exchanged molecular sieve and 5 g of silica were added, and the mixture was refluxed for 5 hours, and the slurry was dried by a spray drying apparatus.
  • the dried powder was placed in a muffle furnace and heated to 740 Torr for 5 hours. After cooling, the catalyst was obtained, and the catalyst was passed through a 100 mesh sieve.
  • the chemical formula of the catalyst is: F e ⁇ m Co 0 . 08 Cr. ,. 8 + carrier 31.57 wt%
  • the catalyst activity was evaluated under the following conditions: 39 A fluidized bed reactor having an inner diameter of ⁇ , a reaction temperature of 650 Torr, and a pressure of 0.15 MPa. The water/naphtha weight ratio is 3:1, the catalyst loading is 20 grams, and the loading is 1 gram of naphtha per gram of catalyst per hour. Gas products were collected for gas phase color analysis, product distribution and ethylene + propylene yield are shown in Table 2. Table 2 Gas phase product distribution and ethylene + propylene yield
  • the chemical formula of the catalyst was obtained as follows: Co 0 . 06 Zn 0 . 06 Cu 0 . 08 Ce 0 . 09 P 0 . 08 O x + carrier 40.5%.
  • a hydrogen type mordenite having a ratio of 5 g of silica to alumina of 20 and a hydrogen type of 5 g of silicon to aluminum of 40 MCM - 22, 5 g of a hydrogen type beta zeolite having a ratio of 30 to 37 aluminum oxide and 5 g of silica were placed in the solution, and the same as in Example 1.
  • the chemical formula of the catalyst was: Fe 0 . 05 Zn 0 . 06 Ce 0 . 09 Ca 0 . 04 P 0 . 08 O x + carrier 39.7%.
  • the chemical formula of the catalyst is: Mn. E8 Co 0 . 06 Ce 0 . 09 P 0 . 08 O x + carrier 46 ⁇ 6%.
  • the product yield is shown in Table 4.
  • the chemical formula of the catalyst was obtained as follows: Mn . 8 Co 0 . 06 Ce 0 . 09 P 0 . 08 O x + carrier 46.6%.
  • the product yield is shown in Table 4.
  • the chemical formula of the catalyst is: Co. Q6 Cr 0 . 06 + 45.1% carrier (without molecular sieve).
  • Slurry B was obtained in the same manner as in Example 1 and directly added to the same ZSM-5 molecular sieve and silica.
  • the catalyst composition was the same as in Example 1 without a load process, and the mixture was directly sprayed and sprayed.
  • the evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 5.
  • the slurry B was obtained in the same manner as in Example 1, and the same amount of ZSM-5/mordenite composite molecular sieve and silica having a ratio of silica to alumina of 20 were added, and a catalyst was obtained in the same manner.
  • the evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 5.
  • Slurry B was obtained in the same manner as in Example 1 and the same amount of ZSM having a ratio of silica to alumina of 20 was added.
  • the slurry B was obtained in the same manner as in Example 1, and the same amount of ⁇ zeolite/mordenite composite molecular sieve and silica having a ratio of silica to alumina of 20 were added, and a catalyst was obtained in the same manner.
  • the evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 5. [Embodiment 12]
  • the slurry was prepared in the same manner as in Example 1, and 5 g of a hydrogen-type ZSM-5 having a ratio of silicon to aluminum of 120, 10 g of a ZSM-5/mordenite composite molecular sieve having a ratio of silica to alumina of 20 and 5 g of silica were added.
  • the catalyst was prepared in the same manner.
  • the evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 5.
  • the slurry was prepared in the same manner as in Example 1 and 12 g of a hydrogen type ZSM having a ratio of silicon to aluminum of 150 was added.
  • the composition formula was: Fe ⁇ Co 0 . 08 Cr 0 . 08 La 0 . 04 P 0 . 05 O x + carrier 21.32 (% by weight) of the catalyst, evaluated according to the method of Example 1, the result As shown in Table 5.
  • Slurry B was obtained in the same manner as in Example 1, and 20 g of a hydrogen type ZSM-5/Mordenite having a ratio of silica to alumina of 30 was added as a carrier to prepare a chemical formula: F e (m Co 0 . 08 Cr 0 . 08 La 0 . 04 P 0 . 05 O x + support 31.6 (% by weight) of the catalyst, which was evaluated in the same manner as in Example 1, and the results are shown in Table 5.
  • Example 6 Using the catalyst prepared in Example 1, using light diesel oil having a boiling point of less than 350 Torr as a reaction material, the evaluation was carried out under the same conditions as in Example 1, and the results are shown in Table 6.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Description

催化裂解流化床催化剂 技术领域
本发明涉及一种催化裂解流化床催化剂， 特别是关于一种石脑油 催化裂解制乙烯丙烯的流化床催化剂。
背景技术
目前制乙烯丙烯的最主要的方法是蒸汽热裂解。 所采用最多的原 料是石脑油。 但蒸汽热裂解石脑油存在着反应温度高， 工艺条件苛刻， 对设备尤其是炉管材料要求高， 损耗大的缺点。 为此人们开展了各种 有意义的研究， 其中催化裂解是最有吸引力， 也是最有前途的一项。 目标在于寻找一种合适的裂解催化剂， 提高乙烯丙烯的选择性， 降低 反应温度， 同时可以在乙烯丙烯的收率上有一定的灵活性。
从现有的文献来看， 多数催化裂解研究者多用高硅铝比的分子筛 作催化材料， 而且用高价态的金属离子进行交换和浸渍。 但分子筛催 化剂具有水热稳定性差， 难以再生的缺点。
美国专利 USP6211104和国内专利 CN1504540A采用一种含 10 - 70 重量。 /。粘土， 5 ~ 85 重量％无机氧化物， 1 ~ 50 重量％分子筛组成 催化剂， 对传统蒸汽热裂解的各种原料， 显示出了很好的转化为轻烯 烃的活性， 尤其是乙烯。 用的分子筛， 是由高硅铝比的 0 ~ 25重量％¥ 沸石或具有 MFI结构的 ZSM分子筛， 由磷 /Al、 Mg或 Ca浸渍而成， 基本上也属于单純分子筛类催化剂。
除此以外， 人们用氧化物作催化剂。
美国 Phillips公司的专利 US4620051和 US4705769采用了以氧化 锰或氧化铁为活性组分， 添加了稀土元素 La， 以及碱土金属 Mg的氧 化物催化剂， 裂解 C3、 C4原料。 Mn，Mg/Al203催化剂在实验室的固 定床反应器中， 700Ό， 水与丁烷的摩尔比为 1 : 1， 丁烷的转化率可 达 80%， 乙烯， 丙烯的选择性为 34%和 20%。 该两个专利声称也可 以用石脑油和流化床反应器。
意大利恩尼切姆公司的专利 CN1317546A 涉及化学式为 12CaO'7Al203的蒸汽裂解反应催化剂。 原料可以用石脑油， 操作温度 720 ~ 800*C , 在 1.1 ~ 1·8 个大气压下， 接触时间 0.07 ~ 0.2 秒， 乙烯 和丙烯的产率可达 43%。
前苏联专利 USSR Patl298240.1987 用负载于浮石或陶瓷上的 Zr203和钒酸钾， 温度 660 ~ 780Ό中型装置上空速为 2_5 小时 -1， 水 / 直馏汽油重量比 1 ： 1。 以正构烷烃 C7~ 17, 环己垸， 直馏汽油为原料， 乙烯产率可达到 46%， 丙烯 8.8%。
中国专利 CN1480255A介绍一种氧化物催化剂，用石脑油为原料， 在 780 下催化裂解制乙烯丙烯， 乙烯 +丙烯收率可达到 47%。
综上所述， 分子筛作为主要的裂解催化剂受到了人们的重视， 但 与氧化物混合使用的例子， 还未见报道。
发明内容
本发明所要解决的技术问题是现有技术催化裂解制乙烯丙蟑中反 应温度较高、 催化剂低温活性低和选择性较差的问题， 提供一种新的 催化裂解流化床催化剂。 使用该催化剂催化裂解石脑油制乙烯丙浠， 不但可以降低催化裂解温度， 还可以提高催化剂的选择性的优点。
为解决上述技术问题， 本发明采用的技术方案如下： 一种催化裂 解流化床催化剂， 含有选自 Si02、 A1203、 分子筛和复合分子筛中的 至少一种的载体和以原子比计化学式如下的组合物：
Bb Pc x
式中 A选自稀土元素中的至少一种；
B选自预、 Ι Β、 Π Β、 VHB、 VIB、 I A和 Π A中的至少一种元素； a的取值范围为 0.01 - 0.5;
b的取值范围为 0.01 ~ 0.5;
c的取值范围为 0.01 ~ 0.5;
X为满足催化剂中各元素化合价所需的氧原子总数；
分子筛任选自 ZSM-5、 Y沸石、 β沸石、 MCM-22、 SAPO-34和 丝光沸石中的至少一种， 复合分子筛为 ZSM-5、 Y 沸石、 P沸石、 MCM-22、 SAPO-34 或丝光沸石中的至少两种分子筛共同生长成的复 合物；
其中催化剂中分子筛的用量以重量百分比计为催化剂重量的 0 ~ 60%。
上述技术方案中， a 的取值优选范围为 0.01 ~ 0.3; b 的取值优选 范围为 0.01 ~ 0.3； c的取值优选范围为 0·01 ~ 0·3。 稀土元素的优选方 案为选自 La和 Ce中的至少一种。環族元素的优选方案为选自 Fe、 Co 和 Ni中的至少一种； I B元素的优选方案为选自 Cu和 Ag中的至少 一种； ΠΒ元素的优选方案为 Zn; VHB元素的优选方案为 Mn; VIB 元素的优选方案为选自 Cr、 Mo和其混合物； I A元素的优选方案为 选自 Li、 Na和 K中的至少一种； ΠΑ元素的优选方案为选自 Mg、 Ca、 Ba和 Sr中的至少一种。 分子筛优选方案为选自 ZSM-5、 Y、 丝光沸 石和 β沸石中的至少一种， 复合分子筛选自 ZSM- 5/丝光沸石、 ZSM -5/Υ沸石和 ZSM- 5/β 沸石中的至少一种； 分子筛和复合分子筛的 硅铝摩尔比 Si02/Al203优选范围为 10 ~ 500， 更优选范围为 20 ~ 300; 催化剂中分子筛的用量以重量百分比计优选范围为催化剂重量的 10~ 60% , 优选 20-50%。
本发明的催化裂解流化床催化剂用于重油、 轻柴油、 轻汽油、 催 化裂化汽油、 瓦斯油、 凝析油、 碳四烯烃或碳五烯烃的催化裂解。
本发明催化裂解流化床催化剂的制备， 所用的原料 A类元素用的 是相应的硝酸盐、 草酸盐、 或氧化物。 B类元素用的是相应的硝酸盐、 草酸盐、 乙酸盐或可溶性！ ¾化物。 所用的礫元素来源于磷酸、 磷酸三 铵、 磷酸氢二铵、 磷酸二氢铵。
催化剂制备方法中， 活性元素可以浸渍在分子筛上， 也可以直接 和分子筛均勾混合后成型。 制备催化剂的成形方式是将加入了各组分 元素和载体的浆液， 在 70~80Ό的水浴上加热回流 5小时后进行喷雾 干燥。 得到的粉末在马福炉中焙烧， 温度为 600~750Ό， 焙烧时间为 3-10小时。
本发明由于采用了具有酸性、 择形性和高比表面积的 Si02、 A1203、 分子筛或复合分子筛中的至少一种作为裂解助剂， 有利于烃类 原料按正碳离子机理裂解， 多产低碳烯烃， 同具有氧化还原性的活性 组份配合， 产生协同作用， 在相对较低温度 (580~650Ό)下， 达到较 好的催化裂解效果， 获得了较高的乙烯丙烯收率， 取得了较好的技术 效果。
为了考评本发明所涉及的催化剂活性， 用石脑油 （具体指标见表 1) 为原料。 反应的温度范围为 580~650Ό， 催化剂负荷为 0.5 ~ 2克 石脑油 /克催化剂 ·小时， 水 /石脑油重量比为 0.5~3： 1。 流化床反应 器的内径为 39亳米， 反应压力 0~0.2MPa。 表 1石脑油原料指标
Figure imgf000005_0002
下面通过实施例对本发明作进一步的阐述。 具体实施方式
【实施例 1】
将 2克硝酸铵溶解于 100亳升水中，放入 20克 ZSM-5分子筛（硅 铝摩尔比 Si02/Al203为 400 )原粉。 90Ό交换 2 小时后， 过滤， 得滤 饼。
取硝酸铁 16.2克， 硝酸钴 7.86克， 硝酸铬 12.23克和硝酸镧 2.4 克将它们一起溶解于 250亳升水中， 得到溶液 。 溶解 4.65克磷酸氢 二铵于 100亳升水中， 将其倒入 A溶液中， 搅拌均勾， 得到浆液8。
将浆液 B置于 70 ~ 80Ό水浴上加热，加入上述交换好的分子筛 15 克和二氧化硅 5克， 回流 5小时， 用喷雾干燥设备将浆液干燥成型。
将干燥后的粉末， 置于马福炉中升温至 740Ό , 灼烧 5 小时。 冷 却后得催化剂， 再将催化剂过 100目筛。
得到催化剂化学式为： Fe<m Co0.08 Cr。,。8
Figure imgf000005_0001
+载体 31.57 重量％
在以下条件下进行催化剂活性评价： 39 亳米内径的流化床反应 器， 反应温度 650Ό , 压力 0.15MPa。 水 /石脑油重量比 3： 1， 催化剂 装量为 20克,负荷为 1克石脑油 /克催化剂 ·小时。 收集气体产物， 进 行气相色讲分析， 产物分布及乙烯 +丙烯收率见表 2。 表 2气相产物分布及乙烯 +丙烯产率
Figure imgf000006_0001
【实施例 2】
将 2克硝酸铵溶解于 100亳升水中， 放入 20克 Y分子歸 （硅铝 摩尔比 Si02/Al203为 20 )原粉。 90Ό交换 2小时后， 过滤， 得滤饼。
取硝酸镍 7.27克， 硝酸铬 8.48克， 硝酸铈 5.44克， 溶解于 250 亳升水中， 得溶液 A。 溶解 6.54克磷酸氢二铵于 100亳升水中， 将其 倒入溶液 A中， 搅拌均勾， 得到浆液8。
将交换好的分子歸 15克、 二氧化硅 5克和氧化铝 2克放入浆液 B中， 其它同实施例 1， 得到催化剂化学式为：
io.07 Cr0.06 Ce0.09P0.08Ox +载体 44.9%
催化剂评价同实例 1， 裂解产物分布及乙烯 +丙烯收率见表 3。 表 3气相产物分布及乙烯 +丙烯产率
Figure imgf000007_0001
【实施例 3】
取硝酸钴 5.49克， 硝酸锌 5.60克， 硝酸铈 5.44克， 硝酸铜 6.30 克， 溶解于 250毫升水中， 得溶液 A。 溶解 6.54克磷酸氢二铵于 100 亳升水中， 将其倒入溶液 A中， 搅拌均勾， 得到浆液8。
将 10克硅铝比为 120的氢型 ZSM - 5分子筛、 5克硅铝比为 30 的氢型 P沸石和 5克二氧化硅放入浆液 B中， 其它同实施例 1。
得到催化剂化学式为： Co0.06 Zn0.06 Cu0.08Ce0.09P0.08Ox +载体 40.5%。
产物收率见表 4。
【实施例 4】
取硝酸铁 7.62克， 硝酸锌 5.60克， 硝酸铈 5.44克， 硝酸钙 5.18 克， 溶解于 250亳升水中， 得溶液 A。 溶解 6.54克磷酸氢二铵于 100 亳升水中， 将其倒入溶液 A中， 搅拌均勾， 得到浆液8。
将将 5克硅铝比为 20的氢型丝光沸石、 5克硅铝比为 40的氢型 MCM - 22、 5克硅铝比为 30的氢型 β沸石和 5克二氧化硅放入溶液 中， 其它同实施例 1。
得到催化剂化学式为： Fe0.05 Zn0.06 Ce0.09Ca0.04P0.08Ox +载体 39.7%。
产物收率见表 4。
【实施例 5】
取硝酸钴 5.49克， 50%的硝酸锰溶液 10.81克， 硝酸铈 5.44克， 溶解于 250亳升水中， 得溶液 A。 溶解 6.54克磷酸氢二铵于 100亳升 水中， 将其倒入溶液 A中， 搅拌均匀， 得到浆液6。
将 20克氧化铝放入浆液 B中， 其它同实施例 1。
得到催化剂化学式为： Mn。.e8 Co0.06 Ce0.09P0.08Ox +载体 46·6%。 产物收率见表 4。
【实施例 6】
取硝酸钴 5.49克， 50%的硝酸锰溶液 10.81克， 硝酸铈 5.44克， 溶解于 250毫升水中， 得溶液 Α。 溶解 6.54克磷酸氢二铵于 100亳升 水中， 将其倒入溶液 Α中， 搅拌均勾， 得到浆液8。
将 20克二氧化硅放入浆液 B中， 其它同实施例 1。
得到催化剂化学式为： Mn . 8 Co0.06 Ce0.09P0.08Ox +载体 46.6%。 产物收率见表 4。
【实施例 7】
取硝酸钴 5.49克， 硝酸铬 8.48克， 硝酸铈 5.44克， 硝酸钾 1.1 克， 溶解于 250亳升水中， 得溶液 A。 溶解 6.54克磷酸氢二铵于 100 亳升水中， 将其倒入溶液 A中， 搅拌均勾， 得到浆液8。
以 15克氧化硅和 5克氧化铝作载体， 放入浆液 B中， 其它同实 施例 1。
得到催化剂化学式为： Co .Q6 Cr0.06
Figure imgf000008_0001
+ 45.1%载体 (不含分子筛）。
产物收率见表 4。 表 4不同载体的产物收率
Figure imgf000009_0001
【实施例 8】
按实施例 1的方法制得浆液 B, 直接加入同样的 ZSM - 5分子筛 和二氧化硅， 不需负载过程， 搅拌均勾后直接喷雾成型， 制得催化剂 组成同实施例 1。 按实施例 1的方法考评， 结果如表 5。
【实施例 9】
取 284克偏硅酸钠， 用 300克蒸馏水溶解成溶液 A, 取 33.3克硫 酸铝， 用 100克蒸馏水制成溶液 B, 把 B溶液緩慢倒入 A溶液中， 强 力搅拌， 然后加入 24.4克乙二胺， 搅拌一段时间后， 用稀硫酸调节 pH 值在 11.5， 控制溶胶的摩尔配比为: Si:Al:乙二胺: Η2Ο=1:0.1: 0.4:40， 把混合溶液放入高压釜中， 在 180 C保温 40小时， 然后取出水洗、 烘 干、 焙烧， 制得 ZSM - 5和丝光沸石的复合分子筛。 用浓度为 5 %的 硝酸铵溶液， 在 70Ό交换两次， 然后焙烧， 重复两次后制得氢型 ZSM - 5/丝光沸石复合分子筛。
按实施例 1的方法制得桨液 B，加入同样量的硅铝比为 20的 ZSM - 5/丝光沸石复合分子筛和二氧化硅， 再按相同的办法制得催化剂。 按实施例 1的方法考评， 结果如表 5。
【实施例 10】
取 284克偏硅酸钠， 用 300克蒸镏水溶解成溶液 A, 取 33.3克硫 酸铝， 用 100克蒸馏水制成溶液 B， 把 B溶液緩慢倒入 A溶液中， 强 力搅拌， 然后加入 24.4克乙二胺， 搅拌一段时间后， 用稀硫酸调节 pH 值在 11左右， 加入 5克 Y沸石晶种， 控制溶胶的摩尔配比为： Si:Al: 乙二胺: Η2Ο=1:0.1: 0.4:40， 把混合溶液放入高压釜中， 在 170Ό保温 36小时， 然后取出水洗、 烘干、 焙烧， 制得 ZSM - 5和 Y沸石的复 合分子筛。 用浓度为 5 %的硝酸铵溶液， 在 70Ό交换两次， 然后焙烧， 重复两次后制得氢型 ZSM - 5/Y沸石复合分子筛。
按实施例 1的方法制得浆液 B，加入同样量的硅铝比为 20的 ZSM
- 5/Y 沸石复合分子筛和二氧化硅， 再按相同的办法制得催化剂。 按 实施例 1的方法考评， 结果如表 5。
【实施例 111
取 284克偏硅酸钠， 用 300克蒸馏水溶解成溶液 A， 取 33.3克硫 酸铝， 用 100克蒸馏水制成溶液 B, 把 B溶液緩慢倒入 A溶液中， 强 力搅拌， 然后加入 24.4克乙二胺 10克四乙基氢氧化铵， 搅拌一段时 间后， 用稀硫酸调节 pH值在 12左右， 加入 5克 P沸石晶种， 控制溶 胶的摩尔配比为： Si:Al:乙二胺: Η2Ο=1:0.1: 0.4:40， 把混合溶液放入 高压釜中， 在 160"€保温 40小时， 然后取出水洗、 烘干、 焙烧， 制得 丝光沸石和 β沸石的复合分子筛。 用浓度为 5 %的硝酸铵溶液， 在 70 °C交换两次， 然后焙烧， 重复两次后制得氢型丝光沸石 / P沸石复合分 子筛。
按实施例 1 的方法制得桨液 B, 加入同样量的硅铝比为 20 的 β 沸石 /丝光沸石复合分子筛和二氧化硅， 再按相同的办法制得催化剂。 按实施例 1的方法考评， 结果如表 5。 【实施例 12】
按实施例 1的方法制得浆液 Β，加入 5克硅铝比为 120的氢型 ZSM - 5、 10克硅铝比为 20的 ZSM - 5/丝光沸石复合分子筛和 5克二氧 化硅， 再按相同的办法制得催化剂。 按实施例 1 的方法考评， 结果如 表 5。
【实施例 13】
按实施例 1的方法制得浆液 Β,加入 12克硅铝比为 150的氢型 ZSM
- 5作为载体， 制得组成化学式为： Fe^ Co0.08 Cr0.08 La0.04P0.05Ox +载 体 21.32 (重量％) 的催化剂， 按实施例 1的方法考评， 结果如表 5。 【实施例 14】
按实施例 1的方法制得浆液 B，加入 20克硅铝比为 30的氢型 ZSM - 5/丝光沸石作为载体， 制得组成化学式为： Fe(m Co0.08 Cr0.08 La0.04P0.05Ox +载体 31.6 (重量％ ) 的催化剂， 按实施例 1的方法考评， 结果如表 5。
表 5
Figure imgf000011_0001
【实施例 15】
用实施例 1 制备的催化剂， 用沸点低于 350Ό的轻柴油为反应原 料， 在与实施例 1相同的条件下考评， 结果如表 6。
【实施例 16】
用实施例 1 制备的催化剂， 用混合碳四 （烷烃： 烯烃 = 1: 1 ) 为 反应原料， 在 550Ό , 水油比为 3: 1， 空速为 1相同的条件下考评， 结果如表 6。
表 6
实施例 乙烯收率 丙烯收率 乙烯 +丙烯收率 实施例 15 28.47% 9.25% 37.72%
实施例 16 12.21% 38.63% 50.84%

Claims

权 利 要 求
1、 一种催化裂解流化床催化剂， 含有选自 Si02、 A1203、 分子筛 和复合分子筛中的至少一种的载体和以原子比计化学式如下的组合 物：
B¾ PA
式中 A选自稀土元素中的至少一种；
B选自 VIII、 Ι Β、 Π Β、 VHB、 VIB、 I A和 Π A中的至少一种元素； a的取值范围为 0.01 - 0.5;
b的取值范围为 0.01 - 0.5;
c的取值范围为 0.01 - 0.5;
X为满足催化剂中各元素化合价所需的氧原子总数；
分子筛选自 ZSM-5、 Y沸石、 β沸石、 MCM-22、 SAPO-34和丝 光沸石中的至少一种， 复合分子筛为 ZSM-5、 Y 沸石、 β沸石、 MCM-22、 SAPO-34 或丝光沸石中的至少两种分子筛共同生长成的复 合物；
其中催化剂中分子筛的用量以重量百分比计为催化剂重量的 0 ~ 60%。
2、 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于 a 的取值范围为 0.01 ~ 0.3; b的取值范围为 0.01 ~ 0.3; c的取值范围为 0.01 ~ 0.3。
3、 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于稀 土元素选自 La和 Ce中的至少一种。
4、 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于覆 族的元素选自 Fe、 Co和 Ni中的至少一种； I B的元素选自 Cu和 Ag 中的至少一种； Π Β的元素是 Zn; VHB的元素选自 Mn; VIB的元素 选自 Cr和 Mo中的至少一种， I A的元素选自 Li、 Na和 K中的至 少一种； Π Α的元素选自 Mg、 Ca、 ： Ba和 Sr中的至少一种。
5、 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于分 子筛选自 ZSM-5、 Y丝光沸石和 β沸石中的至少一种， 复合分子筛选 自 ZSM - 5/丝光沸石、 ZSM - 5/Υ沸石和 ZSM - 5/β沸石中的至少一 种。 6、 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于分 子筛和复合分子筛的硅铝摩尔比 Si02/Al203为 10 ~ 500。
，、 根据权利要求 6 所述催化裂解流化床催化剂， 其特征在于分 子筛和复合分子筛的硅铝摩尔比 Si02/Al203为 20 ~ 300。
8、 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于催 化剂中分子筛的用量以重量百分比计为催化剂重量的 10 - 60 % 。
9. 根据权利要求 1 所述催化裂解流化床催化剂， 其特征在于催 化剂中分子筛的用量以重量百分比计为催化剂重量的 20-50%。
10. 权利要求 1所述催化裂解流化床催化剂， 用于重油、 轻柴油、 轻汽油、 催化裂化汽油、 瓦斯油、 凝析油、 碳四烯烃或碳五烯烃的催 化裂解。
PCT/CN2006/002072 2005-08-15 2006-08-15 Fludized bed catalyst for catalytic pyrolyzing Ceased WO2007019797A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020087006339A KR101347189B1 (ko) 2005-08-15 2006-08-15 접촉 열분해용 유동층 촉매
US12/063,598 US20090288990A1 (en) 2005-08-15 2006-08-15 Catalyst for Catalytic Cracking Fluidized Bed
US12/978,107 US9480975B2 (en) 2005-08-15 2010-12-23 Catalyst for catalytic cracking in a fluidized bed

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2005100287943A CN100391610C (zh) 2005-08-15 2005-08-15 含分子筛的催化裂解流化床催化剂
CN200510028794.3 2005-08-15

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US12/063,598 A-371-Of-International US20090288990A1 (en) 2005-08-15 2006-08-15 Catalyst for Catalytic Cracking Fluidized Bed
US12/978,107 Continuation-In-Part US9480975B2 (en) 2005-08-15 2010-12-23 Catalyst for catalytic cracking in a fluidized bed

Publications (1)

Publication Number Publication Date
WO2007019797A1 true WO2007019797A1 (en) 2007-02-22

Family

ID=37736666

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2006/002072 Ceased WO2007019797A1 (en) 2005-08-15 2006-08-15 Fludized bed catalyst for catalytic pyrolyzing

Country Status (6)

Country Link
US (1) US20090288990A1 (zh)
KR (1) KR101347189B1 (zh)
CN (1) CN100391610C (zh)
RU (1) RU2403972C2 (zh)
SG (1) SG10201506253UA (zh)
WO (1) WO2007019797A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010067379A3 (en) * 2008-12-10 2011-03-24 Reliance Industries Limited A fluid catalytic cracking (fcc) process for manufacturing propylene and ethylene in increased yield
CN104549455A (zh) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 石脑油催化裂解产丙烯的催化剂及其制备方法和石脑油催化裂解产丙烯的方法

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201401522XA (en) * 2011-10-17 2014-05-29 Exxonmobil Res & Eng Co Selective dehydration of alcohols to dialkylethers and integrated alcohol-to-gasoline processes
CN103896709B (zh) * 2012-12-28 2016-01-20 中国石油化工股份有限公司 一种环烷烃开环的催化方法
US10099210B2 (en) 2013-04-29 2018-10-16 Saudi Basic Industries Corporation Catalytic methods for converting naphtha into olefins
RU2544241C1 (ru) 2014-01-22 2015-03-20 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" Способ получения ароматических углеводородов из природного газа и установка для его осуществления
RU2550354C1 (ru) 2014-03-28 2015-05-10 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" Способ получения концентрата ароматических углеводородов из легких алифатических углеводородов и установка для его осуществления
RU2544017C1 (ru) 2014-01-28 2015-03-10 Ольга Васильевна Малова Катализатор и способ ароматизации с3-с4 газов, легких углеводородных фракций алифатических спиртов, а также их смесей
RU2558955C1 (ru) 2014-08-12 2015-08-10 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" Способ получения концентрата ароматических углеводородов из жидких углеводородных фракций и установка для его осуществления
KR102356149B1 (ko) 2014-02-07 2022-01-28 바스프 코포레이션 공급원료의 열분해용 촉매
WO2017155424A1 (en) 2016-03-09 2017-09-14 Limited Liability Company "New Gas Technologies-Synthesis" (Llc "Ngt-Synthesis") Method and plant for producing high-octane gasolines
US9981888B2 (en) * 2016-06-23 2018-05-29 Saudi Arabian Oil Company Processes for high severity fluid catalytic cracking systems
US10870802B2 (en) 2017-05-31 2020-12-22 Saudi Arabian Oil Company High-severity fluidized catalytic cracking systems and processes having partial catalyst recycle
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
CN112138713B (zh) * 2019-06-28 2022-01-04 中国石油化工股份有限公司 一种催化裂解助剂及其制备方法和应用
EA202192284A1 (ru) * 2019-02-20 2021-11-16 Кара Текнолоджиз Инк. Каталитическая структура и способ облагораживания углеводородов в присутствии каталитической структуры
RU2747869C1 (ru) 2020-06-29 2021-05-17 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" (Ооо "Нгт-Синтез") Способ получения бензинов или концентратов ароматических соединений с различным распределением потоков оксигената и олефинсодержащей фракции
US11725150B2 (en) 2020-08-18 2023-08-15 Kara Technologies Inc. Method of light oil desulfurization in the presence of methane containing gas environment and catalyst structure
KR20230090313A (ko) 2020-08-26 2023-06-21 카라 테크놀로지스 아이엔씨. 메탄 함유 가스 환경 및 촉매 구조물의 존재 하에 액체 연료/화학물 생산을 위한 유기 고체 바이오매스 전환
US11332680B2 (en) 2020-09-01 2022-05-17 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of lesser and greater boiling point fractions with steam
US11352575B2 (en) 2020-09-01 2022-06-07 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize hydrotreating of cycle oil
US11230673B1 (en) 2020-09-01 2022-01-25 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of a lesser boiling point fraction with steam
US11434432B2 (en) 2020-09-01 2022-09-06 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of a greater boiling point fraction with steam
US11505754B2 (en) 2020-09-01 2022-11-22 Saudi Arabian Oil Company Processes for producing petrochemical products from atmospheric residues
US11230672B1 (en) 2020-09-01 2022-01-25 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking
US11242493B1 (en) 2020-09-01 2022-02-08 Saudi Arabian Oil Company Methods for processing crude oils to form light olefins
CN112322323A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 按原料类型的多区并联耦合床层控制多级催化反应的方法
CN112322334A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 基于原料性质的多区式耦合控制多级催化裂解方法及装置
CN112322324A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 基于原料类型的多区式耦合控制多级催化裂解方法及装置
CN112322328A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 按原料类型的多区协控耦合床层控制多级催化裂解的方法
CN112322326A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 按原料性质的双区协控耦合床层控制多级催化裂解的方法
CN112322338A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 基于原料类型的多区式耦合控制多级催化裂解方法及装置
CN112322330A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 按原料性质的双区分区耦合床层控制多级催化裂解的方法
CN112322321A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 基于原料性质的多区式耦合控制多级催化裂解方法及装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4886931A (en) * 1987-06-04 1989-12-12 The Standard Oil Company Upgrading low molecular weight hydrocarbons
US6458737B1 (en) * 1999-11-10 2002-10-01 Nippon Shokubai Co., Ltd. Catalyst for oxidizing methylbenzenes and method for producing aromatic aldehyde
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
CN1542090A (zh) * 2003-04-29 2004-11-03 中国石油化工股份有限公司 一种含分子筛和锰的裂化催化剂
RU2242279C2 (ru) * 2002-11-28 2004-12-20 Общество с ограниченной ответственностью "Томскнефтехим" Катализатор для превращения парафиновых углеводородов с2-с5, способ его получения и способ превращения парафиновых углеводородов с2-с5 в низшие олефины
CN1205306C (zh) * 2002-11-29 2005-06-08 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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4621162A (en) * 1985-07-25 1986-11-04 Phillips Petroleum Company Method for conversion of C3 and C4 hydrocarbons to olefinic products
US4620051A (en) * 1985-07-25 1986-10-28 Philips Petroleum Company Dehydrogenation and cracking of C3 and C4 hydrocarbons to less saturated hydrocarbons
DE4042655C2 (de) * 1990-07-11 1996-12-19 Ecolith Zeolithe Gmbh Verwendung eines synthetischen, kristallinen Alumosilikats mit der chemischen Zusammensetzung 0-3M¶2¶O : Al¶2¶O¶3¶ : 15-40SiO¶2¶ : 0-40H¶2¶O zur Gewinnung und Verarbeitung von Aromaten
CA2206891C (en) * 1994-11-23 2007-03-20 Exxon Chemical Patents, Inc. Hydrocarbon conversion process using a zeolite bound zeolite catalyst
CN1072032C (zh) * 1997-09-17 2001-10-03 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
DE69832938T2 (de) * 1997-10-15 2006-08-10 China Petro-Chemical Corp. Krackkatalysator für die Produktion von leichten Olefinen und dessen Herstellung
MXPA02006039A (es) * 1999-12-21 2002-12-09 Grace W R & Co Compuestos de oxido de aluminio de gran area superficial, alto volumen de poros, derivados de trihidrato de alumina y metodos para su preparacion y uso.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4886931A (en) * 1987-06-04 1989-12-12 The Standard Oil Company Upgrading low molecular weight hydrocarbons
US6458737B1 (en) * 1999-11-10 2002-10-01 Nippon Shokubai Co., Ltd. Catalyst for oxidizing methylbenzenes and method for producing aromatic aldehyde
RU2242279C2 (ru) * 2002-11-28 2004-12-20 Общество с ограниченной ответственностью "Томскнефтехим" Катализатор для превращения парафиновых углеводородов с2-с5, способ его получения и способ превращения парафиновых углеводородов с2-с5 в низшие олефины
CN1205306C (zh) * 2002-11-29 2005-06-08 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
CN1542090A (zh) * 2003-04-29 2004-11-03 中国石油化工股份有限公司 一种含分子筛和锰的裂化催化剂

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010067379A3 (en) * 2008-12-10 2011-03-24 Reliance Industries Limited A fluid catalytic cracking (fcc) process for manufacturing propylene and ethylene in increased yield
US8685232B2 (en) 2008-12-10 2014-04-01 Reliance Industries Limited Fluid catalytic cracking (FCC) process for manufacturing propylene and ethylene in increased yield
CN104549455A (zh) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 石脑油催化裂解产丙烯的催化剂及其制备方法和石脑油催化裂解产丙烯的方法

Also Published As

Publication number Publication date
CN100391610C (zh) 2008-06-04
KR20080035701A (ko) 2008-04-23
KR101347189B1 (ko) 2014-01-03
CN1915516A (zh) 2007-02-21
SG10201506253UA (en) 2015-09-29
RU2403972C2 (ru) 2010-11-20
US20090288990A1 (en) 2009-11-26
RU2008109666A (ru) 2009-09-27

Similar Documents

Publication Publication Date Title
WO2007019797A1 (en) Fludized bed catalyst for catalytic pyrolyzing
JP5465822B2 (ja) 接触分解によるエチレンおよびプロピレン製造のための流動層触媒
CN101279287B (zh) 用于催化裂解制烯烃的催化剂
CN102049284B (zh) 一种催化裂化丙烯助剂及其制备方法
CN101491772B (zh) 用于石脑油催化裂解的催化剂
US20020061813A1 (en) Catalytic promoters for the catalytic cracking of hydrocarbons and the preparation thereof
CN102553638B (zh) 一种双微孔-介孔复合分子筛加氢裂化催化剂
CN101745412B (zh) 催化裂化催化剂及制备方法
US9480975B2 (en) Catalyst for catalytic cracking in a fluidized bed
CN101310858B (zh) 一种重油催化裂化催化剂
CN101279284B (zh) 催化裂解制乙烯丙烯的催化剂
CN101347746B (zh) 用于石脑油催化裂解制烯烃的催化剂
CN101428233B (zh) 用于催化裂解的催化剂
CN112642475B (zh) 一种用于烃油转化生产低碳烯烃的催化裂解催化剂
CN100567228C (zh) 催化裂解生产烯烃的方法
CN101348408B (zh) 制乙烯丙烯的石脑油催化裂解方法
CN100532335C (zh) 流化床催化裂解制乙烯和丙烯的方法
CN1048428C (zh) 制取低碳烯烃的多沸石催化剂
CN101190414B (zh) 催化裂解生产烯烃的流化床催化剂
CN101279285B (zh) 制乙烯丙烯的石脑油催化裂解催化剂
CN102453501B (zh) 一种烃油转化方法
CN101190417B (zh) 催化裂解制乙烯丙烯的催化剂
JP5587761B2 (ja) 単環芳香族炭化水素の製造方法
CN102453502A (zh) 烃油转化方法
CN110479362B (zh) 一种多产柴油和多产低碳烯烃的催化剂及其制备方法与应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1020087006339

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2008109666

Country of ref document: RU

WWE Wipo information: entry into national phase

Ref document number: 12063598

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 06775390

Country of ref document: EP

Kind code of ref document: A1